USOO7461594 B2

(12) United States Patent (10) Patent No.: US 7.461,594 B2

Goto (45) Date of Patent: *Dec. 9, 2008

(54) PRINTING PLATE MATERIAL PRINTING (51) Int. Cl.

PLATE MANUFACTURING METHOD, AND B4IN I/O (2006.01)
PRINTING METHOD (52) U.S. Cl. ....................... 101/.457; 101/451; 101/453;
101/467: 101/484; 430/302
(75) Inventor: Kiyoshi Goto, Hachioji (JP) (58) Field of Classification Search .............. 101/463.1,
101/.457
(73) Assignee: Konica Minolta Medical & Graphic, See application file for complete search history.
Inc.,
nc., Tokvo (JP
Tokyo (JP) (56) References Cited
(*) Notice: Subject to any disclaimer, the term of this U.S. PATENT DOCUMENTS
patent is extended or adjusted under 35 6,110,085. A * 8/2000 Schloemer et al. ............ 492.59
U.S.C. 154(b) by 0 days. 2002.0056392 A1* 5, 2002 Sameit et al. ... 101.f484
2005, OO61183 A1* 3/2005 Maehashi ......... ... 101,453
This patent is Subject to a terminal dis 2005/O194087 A1* 9/2005 Rossini et al. .............. 156,190
claimer.
* cited by examiner
(21) Appl. No.: 11/332.583 Primary Examiner Leslie J. Evanisko
Assistant Examiner Joshua Zimmerman
(22) Filed: Jan. 13, 2006 (74) Attorney, Agent, or Firm Lucas & Mercanti, LLP
(65) Prior Publication Data (57) ABSTRACT
US 2006/0207454 A1 Sep. 21, 2006 A printing plate material having an aluminum Support on
which an image forming layer is provided, wherein a wireless
(30) Foreign Application Priority Data IC tag is provided on a part of the printing plate material.
Jan. 18, 2005 (JP) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2005-010102

Mar. 1, 2005 (JP) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2005-0556O1

12 Claims, 9 Drawing Sheets
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U.S. Patent Dec. 9, 2008 Sheet 7 Of 9 US 7.461,594 B2

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U.S. Patent Dec. 9, 2008 Sheet 9 Of 9 US 7.461,594 B2

FIG. 9
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FIG. 10

13
 US 7,461,594 B2
1. 2
PRINTING PLATE MATERIAL PRINTING CPT printing, conditions of a plate-making apparatus are
PLATE MANUFACTURING METHOD, AND used after initial setting, so that desired printed matters may
PRINTING METHOD be obtained.
However, it has been necessary to prepare an exclusive
This application is based on Japanese Patent Application 5 plate-making apparatus respectively and to change condition
Nos. 2005-010102 filed on Jan. 18, 2005, and 2005-055601 setting manually, when using plural types and sizes of print
filed on Mar. 1, 2005, in Japanese Patent Office, the entire ing plate materials, because it is necessary to set a plate
content of which is hereby incorporated by reference. making apparatus and plate-making conditions depending on
types and sizes of printing plate materials for CTP.
BACKGROUND OF THE INVENTION 10 Even in the case of printing by the use of printing plate
materials for CTP, it has been necessary for an operator to set
The present invention relates to a printing plate material for an individual printing condition depending on a type of print
a computer-to-plate (hereinafter referred to as CTP) system ing plate material in the past, because optimum printing con
having an aluminum Support, a plate-making method and a 15 ditions vary depending on printing materials such as a type of
printing method. ink, dampening water and printing paper in addition to types
In recent years, in manufacturing technologies of printing of printing plate materials and image patterns.
plates for offset printing, there have been developed CTPs for ingInplate particular, in the case of in-flight processing type print
materials representing processless printing plate
recording digital data of images directly on a photosensitive
printing plate with a laser light source, and they have been put materials, it is necessary to set optimum conditions constantly
to practical use. for keeping fixed printing quality, because exposure condi
In the field of printing where relatively long plate life is tionsaffected
and water-ink balance conditions in the initial printing
required among the aforesaid technologies, there is known a areHowever, greatly by in-flight developability.
even when the conditions were set individually,
method to use a printing plate material having thereon an it was impossible to avoid occurrence of a width offluctuation
aluminum plate representing a Support and an image forming 25
layer provided on the aluminum plate. to a certain extent in printing quality, because of actual fluc
tuations of manufacturing lot of printing plate materials,
As the aluminum plate, there are generally used those aging performance, efficiency by working environment Such
Subjected to Surface-roughening treatment and anodic treat as temperature and humidity, or of output of exposure light
ment.
Source and in printing conditions.
On the other hand, there is a demand for a printing plate 30 Further, in the past, it was necessary to control developing
material that requires no photographic processing by a pro conditions and printing conditions based on information of
cessing solution containing specific chemicals (for example, exposure conditions and developing conditions recorded on,
an alkali, an acid and a solvent), and can be applied to con for example, a sheet of paper, and it was necessary to control
ventional printing machines, and for example, there are plate-making and printing manually, which was extremely
known printing plate materials for a dry CTP method such as 35 time-consuming and errors of control were easily caused.
a printing plate material of a phase changing type that does On the other hand, in recent years, development of RFID
not require photographic processing at all and a printing plate (wireless IC tag) has been advanced in the field of non-contact
material in which photographic processing is conducted in IC card.
the initial stage of printing on the printing machine and does Owing to the tendency toward a low price and downsizing
not require a development process in particular. 40 of (wireless IC tag), there are known practical use as tools for
As those used for a dry CTP method, there are given, for production control and stock control of commodities includ
example, printing plate materials of an abrasion type ing a field of cards having a high added value (for example,
described in TOKUKAIHEI Nos. 8-507727, 6-186750, see Patent Document 4).
6-199064, 7-314934, 10-58636 and 10-24.4773, and those of (Patent Document 1) TOKUKAI No. 2001-96710
a type in which a thermosensitive image forming layer is 45 (Patent Document 2) TOKUKAI No. 2001-138652
provided on a basematerial and animage portion is formed on (Patent Document 3) TOKUKAI No. 2001-113848
a hydrophilic layer through imagewise heat generation by (Patent Document 4) TOKUKAI No. 2003-67838
laser exposure (for example, Patent Document 1, Patent
Document 2 and Patent Document 3). SUMMARY OF THE INVENTION
The printing plate material having athermosensitive image 50
forming layer for forming an image portion where a laser Objects of the invention are to provide a printing plate
beam is converted into heat on a hydrophilic layer is suitable material, a plate-making method and a printing method,
for forming a high-definition images, because sharp dots are wherein a plate life is long, a fluctuation of printing quality is
formed. 55 reduced, and printed matters having stable quality can be
As the printing plate material for CTP having relatively obtained constantly.
high plate life, there are known printing plate materials each The objects of the invention stated above can be attained by
having therein a photopolymerization type image forming the following items.
layer described in, for example, TOKUKAI Nos. 2002
107916 and 2003-76010. (Item 1)
60
Since halftones are recorded with 100-300 lines of laser A printing plate material having an aluminum Support on
each being converged to 5-30 jum in CTP in general, an IC tag an which
is
image forming layer is provided, wherein a wireless
provided on a part of the printing plate material.
individual halftone is recorded with plural laser beams as a
rule. (Item 2)
In a principle, therefore, it is possible to change gradation 65 The printing plate material described in Item 1, wherein the
reproduction for printing optionally, by changing exposure wireless IC tag is installed on the printing plate material
pattern and output of laser exposure, thus, in conventional through an insulating object.
 US 7,461,594 B2
3 4
(Item3) (Item 15)
The printing plate material described in Item 1 or Item 2, A packaging object for packaging an aggregate of litho
wherein the wireless IC tag is on the same plane as that on graphic printing plate materials, wherein a wireless IC tag is
which the printing plate material is. installed.
(Item 4) (Item 16)
The printing plate material described in any one of Item
1-Item 3, wherein the printing plate material is rectangular, An aggregate of lithographic printing plate materials
and the wireless IC tag is in the rectangle. wherein the aggregate is packaged by the packaging object
10 for packaging an aggregate of lithographic printing plate
(Item 5) materials described in Item 15.
The printing plate material described in Item 1, wherein the
wireless IC tag is pasted on the aluminum Support by means (Item 17)
of an insulating adhesive layer. A plate-making and printing method for conducting plate
(Item 6) 15 making and printing by using the aggregate of lithographic
The printing plate material described in Item 5, wherein the printing plate materials described in Item 16, wherein the
wireless IC tag pasted on the aluminum Support by means of wireless IC tag holds data of information concerning the
an insulating adhesive layer is further covered by an insulat lithographic printing plate materials, and plate-making con
ing object. ditions for the plate-making or printing conditions for the
(Item 7) printing are established by the use of that data.
The printing plate material described in any one of Item Owing to the items stated above, it is possible to provide a
1-Item 6, wherein the wireless IC tag holds data of informa printing plate material, a plate-making method and a printing
tion concerning the printing plate material. method wherein a plate life is long, fluctuations in quality of
(Item 8)
25 printing are reduced and printed matters having stable quality
The printing plate material described in Item 7, wherein the can be obtained constantly, in the printing employing printing
information concerning the printing plate material is infor plate materials for CTP.
mation about manufacturing, information about performance BRIEF DESCRIPTION OF THE INVENTION
or information about plate-making processing conditions. 30
(Item 9) FIG. 1 is a schematic diagram for a plan view and a cross
A plate-making method for making the printing plate mate sectional view showing an example of a printing plate mate
rial described in Item 7 or Item 8, wherein imagewise expo rial of the invention.
Sure is carried out by controlling imagewise exposure condi
tions based on data of information concerning the printing 35 FIG. 2 is a schematic diagram for a plan view and a cross
plate material. sectional view showing an example of a printing plate mate
rial of the invention.
(Item 10) FIG. 3 is a schematic diagram for a plan view and a cross
The plate-making method described in Item 9, wherein sectional view showing an example of a printing plate mate
information concerning the printing plate material is infor 40
rial of the invention.
mation of sensitiveness.
FIG. 4 is a schematic diagram for a plan view and a cross
(Item 11) sectional view showing an example of a printing plate mate
A plate-making method for making the printing plate mate rial of the invention.
rial described in Item 7 or Item 8, wherein photographic 45 FIG. 5 is a schematic diagram for a plan view and a cross
processing is carried out by controlling photographic pro sectional view showing an example of a printing plate mate
cessing conditions based on data of information concerning rial of the invention.
the printing plate material.
FIG. 6 is a schematic diagram for a plan view and a cross
(Item 12) 50
sectional view showing an example of a printing plate mate
The plate-making method according to Item 11, wherein rial of the invention.
information concerning the printing plate material includes FIG. 7 is a schematic diagram for a plan view and a cross
aging information after manufacturing the printing plate sectional view showing an example of a printing plate mate
material and information of exposure conditions. rial of the invention.
(Item 13) 55 FIG. 8 is a schematic diagram showing an embodiment of
A printing method for printing by using a printing plate a packaging object for lithographic printing plate materials
made by conducting imagewise exposure and photographic and an aggregate of lithographic printing plate materials of
processing on the printing plate material described in Item 7 the invention.
or Item 8, wherein printing conditions are controlled based on FIG. 9 is a schematic diagram showing another embodi
data of information concerning the printing plate material for 60
ment of a packaging object for lithographic printing plate
conducting printing. materials and an aggregate of lithographic printing plate
(Item 14) materials of the invention.
The printing method according to Item 13, wherein infor FIG. 10 is a schematic diagram showing still another
mation concerning the printing plate material includes infor 65 embodiment of a packaging object for lithographic printing
mation of exposure conditions and information of photo plate materials and an aggregate of lithographic printing plate
graphic processing conditions. materials of the invention.
 US 7,461,594 B2
5 6
DETAILED DESCRIPTION OF THE PREFERRED In the invention, a configuration wherein a wireless IC tag
EMBODIMENT and a printing plate material are on the same plane is prefer
able from the viewpoint of easy communication of informa
The invention will be explained in detail as follows. tion.
The invention is characterized in a printing plate material In the invention, a configuration wherein a wireless IC tag
having an image forming layer on an aluminum Support to and an insulating object are on the same plane as that for the
have a wireless IC tag that is provided on a part of the printing printing plate material is preferable from the viewpoint of
plate material. easy handling.
In the invention, by providing a wireless IC tag on a print Being on the same plane as that for the printing plate
ing plate material, it is possible to obtain a printing plate 10 material means the existence within a range Surrounded by a
material which is a printing plate material for CTP wherein a Surface on one side of the printing plate material plus a Sur
plate life is long, fluctuations in printing quality are reduced face extended from the aforesaid Surface, and by a Surface on
and printed matters having stable quality can be obtained the other side plus its extended surface, and in other words, it
constantly. means that the printing plate material does not have a protru
A printing plate material of the invention has, on a Surface 15 sion of the wireless IC tag at least on its obverse side and on
of one side of an aluminum Support, an image forming layer its reverse side.
where a printing plate can be made by digital devices such as For arranging the wireless IC tag to be on the same plane as
a laser, a thermal head and an ink-jet head. that for the printing plate material, it is possible to cut off a
Among them, effects of the invention can be exhibited part of the printing plate material, and thereby to fix the
remarkably on the printing plate material used especially for wireless IC tag at the cutout portion on the printing plate
laser exposure. material through an insulating object.
A wireless IC tag (RF-ID) used in the invention is one that As a method for the fixing, there is given a method, for
houses therein at least a semiconductor memory and a coil example, wherein an insulating object is fixed on the circum
(antenna) for two-way transmission, and is constructed so ference of the wireless IC tag, and this insulating object is
that it can communicate information with an outer exclusive 25 fixed on the cutout portion.
reader/writer on a noncontact basis. As a form of the insulating object, there are given a plate
Though the wireless IC tag is provided on a part of the shaped object that is hollowed out so that the wireless IC tag
printing plate material, it is preferable that it is provided on a may be embedded therein, and a net-shaped object that is
portion that does not affect on printing Substantially, and constructed so that the wireless IC tag may be inserted
30 therein.
preferable is a portion in the vicinity of the end portion of the
printing plate material. It is preferable that the printing plate material of the inven
As a configuration for the wireless IC tag to be installed on tion is in a rectangular shape.
the printing plate material, there is given a configuration The wireless IC tag may be installed to be adjacent to this
where the wireless IC tag is pasted on the surface on the side rectangle, and preferable is that the wireless IC tag is arranged
of the printing plate material having an image forming layer 35 within a range of the rectangle, namely, within this rectangle.
or on the Surface on the opposite side thereof, for example, or As a position for the wireless IC tag within the rectangle to
a configuration wherein the wireless IC tag is installed on the bearranged, a position near the end portion of the rectangle as
same plane as that on which the aluminum Support is pro stated above is preferable.
vided. Each of FIGS. 1-7 shows an example of the embodiment of
40 the printing plate material of the invention on which the
As a method to install the wireless IC tag in the invention, wireless IC tag is installed.
it is a preferable configuration that the wireless IC tag is Each of FIGS. 1-7 shows a schematic diagram for a plan
installed on the printing plate material through an insulating view and a cross-sectional view of a printing plate material.
object. Each of FIGS. 1, 2, 3, 4 and 7 is an illustration of an
After receiving a radio wave coming from a reader/writer 45 example of the wireless IC tag which is on the same plane as
with an antenna, the wireless IC tag generates electric power that for the printing plate material.
with electromotive force by electromagnetic induction. This In FIG. 1, wireless IC tag 5 is pasted on aluminum support
electric power operates an electric circuit inside the wireless 2 through insulating adhesive agents, and insulating object 4
IC tag, and control data are communicated with a reader/ is further pasted on the wireless IC tag 5. Owing to this
writer. Through this communication, information from a 50 configuration, the wireless IC tag 5 is isolated electrically
reader/writer is received to be stored in a semiconductor from the circumstance, and is protected from the outside by
memory, or information stored is sent to the reader/writer. the insulating object 4 that functions as a protective sheet.
As stated above, the wireless IC tag can be used semiper In each of FIGS. 2 and 3, a part of rectangular printing plate
manently because it requires no power Supply, but, for gen material 1 having aluminum Support 2 and image forming
erating electric powerthrough electromagnetic induction, it is 55 layer 3 is hollowed out, and wireless IC tag 5 is fixed on the
important to separate the wireless IC tag electrically from hollowed out portion through insulating object 4. Owing to
other electric conductors with an insulating object. this, the wireless IC tag is installed to be on the same plane as
For this reason, when installing the wireless IC tag on the that for the aluminum Support.
aluminum Support of the printing plate material, for example, In FIG. 4, the wireless IC tag 5 is fixed on the same plane
it is necessary to interpose an insulating object between the 60 as that for the printing plate material, although the position of
aluminum Support and the wireless IC tag. the fixing is out of a rectangle of the printing plate material.
As this configuration, there is considered one wherein the In FIG. 7, a part of the rectangular printing plate material is
wireless IC tag is installed on the aluminum Support by means cut out, and insulating object 4 in which wireless IC tag 5 is
of insulating adhesive agents, or one wherein an insulating embedded is fixed on the cut out portion.
object such as an insulating sheet or a two-sided adhesive and 65 Each of FIGS. 5 and 6 is one illustrating another example
insulating tape is provided on the aluminum Support, and the of the printing plate material on which the wireless IC tag is
wireless IC tag is provided on that insulating object. installed.
 US 7,461,594 B2
7 8
The wireless IC tag relating to the invention may also be configuration wherein a wireless IC tag is pasted on the pack
pasted on the insulating object processed, for example, to be aging object so that a convex portion may be formed.
seal-shaped. Each of FIGS. 8, 9 and 10 shows an example of the pack
As a specific example of a seal-shaped wireless IC tag, aging object of the invention on which a wireless IC tag is
there is given Contactless Smart Label made by Vanskee Co. installed.
When using a wireless IC tag in the aforesaid seal shape, its In FIG. 8, aggregate of lithographic printing plate materials
thickness is preferably 0.1 mm or less, and more preferable is 10 are held onvertical stacking palette 15that is made of steel,
0.07 mm or less. holding wooden plate 14, and wireless IC tag 12 is fixed on
Though the Smaller area of a wireless IC tag seal is more the upperportion of the wooden plate 14through unillustrated
preferable, it is necessary to secure an area for an antenna for 10 insulating object and adhesive agents.
making Sure communication possible. In FIG.9, aggregate 1 of lithographic printing plate mate
For pasting a wireless IC tag seal on the printing plate rials is loaded in packaging object 13 representing a box
material, a rectangular wireless IC tag seal is preferable, and shaped cassette made of plastic, and wireless IC tag 12 is fixed
a length of a shorter side is 25 mm or less, and preferable is 15 on the upper portion of the packaging object 13 through
mm or less and more preferable is 10 mm or less. 15 unillustrated adhesive agents.
It is also a preferable configuration that the wireless IC tag In FIG. 10, aggregate 10 of lithographic printing plate
seal adheres to the reverse side of the end portion of the materials is held on Stand 17, an upper portion of lithographic
printing plate material through an insulating object. printing plate materials 10 is covered by cover 18 that is made
As a wireless IC tag to be pasted that is used when pasting of corrugated cardboard, and wireless IC tag 12 is fixed on the
on the reverse side, there is given (Accuwave, OMH-4230) cover 18 through unillustrated adhesive agents, in packaging
manufactured by DAI NIPPON PRINTING CO.,LTD. object 13.
As an insulating adhesive agent relating to the invention, In any case of the foregoing, the aggregate 10 of litho
epoxy-based adhesive agents can be used. graphic printing plate materials may also be covered by a
As an insulating object relating to the invention, 50-200 moisture-proof sheet.
um-thick PET (polyethylene terephthalate) film, PP 25 The wireless IC tag relating to the invention holds data of
(polypropylene) film, PE (polyethylene) film and synthetic information concerning printing plate materials.
rubber sheet, for example, are used preferably. As information of data held by the wireless IC tag, there are
A printing plate material of the invention is one on which a given pieces of information about printing including 1) a type
wireless IC tag is pasted on a part thereof, and it can commu of a printing plate, 2) a product lot, 3) printing plate sizes
nicate information with a reader/writer installed in a plate
30 (width, length and thickness), 4) date of manufacturing (expi
making equipment, owing to the wireless IC tag installed ration date), 5) manufacturing information Such as informa
therein, and it can communicate information with a reader/ tion of troubles in manufacturing (positions and types), 6)
writer installed in a printing machine. performance information Such as sensitivity information of a
As another embodiment of the invention, when a wireless printing plate material, 7) exposure conditions (light Source
IC tag is installed in a packaging object, fluctuations in print 35 output, revolutions per minute of a photosensitive drum), 8)
ing quality can be reduced and printed matters with stable plate-making apparatus information Such as development
quality can be obtained constantly, in the plate-making and time and development temperature and 9) printing conditions
printing methods employing an aggregate of lithographic (pre-dampening conditions, printing pressure, water-ink bal
printing plate materials. ance).
An aggregate of lithographic printing plate materials relat
40 Though the aforesaid pieces of information can be inputted
ing to the invention is one of lithographic printing plate mate in any manner optionally, it is also possible to write in with a
rials having, on its Support, an image forming layer which can reader/writer after manufacturing, after imagewise exposure
or after development.
make a printing plate by digital devices such as a laser, a By holding these pieces of information in the wireless IC
thermal head and an ink-jet head, and the invention can be 45 tag and by utilizing them, it is possible to control a plate
applied preferably to an aggregate of lithographic printing making process (exposure process and development process)
plate materials which have the same manufacturing condi and a printing process efficiently, so that fluctuations in qual
tions, preservation conditions after manufacturing and plate ity of printed matters may be reduced.
making conditions. In particular, if exposure conditions are held in the wireless
A packaging object for an aggregate of lithographic print 50 IC tag not only as a single condition for a production lot or for
ing plate materials of the invention is one that can hold a large a type of printing plate material but also as a function with
number of lithographic printing plate materials as an aggre plate-making apparatus conditions such as ambient tempera
gate, and in particular, a medium capable of holding in a ture and humidity and exposure output during the exposure, it
movable manner as an aggregate is preferable. is possible to determine plate-making conditions by compar
As a medium capable of holding in a movable manner, 55 ing and calculating data of peculiar information of printing
there are given, for example, packing paper having functions plate materials and data of plate-making apparatus condi
of light shielding and moisture proofing, a cassette-shaped tions, and thereby to reduce fluctuations in quality of printed
casing having a function of light shielding and palettes for matters through the control at higher accuracy.
Vertical stacking and horizontal stacking. In the case of printing plate materials which vary in terms
As a method of installing a wireless IC tag in a packaging 60 of performance on an aging basis after manufacturing, if the
object, it is possible to fix by a method to paste by using relationship between elapsed time after manufacturing and
adhesive agents, but, it is preferable to fix through an insulat optimum plate-making conditions is held as data of peculiar
ing object when a packaging object is made of metal. information for plate-making, it is possible to correct Substan
As a configuration to fix a wireless IC tag on a packaging tial fluctuations of performance, and thereby to make appro
object, there are given a configuration wherein a recessed 65 priate performance to be exhibited.
portion is provided on a part of the packaging object, and a In the plate-making method of the invention, imagewise
wireless IC tag is embedded in the recessed portion, and a exposure is carried out by controlling imagewise exposure
 US 7,461,594 B2
10
conditions based on data held in the wireless IC tag for print (Aluminum Support)
ing plate materials and packaging objects. An aluminum Support according to this invention is an
Further, in the plate-making method of the invention, pho aluminum plate material which can hold an image forming
tographic processing is carried out by controlling develop layer.
ment conditions based on data held in the wireless IC tag for As an aluminum Support according to this invention, pure
printing plate materials and packaging objects. aluminum or aluminum alloys can be utilized.
AS aluminum alloys, various types can be utilized and, for
Namely, in the plate-making method of the invention, data example, utilized are alloys of metal. Such as silica, copper,
held in the wireless IC tag for printing plate materials and manganese, magnesium, chromium, Zinc, lead, bismuth,
packaging objects, plate-making apparatus information and 10 nickel, titanium, Sodium and iron, with aluminum.
data of the plate-making apparatus information are compared An aluminum Support is provided with a hydrophilic Sur
and calculated, and imagewise exposure conditions and pho face on the side having an image forming layer, and the
tographic processing conditions are controlled based on the hydrophilic surface has been preferably roughened.
results of the calculation. An aluminum Support is preferably subjected to a degrease
The plate-making apparatus information includes output 15 treatment to eliminate rolling oil on the aluminum Surface
information of a light source for exposure, ambient informa prior to a Surface roughening treatment. As a degrease treat
tion for exposure, information of developer solutions, devel ment, employed are such as a degrease treatment using a
opment time and information of development temperature. Solvent such as trichlene and thinner, and an emulsion
degrease treatment using an emulsion of such as kecirone and
The data held in the wireless IC tag for printing plate triethanolamine. Further, in a degrease treatment, an alkaline
materials and packaging objects are data of sensitivity infor aqueous solution of Such as sodium hydroxide, potassium
mation of printing plate materials, and data of plate-making hydroxide, Sodium carbonate and sodium phosphate can be
apparatus information are data of output conditions for the utilized. In the case of utilizing an alkali aqueous Solution for
light source for exposure and of exposure ambient conditions, a degrease treatment, dirt and oxidized film, which cannot be
and great effects are exhibited when these data are compared 25 eliminated only by the above-described degrease treatment,
and calculated to control imagewise exposure conditions can be also eliminated.
based on the results of the calculation. In the case of an alkaline aqueous solution having been
The data held in the wireless IC tag for printing plate utilized for a degrease treatment, the aluminum Support is
materials and packaging objects are data of aging information preferably subjected to a neutralizing treatment by being
after manufacturing for printing plate materials and/or expo 30 immersed in acid Such as phosphoric acid, nitric acid, hydro
Sure conditions, and data of plate-making apparatus informa chloric acid, Sulfuric acid and chromic acid; or mixed acid
tion are data of development temperature and development thereof. When electrolytic surface roughening is performed
time for photographing processing, and great effects are after a neutralizing treatment, acid utilized in a neutralizing
exhibited when these data are compared and calculated to treatment specifically preferably coincides with acid used in
control conditions for photographic processing based on the 35 electrolytic Surface roughening.
results of the calculation. Roughening of a Support is performed by an electrolytic
It is possible to add additional information on the wireless roughening treatment according to a commonly known
IC tag in the course of using printing plate materials in the method, however, a roughening treatment, in which an appro
plate-making apparatus, and information to be added priate treating degree of chemical roughening or mechanical
includes 1) remaining length of materials and 2) plate-making 40 roughening is combined as a preliminary treatment, may be
history (the date and time, exposure conditions, output image performed.
data ID, development conditions and printing conditions). For a chemical roughening treatment, an alkaline aqueous
Solution of Such as sodium hydroxide, potassium hydroxide,
In the printing method of the invention, printing is carried Sodium carbonate and Sodium phosphate is utilized similar to
out by using a printing plate that is made by conducting 45 a degreasing treatment.
imagewise exposure and photographic processing for the It is preferable to provide a neutralizing treatment after the
printing plate material having thereon a wireless IC tag on chemical roughening treatment by immersing the Support in
which data of information about printing plate material are acid such as phosphoric acid, nitric acid, hydrochloric acid
held, and printing conditions are controlled for performing and chromic acid or mixed acid thereof. In the case of an
printing based on data of information concerning printing 50 electrolytic Surface roughening being performed after a neu
plate material held on the wireless IC tag. tralizing treatment, acid utilized for neutralization preferably
Namely, in the printing method of the invention, data held coincides with acid used in electrolytic Surface roughening.
in the wireless IC tag during the period up to the plate-making A mechanical roughening treatment method is not specifi
process are read by a reading means attached on a printing cally limited, however, preferable are blush grinding and
machine from the wireless IC tag, and those data and data of 55 horning grinding.
printing machine information for the printing machine are A substrate which has been mechanically surface rough
compared and calculated, thus, printing conditions are con ened is preferably immersed in an aqueous solution of acid or
trolled based on the results of the calculation for performing alkali to etch the Surface, in order to eliminate Such as an
printing. abrasive and aluminum dust encroached on the Substrate Sur
Though printing machine information includes pre-damp 60 face, or to control the pit shape. Acid includes such as Sulfuric
ening conditions, printing pressure conditions, an amount of acid, persulfuric acid, hydrofluoric acid, phosphoric acid,
Supply for wetting water and information about printing nitric acid and hydrochloric acid, and base includes Such as
paper, it is possible to control higher accurate printing con Sodium hydroxide, potassium hydroxide, Sodium carbonate
ditions, by using data obtained by comparing and calculating and Sodium phosphate. Among them, an aqueous Solution of
the aforesaid information and another information that varies 65 alkali is preferably utilized.
for each printing plate Such as printing colors and image By utilizing an abrasive having a particle size of not more
aaS. than #400 in mechanical roughening and performing an etch
 US 7,461,594 B2
11 12
ing treatment by an alkali solution after the mechanical treatment. In this invention, for an anodic oxidation treat
roughening treatment, a complicated roughened structure by ment, preferably utilized is a method in which an aqueous
a mechanical roughening treatment can be changed into the solution containing 10-50 weight % of such as sulfuric acid
Surface having Smooth roughness. and/orphosphoric acid is employed as an electrolytic Solution
In the case that the above Support has been immersing and electrolysis is performed at a current density of 1-10
treated with an alkaline aqueous solution, it is preferable to be A/dmf, however, also utilized can be a method in which
Subjected to a neutralization treatment by being immersed in electrolysis is performed at a high current density in Sulfuric
acid such as phosphoric acid, nitric acid, Sulfuric acid and acid as described in U.S. Pat. No. 1,412,768, and a method in
chromic acid or mixed acid thereof. which electrolysis is performed by use of phosphoric acid as
When an electrolytic roughening treatment is performed 10 described in U.S. Pat. No. 3,511,661.
after a neutralizing treatment, acid utilized in a neutralizing A Support having been anodic oxidation treated may be
treatment specifically preferably coincides with acid used in appropriately subjected to a sealing treatment. The sealing
an electrolytic roughening treatment. treatment can be performed by a commonly known method
In an electrolytic roughening treatment, roughening is gen Such as a hot water treatment, a boiling water treatment, a
erally performed by utilizing alternating current in an acid 15 vapor treatment, a dichromate aqueous solution treatment, a
electrolytic Solution. As an acid electrolytic solution, those nitrite treatment and an ammonium acetate treatment.
utilized in an ordinary electrolytic roughening treatment can Further, a Support having been anodic oxidation treated is
be employed, however, a hydrochloric acid type or nitric acid also appropriately subjected to a surface treatment other than
type electrolytic solution is preferably utilized and a hydro the above-described sealing treatment. The surface treatment
chloric acid type electrolytic solution is specifically prefer includes commonly known treatments such as a silicate treat
ably utilized in this invention. ment, a phosphate treatment, various organic solvent treat
As an electric Source wave form utilized in electrolysis, ments, a PVPA treatment and boehmite treatment. Further, a
various wave forms such as a rectangular wave, a trapezoid treatment by an aqueous Solution containing hydrogencar
wave and a serrate wave can be utilized, however, preferable bonate as described in JP-A No. 8-314157, and an organic
is a sine wave. 25 acid treatment by Such as citric acid may be performed in
Further, a divisional electrolytic roughening treatment Succession to a treatment by an aqueous Solution containing
such as disclosed in JP-A No. 10-869 (JP-A refers to Japanese hydrogencarbonate.
Patent Publication Open to Public Inspection) is also prefer
ably utilized. (Image Formation Layer)
A Voltage applied in an electrolytic roughening utilizing a 30 The image formation layer in the invention is a layer
nitric acid type electrolytic solution is preferably 1-50 V and capable of forming an image by imagewise exposure. As the
more preferably 5-30 V. A current density (a peak value) is image formation layer, a positive or negative Working image
preferably 10-200A/dm and more preferably 20-150A/dm. formation layer used in a conventional light sensitive plano
A quantity of electricity is 100-2000 C/dmf, preferably graphic printing plate material can be used.
200-1500 C/dm and more preferably 200-1000 C/dm, as a 35 As the image formation layer in the invention, athermosen
total of the whole treatment process. sitive image formation layer or polymerizable image forma
The temperature is preferably 10-50° C. and more prefer tion layer is preferably used.
ably 15-45° C. A concentration of nitric acid is preferably As the thermosensitive image formation layer, a layer
0.1-5 weight %. capable of forming an image employing heat generated due to
Into an electrolytic solution, Such as nitrate, chloride, 40 laser exposure is preferred.
amines, aldehydes, phosphoric acid, chromic acid, boric acid, As the layer capable of forming an image employing heat
acetic acid and Oxalic acid can be added. generated due to laser exposure, a positive working ther
The substrate having been subjected to an electrolytic mosensitive image formation layer containing a compound
roughening treatment is preferably immersed in an alkaline capable of being decomposed by an acid or a negative work
solution to perform etching of the surface for the purpose of 45 ing image formation layer Such as a thermosensitive image
Such as eliminating Smuts from the Surface and to control the formation layer containing a polymerizable composition or a
pit shape. thermosensitive image formation layer containing thermo
An alkaline aqueous Solution includes an aqueous Solution plastic particles are preferably used.
of Such as sodium hydroxide, potassium hydroxide, sodium As the positive working image formation layer containing
carbonate and sodium phosphate. 50 a compound capable of being decomposed by an acid, there
By performing an etching treatment with an alkaline aque is, for example, an image formation layer comprising a pho
ous solution, initial printability and prevention of scumming tolytically acid generating compound capable of generating
are improved when an image forming layer is provided. an acid on laser exposure, an acid decomposable compound,
In the case that the above Support has been immersing which is capable of being decomposed by an acid to increase
treated with an alkaline aqueous solution, it is preferable to be 55 solubility to a developer, and an infrared absorber, as dis
Subjected to a neutralization treatment by being immersed in closed in Japanese Patent O.P.I. Publication Nos. 9-171254.
acid such as phosphoric acid, nitric acid, Sulfuric acid and As the photolytically acid generating compound there are
chromic acid or mixed acid thereof. When an anodic oxida various conventional compounds and mixtures. For example,
tion treatment is performed after a neutralizing treatment, a salt of diazonium, phosphonium, Sulfonium or iodonium
acid utilized in a neutralizing treatment specifically prefer 60 ion with BF, PF, SbF. SiFi or CIO, an organic halo
ably coincides with acid used in an anodic oxidation treat gen containing compound, o-quinonediazide Sulfonylchlo
ment. ride or a mixture of an organic metal and an organic halogen
An anodic oxidation treatment is performed after rough containing compound is a compound capable of generating or
ening treatment. releasing an acid on irradiation of an active light, and can be
A method of anodic oxidation treatment is not specifically 65 used as the photolytically acid generating compound in the
limited and commonly known method can be utilized. Oxi invention. The organic halogen-containing compound known
dation film is formed on a Substrate by an anodic oxidation as an photoinitiator capable of forming a free radical is a
 US 7,461,594 B2
13 14
compound capable of generating a hydrogen halide and can phthalocyanine compound, a naphthalocyanine compound,
be used as the photolytically acid generating compound. The an azo compound, a thioamide compound, a dithiol com
examples of the organic halogen containing compound pound or an indoaniline compound. Exemplarily, the light
capable of forming a hydrogen halide include those disclosed to-heat conversion materials include those disclosed in Japa
in U.S. Pat. Nos. 3,515,552, 3,536,489 and 3,779,778 and 5 nese Patent O.P.I. Publication Nos. 63-13919.1, 64-33547,
West German Patent No. 2.243,621, and compounds gener 1-160683, 1-280750, 1-293342, 2-2074, 3-26593, 3-30991,
ating an acid by photodegradation disclosed in West German 3-34891, 3-36093, 3-36094, 3-36095, 3-42281,3-97589 and
Patent No. 2,610,842. As the photolytically acid generating 3-103476. These compounds may be used singly or in com
compound, o-naphthoduinone diazide-4-Sulfonylhalo bination.
genides disclosed in Japanese Patent O.P.I. Publication No. 10 Those described in Japanese Patent O.P.I. Publication Nos.
50-30209 can be also used. 11-240270, 11-265062, 2000-30.9174, 2002-4.9147, 2001
As the photolytically acid generating compound, an 162965, 2002-144750, and 2001-219667 can be preferably
organic halogen-containing compound is preferred in view of used.
sensitivity to infrared rays and storage stability. The organic Other Light-to-heat Conversion Materials
halogen-containing compound is preferably a halogenated 15
In addition to the above light-to-heat conversion dye, other
alkyl-containing triazines or a halogenated alkyl-containing light-to-heat conversion materials may be used.
oxadiazoles, and especially preferably a halogenated alkyl Examples of the light-to-heat conversion material include
containing S-triazines. carbon, graphite, a metal and a metal oxide.
The content of the photolytically acid generating com Furnace black and acetylene black is preferably used as the
pound in the image formation layer is preferably 0.1 to 20% carbon. The graininess (do) thereof is preferably not more
by weight, and more preferably 0.2 to 10% by weight based than 100 nm, and more preferably not more than 50 nm.
on the total weight of the solid components of the image The graphite is one having a particle size of preferably not
formation layer, although the content broadly varies depend more than 0.5um, more preferably not more than 100 nm, and
ing on its chemical properties, or kinds or physical properties most preferably not more than 50 nm.
of image formation layer used. 25
As the metal, any metal can be used as long as the metal is
As the acid decomposable compound, there are a com in a form of fine particles having preferably a particle size of
pound having a C-O-C bond disclosed in Japanese Patent not more than 0.5um, more preferably not more than 100 nm,
O.P.I. Publication Nos. 48-89003, 51-120714, 53-133429, and most preferably not more than 50 nm. The metal may
55-12995, 55-126236 and 56-17345, a compound having an have any shape Such as spherical, flaky and needle-like. Col
Si-O-C bond disclosed in Japanese Patent O.P.I. Publica 30
tion Nos. 60-37549 and 60-121446, another acid decompos loidal metal particles such as those of silver or gold are
particularly preferred.
able compound disclosed in Japanese Patent O.P.I. Publica As the metal oxide, materials having black color in the
tion Nos. 60-3625 and 60-10247, a compound having an visible regions or materials which are electro-conductive or
Si N bond disclosed in Japanese Patent O.P.I. Publication semi-conductive can be used.
No. 62-222246, a carbonic acid ester disclosed in Japanese 35
Patent O.P.I. Publication No. 62-251743, an orthocarbonic Examples of the former include black iron oxide and black
acid ester disclosed in Japanese Patent O.P.I. Publication No. complex metal oxides containing at least two metals.
62-209451, an orthotitanic acid ester disclosed in Japanese Examples of the latter include Sb-doped SnO (ATO), Sn
Patent O.P.I. Publication No. 62-280841, an orthosilicic acid added In-O (ITO), TiO, TiO prepared by reducing TiO,
ester disclosed in Japanese Patent O.P.I. Publication No. 40 (titanium oxide nitride, generally titanium black).
62-280842, an acetal or ketal disclosed in Japanese Patent Particles prepared by covering a core material Such as
O.P.I. Publication No. 63-10153 and a compound having a BaSO, TiO, 9Al-O.2BO and KO.nTiO, with these metal
oxides is usable.
C S bond disclosed in Japanese Patent O.P.I. Publication These oxides are particles having aparticle size of not more
No. 62-244038. Of these compounds, the compound having a
C-O-C bond, the compound having an Si-O-C bond, 45 than 0.5 Lum, preferably not more than 100 nm, and more
the orthocarbonic acid ester, the acetal or ketal or the preferably not more than 50 nm.
silylether disclosed in Japanese Patent O.P.I. Publication Nos. As these light-to-heat conversion materials, black iron
53-133429, 56-17345, 60-121446, 60-37549, 62-209451 and oxide or black complex metal oxides containing at least two
63-10153 are preferable. metals are more preferred.
The content of the acid decomposable compound in the 50 Examples of the black complex metal oxides include com
image formation layer is preferably 5 to 70% by weight, and plex metal oxides comprising at least two selected from Al.
more preferably 10 to 50% by weight based on the total Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, and Ba. These can be
weight of the solid components of the image formation layer. prepared according to the methods disclosed in Japanese
The acid decomposable compounds may be used alone or as Patent O.P.I. Publication Nos. 9-27393, 9-25126, 9-237570,
an admixture of two or more kinds thereof. 55 9-241529 and 10-231441.
The image formation layer in the invention preferably con The complex metal oxide used in the invention is prefer
tains a light-to-heat conversion material which is capable of ably a complex Cu—Cr—Mn type metal oxide or a
changing exposure light to heat. Examples of the light-to-heat Cu-Fe Mn type metal oxide. The Cu—Cr—Mn type
conversion material include the following light-to-heat con metal oxides are preferably subjected to the treatment dis
version dye or light-to-heat conversion material Substances. 60 closed in Japanese Patent O.P.I. Publication Nos. 8-27393 in
order to reduce isolation of a 6-valent chromium ion. These
(O124) Light-to-heat Conversion Dye complex metal oxides have a high color density and a high
Examples of the light-to-heat conversion dye include a light heat conversion efficiency as compared with another
general infrared absorbing dye Such as a cyanine dye, a chlo metal oxide.
conium dye, a polymethine dye, an azulenium dye, a squale 65 The primary average particle size of these complex metal
nium dye, a thiopyrylium dye, a naphthoguinone dye or an oxides is preferably from 0.001 to 1.0 um, and more prefer
anthraquinone dye, and an organometallic complex Such as a ably from 0.01 to 0.5um. The primary average particle size of
 US 7,461,594 B2
15 16
from 0.001 to 1.0 um improves a light heat conversion effi closed in J. Kosar, “Light Sensitive Systems’. Paragraph 5,
ciency relative to the addition amount of the particles, and the and those disclosed in British Patent No. 1,459,563.
primary average particle size of from 0.05 to 0.5um further The content of the polymerization initiator in the image
improves a light heat conversion efficiency relative to the formation layer is not specifically limited, but is preferably
addition amount of the particles. The light heat conversion from 0.1 to 20% by weight, and more preferably from 0.8 to
efficiency relative to the addition amount of the particles 15% by weight.
depends on a dispersity of the particles, and the well-dis
persed particles have a high light heat conversion efficiency. ((c) Polymerizable Ethylenically Unsaturated Monomer)
Accordingly, these complex metal oxide particles are pref The polymerizable ethylenically unsaturated monomer is a
erably dispersed according to a known dispersing method, 10 compound having a polymerizable unsaturated group.
separately to a dispersion liquid (paste), before being added to Examples thereof include conventional radical polymeriZ
a coating liquid for the particle containing layer. The metal able monomers, and polyfunctional monomers having plural
oxides having a primary average particle size of less than ethylenically unsaturated bond and polyfunctional oligomers
0.001 are not preferred since they are difficult to disperse. A used in UV-curable resins.
dispersant is optionally used for dispersion. The addition 15 A prepolymer can be used as described above, and the
amount of the dispersant is preferably from 0.01 to 5% by prepolymer can be used singly, as an admixture of the above
weight, and more preferably from 0.1 to 2% by weight, based described monomers and/or oligomers.
on the weight of the complex metal oxide particles. (Polymer Binder)
The image formation layer optionally contains a binder.
The light-to-heat conversion dye or light-to-heat conver The image formation layer in the invention can contain a
sion material described above may be contained in the image polymer binder.
formation layer or in a layer adjacent thereto. Examples of the polymer binder include a polyacrylate
resin, a polyvinylbutyral resin, a polyurethane resin, a polya
Light-sensitive Image Formation Layer Containing a Poly mide resin, a polyester resin, an epoxy resin, a phenol resin, a
merizable Component 25 polycarbonate resin, a polyvinyl butyral resin, a polyvinyl
As an image formation layer containing a polymerizable formal resin, a shellac resin, or another natural resin. These
component, there is an image formation layer containing a polymer binder can be used as an admixture of two or more
light-to-heat conversion material (a) having an absorption thereof.
band in a wavelength region of from 700 to 1300 nm, a (Polymerization Inhibitor)
polymerization initiator (b) and a polymerizable ethyleni 30
cally unsaturated monomer (c). The image formation layer in the invention can optionally
a polymerization inhibitor.
(Light-to-heat Conversion Material (a) Having an Absorption As the polymerization inhibitor, there is for example, a
Band in a Wavelength Region of from 700 to 1300 nm) hindered amine with a pKb of from 7 to 14 having a piperidine
As the light-to-heat conversion material (a) having an skeleton.
absorption band in a wavelength region of from 700 to 1300 35
The polymerization inhibitor content is preferably from
nm, There are the infrared absorbing dyes described above. 0.001 to 10% by weight, more preferably from 0.01 to 10% by
Preferred are dyes such as cyanine dyes, squalirium dyes, weight, and still more preferably from 0.1 to 5% by weight
oxonol dyes, pyrylium dyes, thiopyrylium dyes, polymethine based on the total solid content of polymerizable unsaturated
dyes, oil soluble phthalocyanine dyes, triarylamine dyes, group-containing compound in the image formation layer.
thiazolium dyes, oxazolium dyes, polyaniline dyes, polypyr 40
role dyes and polythiophene dyes. The image formation layer can contain a colorant. As the
Besides the above, pigments such as carbon black, titanium colorant can be used known materials including commer
black, iron oxide powder, and colloidal silver can be prefer cially available materials. Examples of the colorant include
ably used. Cyanine dyes as dyes, and carbon black as pig those described in revised edition “Ganryo Binran, edited by
45 Nippon Ganryo Gijutu Kyoukai (publishe by Seibunndou
ments are especially preferred, in view of extinction coeffi Sinkosha), or “Color Index Binran. Pigment is preferred.
cient, light-to-heat conversion efficiency and cost. Kinds of the pigment include black pigment, yellow pig
The content of the light-to-heat conversion material having ment, red pigment, brown pigment, violet pigment, blue pig
an absorption band in a wavelength region of from 700 to ment, green pigment, fluorescent pigment, and metal powder
1300 nm in the image formation layer is preferably from 0.5 50 pigment. Examples of the pigment include inorganic pigment
to 15% by weight and more preferably from 1 to 5% by (such as titanium dioxide, carbon black, graphite, Zinc oxide,
weight. Further, the content of the colorant in the image Prussian blue, cadmium sulfide, iron oxide, or chromate of
formation layer is different due to extinction coefficient of the lead, zinc, barium or calcium); and organic pigment (such as
colorant, but is preferably an amount giving a reflection den aZO pigment, thioindigo pigment, anthraquinone pigment,
sity of from 0.3 to 3.0, and preferably from 0.5 to 2.0. For 55 anthanthrone pigment, triphenedioxazine pigment, vat dye
example, in order to obtain the above reflection density, the pigment, phthalocyanine pigment or its derivative, or quina
content of the cyanine dye in the image formation layer is 10 cridone pigment).
to 100 mg/m. Among these pigment, pigment is preferably used which
This light-to-heat conversion material also may be con does not substantially have absorption in the absorption
tained in the image formation layer or in a layer adjacent 60 wavelength regions of a spectral sensitizing dye used accord
thereto.
ing to a laser for exposure. The absorption of the pigment used
((b) Polymerization Initiator) is not more than 0.05, obtained from the reflection spectrum
The photopolymerization initiator is a compound capable of the pigment measuredemploying an integrating sphere and
of initiating polymerization of an unsaturated monomer by employing light with the wavelength of the laser used. The
laser. Examples thereof include carbonyl compounds, 65 pigment content is preferably 0.1 to 10% by weight, and more
organic Sulfur compounds, peroxides, redox compounds, azo preferably 0.2 to 5% by weight, based on the total solid
or diazo compounds, halides and photo-reducing dyes dis content of image formation layer.
 US 7,461,594 B2
17 18
Light-sensitive Image Formation Layer Containing a Ther aralkyl polyether modified, epoxy polyether modified, alco
moplastic Material hol modified, fluorine modified, amino modified, mercapto
As a light-sensitive image formation layer containing a modified, epoxy modified, or allyl modified; fluorine atom
thermoplastic material, an image formation layer containing containing Surfactants of perfluoroalkyl ethyleneoxide
heat melting particles or heat fusing particles may be prefer adduct; and others such as lipid-containing material, biosur
able, in particular, an image formation layer usable in a so factant, or oligo Soap. At least one kind of these can be used.
called process-less CTP. Preferred examples of the cationic surfactant include alky
(Heat-melting Particles) lamine salts or acylamine salts such as primary amine salts,
The heat-melting particles used in the invention are par acylaminoethylamine salts, N-alkylpolyalkylene polyamine
ticularly particles having a low melt viscosity, or particles 10 salts, fatty acid polyethylene polyamide, amides or their salts,
formed from materials generally classified into wax. or amine salts; quaternary ammonium salts or ammonium
The materials preferably have a softening point of from 40° salts having an amide bond such as alkyltrimethylammonium
salt, dialkyldimethylammonium salt, alkyldimethylbenzyl
C. to 120° C. and a melting point of from 60° C. to 150° C. ammonium salt, alkylpridium salt, acylaminoethylmethyldi
and more preferably a softening point of from 40°C. to 100° 15 ethyl ammonium salt, acylaminopropyldimethylbenzyl
C. and a melting point of from 60°C. to 120° C. ammonium salt, acylaminopropyl-diethylhydroxyethyl
Materials usable include paraffin, polyolefin, polyethylene ammonium salt, acylaminoethyl pyridinium salt, or diacy
wax, microcrystalline wax, and fatty acid wax. laminoethyl ammonium salt; ammonium salts having an ester
The molecular weight thereofisapproximately from 800 to bond or an ether bond such as diacyloxyethylmethylhydroxy
10,000. A polar group Such as a hydroxyl group, an ester ethyl ammonium salt or alkyloxymethyl pyridinium salt; imi
group, a carboxyl group, an aldehyde group and a peroxide dazolines or imidazolium salts such as alkyl imidazoline,
group may be introduced into the wax by oxidation to 1-hydroxyethyl-2-alkyl imidazoline, or 1-acylaminoethyl-2-
increase the emulsification ability. alkylimidazolium salt; amine derivatives Such as alkylpoly
Moreover, Stearoamide, linolenamide, laurylamide, myri oxyethylene amine, N-alkylaminopropylamine, N-acylpoly
stylamide, hardened cattle fatty acid amide, parmitylamide, 25 ethylene polyamine, acylpolyethylene polyamine, or fatty
oleylamide, rice bran oil fatty acid amide, palm oil fatty acid acid triethanolamine ester, and others such as lipid-contain
amide, a methylol compound of the above-mentioned amide ing material, bioSurfactant or oligo Soap. At least one kind of
compounds, methylenebissteaStearoamide and ethylenebi these can be used.
ssteastearoamide may be added to the wax to lower the soft Preferred examples of the anionic surfactant include car
ening point or to raise the working efficiency. A cumarone 30 boxylic acid salts such as fatty acid salt, rosin group, naph
indene resin, a rosin-modified phenol resin, a terpene thenegroup, ether carboxylate, alkenyl Succinate, N-acyl sar
modified phenol resin, a xylene resin, a ketone resin, an acryl cosine salt, N-acylglutamate, sulfuric acid primary alkyl salt,
resin, an ionomer and a copolymer of these resins may also be Sulfuric acid secondary alkyl salt, Sulfuric acid alkyl polyoxy
usable. ethylene salt, Sulfuric acid alkylphenyl polyoxyethylene salt,
Among them, polyethylene, microcrystalline wax, fatty 35 Sulfuric acid mono-acylglycerin Salt, acylamino Sulfuric acid
acid ester and fatty acid are preferably contained. A high ester salt, Sulfuric acid oil, or Sulfation aliphatic acid alkyl
sensitive image formation can be performed since these mate ester, Sulfonic acid such as C-olefin Sulfonate, secondary
rials each have a relative low melting point and a low melt alkane Sulfonate, C.-Sulfo aliphatic acid, acyl isethionic acid
viscosity. These materials each have a lubrication ability. salt, N-acyl-N-methyl taurine acid, dialkyl sulfo succinate,
Accordingly, even when a shearing force is applied to the 40 alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkyl
Surface layer of the printing plate precursor, the layer damage diphenyl ether disulfonate, petroleum Sulfonate, or lignin
is minimized, and resistance to contaminations which may be Sulfonate; phosphoric ester acid salt such as phosphoric acid
caused by Scratch is further enhanced. alkyl salt or phosphoric acid alkyl polyoxyethylene salt, sili
The heat-melting particles are preferably dispersible in con atom-containing anionic Surfactant such as Sulfonic acid
water. The average particle size thereof is preferably from 45 modified or carboxyl modified; fluorine atom-containing Sur
0.01 to 10 um, and more preferably from 0.05 to 3 um. factant Such as perfluoro alkyl carboxylic acid salt, perfluoro
When the average particle size is larger than 10 um, an alkyl Sulfonic acid salt, perfluoro alkyl phosphoric acid ester,
image resolution will be lowered. or perfluoro alkyl trimethyl ammonium salt; and others such
When two or more kinds of the particles are used, the as lipid-containing material, biosurfactant, or oligo Soap. At
average particle size difference between the different par 50 least one kind of these can be used.
ticles is preferably not less than 0.1 um. Preferred examples of the polymeric surfactant include
A nonionic Surfactant, an anionic Surfactant, a cationic polymer or copolymer of poly alkyl (meth) acrylic acid Such
Surfactant, or a polymeric Surfactant is preferably employed as poly (meth) acrylate, butyl (meth) acrylate acrylic acid
to disperse these heat-melting particles in water. A heat-melt copolymer, ethylene-acrylic acid copolymer, or ethylene
ing particle aqueous dispersion, containing these surfactants, 55 methacrylic acid copolymer; maleic acid copolymer Such as
can be stabilized, providing a uniform coat with no deficien vinyl acetate-maleic anhydride copolymer, styrene-maleic
C1GS. anhydride copolymer, C.-olefin-maleic anhydride copolymer,
Preferred examples of the nonionic surfactant include or diisobutylene-maleic acid copolymer, fumaric acid
polyoxyethylene adducts such as alkyl polyoxyethylene copolymer Such as methyl (meth) acrylate-fumaric acid
ether, alkyl polyoxyethylene, polyoxypropylene ether, fatty 60 copolymer or vinyl acetate-fumaric acid copolymer, aromatic
acid polyoxyethylene ester, fatty acid polyoxyethylene Sor Sulfonic-acid formalin condensation product such as naph
bitan ester, fatty acid polyoxyethylene sorbitol ester, poly thalene Sulfonic acid formalin condensation product, butyl
oxyethylene castor oil, polyoxyethylene adduct of acetylene naphthalene Sulfonic acid formalin condensation product, or
glycol, and alkyl polyoxyethylene amine or amide; polyols cresol Sulfonic-acid formalin condensation product; poly
Such as fatty acid Sorbitan ester, fatty acid polyglycerin ester 65 alkylpyridinium salt (including derivatives of the copolymer
and fatty acid Sucrose ester or alkylolamide; silicon atom obtained via copolymerization with vinyl monomer copoly
containing Surfactants, which are polyether modified, alkyl merized with vinylpyridine) such as poly N-methylvinyl pyri
 US 7,461,594 B2
19 20
dinium chloride, or so forth; polyacrylamide, polyvinyl pyr Further, the composition of the heat-fusible particles may
rolidone, poly acryloyl pyrrolidone, polyvinyl alcohol, be continuously varied from the interior to the surface of the
polyethylene glycol; block polymer of polyoxyethylene and particles. The particles may be covered with a different mate
polyoxypropylene; cellulose derivative such as methylcellu rial. As a covering method, known methods such as a micro
lose or carboxymethyl cellulose; and polysaccharide deriva capsule method and a sol-gel method are usable.
tive Such as poly oxyalkylene polysiloxane copolymer, gum The heat-fusible particle content of the layer is preferably
arabic, or arabinogalactan. At least one kind of these can be from 1 to 90% by weight, and more preferably from 5 to 80%
used. As for the above polymeric Surfactant examples, alkali by weight based on the total weight of the layer.
salt Such as sodium, potassium, or ammonium may be (Water-soluble Binder)
allowed to be used in place of a polymeric Surfactant contain 10
Examples of the water-soluble binder used in the image
ing a carboxyl group or a Sulfone group. formation layer include polysaccharides, polyethylene oxide,
The composition of the heat-melting particles may be con polypropylene oxide, polyvinyl alcohol, polyethylene glycol
tinuously varied from the interior to the surface of the par (PEG), polyvinyl ether, latex of a conjugate diene polymer
ticles. The particles may be covered with a different material. Such as styrene-butadiene copolymer or methyl methacry
Known microcapsule production method or Sol-gel method 15
late-butadiene copolymer, acryl polymer latexes, vinyl poly
can be applied for covering the particles. mer latexes, polyacrylamide, polyacrylic acid or its salt, and
The heat-melting particle content of the layer is preferably polyvinyl pyrrolidone. Of these, polyacrylic acid or its salt or
1 to 90% by weight, and more preferably 5 to 80% by weight polysaccharides are preferred, which do not lower printabil
based on the total layer weight. ity.
(Heat-fusible Particles) In the invention, it is preferred that a coating solution for
The heat-fusible particles in the invention include thermo the image formation layer contain lower alcohols such as
plastic hydrophobic polymer particles. Although there is no methanol, ethanol, isopropanol and butanol, in order to
specific limitation to the upper limit of the softening point of improve coating quality.
the thermoplastic hydrophobic polymer particles, the soften 25
The image formation layer can contain light-to-heat con
ing point is preferably lower than the decomposition tempera version materials described later.
ture of the polymer particles. The weight average molecular The dry coating amount of the image formation layer is
weight (Mw) of the polymer is preferably within the range of preferably from 0.1 to 1.5 g/m, and more preferably from
from 10,000 to 1,000,000. 0.15 to 1.0 g/m.
Examples of the polymer consistituting the polymer par 30 Light-sensitive Image Formation Layer Containing a Ther
ticles include a diene (co)polymer Such as polypropylene, moplastic Material
polybutadiene, polyisoprene or an ethylene-butadiene As a light-sensitive image formation layer containing a
copolymer, a synthetic rubber Such as a styrene-butadiene thermoplastic material, an image formation layer containing
copolymer, a methyl methacrylate-butadiene copolymer or particles capable of thermally bridging may be used. Among
an acrylonitrile-butadiene copolymer; a (meth)acrylate (co) 35 them, in particular, an image formation layer usable in a
polymer or a (meth)acrylic acid (co)polymer Such as polym so-called process-less CTP. For example, a light-sensitive
ethyl methacrylate, a methyl methacrylate-(2-ethylhexyl) image formation layer containing a blocked isocyanate com
acrylate copolymer, a methyl methacrylate-methacrylic acid pound may be listed.
copolymer, or a methyl acrylate-(N-methylolacrylamide);
polyacrylonitrile; a vinyl ester (co)polymer Such as a polyvi 40
Blocked Isocyanate Compound
nyl acetate, a vinyl acetate-vinyl propionate copolymer and a The blocked isocyanate compound is a compound obtained
vinyl acetate-ethylene copolymer, or a vinyl acetate-2-hexy by addition reaction of an isocyanate compound with a block
lethyl acrylate copolymer; and polyvinyl chloride, polyvi ing agent described below.
nylidene chloride, polystyrene and a copolymer thereof. The blocked isocyanate compound used in the image for
Among them, the (meth)acrylate polymer, the (meth)acrylic 45
mation layer is preferably in the form of aqueous dispersion
acid (co)polymer, the vinyl ester (co)polymer, the polysty of a compound described below. Coating of the aqueous
rene and the synthetic rubbers are preferably used. dispersion provides good on press developability.
The polymer particles may be prepared from a polymer (Isocyanate Compound)
synthesized by any known method Such as an emulsion poly Examples of the isocyanate compound include an aromatic
merization method, a Suspension polymerization method, a 50 polyisocyanate Such as diphenylmethane diisocyanate
Solution polymerization method and a gas phase polymeriza (MDI), tolylene diisocyanate (TDI), polyphenylpolymethyl
tion method. The particles of the polymer synthesized by the ene polyisocyanate (crude MDI), ornaphthalene diisocyanate
Solution polymerization method or the gas phase polymeriza (NDI); an aliphatic polyisocyanate Such as 1,6-hexamethyl
tion method can be produced by a method in which an organic ene diisocyanate (HDI), or lysine diisocyanate (LDI); an ali
Solution of the polymer is sprayed into an inactive gas and 55 cyclic polyisocyanate Such as isophorone diisocyanate
dried, and a method in which the polymer is dissolved in a (IPDI), dicyclohexylmethane diisocyanate (hydrogenation
water-immiscible solvent, then the resulting solution is dis MDI), or cyclohexylene diisocyanate; an aromatic aliphatic
persed in water or an aqueous medium and the solvent is Polyisocyanate such as xylylene diisocyanate (XDI), or tet
removed by distillation. ramethylxylene diisocyanate (TMXDI); and their modified
In both of the methods, a Surfactant such as Sodium lauryl 60 compounds such as those having a burette group, an isocya
Sulfate, Sodium dodecylbenzenesulfate or polyethylene gly nurate group, a carbodiimide group, oran oxazolidine group);
col, or a water-soluble resin Such as poly(vinyl alcohol) may and a urethane polymer having an isocyanate group in the
be optionally used as a dispersing agent or stabilizing agent. molecular end, which is comprised of an active hydrogen
The heat-fusible particles are preferably dispersible in containing compound with a molecular weight of from 50 to
water. The average particle size of the heat-fusible particles is 65 5,000 and the polyisocyanate described above.
preferably from 0.01 to 10 um, and more preferably from 0.1 The polyisocyanates described in Japanese Patent O.P.I.
to 3 um. Publication No. 10-72520 are preferably used.
 US 7,461,594 B2
21 22
Among those polyisocyanates, tolylene diisocyanate is hexylene glycol, butane diol, hexamethylene glycol, Xylylene
especially preferred in view of high reactivity. glycol, or Sorbitol is preferred, and a low molecular weight
(Blocking Material) polyol having a molecular weight of from 50 to 500 is espe
Examples of the blocking material include an alcohol type cially preferred.
blocking material Such as methanol, or ethanol; a phenol type It is preferred that the content of the polyol is such an
blocking material Such as phenol or cresol; an oxime type amount that the amount of the hydroxyl group of the polyol is
blocking material Such as formaldoxime, acetaldoxime, from 0.1 to 0.9 equivalent of the isocyanate group of the
methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohex isocyanate compound. The above range of the hydroxyl group
anone oxime, acetoxime, diacetyl monoxime, or benzophe of the polyol provides improved storage stability of the
none oxime; an acid amide type blocking material Such as
10 blocked isocyanate compound.
acetanilide, e-caprolactam, or Y-butyrolactam, an active Blocking Method
methylene containing blocking material Such as dimethyl As a blocking method of an isocyanate compound, there is,
malonate or methyl acetoacetate; a mercaptain type blocking for example, a method comprising the steps of dropwise
material Such as butyl mercaptan; an imide type blocking 15
adding a blocking material to the isocyanate compound at 40
material Such as Succinic imide or maleic imide; an imidazole to 120°C. while stirring under an anhydrous condition and an
type blocking material Such as imidazole or 2-methylimida inert gas atmosphere, and after addition, stirring the mixture
Zole; aureatype blocking material Such as urea orthiourea; an solution for additional several hours. In this method, a solvent
amine type blocking material Such as diphenylamine or can be used, and a known catalyst Such as an organometallic
aniline; and an imine type blocking material such as ethylene compound, a tertiary amine or a metal salt can be also used.
imine or polyethylene imine. Among these, the oXime type Examples of the organometallic compound include a tin
blocking material is preferred. catalyst Such as Stannous octoate, dibutyltin diacetate, or
It is preferred that the content of the blocking material is dibutyltin dilaurate; and a lead catalyst such as lead 2-ethyl
Such an amount that the amount of the active hydrogen of the hexanoate. Examples of the tertiary amine include triethy
blocking material is from 1.0 to 1.1 equivalent of the isocy 25
lamine, N,N-dimethylcyclohexylamine, triethylenediamine,
anate group of the isocyanate compound. It is preferred that N,N'-dimethylpiperazine, and diazabicyclo (2.2.2)-octane.
when an active hydrogen-containing additive such as a polyol Examples of the metal salt include cobalt naphthenate, cal
described later is used in combination, the content of the cium naphthenate, and lithium naphthenate. These catalysts
blocking material is such an amount that the total amount of are used in an amount of ordinarily from 0.001 to 2% by
the active hydrogen of the blocking material and the additive 30
weight, and preferably from 0.01 to 1% by weight based on
is from 1.0 to 1.1 equivalent of the isocyanate group of the 100 parts by weight of isocyanate compound.
isocyanate compound. The amountless than 1.0 equivalent of The blocked isocyanate compound in the invention, which
the active hydrogen produces an unreacted isocyanate group, is a reaction product of an isocyanate compound, a polyol.
while the amount exceeding 1.1 equivalent of the active and a blocking material, is obtained by reacting the isocyan
hydrogen results in excess of blocking material, which is 35
ate compound with the polyol, and then reacting a residual
undesirable. isocyanate group with the blocking material or by reacting the
The releasing temperature of blocking material from the isocyanate compound with the blocking material, and then
blocked isocyanate compound is preferably from 80 to 200° reacting a residual isocyanate group with the polyol.
C., more preferably from 80 to 160° C., and still more pref The blocked isocyanate compound in the invention has an
erably from 80 to 130° C. 40
average molecular weight of preferably from 500 to 2,000,
Polyol and more preferably from 600 to 1,000. This range of the
The blocked isocyanate compound in the invention is pref molecular weight provides good reactivity and storage stabil
erably an adduct of an isocyanate with a polyol.
The adduct derived from the polyol can improve storage Manufacture of Aqueous Dispersion
stability of the blocked isocyanate compound. When the 45 The blocked isocyanate compound obtained above is
image formation layer containing the adduct is imagewise added to an aqueous solution containing a surfactant, and
heated, the resulting image increases image strength, result vigorously stirred in a homogenizer to obtain an aqueous
ing in improvement of printing durability. dispersion of blocked isocyanate compound.
Examples of the polyol include a polyhydric alcohol such Examples of the Surfactant include an anionic Surfactant
as propylene glycol, triethylene glycol, glycerin, trimethylol 50 Such as sodium dodecylbenzene Sulfonate, Sodium lauryl Sul
methane, trimethylol propane, pentaerythritol, neopentylgly fate, sodium dodecyldiphenylether disulfonate, or sodium
col, 1.6-hexylene glycol, hexamethylene glycol, Xylylene dialkyl Succinate Sulfonate; a nonionic Surfactant such as
glycol, Sorbitol or Sucrose; polyether polyol which is pre polyoxyethylenealkyl ester or polyoxyethylenealkyl aryl
pared by polymerizing the polyhydric alcohol or a polyamine ester, and an amphoteric Surfactant including an alkyl betaine
with ethylene oxide and/or propylene oxide; polytetrameth 55 Such as lauryl bataines or Stearyl betaine and an amino acid
ylene ether polyol; polycarbonate polyol; polycaprolactone Such as lauryl B-alanine, lauryldi(aminoethyl)glycine, or
polyol; polyester polyol, which is obtained by reacting the octyldi(aminoethyl)glycine. These surfactant may be used
above polyhydric alcohol with polybasic acid Such as adipic singly or in combination. Among these, the nonionic Surfac
acid, phthalic acid, isophthalic acid, terephthalic acid, sebatic tant is preferred.
acid, fumaric acid, maleic acid, oraZelaic acid; polybutadiene 60 The solid content of the aqueous dispersion of the blocked
polyol; acrylpolyol; castor oil; a graft copolymer polyol pre isocyanate compound is preferably from 10 to 80% by
pared by graft polymerization of a vinyl monomer in the weight. The Surfactant content of the aqueous dispersion is
presence of polyether polyol or polyester polyol; and an preferably from 0.01 to 20% by weight based on the solid
epoxy modified polyol. Among these, a polyol having a content of the aqueous dispersion.
molecular weight of from 50 to 5,000 such as propylene 65 When an organic solvent is used in a blocking reaction of
glycol, triethylene glycol, glycerin, trimethylol methane, tri the isocyanate compound, the organic solvent can be removed
methylol propane, pentaerythritol, neopentyl glycol, 1.6- from the resulting aqueous dispersion.
 US 7,461,594 B2
23 24
The image formation layer containing the isocyanate com In addition to the above-described salt, utilized can be salt
pound may contain a water-soluble material. Examples of the of Such as Sulfosalicilic acid, salicylic acid; and of Sugar
water-soluble material include the following compounds. alcohol, Saccharose and D-Sorbite as non-reductive Sugar.
Water-soluble Polymer An organic solvent utilized in an organic solvent contain
Examples of the water-soluble material include a known
5 ing solution is Suitably one having a solubility in water of not
water-soluble polymer, which is soluble in an aqueous Solu more than 10 weight% and is preferably selected from those
tion having a pH of from 4 to 10. having a solubility of not more than 5 weight%.
Typical examples of the water-soluble polymer include For example, listed are 1-phenylethanol, 2-phenyl ethanol,
polysaccharides, polyethylene oxide, polypropylene oxide, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-bu
polyvinyl alcohol, polyethylene glycol (PEG), polyvinyl
10 tanol, 2-phenyl-1-butanol, 2-phenoxy ethanol, 2-benzyloxy
ether, polyacrylic acid, polyacrylic acid salt, polyacrylamide, ethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alco
and polyvinyl pyrrolidone. hol, p-methoxy benzyl alcohol, benzyl alcohol, cyclohex
Among these, polysaccharides, polyacrylic acid, poly anol, 2-methyl cyclohexanol, 2-methyl cyclohexanol, 3-me
acrylic acid salt, polyacrylamide, and polyvinyl pyrrolidone thyl cyclohexanol, 4-methyl cyclohexanol, N-ethanolamine
15 and N-phenyldiethanolamine.
are preferred. In a developer, a surfactant of Such as an anionic type, a
Examples of the polysaccharides include starches, cellulo cationic type, a nonionic type and an amphoteric type; a pH
ses, polyuronic acid and pullulan. Among these, cellulose buffering agent, a reducing agent, organic carboxylic acid and
derivatives such as a methyl cellulose salt, a carboxymethyl a development stabilizer can be appropriately contained.
cellulose salt and a hydroxyethyl cellulose salt are preferred, A development process according to this invention is pref
and a sodium or ammonium salt of carboxymethyl cellulose erably carried out by use of an automatic processor.
is more preferred. An automatic processor preferably utilized is equipped
The polyacrylic acid, polyacrylic acid salt, and polyacry with a mechanism to automatically supply a required quantity
lamide have a molecular weight of preferably from 3,000 to of a replenisher into a development bath, a mechanism to
1,000,000, and more preferably from 5,000 to 500,000. 25 effuse a developing Solution exceeding a predetermined
Of these, polyacrylic acid salt Such as sodium polyacrylate quantity, a mechanism to detect passage of a plate, a mecha
is most preferred. The polyacrylic acid salt efficiently works nism to estimate the processing area of a plate based on
as a hydrophilization agent of the hydrophilic layer, and detection of plate passage, a mechanism to control a replen
enhance hydrophilicity of a hydrophilic layer surface which ishing quantity and/or a replenishing timing of a replenisher
is revealed on on-press development. 30
to be supplied based on the detection of plate passage and/or
Oligosaccharides the estimated processing area, a mechanism to control a tem
As the water-soluble material, oligosaccharides can be perature of a developing solution, a mechanism to detect a pH
used other than the water-soluble polymers described above. and/or conductivity of a developing Solution, and a mecha
Examples of the oligosaccharides include raffinose, treha nism to control a replenishing quantity and/or a replenishing
35
lose, maltose, galactose, Sucrose, and lactose, and trehalose is timing of a replenisher to be supplied based on the pH and/or
especially preferred. conductivity of a developing solution.
Further, in the case of utilizing a process-less CTP image
(Image Formation Printing) forming layer as an image forming layer, the laser exposed
Image formation to prepare a printing plate utilizing a portion forms a hydrophilic image portion while the unex
printing plate material of this invention is preferably per 40
posed portion forms a non-image portion, and this non-image
formed by heating at the time of image exposure. portion is removed on a printing machine to provide a printing
As an exposure method, exposure by a laser is specifically plate, which is Supplied for printing.
preferable. In the invention, exposure for image formation is prefer
After exposure, the plate material is processed by a devel ably scanning exposure, which is carried out employing a
oper to be utilized as a printing plate. 45
laser which can emit light having a wavelength of infrared
As a developer, Such as an alkaline aqueous solution and a and/or near-infrared regions, that is, a wavelength of from 700
Solution containing an organic solvent may be utilized. to 1000 nm.
(Alkali Agent) As the laser, a gas laser can be used, but a semi-conductor
An alkali agent utilized in an alkaline aqueous Solution 50 laser, which emits light having a near-infrared region wave
includes inorganic alkali agents such as sodium silicate, length, is preferably used.
potassium silicate, ammonium silicate, Sodium secondary A device Suitable for the scanning exposure in the inven
phosphate, potassium secondary phosphate, ammonium sec tion may be any device capable of forming an image on the
ondary phosphate, Sodium bicarbonate, potassium bicarbon printing plate material according to image signals from a
ate, ammonium bicarbonate, Sodium carbonate, potassium 55 computer employing a semi-conductor laser.
carbonate, ammonium carbonate, Sodium hydrogencarbon Generally, the Scanning exposures include the following
ate, potassium hydrogencarbonate, ammonium hydrogencar processes.
bonate, sodium borate, potassium borate, ammonium borate, (1) a process in which a plate material provided on a fixed
Sodium hydroxide, potassium hydroxide, ammonium horizontal plate is scanning exposed in two dimensions,
hydroxide and lithium hydroxide. 60 employing one or several laser beams.
Further, utilized can be organic alkali agents such as (2) a process in which the Surface of a plate material pro
monomethylamine, dimethylamine, trimethylamine, mono vided along the inner peripheral wall of a fixed cylinder is
ethylamine, diethylamine, triethylamine, mono-i-propy Subjected to scanning exposure in the rotational direction (in
lamine, di-i-propylamine, tri-i-propylamine, butylamine, the main scanning direction) of the cylinder, employing one
monoethanolamine, diethanolamine, triethanolamine, mono 65 or several lasers located inside the cylinder, moving the lasers
i-propanolamine, di-i-propanolamine, ethyleneimine, ethyl in the normal direction (in the Sub-Scanning direction) to the
enediamine and pyridine. rotational direction of the cylinder.
 US 7,461,594 B2
25 26
(3) a process in which the Surface of a plate material pro Example 1
vided along the outer peripheral wall of a fixed cylinder is
Subjected to scanning exposure in the rotational direction (in
the main scanning direction) of the cylinder, employing one (Preparation of Aluminum Support)
or several lasers located inside the cylinder, moving the lasers An aluminum plate (material: 1050, quality: H16) of 0.24
in the normal direction (in the Sub-Scanning direction) to the thick, 1003 mm wide and 800 mm long, after having been
rotational direction of the cylinder. subjected to a degrease treatment at 60° C. for 1 minute in a
Removal on a press of the image formation layer at non 5% caustic soda aqueous Solution, was subjected to an elec
image portions (unexposed portions) of a printing plate mate trolytic etching treatment, under a condition of a temperature
rial, which is mounted on the plate cylinder, can be carried out 10
of 25°C., a current density of 60A/dm and a processing time
by bringing a dampening roller and an inking roller into of 30 seconds, in a 0.5 mol/l hydrochloric acid aqueous solu
contact with the image formation layer while rotating the tion.
plate cylinder, and can be also carried out according to various
sequences such as those described below or another appro Next, the aluminum plate, after having been Subjected to a
priate sequence. The Supplied amount of dampening Solution 15 desmuttreatment at 60°C. for 10 seconds in a 5% caustic soda
may be adjusted to be greater or Smaller than the amount aqueous solution, was subjected to an anodic oxidation treat
ordinarily Supplied in printing, and the adjustment may be ment under a condition of a temperature of 20°C., a current
carried out stepwise or continuously. density of 3 A/dm and a processing time of 1 minute, in a
(1) A dampening roller is brought into contact with the 20% sulfuric acid solution. Further, the aluminum plate was
image formation layer of a printing plate material on the plate subjected to a hot water sealing treatment with hot water of
cylinder during one to several tens of rotations of the plate 30° C. for 20 seconds, whereby an aluminum support as a
cylinder, and then an inking roller brought into contact with
the image formation layer during the next one to tens of Support for a planographic printing plate material was pre
rotations of the plate cylinder. Thereafter, printing is carried pared.
Out 25 An image forming layer coating solution having the fol
(2) An inking roller is brought into contact with the image lowing composition was coated on the aforesaid aluminum
formation layer of a printing plate material on the plate cyl Support by use of an extrusion coater so as to make a dry layer
inder during one to several tens of rotations of the plate thickness of2 g/m, followed by being dried in the first drying
cylinder, and then a dampening roller brought into contact at 60°C. for 20 seconds and then in the second drying at 100°
with the image formation layer during the next one to tens of 30
rotations of the plate cylinder. Thereafter, printing is carried C. for 40 seconds, whereby a printing plate material was
Out. prepared.
(3) An inking roller and a dampening roller are brought into (Image Forming Layer Coating Composition)
contact with the image formation layer of a printing plate
material on the plate cylinder during one to several tens of
rotations of the plate cylinder. Thereafter, printing is carried
Out.
Binder (binder 1 described below) 20 parts
(Printing) Novolak resin (polycondensation novolak resin of 40 parts
As a printing machine utilized in a printing method accord 40 phenol, m-, p-mixed (6,4) cresol and formaldehyde (a ratio
ing to this invention, utilized can be a planographic off set of phenol to cresol is 64) (all are based on a weight ratio)
printing machine, a planographic off set rotary press and a Acid-induced decomposing compound (acid-induced 20 parts
tabular proofprinting machine, which are well known in the decomposing compound A described below)
art. Photo-induced acid generator A (2-trichloromethyl-5-B- 5 parts
In this invention, alternation of Such as a plate making 45 (2-benzofuryl) vinyl-1,3,4-oxadiazol)
condition, which depends on differences of various printing Infrared absorbent (following IR17) 2 parts
machines such as described above, can be easily made by Propylene glycol monomethylether 1000 parts
means of a wireless tag, whereby a printed matter having
stable quality can be always prepared.
50
(Printing Paper) (Synthesis of Acid-induced Decomposing Compound)
Art paper, coated paper, wood free paper and matt paper, 1,1-dimethoxy cyclohexane (0.5 mol), phenyl cellosolve
which are generally utilized; in addition to various paper (1.0 mol) and 80 mg of p-toluene sulfonate were reacted at
utilizing recycled pulp and various paper utilizing kenuff,
which are for an environmental countermeasure, can be 55
100° C. for 1 hour while being stirred, and the temperature
employed as printing paper. was gradually raised up to 150° C. followed by a reaction at
In this invention, alternation of Such as a plate making 150° C. for 4 hours.
condition, which depends on differences of various paper Ethanol generated by the reaction was meanwhile elimi
Such as described above, can be easily made, whereby a nated by distillation. The system, after having been cooled,
printed matter having stable quality can be always prepared. 60 was added with 500 ml of tetrahydrofuran and 2.5g of potas
EXAMPLES sium carbonate unhydride, and was stirred and filtered.
A solvent was removed from the filtrate under reduced
In the following, this invention will be detailed with refer pressure, followed by elimination of a low boiling point com
ence to examples, however, is not limited thereto. Herein, 65 ponent under a highly reduced pressure, whereby following
“part(s) represents “weight part(s) unless otherwise men acid-induced decomposing compound A, which is viscous
tioned. and oily, was prepared.
 US 7,461,594 B2
27 28
Exposure: 2400 dpi (dpi represents a dot number per 2.54
cm), 9.3 W and 185 rpm (a rotation number of the drum) were
Chemical Structure 1 employed.

( )-o-clich- p-clich-O-( ) 5 (Development)

Automatic processor: InterPlater 85HD (produced by
Glunz & Jensen Corp.)
Developing Solution A:
10
Acid-induced decomposing compound A
Chemical Structure 2 Potassium silicate 100.0 parts
Potassium hydroxide 24.5 parts
CH3 CH3 Caprylic acid 0.2 parts
Maleic acid 2.0 parts
EDTA (ethylenediaminetetraacetatic acid) 0.3 parts
-cis-rich-in-ch-in COOCH CN
15
Water 1840 parts

losi-()—on
Binder 1
Development temperature: 25°C.1°C.
Development time: 20 seconds+1 second
(Finisher)
(Mw = 22000 Mw/Min = 1.5 min:l = 30:40:30) GW-3 (manufactured by Mitsubishi Chemical Corp.)
Chemical Structure 3
(Sensitivity)
25 The minimum quantity of energy at which the exposed
portion of an image forming layer is completely removed

y CECH-CH=CH-C
3 30
after development was measured to be defined as an index of
sensitivity.
A sensitivity was 79 mj/cm for the first sheet and 81
mj/cm for the last sheet; and the mean value was 80 mi/cm.

S3 IR17
35
(Data Writing on Wireless Tag (RF-ID))
By use of the following system as a reader/writer, a sensi
tivity data and a manufactured date were recorded on the rest
1998 sheets of printing plate materials. Recording was pos
sible from a place of 2 m distant. Reader/writer controller:
ME-L1002 (manufactured by Hitachi Maxell Corp.), reader/
writer transceiver/receiver: ME-L4001 (manufactured by
Hitachi Maxell Corp.), and antenna coil: ME-C1001 (manu
Next, this printing plate material was cut into a rectangular 40 factured by Hitachi Maxell Corp.), are utilized by being con
form of 730 mm wide and 600 mm long and 1000 sheets of the nected to a personal computer.
printing plate materials having this size were prepared. Next, manufacturing, exposure, development and inspec
With respect to each of these 1000 sheets, a hole of 3 cm tion (sensitivity measurement) of the printing plate material
square was made at the center of the holding end portion in the above described were repeated 8 times over 1 month to obtain
longitudinal direction (the longitudinal direction at the time 45 a data of 8 lots.
of being mounted on a printing machine) with keeping a
width of 5 mm from the aluminum plate end. Each sensitivity data is shown in table 1.
Next, the RF-ID described below was adhered with a
double coated tape on a transparent PET film having a thick TABLE 1
ness of 175 um and adhered with an adhesive so as to be 50 Lot No. Sensitivity (mj/cm)
arranged at the center of the 3 cm square (the plane view and
the cross sectional view are shown in FIG. 2). The following 8O
85
RF-ID chip (manufactured by Hitachi Maxell, Ltd.) was ulti 92
lized. 85
Protocol: original method 55 83
Carrier frequency: 13.56 MHz 75
68
Memory capacity: 1 Mbit 72
Data transfer rate: 26.48 kbps
Successively, the first sheet and the 1000th sheetamong the
above 1000 sheets were extracted, and subjected to exposure 60 These sensitivity data were converted to data substituted by
and development treatments under the following condition to a rotation number of a corresponding setter and written on an
examine sensitivity data. RF-ID.
(Image Formation) Successively, a part of these lots of a plate was stored in a
conditioning room (dry thermo: <DT storages) (50° C., rela
Exposure Condition 65 tive humidity of 2-3%) and 1 sheet per two days was extracted
Setter: Trendsetter 400 Quantum (manufactured by Creo to perform the above-described exposure and development,
Corp.) whereby sensitivity was measured.
 US 7,461,594 B2
29 30
Further, the mean value of accelerated aging data of 8 lots Finisher:
was determined and a correlation curve between aging days GW-3 (manufactured by Mitsubishi Chemical Corp.)
and sensitivity was calculated when DT-1 is set to 1 week, Development temperature: 25°C.1°C.
which was held on an RF-ID. The development time was controlled by appropriately
In addition to this, relation of aging time and development 5 being varied based on a calculated value with reference to
time to give a constant sensitivity was determined by varying information data of aging after manufacturing and exposure
development time, which was recorded on an RF-ID. condition information held on an RF-ID.
A development time and an exposure time (a rotation num Small dot reproduction (200 lpi, reproduction of small dots
ber of a setter) were determined as a development time and an equivalent to 3% and 5%) and reproduction in a shadow
exposure time (a rotation number of a setter) to give the best 10 portion (200 lpi, shadow reproduction equivalent to 97% and
dot for dot reproduction. 95%) were read on a plate, which were shown in table 2.
A printing material, which has been manufactured in the Herein, as comparison, data of a printing plate, which had
above manner and on an RF-ID of which such as a sensitivity been exposed under an ordinary condition without reading
information, a manufactured date and an aging change infor out the RF-ID information, was also shown in table 2.
mation were written, was Subjected to plate making and print 15
An exposure time at exposure and a development time at
ing process under the following condition over approximately developing were changed depending on data read out from an
half a year. RF-ID; however, the values at that time were visually read out
Herein, sensitivity information and aging information and shown in table 2 together with aging days.
were read before exposure of the printing plate material. Thereafter, the plate described above was used as a printing
(Image Formation) plate. Dot for dot reproduction (small dot/shadow portion) on
Exposure Condition the printed matter was quite same as the visual evaluation
Setter: Trendsetter 400 Quantum (Creo Corp.) results after plate making.
Exposure: 2400 dpi (dpi represents a dot number per 2.54 Further, a printing plate of each lot was able to print up to
cm), 9.3 W. (a rotation number was controlled by appropri 25 300,000 sheets.
ately being changed based on a calculated value with refer (Printing Condition)
ence to data of sensitivity information held on an RF-ID) Printing Machine: DAIYA 1F-1 (produced by Mitsubishi
(Development Process) Heavy Industries, Ltd.)
Automatic processor: InterPlater 85HD (produced by 30
Paper: Coated paper (regenerated pulp content of 20%,
Glunz & Jensen Corp.) manufactured by Hokuetsu Paper Making Co., Ltd.)
Developing solution A: Blanket: SR 100 (SRI Hybrid Co., Ltd.)
Printing ink: Soybean oil ink, Naturalith 100 (Y. M. C. K)
(manufactured by Dainippon Ink & Chemicals Inc.)
Potassium silicate 100.0 parts 35 Dampening solution: H solution SG-51, concentration of
Potassium hydroxide 24.5 parts 1.5% (manufactured by Tokyo Ink Co., Ltd.)
Caprylic acid
Maleic acid
0.2 parts
2.0 parts
Printing speed: 4000 sheets/hour
EDTA (ethylenediaminetetraacetate) 0.3 parts The results are shown in table 2. It is clear from table 2 that
Water 1840 parts a printed matter exhibiting stable dot quality can be always
obtained by a printing plate material and a plate making
method of this invention.

TABLE 2
Small Small
Lot of Exposure dot dot Shadow Shadow
printing rotation RF-ID Development reproduction reproduction reproduction reproduction
plate number information time 200 lpi 200 lpi 200 lpi 200 lpi
material *2 (rpm) feedback (Sec) 5% (*1) 3% (*1) 95% 97% Remarks

1 1 85 ON 30 W.
2 1 78 ON 30 W.
3 1 59 ON 30 W.
4 1 78 ON 30 W.
5 1 8O ON 30 W.
6 1 2O3 ON 30 W.
7 1 223 ON 30 W.
8 1 220 ON 30 W.
1 7 85 ON 28 W.
1 60 82 ON 33 W.
1 120 75 ON 40 W.
1 18O 70 ON 45 W.
3 7 60 ON 30 W.
3 60 55 ON 35 W.
3 120 50 ON 40 W.
3 18O 47 ON 48 W.
7 7 222 ON 30 W.
7 60 219 ON 35 W.
7 120 200 ON 39 W.
7 18O 90 ON 41 W.
1 1 85 OFF 30 Comp.
 US 7,461,594 B2
31 32
TABLE 2-continued
Small Small
Lot of Exposure dot dot Shadow Shadow
printing rotation RF-ID Development reproduction reproduction reproduction reproduction
plate number information time 200 lpi 200 lpi 200 lpi 200 lpi
material *2 (rpm) feedback (Sec) 5% (*1) 3% (*1) 95% 97% Remarks
2 1 85 OFF 30 B B C D Comp.
3 1 85 OFF 30 B B D D Comp.
4 1 85 OFF 30 B B C D Comp.
5 1 85 OFF 30 B B B C Comp.
6 1 85 OFF 30 C D B B Comp.
7 1 85 OFF 30 D D B B Comp.
8 1 85 OFF 30 C D B B Comp.
1 7 85 OFF 30 B D B B Comp.
1 60 85 OFF 30 B B B C Comp.
1 120 85 OFF 30 B B C D Comp.
1 18O 85 OFF 30 A. B D D Comp.
3 7 85 OFF 30 B B C D Comp.
3 60 85 OFF 30 B B D D Comp.
3 120 85 OFF 30 B B D E Comp.
3 18O 85 OFF 30 A. B D E Comp.
7 7 85 OFF 30 C D B B Comp.
7 60 85 OFF 30 C D B B Comp.
7 120 85 OFF 30 D D B B Comp.
7 18O 85 OFF 30 D D C C Comp.

*1 Visual evaluation by use of a loupe,

* 2: Aging days from manufacture to use,
Inv.: Invention,
Comp.: Comparison
*1 Visual evaluation by use of a loupe
A: Dot for dot reproduction is uniform and good.
B: Dot for dot reproduction is good.
C: Deformation is partly observed.
D: Missing and fill-in are partly observed.
E: Dot for dot reproduction is poor.

Further, similar results were obtained when preparation— printing was longer than the former case, whereby a similar
printing of a printing plate material were performed similarly 35 result as described in table 2 was obtained.
to the above-described manner except a wireless tag was (Adhesion of Wireless Tag (RF-ID) in Direct Pasting)
mounted in the forms shown in FIGS. 4 and 7.
The following RF-ID was utilized, being sandwiched
As an insulator, polypropylene was utilized and it is between a synthetic rubber film (2 cmx2 cm) having a thick
adhered on an aluminum Support with an adhesive. 40
ness of 175 um and an aluminum plate, and was pasted up
A printing plate with a wireless tag was possible to be with an adhesive tape.
Smoothly mounted on a printing machine under the same The pasting position was on the back side of the center of
condition as that of a plate without a wireless tag. a holding end portion (being mounted in a form shown in FIG.
5).
Example 2 45 (RF-ID)
Accuwave OMH-4230 (manufactured by Dainippon Print
Next, similar evaluation was performed by changing an ing Co., Ltd.)
adhesion method of an RF-ID on a printing plate into the Thereafter, by utilizing the RF-ID similarly to the above
following 2 types. described manner, writing/reading was carried out to perform
(Adhesion of Wireless Tag (RF-ID) in Protrusion Form) 50 plate making and printing over half a year, in a similar man
ner. The plate making condition was possible to be controlled
A PET film (3 cmx6 cm) having a thickness of 175um was similarly to the above-described manner, except that record
pasted on the back Surface of a photosensitive planographic ing and read of information data had to be performed at a
printing plate, which had been cut (730 mm wide, 600 mm distance of approximately 5 cm, whereby a similar result as
long) after coating and drying similarly to the above-de 55 described in table 2 was obtained.
scribed manner, at the center portion along the extended
longitudinal direction, and an RF-ID similar to one described Example 3
above was adhered with a double coated tape on the center of
a protruded portion (3 cmx3 cm) (mounted in a form shown in (Feedback to Printing Condition)
FIG. 4). 60 Next, utilizing printing plate material lot 1, plate making
Thereafter, by utilizing an RF-ID adhered on the extruded was performed in a similar manner to example 1 except the
potion as described above, writing/reading was carried out following.
and plate making and printing were performed over half a That is, exposure condition 2 (a mark data in which a
year. rotation number was set slower than an ordinary condition by
The plate making condition was possible to be controlled 65 20%) was recorded on a wireless tag (an RF-ID) by a writer
similarly to the above-described manner, except that time immediately before laser exposure and exposure was per
required to be mounted on a printing machine at the time of formed under this condition.
 US 7,461,594 B2
33 34
When a mark data was read utilizing a program, which had Next, this aluminum plate was subjected to an electrolytic
been set based on printing paper and an exposure condition in roughening treatment under a condition of a peak current
advance, by use of an RF-ID reader equipped on a printing density of 50 A/dm by use of alternating current of a sine
machine, a 2-steps feeding paper Supply of wood free paper wave, with an electrolytic Solution containing 10 g/L of
and coated paper was automatically changed into wood free 5 hydrochloric acid and 0.5 g/L of aluminum.
paper to perform printing. Distance between an electrode and the sample surface at
The printed dot image portion on a printed matter was this treatment was set to 10 mm. The electrolytic roughening
observed and the result was shown in table 3. As a compari treatment was carried out by dividing into 12 times and a
son, the case of an exposure condition being not changed was process quantity of electricity (at anode time) per one time
shown. 10 was 40C/dm to make the total process quantity of electricity
The results are shown in table 3. It is clear from table 3 that (at anode time) of 480 C/dm. Further, a pausing time of 4
a printed matter exhibiting stable dot quality can be always seconds was provided between each roughening treatment.
obtained by a printing plate material and a plate making After the electrolytic roughening, the plate was immersed
method of this invention. in a 1 weight 96 Sodium hydroxide aqueous solution kept at

TABLE 3
Small Small
Lot of Aging days Exposure dot dot Shadow Shadow
printing from rotation reproduction reproduction reproduction reproduction
plate manufacture number Printing 200 lpi 200 lpi 200 lpi 200 lpi
material to use (rpm) *2 paper 5% (*1) 3% (*1) 95% (*1) 97% (*1) remarks
1 60 85 ON Coated A. A. A. A. Inv.
paper
1 60 48 ON Wood A. A. A. A. Inv.
free
paper
1 60 85 OFF Wood C C D E Comp.
free
paper

*1 Visual evaluation by use of a loupe,

* 2: RF-ID information feedback to printing
Inv.: Invention,
Comp.: Comparison,
*1 Visual evaluation by use of a loupe
A: Dot for dot reproduction is uniform and good.
B: Dot for dot reproduction is good.
C: Deformation is partly observed.
D: Missing and fill-in are partly observed.
E: Dot for dot reproduction is poor.

The above-described plate was utilized as a printing plate 40 50° C. to be etched so as to make a dissolution amount
thereafter. Dot for dot reproduction (small dot portion/ including Smut on the roughened surface of 2 g/m, followed
shadow portion) on a printed matter was quite same as visual by being washed, and then immersed in a 10% sulfuric acid
evaluation results after plate making. aqueous solution kept at 25°C. for 10 seconds to be neutral
(Printing Condition) ized, followed by being washed. Successively, the plate was
45 Subjected to an anodic oxidation treatment so as to make a
Printing Machine: DAIYA 1F-1 (produced by Mitsubishi quantity of electricity of 150 C/dm under a condition of a
Heavy Industries, Ltd.) constant voltage of 20 V, and was further washed.
Paper: Coated paper (regenerated pulp content of 20%, Next, after the surface water was squeezed, the plate was
manufactured by Hokuetsu Paper Making Co., Ltd.) immersed in a 0.5 weight% sodium trisilicate aqueous solu
Blanket: SR100 (SRI Hybrid Co., Ltd.) 50 tion kept at 70° C. for 30 seconds, and was washed and dried
Printing ink: Soybean oil ink, Naturalith 100 (Y. M. C. K) at 80° C. for 5 minutes, whereby an aluminum support was
(manufactured by Dainippon Ink & Chemicals Inc.) prepared.
Dampening solution: H solution SG-51, concentration of (Image Forming Layer)
1.5% (manufactured by Tokyo Ink Co., Ltd.)
55 (Preparation of Water Dispersion of Blocked Isocyanate
Printing speed: 4000 sheets/hour Compound)
Example 4 (Process-less CTP) Blocked isocyanate of an organic solvent system, in which
a trimethylol propane adduct of trilene diisocyanate had been
blocked by methylethyl ketoxime (solid content of 55 weight
(Preparation of Aluminum Support) 60 %, solvent: a mixed solvent of ethyl acetate and MIBK) of
An aluminum plate (material: 1050, quality: H16) of 0.24 364 weight parts was dissolved in 136 weight parts oftoluene.
mm thick, after having been immersed in a 1 weight 96 Next, after this solution was added with 20 weight parts of
sodium hydroxide aqueous solution at 50° C. to perform a polyoxyethylene alkylphenylether as a dispersant, further
dissolution treatment so as to make a dissolution amount of 2 300 weight parts of pure water was gradually added while
g/m followed by being washed, was immersed in a 0.1 65 stirring, and the mixed solution was strongly stirred by use of
weight% hydrochloric acid aqueous solution at 25°C. for 30 a homogenizer to disperse an oil phase in a water phase.
seconds to be neutralized and then washed. Successively, organic solvents were removed under reduced
 US 7,461,594 B2
35 36
pressure to prepare a blocked isocyanate compound water The pasting up position was at the center portion of the
dispersion having a solid content of 40 weight 96. holding end portion and on the backside of a printing plate
(Preparation of Image Forming Layer Coating Solution) material.
The materials of each composition in the following table (Wireless Tag (RF-ID))
were sufficiently mixed and stirred, followed by being fil
tered, whereby an image forming layer coating Solution hav Accuwave OMH-4230 (manufactured by Dainippon Print
ing a solid content of 5 weight 96 was prepared. ing Co., Ltd.)
Image Forming Layer Coating Solution Composition
10 (Sensitivity Evaluation)
(Numbers in the Table Without Unit Definition Represent This manufacturing was repeated 4 times similar to the
Weight Part(s).) case of a thermal CTP of example 1.
TABLE 4 Successively, after exposure similar to the aforesaid ther
15 mal CTP had been performed, development on a printing
Material 1
machine and printing were performed to determine sensitiv
Blocked Prepared blocked isocyanate compound 10.63 ity information shown in table 5.
isocyanate water dispersion
compound (solid content:40 weight%) (Sensitivity)
Blocked isocyanate compound water
dispersion: WB-700 An exposure quantity to reproduce the original dot data of
(manufactured by Mitsui Takeda Chemical 95% as 94-95% on a printed matter after development on a
Co., Ltd., isocyanate compound;
trimethylolpropane adduct of TDI, machine was defined as sensitivity.
Blocking agent: Oxime system,
dissociation temperature: 120° C., solid TABLE 5
content of 44 weight%) 25
Water Torehalose aqueous solution (product S.OO
soluble name: Toreha, melting point of 97°C., Lot No. Sensitivity (mj/cm)
material an aqueous solution having a solid
content of 10 weight%, manufactured by
Hayashi Bussiness Co., Ltd.) 1 110
Thermoplastic Copolymer emulsion of 30 2 115
micro acrylonitrilestyrenealkyl
particles acrylate methacrylic acid:Yodosol 3 125
GD87B (manufactured by Nippon NSC Co., 4 88
Ltd., mean particle size of 90 nm, Tg of
60° C., solid content of 45 weight%)
Infrared An aqueous solution (Solid content: 1 25.00
35
absorbent weight%)
of water-solublr dye (IR-1) (Method of Image Formation Printing)
Pure water 59.37
Sensitivity information data and manufactured date infor
mation date were recorded on an RF-ID, in a similar manner
40 to example 1.
Data of accelerated aging condition information was mea
sured and recorded on an RF-ID, in a similar manner to
example 1.
45
Printing was performed by use of Daiya 1 F-1 (manufac
(CH2)3SONa tured by Mitsubishi Heavy Industries, Ltd.) as a printing
machine, and utilizing coated paper, 2 weight% of Astromark
Chemical Structure 4 3 (manufactured by Nikken Chemical Laboratory Co., Ltd.)
IR-1 as a dampening solution and Toyo King High Unity M
50 Magenta (manufactured by Toyo Ink Mfg. Co., Ltd.) as ink.
A printing plate after exposure was mounted on a plate
Preparation of Printing Plate drum as it is, a number of wasted paper sheets required to start
With a combination of the aforesaid substrate and the printing being counted by employing a printing condition and
image forming layer coating Solution, an image forming layer an initial printing sequence similar to those in the case of a PS
was coated on the Substrate so as to make a dry coating 55
plate, and dot for dot reproduction of a printed material at
amount of 0.6 g/m to prepare a printing plate material. Dry 100th sheets was evaluated.
ing was performed under a condition of 55° C. for 3 minutes,
and then aging at 60° C. for 24 hours was performed. At the time of printing, data of sensitivity information,
manufactured date information, accelerated aging condition
(Direct Adhesion of Wireless Tag (RF-ID)) 60 information and printing machine information (quantity of a
Similarly to the above-described manner, the following dampening solution) were referred to for calculation,
wireless tag was pasted up at the center of PET film (3 cmx3 whereby printing was performed by controlling quantity of a
cm) having a thickness of 175 um, and the wireless tag was dampening Solution.
pasted up on the aforesaid aluminum Support including an
insulating adhesive layer so as to be sandwiched between 65 The results are shown in table 6. It is clear from table 6 that
PET film and the aluminum support (being mounted in a form a printed matter having stable quality can be always obtained
shown in FIG. 1). by a printing method of this invention.
 US 7,461,594 B2
37 38
TABLE 6
Wasted
number of
Aging Water sheets at Small
Lot of days Exposure quantity at start in the dot Shadow
printing from rotation RF-ID the time of case of reproduction reproduction
plate manufacture number information development development 200 lpi 200 lpi
material to use (rpm) feedback on a machine (*2) on a machine 3% (*1) 97% (* 1) Remarks
1 1 70 ON O 4 A. A. W.
2 1 60 ON O 4 A. A. W.
3 1 51 ON O 3 A. A. W.
4 1 81 ON O 5 A. A. W.
1 7 69 ON O 4 A. A. W.
1 60 72 ON +5 4 A. A. W.
1 120 66 ON +21 4 A. A. W.
1 18O 70 ON +25 5 A. A. W.
2 7 64 ON +2 3 A. A. W.
2 60 51 ON +5 4 A. A. W.
2 120 48 ON +23 5 A. A. W.
2 18O 41 ON +27 4 A. A. W.
3 7 59 ON +4 3 A. A. W.
3 60 55 ON +15 4 A. A. W.
3 120 45 ON +27 5 A. A. W.
3 18O 37 ON +31 5 A. A. W.
4 7 90 ON O 3 A. A. W.
4 60 87 ON +5 4 A. A. W.
4 120 8O ON +21 4 A. A. W.
4 18O 68 ON +26 5 A. A. W.
1 1 70 OFF O 5 A. A. Comp.
2 1 70 OFF O 7 C C Comp.
3 1 70 OFF O 9 D C Comp.
4 1 70 OFF O 8 C D Comp.
1 7 70 OFF O 5 C C Comp.
1 60 70 OFF O 7 C C Comp.
1 120 70 OFF O 22 C D Comp.
1 18O 70 OFF O 30 C E Comp.
2 7 70 OFF O 2O C B Comp.
2 60 70 OFF O 22 C B Comp.
2 120 70 OFF O 28 C D Comp.
2 18O 70 OFF O 33 C E Comp.
3 7 70 OFF O 2O D B Comp.
3 60 70 OFF O 22 D C Comp.
3 120 70 OFF O 35 C D Comp.
3 18O 70 OFF O 36 C E Comp.
4 7 70 OFF O 2O C B Comp.
4 60 70 OFF O 28 C B Comp.
4 120 70 OFF O 36 C D Comp.
4 18O 70 OFF O 39 C E Comp.

*1 Same as described above,

* 2: Water quantity of development on a machine represents water quantity at the start of printing (relative value of a water quan
tity gage, for example, +10 means a water quantity larger by 10%)
Inv.: Invention,
Comp.: Comparison
*1 Same as described above,
* 2: Water quantity of development on a machine represents water quantity at the start of printing (relative value of a water quan
tity gage, for example, +10 means a water quantity larger by 10%)
50
Example 5 changed for control depending on the value calculated refer
ring to data of aging information after manufacturing and
500 sheets having an excellent coating behavior were exposure condition information, which were held on an RF
selected among the printing plate materials of example 1, ID.
which were mounted without an interleaf on a pallet of a 55 As a result, it has been proved that a printed matter exhib
lateral type, which was shown in FIG. 8, and packed with iting stable quality can be always obtained similar to example
moisture-tight paper. 1.
Herein, as a mounting table, utilized one made of stainless What is claimed is:
steel. 1. A planographic printing plate material comprising an
Successively, after a SBR rubber plate of 5 cm square and 60 aluminum Support, an image forming layer provided on a part
3 mm thick was adhered on the top of a wood plate with a of the aluminum Support for forming an image in response to
double-coated tape, the aforesaid RF-ID was adhered on the imagewise exposure; and a wireless ICrag provided on a part
center thereof, and sensitivity information (a power and a of the aluminum Support;
rotation index of a setter) and manufactured date information wherein the wireless IC tag contains sensitivity informa
were written therein under the following writing condition. 65 tion of the image forming layer and in order to make the
At the time of image formation, in a similar manner to planographic printing material the following steps are
example 1. Such as development time was appropriately performed:
 US 7,461,594 B2
39 40
measuring the sensitivity of the image forming layer at the 8. A printing method comprising steps of
time of manufacture so as to obtain sensitivity informa conducting imagewise exposure and developing the plano
tion of the image forming layer; and graphic printing plate material described in claim 1, and
recording the obtained sensitivity information in the wire conducting printing by controlling printing conditions
less IC tag. based on data of information concerning the plano
2. The planographic printing plate of claim 1, wherein a graphic printing plate material.
manufactured date of the planographic printing plate material 9. The printing method according to claim 8, wherein the
and aging information of the sensitivity of the image forming information concerning the planographic printing plate mate
layer are recorded in the wireless IC tag. rial includes information of exposure conditions and infor
3. The planographic printing plate of claim 2, wherein a 10 mation of photographic processing conditions.
correlation curve between aging days and the sensitivity is 10. A method for producing a planographic printing plate
recorded in the wireless IC tag. material comprising an aluminum Support, an image forming
4. A plate-making method comprising: layer provided on a part of the aluminum Support for forming
imagewise exposing the printing plate material described an image in response to imagewise exposure; and a wireless
in claim 1 by controlling imagewise exposure conditions 15 IC tag provided on a part of the aluminum Support, wherein
based on the data of information concerning the plano the wireless IC tag contains sensitivity information of the
graphic printing plate material. image forming layer, said method comprising:
5. The plate-making method described in claim 4, wherein measuring the sensitivity of the image forming layer at the
information concerning the printing plate material is infor time of manufacture so as to obtain sensitivity informa
mation of sensitivity. tion of the image forming layer, and
6. A plate-making method comprising: recording the obtained sensitivity information in the wire
developing processing the planographic printing plate less IC tag.
material described in claim 1 by controlling developing 11. The method of claim 10, wherein a manufactured date
of the planographic printing plate material and aging infor
processing conditions based on the data of information 25 mation of the sensitivity of the image forming layer are
concerning the printing plate material. recorded in the wireless IC tag.
7. The plate-making method according to claim 6, wherein 12. The method of claim 11, wherein a correlation curve
the information concerning the printing plate material between aging days and the sensitivity is recorded in the
includes aging information after manufacturing the plano wireless IC tag.
graphic printing plate material and information of exposure
conditions.