Note: Descriptions are shown in the official language in which they were submitted.
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THERMAL WATERLESS LITHOGRAPHIC PRINTING PLATES
BACKGROUND OF THE INVENTION
1. Field of the invention
The invention relates to thermal waterless lithographic printing plates
comprising layers of inherent near infrared absorbing polymers for computer-
to-plate and digital-offset-press technologies. More specially, this invention
relates to thermal waterless lithographic printing plates, which can be imaged
with near infrared laser light and which do not require post chemical
processing step.
2. The prior art
Thermal waterless lithographic printing plates are known. For example, U.S.
patents 5,310,869 and 5,339,737 describe thermal waterless lithographic
printing plates comprising an ink-repelling layer overlying a near infrared
absorbing imaging layer. The ink-repelling layer is transparent to radiation
and comprises mainly cross-linked silicone polymers. The near infrared
absorbing imaging layer contains binder resins and near infrared absorbing
materials, such as carbon black and molecular dyes. These thermal waterless
lithographic printing plates require high doses of laser energy to ablate the
near infrared absorbing layer and weaken the adhesion of the ink repelling
cross-linked silicone polymer layer. In addition, the exposed area of the
plate
must be removed during a further chemical processing step to become an
image area.
U.S. Patent 5,379,698 also describes thermal waterless lithographic printing
plates, which comprise ink repelling cross-linked silicone polymers overlying
a
thin metallic or metal oxide film of titanium deposited on a substrate as a
laser
imaging layer. In a similar technology, U.S. Patent 5,487,338 teaches to use
an infrared reflective layer situated below the near infrared absorbing layer.
Manufacturing of such printing plates requires vacuum deposition of the
corresponding metals. Hence it is very expensive.
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W09831550, W09700175 and W09401280 also describe thermal waterless
lithographic printing plates, which comprise a layer of ink repelling cross-
linked silicone polymers overlying a near infrared absorbing imaging layer
containing binder resins and near infrared absorbing pigments, dyes or thin
metal films. Again, such thermal waterless lithographic printing require high
laser energy doses for imaging.
W09706956 also describes thermal waterless lithographic printing plates,
which comprise a near infrared absorbing layer containing binder resins and
near infrared absorption dyes or pigments, and a overlying transparent
hydrophobic layer containing fluorinated polymeric materials soluble in
fluorinated solvents. Upon exposure to near infrared laser radiation, the
exposed area is ablated and accepts ink, while the non-exposed area still
repels ink. One drawback of such plates is that the non-exposed area is
sensitive to handling and easily becomes dirty on press.
EP0764522 also provides a thermal waterless printing plate containing a near
infrared transparent cross-linked silicone polymer ink repelling layer and a
near infrared absorbing imaging layer. The ink repelling layer and near
infrared absorbing imaging layers contain cross-linked functionality, which
form interlayer cross-linked bonds to increase the run length on press. Such
printing plate requires high laser energy doses for imaging and requires a
chemical processing step.
W09911467 also provides a thermal waterless lithographic printing plate,
comprising a layer of ink repelling cross-linked silicone polymer overlying a
near infrared absorbing imaging layer containing polyurethane resins and
near infrared absorption dyes. Although, such printing plate exhibits faster
laser imaging speed, they are very sensitive to the different developers used
in the final chemical processing step.
Thus there remains a need for an improved thermal waterless lithographic
printing plate which overcomes the drawbacks of the prior art.
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The main objects is to provide lithographic printing plate coating
compositions
which combine the advantages of: long-life printing plates, absence of phase
separation of the overlaid coatings, easily manufactured and inexpensive
coating formulations, coatings which may be precisely and rapidly imaged
with laser accuracy.
SUMMARY OF THE INVENTION
This invention relates to thermal waterless lithographic printing plates for
computer-to-plate and digital-offset-press technologies. More specially, this
invention relates to thermal lithographic printing plates comprising:
In general terms, the present invention provides a thermal waterless printing
plate suitable for near infrared laser imaging, said printing plate
comprising:
(i) a support substrate, and (ii) a composite top layer consisting of:
(a) a near infrared absorbing adhesion promoting layer applied to the
support substrate and
(b) a near infrared absorbing ink repelling cross-linked silicone polymer
layer.
Also provided are coatings for making the printing plate of the present
invention.
The thermal waterless lithographic printing plates of this invention can be
imaged with near infrared laser lights having a radiation between about 780
and about 1200 nm. Depending on the laser imaging energy doses, the
imaged plates may not require post chemical processing step.
Other objects and further scope of applicability of the present invention will
become apparent from the detailed description given hereinafter. It should be
understood, however, that this detailed description, while indicating
preferred
embodiments of the invention, is given by way of illustration only, since
various changes and modifications within the spirit and scope of the invention
will become apparent to those skilled in the art.
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DETAILED DESCRIPTION OF THE INVENTION
This invention relates to thermal waterless lithographic printing plates for
computer-to-plate and digital-offset-press technologies. More specially, this
invention relates to thermal waterless lithographic printing plates, which can
be imaged with near infrared laser light having a radiation between about 780
and about 1200 nm. The thermal waterless lithographic printing plates of this
invention comprise (I) a support substrate, and (II) a composite top layer
consisting of an inherent near infrared absorbing ink-repelling composite
comprising inherent near infrared absorbing polymers.
Support substrate:
The support substrate of this invention may be any sheet material such as
metal, plastic and paper. The surface of the substrate may be treated to
enhance the adhesion by techniques known in the art. For example, the
surface of aluminum sheet may be treated by metal finishing techniques
including electrochemical roughening, chemical roughening, mechanical
roughening, anodizing and the like. The surface of plastic sheets may be
modified by corona treatment and chemical etchings.
The near infrared absorbing ink repelling composite layer:
The near infrared absorbing ink repelling composite layer of this invention
comprises (a) a near infrared absorbing adhesion promoting layer, which is
applied between a support substrate and (b) a near infrared absorbing ink
repelling cross-linked silicone polymer layer.
(a) The near infrared absorbing adhesion promoting layer comprises
mainly inherent near infrared absorbing polymer having reactive
functionality, which can form covalent bonds with the near infrared
absorbing ink repelling cross-linked silicone polymer layer. The near
infrared absorbing adhesion promoting polymers exhibit strong absorption
band between 780 and 1200nm. The preferred class of near infrared
absorbing polymers of this invention is urethane polymers, which are
obtained from the reactions of alkyl or aryl compounds containing
diisocyanate functional groups with near infrared absorption chromophore
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containing alcohol functional groups and certain tertiary alcohol. The
inherent near infrared absorbing polyurethane of this invention may be
represented according to formula I.
5
T A
a b
Formula I
wherein
= a and b represent molar ratios, which vary from 0.1 to 0.9.
= T represents near infrared transparent repeating segment, which
may have a structure according to Formula II, III, IV, and V.
H3 H3
HNCOO C C OCONH
1 1
CH3 CH3
Formula II
H3 H3
HNCOO C CH2 CH2 C OCONH
I I
CH3 CH3
Formula III
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H3 H3
HNCOO C C= C- C OCONH
1
CH3 CH3
Formula IV
H3 H3
HNCOO C O C OCONH
I
CH3 CH3
Formula V
= A represents near infrared absorbing repeating segment, which
may have a structure according the Formula VI.
R2 R2
.--., --,,
. ' /
D1 R1 D2 i2
~ ~
R3
(CH2)m n (CH2)m
X1
Formula VI
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wherein
= ZI and Z2 represent sufficient atoms to form a fused
substituted or unsubstituted aromatic rings, such as phenyl and
naphthyl.
= D1 and D2 represent -0-, -S-, -Se-, -CH = CH-, and -C(CH3)Z-
= R1 and R2 represent alkyl, alkyloxy, alkyl halide, alkyl pyridine,
allyloxy, vinyloxy, alkylthio, arylthio, aminothiophenol, sulfoalkyl,
and carboxyalkyl substitution.
= R3 represents hydrogen, alkyl, and aryl substitution.
= X1 represents an anionic counter ion selected from bromide,
chloride, iodide, tosylate, triflate, trifluoromethane carbonate,
dodecyl benzosylfonate and tetrafluoroborate.
= n represents 0 and 1.
= m varies from 1 to 18.
The inherent near infrared absorbing polymers of this invention exhibit
strong absorption band between 780 and 1200 nm. They may have glass
transition temperature between 110 and 150 C and decomposition
temperature between 180 and 300 C.
Optionally, the near infrared absorbing adhesion promoting layer of this
invention may contain binder resins, which are transparent to near
infrared radiation. The preferred binder resins are polymers containing
monomer units derived from nitrocellulose, hydroxyalkylcellulose, styrene,
carbonate, amide, urethane, acrylate, vinyl alcohol, and ester.
Upon exposure to near infrared radiation between 780 and 1200 nm, the
near infrared absorption segments containing in the polymer backbone
convert the photo-energy into heat, which induce the thermal
fragmentation and decomposition of the near infrared transparent
segments via cleavage mechanism described by Foley et. al. (U.S. Patent
5,156,938) according to Formula VII.
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C
1 H3 ~H3
HNCOO C O C OCONH
1 1
CH3 CH3
Heat
NH2 + CO2 + + CO2 + H 2 N
H3C CH3
Formula VII
(b) The near infrared absorbing ink-repelling layer of this invention
comprises cross-linked silicone polymers having near infrared absorption
repeating units. The near infrared absorbing repeating units form covalent
bonds with the cross-linked silicone polymeric networks according to
Formula VIII, IX and X:
R4 R4
1 1
O Si O Si
1 1
B R4
Formula VIII
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i4 R4
O Si B Si
1 1
R4 R4
Formula IX
i4 R4
O
Si O
I I
R4 R4
R4 S i R4
I
O
Formula X
wherein
=-(R4)2 - Si - O- represents a cross-linked silicone polymeric networks.
= R4 represents methyl, ethyl and aryl substitution of the cross-linked
silicone polymeric networks.
= B represents near infrared absorbing repeating units, which exhibits
strong absorption bands between 780 and 1200 nm. The near infrared
absorption repeating units comprise derivatives of indole,
benz[e]indole, benz[cd]indole, benzothiazole, napthothiazole,
benzoxazole, napthoxazole, benzselenazole, and napthoselenazole,
which can be represented according to Formula XI, XII and XIII:
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R6 R6
.-- , ,
D 1 R5 D2
+ Z2
5 T
N~
\ ~ - - ~ R8 n R7 R8
X2
10 Formula XI
R6
.--,, R5 R6
D1 D2 Z2
IV~ N
R7 --
(CH2)m n (CH2)m
X2
Formula XII
R6
R6
I D1 R5 D2 ~2
NJ N
-- R7 --
(CH2)m n (CH2)m
X2
Formula XIII
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wherein
= ZI and Z2 represent sufficient atoms to form a fused substituted
or unsubstituted aromatic rings, such as phenyl and naphthyl.
= D1 and D2 represent -0-, -S-, -Se-, -CH = CH-, and -C(CH3)2-
= R5 represents alkyl, alkyloxy, alkyl halide, pyridine, alkyl pyridine
and alkylthio.
= R6 represents alkyl, sulfonyl alkyl, and carboxy alkyl
substitution.
= R7 represents hydrogen, alkyl and aryl substitution.
= R8 represents alkyl, benzyl, alkyl amine, alkyl sulfonic acid, alkyl
carboxylic acid substitution.
= X2 represents an anionic counter ion selected from bromide,
chloride, iodide, tosylate, triflate, trifluoromethane carbonate,
dodecyl benzosylfonate and tetrafluoroborate.
= n represents 0 and 1.
= m varies from 1 to 18.
The near infrared absorbing ink repelling cross-linked silicone polymers of
this invention may be obtained by the in-situ addition reactions of
poly(hydroalkylsiloxane) with poly(dialkylsiloxane) and near infrared
absorption molecules containing alkenyl functional groups under presence
of metal complex catalysts, such as hydrogen hexachloro platinate. They
may also be obtained by the condensation reactions of
poly(dialkylsiloxane) containing silanol functional groups with organic
compounds containing acyloxy or alkoxy silane functional groups under
presence of carboxylic acid salt of zinc, tin, iron or titanium catalyst.
Upon exposure to near infrared radiation between 780 and 1200 nm, the
near infrared absorption segments containing in the cross-linked silicone
polymer backbone convert the photo-energy into heat, which induces the
thermal fragmentation and decomposition of the polymeric networks. The
thermal fragmentation of the near infrared absorbing ink repelling layer
combining with thermal fragmentation of the near infrared absorbing
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adhesion promoting beneath layer result in the formation of low molecular
weight materials. These decomposed products are easily removed by the
printing inks on the printing press during roll up period. The laser
exposure area eventually becomes accepting inks and the non-exposure
area still repelling inks.
Synthesis of near infrared absorbing adhesion promoting polymers:
All the polymerization was performed in a three-neck flask reactor equipped
with magnetic stirrer, heating metal, temperature controller, water condenser,
and nitrogen inlet. The completion of the reaction was followed by infrared
spectrophotometer. The optical and thermal characteristics of the obtained
polymers were characterized by spectroscopic and differential scanning
calorimetric techniques.
Synthesis of inherent near infrared absorbing adhesion promoting
polymers: Examples 1 to 5
EXAMPLE 1
Synthesis of near infrared absorption polymer ADS-001-CTP
Near infrared absorption polymer ADS-00-1 CTP was synthesized by slowly
adding 21.2 parts of trimethyl-1,6-diisocyanatohexane (available from Aldrich
Chemicals) into a solution containing 100 parts of N-methyl pyrrolidinone, 6.8
parts of 2-[2-[2-choloro-3-[2-(1,3-dihydro-l-(2-hydroxyethyl)-3,3-dimethyl-2H-
benz[e]indol-2-ylidene)ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-(2-
hydroxyethyl) -3,3-dimethyl-1 H-benz[e]indolium perchlorate (available from
American Dye Source, Inc.), 18.0 parts of a,a,a',a'-tetramethyl-1,4-
benzenedimethanol (available from Aldrich Chemicals) and 0.5 parts of
dibutyltin dilaurate (available from Aldrich Chemicals) at 60 C under
nitrogen
atmosphere and constant stirring. Completion of the polymerization was
indicated by the disappearance on NCO absorption bands in the infrared
spectra. The product was precipitated in water and then collected by vacuum
filtration, washed copiously with water and dried in air until constant
weight.
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The obtained near infrared absorption polymer has glass transition and
decomposition temperatures at around 133 C and 214 C, respectively. The
film of near infrared absorption polymer ADS-001-CTP on polyester film
shows a broad absorption band having a maximum at around 842 nm. The
ideal structure of ADS-001-CTP can be represented as following:
O CH3 CH3 0
CH3 I H3C
+ O
N~ N
HNCOO C104 OCONH
H C CH3
H3C C CH3
0.20
H3 CH3 H3 CH3
',,-,,,,~HNCOO-C O C OCONH
C I I
0.80 I I CH 3 CH3
H CH3
Structure of ADS-001-CTP
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EXAMPLE 2
Synthesis of near infrared absorption polymer ADS-002-CTP
Near infrared absorption polymer ADS-002-CTP was synthesized by slowly
adding 26.0 parts of methylene bis(4-cyclohexylisocyanate) (available from
Bayer) into a solution containing 100 parts of N-methyl pyrrolidinone, 6.8
parts
of 2-[2-[2-choloro-3-[2-(1,3-dihydro-1-(2-hydroxyethyl)-3,3-dimethyl-2H-
benz[e]indol -2-ylidene)ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-(2-
hydroxyethyl)-3,3-dimethyl-1 H-benz[e]indolium perchlorate (available from
American Dye Source, Inc.), 18.0 parts of a,a,a',a'-tetramethyl-1,4-
benzenedimethanol (available from Aldrich Chemicals) and 0.5 parts of
dibutyltin dilaurate (available from Aldrich Chemicals) at 60 C under
nitrogen
atmosphere and constant stirring. Completion of the polymerization was
indicated by the disappearance on NCO absorption bands in the infrared
spectra. The product was precipitated in water and then collected by vacuum
filtration, washed copiously with water and dried in air until constant
weight.
The ADS-002-CTP near infrared absorbing polymer has the glass transition
and decomposition temperatures at around 132 C and 214 C, respectively.
The film of near infrared absorption polymer ADS-002-CTP on polyester film
shows a broad absorption band having a maximum at around 839 nm. The
ideal structure of ADS-002-CTP can be represented as following:
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5
O C/ / / N
15 HNCOO C104 OCONH
CH2
H3 CH3 0.20
CH H30 2 OCONH
0.80 I I
CH3 CH3
Structure of ADS-002-CTP
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EXAMPLE 3
Synthesis of near infrared absorption polymer ADS-003-CTP
Near infrared absorption polymer ADS-003-CTP was synthesized by slowly
adding 21.2 parts of trimethyl-1,6-diisocyanatohexane (available from Aldrich
Chemicals) into a solution containing 100 parts of N-methyl pyrrolidinone, 6.4
parts of 2-[2-[2-allyloxy-3-[2-(1,3-dihydro-l-(2-hydroxyethyl)-3,3-dimethyl-2H-
benz[e]indol-2-ylidene)ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-(2-
hydroxyethyl) -3,3-dimethyl-1 H-benz[e]indolium perchlorate (available from
American Dye Source, Inc.), 18.0 parts of a,a,a',a'-tetramethyl-1,4-
benzenedimethanol (available from Aldrich Chemicals) and 0.5 parts of
dibutyltin dilaurate (available from Aldrich Chemicals) at 60 C under
nitrogen
atmosphere and constant stirring for 6 hours. To the reaction mixture, 6 parts
of sodium allyloxylate in 14 parts of allyl alcohol was slowly added and the
reaction was continued for additional 4 hours. The reaction mixture was
cooled down to room temperature. The product was precipitated in water and
then collected by vacuum filtration, washed copiously with water and dried in
air until constant weight. The film of near infrared absorption polymer ADS-
003-CTP on polyester film shows a broad absorption band having a maximum
at around 832 nm. The ideal structure of ADS-003-CTP can be represented
as following:
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I
CH3 CH3 O
CH3 H3C O
+
N~ N
HNCOO C104 OCONH
H C CH3
H3C C CH3
0.20
3 CH3 I
CH ?H3 CH3
HNCOO-C O C OCONH
I I
0.80 I I CH3 CH3
H CH3
Structure of ADS-003-CTP
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EXAMPLE 4
Synthesis of linear near infrared absorption polymer ADS-004-CTP
Near infrared absorption polymer ADS-004-CTP was synthesized by slowly
adding 26.0 parts of methylene bis(4-cyclohexylisocyanate) (available from
Bayer) into a solution containing 100 parts of N-methyl pyrrolidinone, 6.8
parts
of 2-[2-[2-choloro-3-[2-(1,3-dihydro-1-(2-hydroxyethyl)-3,3-dimethyl-2H-
benz[e]indol -2-ylidene)ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-(2-
hydroxyethyl)-3,3-dimethyl-1 H-benz[e]indolium perchlorate (available from
American Dye Source, Inc.), 11.6 parts of a,a,a',a'-tetramethyl-1,4-
benzenedimethanol (available from Aldrich Chemicals), 2.6 parts of 3-allyl-
1,2-propanediol (available from Aldrich Chemical) and 0.5 parts of dibutyltin
dilaurate (available from Aldrich Chemicals) at 60 C under nitrogen
atmosphere and constant stirring. Completion of the polymerization was
indicated by the disappearance on NCO absorption bands in the infrared
spectra. The reaction mixture was cooled down to room temperature. The
product was precipitated in water and then collected by vacuum filtration,
washed copiously with water and dried in air until constant weight. The ADS-
004-CTP near infrared absorbing polymer has the glass transition and
decomposition temperatures at around 113 and 210 C, respectively. The film
of near infrared absorption polymer ADS-004-CTP on polyester film shows a
broad absorption band having a maximum at around 841 nm. The ideal
structure of ADS-004-CTP can be represented as following:
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O CH3 CH3 O
O + CH CI H
3C O
N~ N
HNCOO C104 OCONH
OCONH CH
O 0.2
I
C=0
NH
0.6
CH2
CH2
0.20 ?H3 CH3
I
HNCOO-C O C OCONH
I I
CH3 CH3
Structure of ADS-004-CTP
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EXAMPLE 5
Synthesis of near infrared absorption polymer ADS-005-CTP
Near infrared absorption polymer ADS-CTP-005 was synthesized by slowly
5 adding 21.2 parts of trimethyl-1,6-diisocyanatohexane (available from
Aldrich
Chemicals) into a solution containing 100 parts of N-methyl pyrrolidinone, 6.8
parts of 2-[2-[2-choloro-3-[2-(1,3-dihydro-l-(2-hydroxyethyl)-3,3-dimethyl-2H-
benz[e]indol-2-ylidene)ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-(2-
hydroxyethyl) -3,3-dimethyl-1 H-benz[e]indolium perchlorate (available from
10 American Dye Source, Inc.), 11.6 parts of a,a,a',a'-tetramethyl-1,4-
benzenedimethanol (available from Aldrich Chemicals), 3.4 parts of 2,6-
bis(hydroxymethyl)-p-cresol and 0.5 parts of dibutyl tin (available from
Aldrich
Chemicals) at 60 C under nitrogen atmosphere and constant stirring for 6
hours. Completion of the polymerization was indicated by the disappearance
15 on NCO absorption bands in the infrared spectra. The product was
precipitated in water and then collected by vacuum filtration, washed
copiously with water and dried in air until constant weight. The ADS-005-CTP
near infrared absorbing polymer has the glass transition and decomposition
temperatures at around 117 and 215 C, respectively. The film of near infrared
20 absorption polymer ADS-005-CTP on polyester film shows a broad absorption
band having a maximum at around 841 nm. The ideal structure of ADS-005-
CTP can be represented as following:
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O CH3 CH3 O
O CH3 I H3C O
+
N~ / N
HNCOO Ci04 OCONH
H C CH3
H3C C CH3
0.20
H3 CH3 CH3
C~~ I HNCOO OCONH
I C O
0.20 H
CH3
OH
OCONH
I
3~3C C CH3
O
H3C C CH3
I ~H3 CH3
OCONH-,_/--,,/~ I
C C
I I 0.60
CH3
Structure of ADS-005-CTP
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Synthesis of near infrared absorbing cross-linked silicone polymers:
Examples 6 to 12
EXAMPLE 6
Preparation of near infrared absorbing ink repelling cross-linked silicone
polymer, ADS-001-Si
The near infrared absorbing ink repelling cross-linked silicone polymer was
prepared by adding 300 parts of water containing 1.0 part of 2-[2-[2-allyloxy-
3-
[2-(1,3-dihydro-1-(4-sulfobutyl)-3,3-dimethyl-2H-benz[e]indol-2-ylidene)
ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-(4-sulfobutyl)-3,3-dimethyl-1 H-
benz[e]indolium inner salt (available from American Dye Source, Inc.) into a
solution containing 50 parts of reactive silicone polymeric emulsion (Syl-Off
7910, available from Dow Corning, 40 % solid weight), 50 parts of silicone
polymeric cross-linker emulsion containing platinum catalyst (Syl-Off 7922,
available from Dow Corning, 40 % solid weight) and 1.5 parts of silicone
wetting agent (Q2-5211, available from Dow Corning). The freshly prepared
polymeric solution was coated on an anodized aluminum substrate using a
wire wound rod. The coating was dried under hot air stream and then further
cured at 120 C for 5 minutes to produce a uniform coating film having a
coating weight around 1.0 g/m2. The UV-Vis-NIR spectrum of the resulted
polymer on polyester film shows a broad absorption band having a maximum
at 840 nm. The ideal structure of the near infrared absorbing ink repelling
cross-linked silicone polymer can be represented as following:
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H3 H
O Si O Si
CH3
O CH3 CH3 O
+
O CH3 O H3C O
N
SO3 SO3 H
Structure of ADS-001-Si
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EXAMPLE 7
Preparation of near infrared absorbing ink repelling cross-linked silicone
polymer, ADS-002-Si
The near infrared absorbing ink repelling cross-linked silicone polymer was
prepared by adding 300 parts of water containing 1.0 part of 2-[2-[2-chloro-3-
[2-(1, 3-dihydro-1-allyl-3,3-dimethyl-7-sulfonyl-2H-benz[e]indol-2-ylidene)
ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-allyl-3,3-dimethyl-7-sulfonyl-1 H-
benz[e]indolium 4-methylbenzenesulfonic acid (available from American Dye
Source, Inc.) into a solution containing 50 parts of reactive silicone
emulsion
(Syl-Off 7910, available from Dow Corning, 40 % solid weight), 50 parts of
reactive silicone emulsion with platinum catalyst (Syl-Off 7922, available
from
Dow Corning, 40 % solid weight) and 1.5 parts of wetting agent (Q2-5211,
available from Dow Corning). The freshly prepared polymeric solution was
coated on an anodized aluminum substrate using a wire wound rod. The
coating was dried under hot air stream and then further cured at 120 C for 5
minutes to produce a uniform coating film having a coating weight around 1.0
g/m2. The UV-Vis-NIR spectrum of the resulted polymer on polyester film
shows a broad absorption band having a maximum at 842 nm. The ideal
structure of the near infrared absorbing ink repelling cross-linked silicone
polymer can be represented as following:
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H O S03H
OO+ C H C H O
CH3 CI H O
N~ N
CH3 H S03 H
10 I 3
O Si O Si CH3 H3C Si O Si O
I I I I
CH3 CH3 CH3 CH3
Structure of ADS-003-Si
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EXAMPLE 8
Preparation of near infrared absorbing ink repelling cross-linked silicone
polymer, ADS-003-Si
The near infrared absorbing ink repelling cross-linked silicone polymer was
prepared by adding 300 parts of water containing 1.0 part of 2-[2-[2-allyloxy-
3-
[2-(1,3-dihydro-l-allyl-3,3-dimethyl-7-sulfonyl-2H-benz[e]indol-2-
ylidene)ethylidene]-1-cyclohexene-l-yljethenyl]-1-allyl-3, 3-dimethyl-7-
sulfonyl-
1 H-benz[e]indolium 4-methylbenzenesulfonic acid (available from American
Dye Source, Inc.) into a solution containing 50 parts of reactive silicone
emulsion (Syl-Off 7910, available from Dow Corning, 40 % solid weight), 50
parts of reactive silicone emulsion with platinum catalyst (Syl-Off 7922,
available from Dow Corning, 40 % solid weight) and 1.5 parts of wetting agent
(Q2-5211, available from Dow Corning). The freshly prepared polymeric
solution was coated on an anodized aluminum substrate using a wire wound
rod. The coating was dried under hot air stream and then further cured at 120
C for 5 minutes to produce a uniform coating film having a coating weight
around 1.0 g/m2. The UV-Vis-NIR spectrum of the resulted polymer on
polyester film shows a broad absorption band having a maximum at 837 nm.
The ideal structure of the near infrared absorbing ink repelling cross-linked
silicone polymer can be represented as following:
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H3 CH3
H3C Si O Si O
I
CH3
H03S SO 3H
CH3 CH3 O
CH3 O H3C
N~ N
CH3 H3C O S03 H3
5 1
O Si O Si CH3 H3C Si O Si O
I I I I
CH3 CH3 CH3 CH3
Structure of ADS-003-Si
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EXAMPLE 9
Preparation of near infrared absorbing ink repelling cross-linked silicone
polymer, ADS-004-Si
The near infrared absorbing ink repelling cross-linked silicone polymer was
prepared by adding a solution containing 10 parts of methyl ethyl ketone
dissolving with 0.10 parts of 2-[2-[2-allyloxy-3-[2-(1,3-dihydro-l-heptyl-3,3-
dimethyl-2H-benz[e]indol-2-ylidene)ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-
heptyl)-3,3-dimethyl-1 H-benz[e]indolium 4-methyl benzenesulfonate (available
from American Dye Source, Inc.) into a solution containing 2.0 parts of
polydimethylsiloxane divinyl terminated (PS445, availble from United
Chemical), 1.0 part of high molecular weight polydimethylsiloxane divinyl
terminated (PS225, availble from United Chemical), 1.0 part of
polyhydromethylsiloxane (SL6020, available from GE Silicones), 0.1 parts of
platinum catalyst (PC075, available from United Chemical), 0.06 parts of
volatile inhibitor (SL6020, available from GE Silicones) into a solution
containing 45 parts of lsoparafin solution (IsoPar-E, available from Exxon
Chemical), The solution was filtered to remove any solid residue. The freshly
prepared polymeric solution was coated on an anodized aluminum substrate
using a wire wound rod. The coating was dried under hot air stream and then
further cured at 120 C for 5 minutes to produce a uniform coating film having
a coating weight around 1.0 g/m2. The UV-Vis-NIR spectrum of the resulted
polymer on polyester film shows a broad absorption band having a maximum
at 835 nm. The ideal structure of the near infrared absorbing ink repelling
cross-linked silicone polymer can be represented as following:
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T3?H3
O Si O Si
CH3
O CH3 CH3 O
CH3 O H3C
N
I I
C7H15 C7H15
H3C O S03
Structure of ADS-004-Si
CA 02279299 1999-07-29
EXAMPLE 10
Preparation of near infrared absorbing ink repelling cross-linked silicone
polymer, ADS-005-Si
5 The near infrared absorbing ink repelling cross-linked silicone polymer was
prepared similarly to that of Example 4, excepted that 2-[2-[2-dodecyloxy-3-[2-
(1,3-dihydro-l-allyl-3,3-dimethyl-2H-benz[e]indol-2-ylidene)ethylidene]-1-
cyclohexene-1-yljethenylj-l-allyl-3,3-dimethyl-1 H-benz[e]indolium 4-methyl
benzenesulfonate (available from American Dye Source, Inc.) was used to
10 replace 2-[2-[2-allyloxy-3-[2-(1,3-dihydro-l-heptyl-3,3-dimethyl-2H-
benz[e]indol-2-ylidene)ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-heptyl-3,3-
dimethyl-1 H-benz[e]indolium 4-methylbenzenesulfonate. The freshly prepared
polymeric solution was coated on an anodized aluminum substrate using a
wire wound rod. The coating was dried under hot air stream and then further
15 cured at 120 C for 5 minutes to produce a uniform coating film having a
coating weight around 1.0 g/m2. The UV-Vis-NIR spectrum of the resulted
polymer on polyester film shows a broad absorption band having a maximum
at 829 nm. The ideal structure of the near infrared absorbing ink repelling
cross-linked silicone polymer can be represented as following:
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O C12H25
CH3 CH3 O
O CH3 H3C O
N~ N
CH H3C S03
3 H3
O Si O Si CH3 H3C Si O Si O
I I I I
CH3 CH3 CH3 CH3
Structure of ADS-005-Si
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EXAMPLE 11
Preparation of near infrared absorbing ink repelling cross-linked silicone
polymer, ADS-006-Si
The near infrared absorbing ink repelling cross-linked silicone polymer was
prepared similarly to that of Example 4, excepted that 2-[2-[2-dodecyloxy-4-
tert-butyl-3-[2-(1,3-dihydro-l-allyl-3,3-dimethyl-2H-benz[e]indol-2-ylidene)
ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-allyl-3,3-dimethyl-1 H-
benz[e]indolium 4-methyl benzenesulfonate (available from American Dye
Source, Inc.) was used to replace 2-[2-[2-allyloxy-3-[2-(1,3-dihydro-l-heptyl-
3, 3-dimethyl-2H-benz[e]indol-2-ylidene)ethylidene]-1-cyclohexene-1-
yl]ethenyl]-1-heptyl-3,3-dimethyl-1 H-benz[e]indolium 4-
methylbenzenesulfonate. The freshly prepared polymeric solution was coated
on an anodized aluminum substrate using a wire wound rod. The coating was
dried under hot air stream and then further cured at 120 C for 5 minutes to
produce a uniform coating film having a coating weight around 1.0 g/m2. The
UV-Vis-NIR spectrum of the resulted polymer on polyester film shows a broad
absorption band having a maximum at 829 nm. The ideal structure of the near
infrared absorbing ink repelling cross-linked silicone polymer can be
represented as follows:
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C12 H25
CH3 I CH3 O
CH3 O H3C
O
N~ N
CH3 H3C C CH3 I _
TH
3
CH3
O Si O Si CH3 H3C Si O Si O-
I I H C SO I I -
CH3 CH3 3 3 CH CH
3 3
Structure of ADS-006-Si
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EXAMPLE 12
Preparation of near infrared absorbing ink repelling cross-linked silicone
polymer, ADS-007-Si
The near infrared absorbing ink repelling cross-linked silicone polymer was
prepared similarly to that of Example 4, excepted that 2-[2-[2-allyloxy-3-[2-
(1, 3-dihydro-l-(octyl-8-ene)-3,3-dimethyl-2H-benz[e]indol-2-
ylidene)ethylidene]-1-cyclohexene-1-yl]ethenyl]-1-(octyl-8-ene)-3, 3-dimethyl-
1 H-benz[e]indolium 4-methylbenzenesulfonate (available from American Dye
Source, Inc.) was used to replace 2-[2-[2-allyloxy-3-[2-(1,3-dihydro-l-heptyl-
3,3-dimethyl-2H-benz[e]indol-2-ylidene)ethylidene]-1-cyclohexene-l-
yl]ethenyl]-1-heptyl)-3,3-dimethyl-lH-benz[e]indolium 4-methyl. The freshly
prepared polymeric solution was coated on an anodized aluminum substrate
using a wire wound rod. The coating was dried under hot air stream and then
further cured at 120 C for 5 minutes to produce a uniform coating film having
a coating weight around 1.0 g/m2. The UV-Vis-NIR spectrum of the resulted
polymer on polyester film shows a broad absorption band having a maximum
at 829 nm. The ideal structure of the near infrared absorbing ink repelling
cross-linked silicone polymer can be represented as following:
25
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H3 CH3
I
H3C Si O Si O
5 I
CH3
O CH3 CH3 O
10 +
N~ N
~ cH3 0 H3c 0
H3C O SO3
C H3 H3
O Si O Si CH3 H3C Si O Si O
I I I I
CH3 CH3 CH3 CH3
Structure of ADS-007-Si
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Preparation and imaqinq of waterless printing plates:
Examples 13 to 18
EXAMPLE 13
A waterless printing plate was prepared by dissolving 10.0 parts of ADS-001-
CTP from Example 1 in 90.0 parts of solvent system containing 35 %
methoxyethanol, 30 % methyl ethyl ketone and 35 % methanol. The near
infrared absorption polymeric solution was filtered to remove any solid
residues. It was than coated on an anodized aluminum substrate using a wire-
wound rod and dried under hot air stream at 80 C for 5 minutes to produce a
uniform coating having a coating weight at around 1.5 g/mz. The solution of
near infrared absorbing ink repelling cross-linked silicone polymer was
prepared similarly to Example 6. It was then coated on the near infrared
absorbing adhesion ink promoting layer using a wire-wound rod. The coating
was dried under hot air stream and cured at 120 C for 5 minutes to produce a
uniform coating having a coating weight at around 1.0 g/m2. The plate was
imaged with a home-built laser image-setter, which was equipped with an
aluminum drum, a single beam 1 watt solid state diode laser emitting at 830
nm (available from Optopower) at energy density between 200 and 800
mJ/cm2. The plate was tested on an AB Dick press with Sun Chemical Drilith
"H" Cyan Ink (available from Sun Chemical) in the absence of fountain
solution. Before printing, the debris at the exposed area was gently cleaned
with a cotton cloth wetted with soap water. The exposed area produced high
optical printing image while the non-exposed area remained clean. The plate
can be printed to more than 10,000 copies without deterioration.
EXAMPLE 14
A waterless printing plate was prepared similarly to the procedure of Example
13, excepted that the near infrared absorbing ink repelling cross-linked
silicone polymer layer prepared similarly to Example 7 (i.e., ADS-002-Si) was
used to coated on the near infrared absorbing adhesion promoting layer using
a wire-wound rod. The coating was dried under hot air and cured at 120 C for
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minutes to produce a uniform coating having a coating weight at around 1.0
g/m2. The plate was imaged with a home-built laser image-setter, which was
equipped with an aluminum drum, a single beam 1 watt solid state diode laser
emitting at 830 nm (available from Optopower) at energy density between 200
5 and 800 mJ/cm2. The plate was tested on an AB Dick press with Sun
Chemical Drilith "H" Cyan Ink (available from Sun Chemical) in the absence of
fountain solution. Before printing, the debris at the exposed area was gently
cleaned with a cotton cloth wetted with soap water. The exposed area
produced high optical printing image while the non-exposed area remained
clean. The plate can be printed to more than 10,000 copies without
deterioration.
EXAMPLE 15
A waterless printing plate was prepared similarly to the procedure of Example
13, excepted that the near infrared absorbing ink repelling cross-linked
silicone polymer layer prepared similarly to Example 8 (i.e., ADS-003-Si) was
used to coated on the near infrared absorbing adhesion promoting layer using
a wire-wound rod. The coating was dried under hot air and cured at 120 C for
5 minutes to produce a uniform coating having a coating weight at around 1.0
g/m2. The plate was imaged with a home-built laser image-setter, which was
equipped with an aluminum drum, a single beam 1 watt solid state diode laser
emitting at 830 nm (available from Optopower) at energy density between 200
and 800 mJ/cm2. The plate was tested on an AB Dick press with Sun
Chemical Drilith "H" Ink (available from Sun Chemical) in the absence of
fountain solution. Before printing, the debris at the exposed area was gently
cleaned with a cotton cloth wetted with soap water. The exposed area
produced high optical printing image while the non-exposed area remained
clean. The plate can be printed to more than 10,000 copies without
deterioration.
EXAMPLE 16
A waterless printing plate was prepared similarly to the procedure of Example
13, excepted that the near infrared absorbing ink repelling cross-linked
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silicone polymer obtained similarly to Example 9 (i.e., ADS-004-Si) was used
to coat on the near infrared absorbing adhesion promoting layer using a wire-
wound rod. The coating was dried under hot air and cured at 120 C for 5
minutes to produce a uniform coating having a coating weight at around 1.0
g/m2. The plate was imaged with a home-built laser image-setter, which was
equipped with an aluminum drum, a single beam 1 watt solid state diode laser
emitting at 830 nm (available from Optopower) at energy density between 200
and 800 mJ/cm2. The plate was tested on an AB Dick press with Sun
Chemical Drilith "H" Cyan Ink (available from Sun Chemical) in the absence of
fountain solution. Before printing, the debris at the exposed area was gently
cleaned with a cotton cloth wetted with soap water. The exposed area
produced high optical printing image while the non-exposed area remained
clean. The plate can be printed to more than 10,000 copies without
deterioration.
EXAMPLE 17
A waterless printing plate was prepared similarly to the procedure of Example
13, excepted that the near infrared absorbing ink repelling cross-linked
silicone polymer obtained similarly to Example 12 (i.e., ADS-007-Si) was used
to coat on the near infrared absorbing adhesion promoting layer using a wire-
wound rod. The coating was dried under hot air and cured at 120 C for 5
minutes to produce a uniform coating having a coating weight at around 1.0
g/m2. The plate was imaged with a home-built laser image-setter, which was
equipped with an aluminum drum, a single beam 1 watt solid state diode laser
emitting at 830 nm (available from Optopower) at energy density between 200
and 800 mJ/cm2. The plate was tested on an AB Dick press with Sun
Chemical Drilith "H" Cyan Ink (available from Sun Chemical) in the absence of
fountain solution. Before printing, the debris at the exposed area was gently
cleaned with a cotton cloth wetted with soap water. The exposed area
produced high optical printing image while the non-exposed area remained
clean. The plate can be printed to more than 10,000 copies without
deterioration.
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EXAMPLE 18
A waterless printing plate was prepared similarly to Example 15, excepted
that the near infrared absorbing polymer obtained from Example 3 (i.e., ADS-
003-CTP) was used to prepare the near infrared adhesion promoting layer.
The plate was imaged with a home-built laser image-setter, which was
equipped with an aluminum drum, a single beam 1 watt solid state diode laser
emitting at 830 nm (available from Optopower) at energy density between 200
and 800 mJ/cm2. The plate was tested on an AB Dick duplicator press with
Sun Chemical Drilith "H" Cyan Ink (available from Sun Chemical) in the
absence of fountain solution. Before printing, the debris at the exposed area
was gently cleaned with a cotton cloth wetted with soap water. The exposed
area produced high optical printing image while the non-exposed area
remained clean. The plate can be printed to more than 10,000 copies without
deterioration.
Although the invention has been described above with respect with one
specific form, it will be evident to a person skilled in the art that it may
be
modified and refined in various ways. It is therefore wished to have it
understood that the present invention should not be limited in scope, except
by the terms of the following claims.
