MATERIALS FOR LITHOGRAPHIC PLATES COATINGS, LITHOGRAPHIC PLATES AND COATINGS CONTAINING SAME, METHODS OF PREPARATION AND USE

Description

BRIEF DESCRIPTION OF THE DRAWINGS

In the appended drawings:

FIG. 1 is the ideal structure of acetal copolymer PVA-01

FIG. 2 is the ideal structure of acetal copolymer PVA-02;

FIG. 3 is the ideal structure of acetal copolymer PVA-03;

FIG. 4 is the ideal structure of acetal copolymer PVA-04;

FIG. 5 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 6 is the possible structure of a specific embodiment of a n iodonium salt of the present invention;

FIG. 7 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 8 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 9 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 10 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 11 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 12 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 13 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 14 is the ideal structure of a specific embodiment of an iodonium salt synthesized from fluorene compound;

FIG. 15 is the ideal structure of polymer binder RPB-01;

FIG. 16 is the ideal structure of polymer binder RPB-03;

FIG. 17 is the ideal structure of polymer binder RPB-04;

FIG. 18 is the ideal structure of polymer binder RPB-05;

FIG. 19 is the ideal structure of polymer binder RPB-06;

FIG. 20 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 21 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 22 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 23 is the possible structure of a specific embodiment of an iodonium salt of the present invention;

FIG. 24 is the possible structure of a specific embodiment of an iodonium salt of the present invention; and

FIG. 25 is the possible structure of a specific embodiment of an iodonium salt of the present invention.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

The present invention is illustrated in further details by the following non-limiting examples.

In these examples, these syntheses were performed in a 4 necks glass reactor equipped with a water condenser, a mechanical stirrer, a dropping funnel and a nitrogen or air gas inlet. The molecular structures of the obtained materials were determined by proton NMR and FTIR spectroscopy. The average molecular weight of the copolymers obtained was determined by size exclusion chromatography (SEC), using N,N-dimethylformamide (DMF) solutions and calibrated with polystyrene standards. The UV-Visible near-infrared spectra of the synthesized polymers were measured in methanol solutions or on the solid films using a UV-VIS spectrophotometer (PerkinElmer, Model Lambda 35).

Also, the coated plates were imaged using Creo Trendsetter 3244 equipped with 830 nm lasers. The imaged plate was mounted on AB Dick duplicator press using black ink (available from Pacific Inks, Vietnam) and fountain solution containing 3.0 parts of MYLAN-FS100 in 97.0 parts of water (available from MyLan Chemicals Inc., Vietnam).

Synthesis of the Reactive Near-Infrared Sensitizing Acetal Copolymers (Dyes):
Example 1

The thermally reactive near-infrared sensitizing acetal copolymer PVA-01 was synthesized by adding, by portions, 90 grams of polyvinyl alcohol (Celvol™ 103, a 98% hydrolyzed polyvinyl acetate having an average molecular weight of about 18,000) to a reaction flask containing 500 grams of dimethylsulfoxide (DMSO) at 60° C., under nitrogen atmosphere and with constant stirring. After complete dissolution, 3 ml of concentrated sulfuric acid, which acts as a catalyst for this reaction, were added to the flask. After thirty minutes, 12.2 grams of 4-hydroxybenzaldehyde (100 mmole, available from Sigma-Aldrich, Canada) were slowly added to the flask and the mixture was stirred at 60° C. for 4 hours. Then, 1 gram of sodium hydride (60% in mineral oil, available from Sigma-Aldrich, Canada) was slowly added into the reaction. After hydrogen gas was no longer produced from the reaction, 3.0 grams of 3-bromopropyl-methacryloyl-ethyl carbamate (see structure below, available from American Dye Source Inc., Canada) was added into the reaction mixture.

The reaction was continued for 30 minutes, then 20 grams of 2-[2-[2-chloro-3-[[1,3-dihydro-1,1-dimethyl-3-(4-sulfonylbutyl)-2H-benzo[e]indol-2-ylidene]-ethylidene]-1-cyclohexen-1-yl]ethenyl]-1,1-dimethyl-3-(4-sulfonylbutyl)-1H-benzo[e]indolium hydroxy inner salt, sodium salt (13 mmole, available from American Dye Source, Inc.) was slowly added to the flask. The resulting mixture was stirred at 60° C. for another 5 hours. The reaction product was precipitated in acetone, filtered and washed copiously with acetone. It was then dried in air until constant weight.

The UV-Vis-NIR spectrum of the obtained PVA-01 thermally reactive near-infrared absorbing acetal copolymer was recorded in methanol and exhibited a strong absorption band at 803 nm. The ideal structure of the PVA-01 near-infrared absorbing acetal copolymer is shown in FIG. 1, wherein a=6.65%, b=1.00%, c=2.35%, d=88.00% and e=2.00%.

Example 2

The thermally reactive near-infrared absorbing acetal copolymer PVA-01 was synthesized by adding, by portions, 90 grams of polyvinyl alcohol (Celvol™ 103, a 98% hydrolyzed polyvinyl acetate having an average molecular weight of about 18,000) to a reaction flask containing 500 grams of dimethylsulfoxide (DMSO) at 60° C., under nitrogen atmosphere and with constant stirring. After complete dissolution, 3 ml of concentrated sulfuric acid, which acts as a catalyst for this reaction, were added to the flask. After thirty minutes, 12.2 grams of 4-hydroxybenzaldehyde (100 mmole, available from Sigma-Aldrich, Canada) were slowly added to the flask and the mixture was stirred at 60° C. for 4 hours. Then, 1 gram of sodium hydride (60% in mineral oil, available from Sigma-Aldrich, Canada) was slowly added into the reaction. After hydrogen gas was no longer produced from the reaction, 3.0 grams of 3-bromopropyl-methacryloyl-ethyl carbamate was added into the reaction mixture. The reaction was continued for 30 minutes, then 20 grams of 2-[2-[2-chloro-3-[2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-ethylidene]-1-cyclohexen-1-yl]ethenyl]-1,3,3-trimethyl-1H-indolium chloride (available from American Dye Source, Inc.) was slowly added to the flask. The resulting mixture was stirred at 60° C. for another 3 hours. Then, 5 grams of sodium tetraphenylborate was added into the reaction flask and it continued to stir for additional 2 hours. The reaction product was precipitated in de-ionized water, filtered and washed copiously with water. It was then dried in air until constant weight.

The UV-Vis-NIR spectrum of the obtained PVA-02 thermally reactive near-infrared absorbing acetal copolymer was recorded on a thin film and exhibited a strong absorption band at 800 nm. The ideal structure of the PVA-02 near-infrared absorbing acetal copolymer is shown in FIG. 2, wherein a=5.15%, b=1.00%, c=3.85%, d=88.00% and e=2.00%.

Example 3

The thermally reactive near-infrared absorbing acetal copolymer, PVA-01, was synthesized by adding, by portions, 90 grams of polyvinyl alcohol (Celvol™ 103, a 98% hydrolyzed polyvinyl acetate having an average molecular weight of about 18,000) to a reaction flask containing 500 grams of dimethylsulfoxide (DMSO) at 60° C., under nitrogen atmosphere and with constant stirring. After complete dissolution, 3 ml of concentrated sulfuric acid, which acts as a catalyst for this reaction, were added to the flask. After thirty minutes, 6.1 grams of 4-hydroxybenzaldehyde (available from Sigma-Aldrich, Canada) were slowly added to the flask and the mixture was stirred at 60° C. for 4 hours. Then, 0.5 grams of sodium hydride (60% in mineral oil, After hydrogen gas was no longer produced from the reaction, 10 grams near infrared absorption containing reactive functional groups having the structure shown below (available from American Dye Source, Inc.) was slowly added to the flask.

The resulting mixture was stirred at 50° C. for another 5 hours. The reaction product was precipitated in 10 liters of de-ionized water, filtered and washed copiously with water. It was then dried in air until constant weight.

The UV-Vis-NIR spectrum of the obtained PVA-03 thermally reactive near-infrared absorbing acetal copolymer was recorded on a thin film and exhibited a strong absorption band at 830 nm. The ideal structure of the near infrared absorbing acetal copolymer PVA-03 is shown in FIG. 3, wherein a=3.42%, c=1.58%, d=93.00% and e=2.00%.

Example 4

Bromo-Terminated poly(ethylene glycol)acrylate

The reaction was continued for 30 minutes, then 20 grams of 2-[2-[2-chloro-3-[2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-ethyl idene]-1-cyclohexen-1-yl]ethenyl]-1,3,3-trimethyl-1H-indolium 4-methylbenzene sulfonate (available from American Dye Source, Inc.) was slowly added to the flask. The resulting mixture was stirred at 60° C. for another 3 hours. Then, 5 grams of sodium tetraphenylborate was added into the reaction flask and it continued to stir for additional 2 hours. The reaction product was precipitated in de-ionized water, filtered and washed copiously with water. It was then dried in air until constant weight.

The UV-Vis-NIR spectrum of the obtained PVA-04 thermally reactive near-infrared absorbing acetal copolymer was recorded on a thin film and exhibited a strong absorption band at 800 nm. The ideal structure of the PVA-04 near-infrared absorbing acetal copolymer is shown in FIG. 4, wherein a=5.15%, b=1.00%, c=3.85%, d=88.00% and e=2.00%.

Synthesis of Reactive Iodonium Salts:

For the ease of manufacturing and cost effectiveness, the iodonium salts containing reactive functional groups may be synthesized and used as a mixture of various salts. Further, this mixture may be used directly without further purification.

Example 5

A mixture of reactive iodonium tetraphenylborate having possible structures as in FIGS. 5, 6, 7, 8, 9 and 10 was obtained by heating 320 grams of 1,3-dioxolane solution containing 573 grams of Desmodur™ N100 (available from Bayer Canada), 60 grams of 2-hydroxyethylacrylate (available from Sigma-Aldrich, Canada), 245 grams of poly(ethylene glycol) acrylate (Mn ˜375, available from Sigma-Aldrich, Canada), 500 grams of pentaerythritol triacrylate (SR-444, available from Sartomer, USA), 1 gram of hydroquinone (available from Sigma-Aldrich, Canada) and 1 gram of dibutyl tin dilaurate (available from Sigma-Aldrich, Canada) to 60° C. under an oxygen atmosphere and constant stirring for 10 hours. A sample of reaction mixture was withdraw from the reaction flask and its FTIR spectrum, recorded on KBr pellet, showed a —N═C═O peak at 2274 cm⁻¹. Then, 150 grams of [4-(2-hydroxy-1-tetradecyloxy)phenyl]phenyliodonium tetraphenylborate (available from American Dye Source Inc., Canada) was slowly added into the reaction mixture, which was stirred at 60° C. for an additional 6 hours. The FTIR spectrum then indicated that the —N═C═O peak at 2274 cm⁻¹had disappeared, which was indicative of the completion of the reaction. The clear viscous product obtained was ready for use.

Example 6

A mixture of reactive iodonium tetraphenylborate having possible structures as in FIGS. 6, 7 and 8) was obtained by heating 320 grams of anhydrous methyl ethyl ketone solution containing 573 grams of Desmodur™ N100 (available from Lanxess, Canada), 138 grams of 2-hydroxyethylacrylate (available from Sigma-Aldrich, Canada), and 500 grams of pentaerythritol triacrylate (SR-444, available from Sartomer, USA), 1 gram of hydroquinone (available from Sigma-Aldrich, Canada) and 1 gram of dibutyl tin dilaurate (available from Sigma-Aldrich, Canada) to 60° C. under an oxygen atmosphere and constant stirring for 10 hours. A sample of reaction mixture was withdraw from the reaction flask and its FTIR spectrum, recorded on KBr pellet, showed a —N═C═O peak at 2274 cm⁻¹. Then, 150 grams of [4-(2-hydroxy-1-tetradecyloxy)phenyl]phenyliodonium tetraphenylborate (available from American Dye Source Inc., Canada) was slowly added into the reaction mixture, which was stirred at 60° C. for an additional 6 hours. The FTIR spectrum then indicated that the —N═C═O peak at 2274 cm⁻¹had disappeared, which was indicative of the completion of the reaction. The clear viscous product obtained was ready for use.

Example 7

A mixture of reactive iodonium tetraphenylborate having possible structures as in FIGS. 8, 9 and 10 was obtained by heating 320 grams of methyl ethyl ketone solution containing 573 grams of Desmodur™ N100 (available from Lanxess, Canada), 430 grams of poly(ethylene glycol) acrylate (Mn ˜375, available from Sigma-Aldrich, Canada), 500 grams of pentaerythritol triacrylate (SR-444, available from Sartomer, USA) and 1 gram of hydroquinone (available from Sigma-Aldrich, Canada) and 1 gram of dibutyl tin dilaurate (available from Sigma-Aldrich, Canada) to 60° C. under oxygen atmosphere and constant stirring for 10 hours. A sample of reaction mixture was withdraw from the reaction flask and its FTIR spectrum, recorded on KBr pellet, showed a —N═C═O peak at 2274 cm⁻¹. Then, 150 grams of [4-(2-hydroxy-1-tetradecyloxy)phenyl]phenyliodonium tetraphenylborate (available from American Dye Source Inc., Canada) was slowly added into the reaction mixture, which was stirred at 60° C. for an additional 6 hours. The FTIR spectrum then indicated that the —N═C═O peak at 2274 cm⁻¹had disappeared, which was indicative of the completion of the reaction. The clear viscous product obtained was ready for use.

Example 8

A mixture of reactive iodonium tetraphenylborate having possible structures as in FIGS. 6, 7, 11, 12 and 13 was obtained by heating 320 grams of 1,3-dioxolane solution containing 573 grams of Desmodur™ N100 (available from Bayer Canada), 50 grams of 2-hydroxyethylmethacrylate (available from Sigma-Aldrich, Canada), 275 grams of pentaerythritol triacrylate (SR-444, available from Sartomer, USA), 780 grams of dipentaerythritol pentaacrylate (SR-399 available from Sartomer, USA), 1 gram of hydroquinone (available from Sigma-Aldrich, Canada) and 1 gram of dibutyl tin dilaurate (available from Sigma-Aldrich, Canada) to 60° C. under an oxygen atmosphere and constant stirring for 10 hours. A sample of reaction mixture was withdraw from the reaction flask and its FTIR spectrum, recorded on KBr pellet, showed a —N═C═O peak at 2274 cm⁻¹. Then, 150 grams of [4-(2-hydroxy-1-tetradecyloxy)phenyl]phenyliodonium tetraphenylborate (available from American Dye Source Inc., Canada) was slowly added into the reaction mixture, which was stirred at 60° C. for an additional 6 hours. The FTIR spectrum indicated that the —N═C═O peak at 2274 cm⁻¹had disappeared, which was indicative of the completion of the reaction. The clear viscous product obtained was ready for use.

Example 9

A mixture of reactive iodonium tetraphenylborate having possible structures as in FIGS. 7, 9, 10, 11 and 12 was obtained by heating 137 grams of 1,3-dioxolane solution containing 245 grams of Desmodur™ N100 (available from Bayer Canada), 310 grams of poly(ethylene glycol) acrylate (Mn ˜375, available from Sigma-Aldrich, Canada), 244 grams of pentaerythritol triacrylate (SR-444, available from Sartomer, USA), 100 grams of dipentaerythritol pentaacrylate (SR-399 available from Sartomer, USA), 1 gram of hydroquinone (available from Sigma-Aldrich, Canada) and 1 gram of dibutyl tin dilaurate (available from Sigma-Aldrich, Canada) to 60° C. under an oxygen atmosphere and constant stirring for 10 hours. A sample of reaction mixture was withdraw from the reaction flask and its FTIR spectrum, recorded on KBr pellet, showed a —N═C═O peak at 2274 cm⁻¹. Then, 75 grams of [4-(2-hydroxy-1-tetradecyloxy)phenyl]phenyliodonium tetraphenylborate (available from American Dye Source Inc., Canada) was slowly added into the reaction mixture, which was stirred at 60° C. for an additional 6 hours. The FTIR spectrum then indicated that the —N═C═O peak at 2274 cm⁻¹had disappeared, which was indicative of the completion of the reaction. The clear viscous product obtained was ready for use.

Example 10

Reactive iodonium salt having the structure as shown in FIG. 14 was synthesized by slowly adding 31.5 grams of 2-isocyanato-ethylmethacrylate into 300 ml solution of 1,3-dioxolane dissolving with 80 grams of [2-[9,9-(3-hydroxypropyl)fluorenyl]4-methylphenyliodonium triphenyl-n-butylborate and 0.1 grams of dibutyl tin dilaurate at 60° C. under constant stirring and an oxygen atmosphere. The reaction was monitored by FTIR, which indicated that the reaction was completed within 5 hours. The product was precipitated in de-ionized water, filtered and washed copiously with de-ionized water. It was then washed with ether and dried in air until constant weight.

The iodonium salts of FIGS. 20-25 were also synthesized.

Synthesis of Thermally Reactive Polymer Binders:
Example 11

The thermally reactive polymer binder, RPB-01 was synthesized by adding, by portions, 25 grams of hydroxypropyl cellulose (Klucel® E, available from Hercules, USA) to a reaction flask containing 500 grams of 1,3-dioxolane at 60° C., under air atmosphere and with constant stirring. After complete dissolution, 3 drops of dibutyl tin dilaurate, which acts as a catalyst for this reaction, were added to the flask. Then, 5.0 grams of 2-isocyanatoethylmethacrylate (available from American Dye Source, Canada) were slowly added to the reaction flask and the mixture was stirred at 60° C. for 7 hours. FTIR spectrum of the polymer on KBr pellet indicated that the reaction was completed with the disappearance of the —N═C═O peak at 2274 cm⁻¹. The ideal structure of RPB-01 is shown in FIG. 15. n-Propanol was added into the reaction to provide 5.0% solid content solution.

Example 12

The reactive polymer binder, RPB-02 was synthesized in way similar to that of Example 11 with the exception that 10 grams of 2-isocyanatoethylmethacrylate was used in the reaction. The ideal structure of RPB-02 is similar to that of RPB-01 with more reactive functional groups present in the polymer. n-Propanol was added into the reaction to provide 5.0% solid content solution.

Example 13

The reactive polymer binder RPB-03 was synthesized by adding, by portions, 90 grams of polyvinyl alcohol (Celvol™ 103, a 98% hydrolyzed polyvinyl acetate having an average molecular weight of about 18,000) to a reaction flask containing 500 grams of dimethylsulfoxide (DMSO) at 60° C., under nitrogen atmosphere and with constant stirring. After complete dissolution, 3 ml of concentrated sulfuric acid, which acts as a catalyst for this reaction, were added to the flask. After thirty minutes, 12.2 grams of 4-hydroxybenzaldehyde (100 mmole, available from Sigma-Aldrich, Canada) were slowly added to the flask and the mixture was stirred at 60° C. for 4 hours. Then, 0.5 gram of sodium hydride (60% in mineral oil, available from Sigma-Aldrich, Canada) was slowly added into the reaction. After hydrogen gas was no longer produced from the reaction, 3.0 grams of 3-bromopropyl-methacryloyl-ethyl carbamate was added into the reaction mixture. The reaction was continued for 5 hours at 60° C. The product was precipitated in de-ionized water, filtered and washed copiously with de-ionized water. It was then dried in air until constant weight. The ideal structure of RPB-03 is shown in FIG. 16, wherein a=9.00%, b=1.00%, d=88.00% and e=2.00%.

Example 14

The reactive polymer binder RPB-04 was synthesized by adding, by portions, 90 grams of polyvinyl alcohol (Celvol™ 103, a 98% hydrolyzed polyvinyl acetate having an average molecular weight of about 18,000) to a reaction flask containing 500 grams of dimethylsulfoxide (DMSO) at 60° C., under nitrogen atmosphere and with constant stirring. After complete dissolution, 3 ml of concentrated sulfuric acid, which acts as a catalyst for this reaction, were added to the flask. After thirty minutes, 6.5 grams of butyraldehyde and 2.35 grams of acryloyl-propyloxybenzaldehyde (available from American Dye Source Inc., Canada) were added into the reaction mixture. The reaction was continued for 5 hours at 60° C. The product was precipitated in de-ionized water, filtered and washed copiously with de-ionized water. It was then dried in air until constant weight. The ideal structure of RPB-04 is shown in FIG. 17, wherein a=9.00%, b=1.00%, d=88.00% and e=2.00%.

Example 15

The reactive polymer binder, RPB-05 was synthesized by heating a mixture of 200 grams of anhydrous 1,3-dioxolane, dissolving with 15.0 g poly(ethylene glycol) acrylate (Mn ˜2,010, available from American Dye Source Inc., Canada), 15.0 g styrene, 50.0 g acrylonitrile and in a 1 L 4-neck flask at 75° C. under a nitrogen atmosphere and constant stirring. After heating for 30 minutes, 0.5 g of Vazo™ 64 was added to the reaction mixture. After 10 hours of polymerization at 75° C., another 0.5 g of Vazo™ 64 was added into the reaction mixture and the polymerization was continued for another 14 hours. Air was introduced into the reaction mixture and it stirring at 75° C. continued for an additional 2 hours to terminate the polymerization. The reaction temperature was lowered to 5° C. and 4 grams of triethylamine were added into the reaction mixture. Then, a solution containing 10 grams of 1,3-dioxolane and 2 grams of acryloyl chloride was slowly introduced into the reaction. The reaction was stirred at room temperature for 5 hours. The product was precipitated in water and dried until constant weight. The molecular weight of RPB-03 was determined to be around 28,000 with a polymer dispersity of 1.4. The ideal structure of RPB-05 is shown in FIG. 18, wherein a=86.16%, b=13.16% and c=0.68%.

An emulsion of RPB-05 was prepared by slowly adding 50 grams of de-ionized water into 200 grams n-propanol solution, in which 80 grams of RPB-03 were dissolved, using a high shear mixer set at 7,500 rpm.

Example 16

The reactive polymer binder, RPB-06 was synthesized by heating a mixture of 200 grams of n-propanol and 50 grams of de-ionized water, which in which 15.0 g poly(ethylene glycol) acrylate (Mn ˜2,000, available from American Dye Source Inc., Canada) were dissolved, 5.0 grams of N-methoxymethylmethacrylamide (available from American Dye Source Inc., Canada), 15.0 g styrene and 50.0 g acrylonitrile, in a 1 L 4-neck flask at 75° C. under a nitrogen atmosphere and constant stirring. After heating for 30 minutes, 0.5 g of Vazo™ 64 was added into the reaction mixture. The solution became hazy within 30 minutes of polymerization. After polymerization for 10 hours at 75° C., another 0.5 g of Vazo™ 64 was added into the reaction mixture and the polymerization was continued for another 14 hours. Air was introduced into the reaction mixture and stirring at 75° C. was continued for an additional 2 hours to terminate the polymerization. The molecular weight of RPB-06 was determined to be around 29,000 with polymer dispersity of 1.7. The ideal structure of RPB-06 is shown in FIG. 19, wherein a=82.88%, b=12.66%, c=3.81% and d=0.65%.

On-Press Developable Negative-Working Lithographic Printing Plates
Example 17

A coating solution with the following composition was coated on a brush-grained, phosphoric acid anodized aluminum substrate using wire-wound rod and dried at 80° C. with hot air. The obtained coating weight was around 1.0 g/m².

From

Composition
example
% by Solid Weight

PVA-01
1
2.00

Iodonium Salt Mixture
9
5.00

RPB-01
10
0.50

RPB-05
14
2.15

3-Mercapto triazol

0.25

Blue Color Former(*)

0.10

n-Propanol

90.0

Water

10.0

BYK 336

0.10

(*)Blue Color Former is Blue-63 (available from Yamamoto Chemicals Inc., Japan)

The plate was imaged between 100 and 250 mJ/cm²and mounted on the AB Dick press. High quality printing image was obtained on paper after 10 impressions. The plate can be used to print more than 20,000 high-resolution copies.

Example 18

From

Composition
example
% by Solid Weight

PVA-02
2
2.00

Iodonium Salt Mixture
9
5.00

RPB-01
10
0.50

RPB-05
14
2.15

3-Mercapto triazol

0.25

Blue Color Former(*)

0.10

n-Propanol

90.0

Water

10.0

BYK 336

0.10

(*)Blue Color Former is Blue-63 (available from Yamamoto Chemicals Inc., Japan)

Example 19

From

Composition
example
% by Solid Weight

PVA-01
1
2.00

Iodonium Salt Mixture
9
5.00

RPB-01
10
0.50

RPB-06
15
2.15

3-Mercapto triazol

0.25

Blue Color Former(*)

0.10

n-Propanol

90.0

Water

10.0

BYK 336

0.10

(*)Blue Color Former is Blue-63 (available from Yamamoto Chemicals Inc., Japan)

Example 20

From

Composition
example
% by Solid Weight

PVA-01
1
2.00

Iodonium Salt Mixture
9
5.00

RPB-01
10
1.00

RPB-03
15
1.65

3-Mercapto triazol

0.25

Blue Color Former(*)

0.10

n-Propanol

90.0

Water

10.0

BYK 336

0.10

(*)Blue Color Former is Blue-63 (available from Yamamoto Chemicals Inc., Japan)

Example 21

From

Composition
example
% by Solid Weight

PVA-01
1
2.00

Iodonium Salt Mixture
9
5.00

RPB-01
10
1.00

RPB-04
15
1.65

3-Mercapto triazol

0.25

Blue Color Former(*)

0.10

n-Propanol

90.0

Water

10.0

BYK 336

0.10

(*)Blue Color Former is Blue-63 (available from Yamamoto Chemicals Inc., Japan)

Although the present invention has been described hereinabove by way of specific embodiments thereof, it can be modified, without departing from the spirit and nature of the subject invention as defined in the appended claims.

Claims

1. An iodonium salt having attached thereto at least one first functional group capable of undergoing cationic or radical polymerization.
2. The iodonium salt of claim 1 wherein said first functional group is acrylate, methacrylate or vinyl ether.
3. The iodonium salt of claim 1 wherein said first functional group is attached to an aryl ring of the iodonium salt via an urethane or an urea bond.
4. The iodonium salt of claim 3 having as a general formula:
5. The iodonium salt of claim 1 having as a general formula:
6. A method of preparing the iodonium salts of claim 2 comprising attaching a pendant group to an iodonium salt, wherein said pendant group is obtained by reacting a mono-isocyanate, a di-isocyanate or a poly-isocyanate with an amine or an alcohol, wherein said amine or alcohol are terminated by an acrylate, a methacrylate or a vinyl-ether.
7. A lithographic printing plate coating solution comprising the iodonium salt of claim 1 or a mixture thereof.
8. The coating solution of claim 7 further comprising a near infrared absorbing dye.
9. The coating solution of claim 8 wherein said near infrared absorbing dye is a first acetal copolymer or a mixture thereof.
10. The coating solution of claim 9 wherein said first acetal copolymer has attached thereto at least one second functional group capable of undergoing cationic or radical polymerization.
11. The coating solution of claims 9 wherein the first acetal copolymer has the following structure:
12. The coating solution of claim 11 wherein G1 is linear alkyl, branched alkyl, linear aryl or branched aryl, wherein said linear alkyl, branched alkyl, said linear aryl or branched aryl comprise a cyano, hydroxy, dialkylamino, trialkylammonium salts, ethylene oxide, propylene oxide methylbenzylsufonyl-carbamat, carboxylic acid or phosphoric acid functional group.
13. The coating solution of claim 11 wherein G2 is linear alkyl, branched alkyl, linear aryl or branched aryl, wherein said linear alkyl, branched alkyl, linear aryl or branched aryl has attached thereto said second functional group.
14. The coating solution of claim 13 wherein said second functional group is vinyl ether, alkoxy-methyl acrylamide, alkoxy methacrylamide, acrylate or methacrylate.
15. The coating solution of claim 11 wherein G3
16. The coating solution of claim 7 further comprising a polymer binder.
17. The coating solution of claim 16 wherein said polymer binder has attached thereto at least one third functional group capable of undergoing cationic or radical polymerization.
18. The coating solution of claim 17 wherein said third functional group is acrylate, methacrylate, vinyl ether, hydroxyl, alkoxy-methyl acrylamide, alkoxy methacrylamide, N-methoxymethylacrylamide or N-methoxymethylmethacrylamide.
19. The coating solution of any one or claims 16 wherein said polymer binder is a second acetal copolymer of general formula:
20. The coating solution of claim 19 wherein G1 is linear alkyl, branched alkyl, linear aryl or branched aryl, wherein said linear alkyl, branched alkyl, linear aryl or branched aryl comprise a cyano, hydroxy, dialkylamino, trialkylammonium salts, ethylene oxide, propylene oxide methylbenzylsufonyl-carbamat, carboxylic acid or phosphoric acid functional group.
21. The coating solution of claim 19 wherein G2 is linear alkyl, branched alkyl, linear aryl or branched aryl, wherein said linear alkyl, branched alkyl, linear aryl or branched aryl has attached thereto said third functional group.
22. The coating solution of claim 17 wherein said polymer binder is selected from the group consisting of solvent-soluble cellulose ether and water-soluble cellulose ether or a mixture thereof, said cellulose ethers having attached thereto said third functional group.
23. The coating solution of claim 22 wherein said polymer binder has the following structure:
24. The coating solution of claim 16 wherein said polymer binder is a copolymer comprising one or more first monomers of formula:
25. A negative working lithographic printing plate comprising a coating produced by depositing the coating solution of claim 7 onto a substrate.
26. An acetal copolymer having attached thereto at least one functional group capable of undergoing cationic or radical polymerization.
27. The acetal copolymer of claim 26 being:
28. The acetal copolymer of claim 27 wherein G1 is linear alkyl, branched alkyl, linear aryl or branched aryl, wherein said linear alkyl, branched alkyl, linear aryl or branched aryl comprise a cyano, hydroxy, dialkylamino, trialkylammonium salts, ethylene oxide, propylene oxide methylbenzylsufonyl-carbamat, carboxylic acid or phosphoric acid functional group.
29. The acetal copolymer of claim 27 wherein G2 is linear alkyl, branched alkyl, linear aryl or branched aryl, wherein said linear alkyl, branched alkyl, linear aryl or branched aryl has attached thereto said functional group.
30. The acetal copolymer of claim 29 wherein said functional group is vinyl ether, alkoxy-methyl acrylamide or alkoxy methacrylamide.
31. The acetal copolymer of any one of claims 27 wherein G3 is
32. The acetal copolymer of claim 31 wherein said near-infrared absorbing chromophore is:
33. A lithographic printing plate coating solution comprising the acetal copolymer of claim 26 or a mixture thereof.
34. The coating solution of claim 33 further comprising an iodonium salt as defined in claim 1
35. The coating solution of claim 33 further comprising a polymer binder as defined in claim 17.
36. A negative working lithographic printing plate comprising a coating produced by depositing the coating solution of claim 33 onto a substrate.
37. A polymer binder for lithographic printing plate coatings having attached thereto at least one functional group capable of undergoing cationic or radical polymerization.
38. The polymer binder of claim 37 wherein said functional group is acrylate, methacrylate, vinyl ether, hydroxyl, alkoxy-methyl acrylamide, alkoxy methacrylamide, N-methoxymethylacrylamide or N-methoxymethylmethacrylamide.
39. The polymer binder of claim 37 having the following structure:
40. The polymer binder of claim 39 wherein G1 is linear alkyl, branched alkyl, linear aryl or branched aryl, wherein said linear alkyl, branched alkyl, linear aryl or branched aryl comprise a cyano, hydroxy, dialkylamino, trialkylammonium salts, ethylene oxide, propylene oxide methylbenzylsufonyl-carbamat, carboxylic acid and phosphoric acid functional group.
41. The polymer binder of claim 39 wherein G2 is linear alkyl, branched alkyl, linear aryl or branched aryl, wherein said linear alkyl, branched alkyl, linear aryl or branched aryl has attached thereto said functional group.
42. The polymer binder of claim 37 being a solvent-soluble cellulose ether, a water-soluble cellulose ether or a mixture thereof, said cellulose ethers having attached thereto said functional group.
43. The polymer binder of claim 42 having the following structure:
44. The polymer binder of claim 43 wherein G5 is
45. The polymer binder of claim 37 being a copolymer comprising one or more first monomers of formula:
46. A lithographic printing plate coating solution comprising the polymer binder of claims 37 or a mixture thereof.
47. The coating solution of claim 46 further comprising an iodonium salt as defined in claim 1.
48. The coating solution of claims 46 further comprising a near infrared absorbing dye as defined in claim 10.
49. A negative working lithographic printing plate comprising a coating produced by depositing the coating solution of claim 46 onto a substrate.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority on U.S. provisional application No. 60/747,474, filed on May 17, 2006, which is herein incorporated by reference.

Provisional Applications (1)

	Number	Date	Country
	60747474	May 2006	US

MATERIALS FOR LITHOGRAPHIC PLATES COATINGS, LITHOGRAPHIC PLATES AND COATINGS CONTAINING SAME, METHODS OF PREPARATION AND USE

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CROSS REFERENCE TO RELATED APPLICATIONS

Provisional Applications (1)