ES2222911T3 - THERMAL LITHOGRAPHIC PLANKS WITHOUT WATER. - Google Patents

Abstract

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. More particularly, 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.

Description

Thermal lithographic plates without water.

Background of the invention 1. Field of the invention

The invention relates to lithographic plates water-free thermal comprising inherent polymer layers, which absorb near infrared, for computer technologies to plate and digital-offset press. More especially This invention relates to thermal lithographic plates without water, in which images with laser light can be formed near the infrared and that do not require a chemical treatment stage later.

2. Prior art

Thermal lithographic plates without water are known. For example, US patents. 5,310,869 and 5,339,737 describe thermal lithographic plates without water that they comprise a layer that repels the ink that covers a layer of Imaging that absorbs near the infrared. The layer that repels ink is transparent to radiation and comprises mainly crosslinked silicone polymers. The layer of Imaging that absorbs near the infrared contains binder resins and materials that absorb near the infrared, such as carbon black and molecular dyes. These thermal lithographic plates without water require high doses of laser energy to erode the absorbing layer near the infrared and weaken the adhesion of the polymer layer of cross-linked silicone that repels ink. In addition, the exposed area of the iron must be removed during a chemical treatment stage additional to get to give an image area.

U.S. Pat. 5,379,698 also describes thermal lithographic plates without water, which include crosslinked silicone polymers that repel ink, which they cover a thin metal or metal oxide film of titanium deposited on a substrate as a formation layer of laser imaging In a similar technology, the patent of the USA 5,487,338 teaches how to use a reflective layer on the infrared located below the absorbing layer near the infrared. The manufacture of such lithographic plates requires vacuum deposition of the corresponding metals. Therefore it is very expensive

WO9831550, WO9700175 and WO9401280 they also describe thermal lithographic plates without water, which they comprise a layer of crosslinked silicone polymers that repel the ink, which covers a layer of imaging that absorbs near the infrared that contains binder resins and fine metal films, dyes or pigments that absorb nearby of the infrared. Again such thermal lithographic printing without water requires high doses of laser energy for the formation of images.

WO9706956 also describes plates thermal lithographs without water, comprising a layer that absorbs near the infrared containing binder and coloring resins or absorption pigments near the infrared, and a hydrophobic layer transparent coating that contains polymeric materials fluorinated soluble in fluorinated solvents. When exposed to laser radiation near the infrared, the exposed area erodes and accept the ink, while the unexposed area still repels the ink. A drawback of such plates is that the area does not exposed is sensitive to manipulation and becomes dirty Easily in the press.

EP0764522 also provides a thermal lithographic plate without water containing a layer that repel ink, crosslinked silicone polymer, transparent, near the infrared and an imaging layer that absorbs near infrared. The layer that repels the ink and the imaging layers that absorb near the infrared contain crosslinked functionality, which forms crosslinked links between layers to increase the length of the press run. Such  Lithographic plate requires high doses of laser energy for the imaging and requires a treatment stage chemical.

WO9911467 also provides a thermal lithographic plate without water, comprising a layer of cross-linked silicone polymer that repels ink, which covers an imaging layer that absorbs near the infrared, containing polyurethane resins and absorption dyes nearby of the infrared. Although such printing plate shows a faster speed of laser imaging, it is very sensitive to the different developers used in the stage of final chemical treatment

Therefore, there remains a need for a thermal lithographic plate without water that overcomes the inconveniences of the prior art.

The main object is to provide compositions of coating of the lithographic plate that combine the Advantages of: long-term printing plates, absence of phase separation of the coatings that cover, cheap and easily manufactured coating formulations, coatings in which images can be formed quickly and accurate with laser accuracy.

Summary of the invention

This invention relates to lithographic plates thermal water-free for ironed and computer technologies digital offset press More especially, this invention refers to thermal lithographic plates that include:

In general terms, the present invention provides a thermal lithographic plate without water suitable for Laser imaging near infrared, said printing plate comprising:

(i)

a support substrate, and (ii) a top layer of composite material consisting of:

(to)

a layer that enhances adhesion, which absorbs near the infrared, applied to the support substrate and

(b)

a crosslinked silicone polymer layer that repels ink, which absorbs near infrared.

Coatings are also provided for Obtain the printing plate of the present invention.

On thermal lithographic plates without water from this invention can be formed with laser lights near the infrared that have a radiation between about 780 and approximately 1200 nm. Depending on the doses of laser energy for the formation of images, the plates in which the  images may not require further treatment stage chemical.

Detailed description of the invention

This invention relates to lithographic plates thermal water-free for ironed and computer technologies digital offset press More specifically, this invention refers to thermal lithographic plates without water, in which can be formed with laser light near infrared which has a radiation of between about 780 and approximately 1200 nm. Thermal lithographic plates without water of this invention comprise (I) a support substrate, and (II) a upper layer of composite material consisting of a material inherent compound, which repels ink, which absorbs near the infrared, which comprises inherent polymers that absorb near of the infrared.

Support substrate

The support substrate of this invention can be any sheet material, such as metal, plastic and paper. The substrate surface can be treated to enhance the adhesion by techniques known in the art. For example, the aluminum sheet surface can be treated by metal finishing techniques that include corrugation electrochemistry, chemical corrugation, mechanical corrugation, anodization and the like. The surface of the plastic sheets can be modified by crown treatment and engravings Chemicals

The layer of composite material, which repels ink, which absorbs near infrared

The composite layer, which repels the ink, which absorbs near the infrared, of this invention comprises (a) a layer that enhances adhesion that absorbs nearby infrared, which is applied between a support substrate and (b) a crosslinked silicone polymer layer that repels ink, which absorbs near infrared.

(a) The layer that enhances adhesion, which absorbs near infrared, it mainly comprises inherent polymer which absorbs near the infrared that has reactive functionality, which can form covalent bonds with the polymer layer of cross-linked silicone that repels ink, which absorbs near the infrared. Polymers that enhance adhesion that absorb near the infrared show a strong absorption band between 780 and 1200 nm. The preferred class of polymers that absorb near of the infrared of this invention are urethane polymers, which are obtained from the reactions of alkyl or aryl compounds that they contain diisocyanate functional groups with a chromophore of near-infrared absorption containing functional groups alcoholics and certain tertiary alcohols. Polyurethane inherent absorbing near the infrared of this invention can represented according to formula I.

Formula I

one

in the that

?

a and b represent molar ratios in which b can vary from 0.1 to 0.2 and a can vary from 0.9 to 0.8.

?

T represents a transparent repeat segment near the infrared, which can have a structure according to the formulas II, III, IV and V.

Formula II

35

Formula III

36

Formula IV

2

Formula V

3

?

A represents a segment of repetition that absorbs near the infrared, which may have a structure according to formula VI.

Formula SAW

4

in the that

?

Z1 and Z2 represent enough atoms to form condensed, substituted or unsubstituted aromatic rings, such like phenyl and naphthyl.

?

D1 and D2 represent -O-, -S-, -Se-, -CH = CH, and -C (CH 3) 2 -

?

R1 and R2 represent alkyl substitution, alkyloxy, alkyl halide, alkyl pyridine, allyloxy, vinyloxyl, alkylthio, arylthio, aminothiophenol, sulfoalkyl and carboxyalkyl.

?

R3 represents replacement of hydrogen, alkyl and aryl

?

X1 represents an anionic counterion selected from bromide, chloride, iodide, tosylate, triflate, carbonate trifluoromethane, dodecyl benzosulfonate and tetrafluoroborate

?

n represents 0 and 1.

?

m varies from 1 to 18.

The inherent polymers that absorb near the Infrared of this invention show a strong absorption band between 780 and 1200 nm. They can have glass transition temperature between 110 and 150ºC and decomposition temperature between 180 and 300 ° C

Optionally, the layer that enhances adhesion, which absorbs near the infrared, of this invention may contain binder resins, which are transparent to nearby radiation of the infrared. Preferred binder resins are polymers containing monomeric units derived from nitrocellulose, hydroxyalkylcellulose, styrene, carbonate, amide, urethane, acrylate, vinyl alcohol and ester.

With exposure to near-infrared radiation between 780 and 1200 nm, near-infrared absorption segments contained in the polymer central chain convert photoelectric energy into heat, which induces thermal breakdown and fragmentation of transparent segments near the infrared by the cleavage mechanism described by Foley et al. (U.S. Patent 5,156,938) according to formula VII.

Formula VII

5

(b) The layer that repels ink, which absorbs near the infrared, of this invention comprises polymers of crosslinked silicone having repeat absorption units near the infrared. The repeating units that absorb nearby infrared form covalent bonds with polymer networks of crosslinked silicone according to formulas VIII, IX and X:

Formula VIII

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7

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Formula IX

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8

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Formula X

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9

in the that

?

- (R4) 2 -Si-O- represents crosslinked polymeric polymer networks.

?

R4 represents substitution of methyl, ethyl and aryl of crosslinked polymeric polymer networks.

?

B represents repeating units that absorb near the infrared, which show strong absorption bands between 780 and 1200 nm. Repeating absorption units near infrared include indole derivatives, benz [e] indole, benz [cd] indole, benzothiazole, naphthiazole, benzoxazole, naphthoxazole, benzselenazole and naphthoselenazole, which can be represented according to formulas XI, XII and XIII:

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Formula XI

10

Formula XII

eleven

Formula XIII

12

in the that

?

Z1 and Z2 represent enough atoms to form condensed, substituted or unsubstituted aromatic rings, such like phenyl and naphthyl.

?

D1 and D2 represent -O-, -S-, -Se-, -CH = CH, and -C (CH 3) 2 -

?

R5 represents alkyl, alkyloxy, halide of alkyl, pyridine, alkyl pyridine and alkylthio.

?

R6 represents alkyl substitution, sulfonylalkyl and carboxyalkyl.

?

R7 represents replacement of hydrogen, alkyl and aryl

?

R8 represents substitution of alkyl, benzyl, alkylamine, alkylsulfonic acid, acid alkylcarboxylic.

?

X2 represents an anionic counterion selected from bromide, chloride, iodide, tosylate, triflate, carbonate trifluoromethane, dodecyl benzosulfonate and tetrafluoroborate

?

n represents 0 and 1.

?

m varies from 1 to 18.

The crosslinked silicone polymers that repel the ink, which absorb near the infrared, of this invention can be obtained by in situ addition reactions of poly (hydroalkylsiloxane) with poly (dialkylsiloxane) and near infrared absorption molecules containing alkenyl functional groups in presence of catalysts of metal complexes, such as hydrogen hexachloroplatinate. They can also be obtained by condensation reactions of poly (dialkylsiloxane) containing silanol functional groups with organic compounds containing acyloxy or alkoxysilane functional groups in the presence of a zinc, tin, iron or titanium carboxylic acid salt catalyst.

With radiation exposure near the infrared between 780 and 1200 nm, the absorption segments near of the infrared contained in the polymer central chain of crosslinked silicone convert photoelectric energy into heat, which which induces the decomposition and thermal fragmentation of polymer networks. Thermal fragmentation of the repellent layer the ink, which absorbs near the infrared, in combination with the thermal fragmentation of the layer below that enhances the adhesion, which absorbs near the infrared, results in formation of low molecular weight materials. These products Decomposed are easily removed using the inks of printing in the printing press during the inking period. The laser exposure zone finally comes to accept the inks and the non-exposure zone still repels the inks.

Synthesis of polymers that enhance adhesion, which absorb near infrared

All polymerization was performed in a reactor three-neck flask equipped with magnetic stirrer, metal heating, temperature controller, water condenser and nitrogen inlet The completion of the reaction was followed by infrared spectrophotometer Optical characteristics and thermal characteristics of the polymers obtained were characterized by spectroscopic and calorimetric scanning techniques differential.

Synthesis of inherent polymers that enhance adhesion, which absorb near infrared

Examples 1 to 5

Example 1 Polymer synthesis ADS-001-CTP with absorption near the infrared

Polymer ADS-001-CTP with absorption near the infrared was synthesized by slowly adding 21.2 parts of trimethyl-1,6-diisocyanatohexane (available from Aldrich Chemicals) in a solution containing 100 parts of N-methyl pyrrolidinone, 6.8 parts of perchlorate of 2- [2- [2-Chloro-3- [2- (1,3-dihydro-1- (2-hydroxyethyl) -3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethyliden] -1-cyclohexen-1-yl] ethenyl] -1- (2-hydroxyethyl) -3,3-dimethyl-1H-benz [e] indole (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 dilaurate of dibutyltin (available from Aldrich Chemicals) at 60 ° C under nitrogen atmosphere and constant agitation. The completion of the polymerization was indicated by disappearance on bands of NCO absorption in infrared spectra. The product is precipitated in water and then collected by vacuum filtration, washed thoroughly with water and dried in the air until reaching a constant weight

The polymer obtained with absorption near the infrared has glass transition temperatures and decomposition of approximately 133 ° C and 214 ° C, respectively. The movie of ADS-001-CTP polymer with absorption near the infrared on polyester film shows a band of wide absorption that has a maximum at approximately 842 nm. The ideal structure of ADS-001-CTP It can be represented as follows:

13

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Structure of ADS-001-CTP

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Example 2 Polymer synthesis ADS-002-CTP with absorption near the infrared

Polymer ADS-002-CTP with absorption near the infrared was synthesized by slowly adding 26.0 parts of methylene bis (4-cyclohexyl isocyanate) (available from Bayer) in a solution containing 100 parts of N-methyl pyrrolidinone, 6.8 parts perchlorate 2- [2- [2-Chloro-3- [2- (1,3-dihydro-1- (2-hydroxyethyl) -3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethyliden] -1-cyclohexen-1-yl] ethenyl] -1- (2-hydroxyethyl) -3,3-dimethyl-1H-benz [e] indole (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 dilaurate of dibutyltin (available from Aldrich Chemicals) at 60 ° C under nitrogen atmosphere and constant agitation. The completion of the polymerization was indicated by disappearance on bands of NCO absorption in infrared spectra. The product is precipitated in water and then collected by vacuum filtration, washed thoroughly with water and dried in the air until reaching a constant weight Polymer ADS-002-CTP absorbing near the infrared has glass transition temperatures and decomposition of approximately 132 ° C and 214 ° C, respectively. The movie of ADS-002-CTP polymer with absorption near the infrared on polyester film shows a band of wide absorption that has a maximum at approximately 839 nm. The ideal structure of ADS-002-CTP It can be represented as follows:

14

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Structure of ADS-002-CTP

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Example 3 Polymer synthesis ADS-003-CTP with absorption near the infrared

ADS-003-CTP polymer with near-infrared absorption was synthesized by slowly adding 21.2 parts of trimethyl-1,6-diisocyanatohexane (available from Aldrich Chemicals) in a solution containing 100 parts of N-methyl pyrrolidinone, 6.4 parts of 2- [2- [2-allyloxy-3- [2- (1,3-dihydro-1- (2-hydroxyethyl) -3,3-dimethyl-2H-benz [e] indole-2- perchlorate] iliden) ethyliden] -1-cyclohexen-1-yl] ethenyl] -1- (2-hydroxyethyl) -3,3-dimethyl-1H-benz [e] indole (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 were slowly added and the reaction was continued for an additional 4 hours. The reaction mixture was cooled to room temperature. The product was precipitated in water and then collected by vacuum filtration, washed thoroughly with water and dried in air until a constant weight was reached. The ADS-003-CTP polymer film with near-infrared absorption on polyester film shows a wide absorption band having a maximum at approximately 832 nm. The ideal structure of ADS-003-CTP can be represented as
follow:

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Structure of ADS-003-CTP

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Example 4 Polymer synthesis ADS-004-CTP linear with absorption near infrared

Polymer ADS-004-CTP with absorption near the infrared was synthesized by slowly adding 26.0 parts of methylene bis (4-cyclohexyl isocyanate) (available from Bayer) in a solution containing 100 parts of N-methyl pyrrolidinone, 6.8 parts perchlorate 2- [2- [2-Chloro-3- [2- (1,3-dihydro-1- (2-hydroxyethyl) -3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethyliden] -1-cyclohexen-1-yl] ethenyl] -1- (2-hydroxyethyl) -3,3-dimethyl-1H-benz [e] indole (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 Chemicals) and 0.5 parts dilaurate of dibutyltin (available from Aldrich Chemicals) at 60 ° C under nitrogen atmosphere and constant agitation. The completion of the polymerization was indicated by disappearance on bands of NCO absorption in infrared spectra. Reaction mixture cooled to room temperature. The product precipitated in water and then collected by vacuum filtration, washed abundantly with water and air dried to reach a weight constant. ADS-004-CTP polymer which absorbs near the infrared has transition temperatures vitreous and decomposition of approximately 113 ° C and 210 ° C, respectively. Polymer film ADS-004-CTP with absorption near the infrared on polyester film shows a band of wide absorption that has a maximum at approximately 841 nm. The ideal structure of ADS-004-CTP It can be represented as follows:

16

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Structure of ADS-004-CTP

Example 5 Polymer synthesis ADS-005-CTP with absorption near the infrared

Polymer ADS-CTP-005 with absorption near the infrared was synthesized by slowly adding 21.2 parts of trimethyl-1,6-diisocyanatohexane (available from Aldrich Chemicals) in a solution containing 100 parts of N-methyl pyrrolidinone, 6.8 parts of perchlorate of 2- [2- [2-Chloro-3- [2- (1,3-dihydro-1- (2-hydroxyethyl) -3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethyliden] -1-cyclohexen-1-yl] ethenyl] -1- (2-hydroxyethyl) -3,3-dimethyl-1H-benz [e] indole (available from 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 dibutyltin (available from Aldrich Chemicals) at 60 ° C under nitrogen atmosphere and stirring constant for 6 hours. The completion of the polymerization is indicated by the disappearance of NCO absorption bands in the infrared spectra The product was precipitated in water and then was collected by vacuum filtration, washed thoroughly with water and dried in the air until reaching a constant weight. He ADS-005-CTP polymer absorbing near the infrared has glass transition temperatures and decomposition of approximately 117 ° C and 215 ° C, respectively. ADS-005-CTP polymer film with near infrared absorption on polyester film shows a wide absorption band that has a maximum at approximately 841 nm. The ideal structure of ADS-005-CTP can be represented as as follows:

17

Structure of ADS-005-CTP

Synthesis of crosslinked silicone polymers that absorb near infrared

Examples 6 to 12

Example 6 Polymer preparation ADS-001-Si reticulated silicone which repels the ink, which absorbs near the infrared

The crosslinked silicone polymer that repels the ink, which absorbs near the infrared, was prepared by adding 300 parts of water containing 1.0 parts of the internal salt of 2- [2- [2-Allyloxy-3- [2- (1,3-dihydro-1- (4-sulfobutyl) -3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethyliden] -1-cyclohexen-1-yl] ethenyl] -1- (4-sulfobutyl) -3,3-dimethyl-1H-benz [e] indole (available from American Dye Source, Inc.), in a solution that It contained 50 parts of reactive silicone polymer emulsion (Syl-Off 7910, available from Dow Corning, 40% in solid weight), 50 parts of polymeric crosslinking emulsion of silicone containing platinum catalyst (Syl-Off 7922, available from Dow Corning, 40% in solid weight) and 1.5 parts silicone wetting agent (Q2-5211, available from Dow Corning). The solution freshly prepared polymer was coated on a substrate of Anodized aluminum using a rolled wire rod. He coating dried under hot air stream and then it further cured at 120 ° C for 5 minutes to produce a uniform coating film that had a weight of coating of approximately 1.0 g / m2. The spectre UV-Vis-NIR of the resulting polymer on polyester film shows a wide absorption band which has a maximum at 840 nm. The ideal polymer structure of cross-linked silicone that repels ink, which absorbs near the infrared, can be represented as follows:

18

Structure of ADS-001-Yes

Example 7 Polymer preparation ADS-002-Si reticulated silicone which repels the ink, which absorbs near the infrared

The crosslinked silicone polymer that repels the ink, which absorbs near the infrared, was prepared by adding 300 parts of water containing 1.0 parts of the acid 2- [2- [2-Chloro-3- [2- (1,3-dihydro-1-allyl-3,3-dimethyl-7-sulfonyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclohexen-1-yl] ethenyl] -1-allyl-3,3-dimethyl-7-sulfonyl-1H-benz [e] indole 4-methylbenzenesulfonic acid (available from American Dye Source, Inc.), in a solution containing 50 emulsion parts of reactive silicone (Syl-Off 7910, available from Dow Corning, 40% solid weight), 50 parts silicone emulsion reactive 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 polymer solution was coated on an anodized aluminum substrate using a rolled rod of wire. The coating was dried under a stream of hot air and then it was further cured at 120 ° C for 5 minutes to produce a uniform coating film that had a weight coating of approximately 1.0 g / m2. The spectre UV-Vis-NIR of the resulting polymer on polyester film shows a wide absorption band which has a maximum at 842 nm. The ideal polymer structure of cross-linked silicone that repels ink, which absorbs near the infrared, can be represented as follows:

19

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Structure of ADS-002-Yes

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Example 8 Polymer preparation ADS-003-Si reticulated silicone which repels the ink, which absorbs near the infrared

The crosslinked silicone polymer that repels the ink, which absorbs near the infrared, was prepared by adding 300 parts of water containing 1.0 parts of the acid 2- [2- [2-Allyloxy-3- [2- (1,3-dihydro-1-allyl-3,3-dimethyl-7-sulfonyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclohexen-1-yl] ethenyl] -1-allyl-3,3-dimethyl-7-sulfonyl-1H-benz [e] indole 4-methylbenzenesulfonic acid (available from American Dye Source, Inc.), in a solution containing 50 emulsion parts of reactive silicone (Syl-Off 7910, available from Dow Corning, 40% solid weight), 50 parts silicone emulsion reactive 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 polymer solution was coated on an anodized aluminum substrate using a rolled rod of wire. The coating was dried under a stream of hot air and then it was further cured at 120 ° C for 5 minutes to produce a uniform coating film that had a weight coating of approximately 1.0 g / m2. The spectre UV-Vis-NIR of the resulting polymer on polyester film shows a wide absorption band which has a maximum at 837 nm. The ideal polymer structure of cross-linked silicone that repels ink, which absorbs near the infrared, can be represented as follows:

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Example 9 Polymer preparation ADS-004-Si crosslinked silicone which repels the ink, which absorbs near the infrared

The crosslinked silicone polymer that repels the ink, which absorbs near the infrared, was prepared by adding a solution containing 10 parts of methyl ethyl ketone dissolving with 0.10 parts of 4-methyl benzenesulfonate from 2- [2- [2-Allyloxy-3- [2- (1,3-dihydro-1-heptyl-3,3-dimethyl-2H-ben [e] indole-2-ylidene) ethylidene] -1-cyclohexen -1-yl] ethenyl] -1-heptyl) -3,3-dimethyl-1H-benz [e] indole (available from American Dye Source, Inc.), in a solution that contained 2.0 parts of finished divinyl polydimethylsiloxane (PS445, available from United Chemical), 1.0 part of finished high molecular weight polydimethylsiloxane divinyl (PS225, available from United Chemical), 1.0 part of polyhydrometilsiloxane (SL6020, available from GE Silicones), 0.1 platinum catalyst parts (PC075, available from United Chemical), 0.06 parts volatile inhibitor (SL6020, available from GE Silicones) in a solution containing 45 parts of the solution of Isoparaffin (IsoPar-E, available from Exxon Chemical) The solution was filtered to remove any residue. solid. The freshly prepared polymer solution was coated on an anodized aluminum substrate using a rolled rod of wire. The coating was dried under a stream of hot air and then it was further cured at 120 ° C for 5 minutes to produce a uniform coating film that had a weight coating of approximately 1.0 g / m2. The spectre UV-Vis-NIR of the resulting polymer on polyester film shows a wide absorption band that  It has a maximum at 835 nm. The ideal polymer structure of cross-linked silicone that repels ink, which absorbs near the infrared, can be represented as follows:

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twenty-one

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Structure of ADS-004-Yes

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Example 10 Polymer preparation ADS-005-Si reticulated silicone which repels the ink, which absorbs near the infrared

The crosslinked silicone polymer that repels the ink, which absorbs near the infrared, was prepared so similar to that of example 4, except that it was used 4-methyl benzenesulfonate 2- [2- [2-Dodecyloxy-3- [2- (1,3-dihydro-1-allyl-3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclohexen -1-yl] ethenyl] -1-allyl-3,3-dimethyl-1 H -benz [e] indole (available from American Dye Source, Inc.) to replace the 4-methyl benzenesulfonate 2- [2- [2-Allyloxy-3- [2- (1,3-dihydro-1-heptyl-3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclohexen -1-yl] ethenyl] -1-heptyl) -3,3-dimethyl-1H-benz [e] indole. The freshly prepared polymer solution was coated on a anodized aluminum substrate using a rolled rod of wire. The coating was dried under a stream of hot air and then it was further cured at 120 ° C for 5 minutes to produce a uniform coating film that had a weight of  coating of approximately 1.0 g / m2. The spectre UV-Vis-NIR of the resulting polymer on polyester film shows a wide absorption band that It has a maximum at 829 nm. The ideal polymer structure of cross-linked silicone that repels ink, which absorbs near the infrared, can be represented as follows:

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22

Example 11 Polymer preparation ADS-006-Si reticulated silicone which repels the ink, which absorbs near the infrared

The crosslinked silicone polymer that repels the ink, which absorbs near the infrared, was prepared in a manner similar to that of Example 4, except that 2- [2- [2-dodecyloxy-4- tert -4-methyl benzenesulfonate] was used. butyl-3- [2- (1,3-dihydro-1-allyl-3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclohexen-1-yl] ethenyl] - 1-allyl-3,3-dimethyl-1H-benz [e] indole (available from American Dye Source, Inc.) to replace 2- [2- [2-allyloxy-3- [2- 4-methylbenzenesulfonate] (1,3-dihydro-1-heptyl-3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclohexen-1-yl] ethenyl] -1-heptyl) -3, 3-dimethyl-1H-
benz [e] indolio. The freshly prepared polymer solution was coated on an anodized aluminum substrate using a rolled wire rod. The coating was dried under a stream of hot air and then further cured at 120 ° C for 5 minutes to produce a uniform coating film having a coating weight of approximately 1.0 g / m2. The UV-Vis-NIR spectrum of the resulting polymer on polyester film shows a broad absorption band having a maximum at 829 nm. The ideal structure of the crosslinked silicone polymer that repels the ink, which absorbs near the infrared, can be represented as follows:

2. 3

Example 12 Polymer preparation ADS-007-Si reticulated silicone which repels the ink, which absorbs near the infrared

The crosslinked silicone polymer that repels the ink, which absorbs near the infrared, was prepared so similar to that of example 4, except that it was used 4-methyl benzenesulfonate 2- [2- [2-Allyloxy-3- [2- (1,3-dihydro-1- (octyl-8-en) -3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclohexen-1-yl] ethenyl] -1- (octyl-8-en) -3,3-dimethyl-1H-benz [e] indole (available from American Dye Source, Inc.) to replace the 4-methyl benzenesulfonate 2- [2- [2-Allyloxy-3- [2- (1,3-dihydro-1-heptyl-3,3-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclohexen -1-yl] ethenyl] -1-heptyl) -3,3-dimethyl-1H-benz [e] indole. The freshly prepared polymer solution was coated on a anodized aluminum substrate using a rolled rod of wire. The coating was dried under a stream of hot air and then it was further cured at 120 ° C for 5 minutes to produce a uniform coating film that had a weight of  coating of approximately 1.0 g / m2. The spectre UV-Vis-NIR polymer result on polyester film shows a wide absorption band that It has a maximum at 829 nm. The ideal polymer structure of cross-linked silicone that repels ink, which absorbs near the infrared, can be represented as follows:

24

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Structure of ADS-007-Yes

Preparation and imaging of printing plates without water

Examples 13 a 18

Example 13

A printing plate without water was prepared dissolving 10.0 parts of ADS-001-CTP of Example 1 at 90.0 parts of the solvent system containing 35% methoxyethanol, 30% methyl ethyl ketone and 35% methanol. The solution polymeric with near-infrared absorption was filtered to Remove any solid residue. Then he dressed on a anodized aluminum substrate using a rolled rod of wire and dried under hot air stream at 80 ° C for 5 minutes to produce a uniform coating that has a weight of coating of approximately 1.5 g / m2. The solution of cross-linked silicone polymer that repels ink, which absorbs near the infrared, it was prepared similarly to the example 6. Then it was coated on the layer that enhances adhesion, which absorbs near the infrared, using a rolled rod of wire. The coating was dried under a stream of hot air and cured at 120 ° C for 5 minutes to produce a coating uniform that has a coating weight of approximately 1.0 g / m2. Images were formed on the plate with an "image laser setter "(image adjustment device) adapted to customer needs, which was equipped with a drum aluminum, a solid state diode laser of 1 watt of lightning only emitting at 830 nm (available from Optopower) at a density of energy between 200 and 800 mJ / cm2. The iron was tested on an AB Dick press with Sun Chemical Drilith "H" Cyan Ink (available from Sun Chemical) in the absence of a wetting solution. Before printing, debris in the exposed area was cleaned  gently with a cotton cloth dampened with soapy water. The exposed area produced an image of great optical impression while that the unexposed area was kept clean. They can be printed up to more than 10,000 copies of the plate without deterioration.

Example 14

A printing plate without water was prepared similar to the procedure of example 13, except that it was used the crosslinked silicone polymer layer that repels the ink, which absorbs near the infrared prepared in a manner similar to that of the example 7 (ie ADS-002-Si) to coat the layer that enhances adhesion, which absorbs nearby infrared, using a rolled wire rod. He coating was dried under a stream of hot air and cured at 120 ° C for 5 minutes to produce a uniform coating that It has a coating weight of approximately 1.0 g / m2. Be they formed images on the plate with a laser image setter adapted to the needs of the client, which was equipped with a Aluminum drum, a 1 watt solid state diode laser single beam emitting at 830 nm (available from Optopower) at a energy density between 200 and 800 mJ / cm2. The iron is tested in a press AB Dick with Ink Sun Chemical Drilith "H" Cyan (available from Sun Chemical) in the absence of a wetting solution. Before printing, debris in the exposed area was cleaned  gently with a cotton cloth dampened with soapy water. The exposed area produced an image of great optical impression while that the unexposed area was kept clean. They can be printed up to more than 10,000 copies of the plate without deterioration.

Example 15

A printing plate without water was prepared similar to the procedure of example 13, except that it was used the crosslinked silicone polymer layer that repels the ink, which absorbs near the infrared prepared in a manner similar to that of the example 8 (ie ADS-003-Si) to coat the layer that enhances adhesion, which absorbs nearby infrared, using a rolled wire rod. He coating was dried under a stream of hot air and cured at 120 ° C for 5 minutes to produce a uniform coating that It has a coating weight of approximately 1.0 g / m2. Be they formed images on the plate with a laser image setter adapted to the needs of the client, which was equipped with a Aluminum drum, a 1 watt solid state diode laser single beam emitting at 830 nm (available from Optopower) at a energy density between 200 and 800 mJ / cm2. The iron is tested in a press AB Dick with Ink Sun Chemical Drilith "H" Cyan (available from Sun Chemical) in the absence of a wetting solution. Before printing, debris in the exposed area was cleaned  gently with a cotton cloth dampened with soapy water. The exposed area produced an image of great optical impression while that the unexposed area was kept clean. They can be printed up to more than 10,000 copies of the plate without deterioration.

Example 16

A printing plate without water was prepared similar to the procedure of example 13, except that it was used crosslinked silicone polymer that repels ink, which absorbs near the infrared obtained similarly to that of example 9 (i.e., ADS-004-Si) to coat the layer that enhances adhesion, which absorbs near the infrared, using a rolled wire rod. The coating dried under hot air flow and cured at 120 ° C for 5 minutes to produce a uniform coating that has a weight of coating of approximately 1.0 g / m2. They formed images on the plate with a laser image setter adapted to the customer needs, which was equipped with a drum aluminum, a solid state diode laser of 1 watt of lightning only emitting at 830 nm (available from Optopower) at a density of energy between 200 and 800 mJ / cm2. The iron was tested on an AB Dick press with Sun Chemical Drilith "H" Cyan Ink (available from Sun Chemical) in the absence of a wetting solution. Before printing, debris in the exposed area was cleaned  gently with a cotton cloth dampened with soapy water. The exposed area produced an image of great optical impression while that the unexposed area was kept clean. They can be printed up to more than 10,000 copies of the plate without deterioration.

Example 17

A printing plate without water was prepared similar to the procedure of example 13, except that it was used crosslinked silicone polymer that repels ink, which absorbs near the infrared obtained similarly to that of example 12 (i.e., ADS-007-Si) to coat the layer that enhances adhesion, which absorbs near the infrared, using a rolled wire rod. The coating dried under hot air flow and cured at 120 ° C for 5 minutes to produce a uniform coating that has a weight of coating of approximately 1.0 g / m2. They formed images on the plate with a laser image setter adapted to the customer needs, which was equipped with a drum aluminum, a solid state diode laser of 1 watt of lightning only emitting at 830 nm (available from Optopower) at a density of energy between 200 and 800 mJ / cm2. The iron was tested on an AB Dick press with Sun Chemical Drilith "H" Cyan Ink (available from Sun Chemical) in the absence of a wetting solution. Before printing, debris in the exposed area was cleaned  gently with a cotton cloth dampened with soapy water. The exposed area produced an image of great optical impression while that the unexposed area was kept clean. They can be printed up to more than 10,000 copies of the plate without deterioration.

Example 18

A printing plate without water was prepared similar to example 15, except that the polymer that was used absorbs near the infrared obtained from example 3 (i.e. ADS-003-CTP) to prepare the layer which enhances adhesion near infrared. Images were formed on the plate with a laser image setter adapted to the customer needs, which was equipped with a drum aluminum, a solid state diode laser of 1 watt of lightning only emitting at 830 nm (available from Optopower) at a density of energy between 200 and 800 mJ / cm2. The iron was tested on an AB Dick duplication press with Sun Chemical Drilith Ink "H" Cyan (available from Sun Chemical) in the absence of solution wetting Before printing, waste in the exposed area they were gently cleaned with a cotton cloth moistened with water soapy The exposed area produced a great impression image optics, while the unexposed area was kept clean. They can print up to more than 10,000 copies of the plate without deterioration.

Claims (6)

1. Cladding composition set printing plate for thermal printing without water, comprising said coating composition set at least two compositions of different components to be applied in relation coating with the first component composition intended applied to a suitable sheet substrate to form a first layer and a second component composition intended to be applied on said first component composition layer once said first layer is dry, said first composition consisting component in a composition that enhances adhesion, which absorbs near the infrared and said second consisting composition in a crosslinked silicone polymer that repels the ink, which absorbs near the infrared; wherein said first component composition which contains polymers that absorb near the infrared sample strong absorption at wavelengths between approximately 780 and approximately 1200 nm, said polymers being able to form covalent bonds with the crosslinked silicone polymer of the second component composition, said polymers having said first component composition a structure according to the formula I: Formula I 25 in the that

?

a and b represent molar ratios in which b can vary from 0.1 to 0.2 and a can vary from 0.9 to 0.8,

?

T represents a transparent repeat segment near the infrared, which can have a structure according to the formulas II, III, IV and V,

Formula II 35 Formula III 36 Formula IV 26

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Formula V

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27

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?

A represents a repeating segment that absorbs near the infrared, which can have a structure according to the formula VI,

Formula SAW

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in the that

?

Z1 and Z2 represent enough atoms to form condensed, substituted or unsubstituted aromatic rings, such like phenyl and naphthyl,

?

D1 and D2 represent -O-, -S-, -Se-, -CH = CH, and -C (CH 3) 2 -

?

R1 and R2 represent alkyl substitution, alkyloxy, alkyl halide, alkyl pyridine, allyloxy, vinyloxyl, alkylthio, arylthio, aminothiophenol, sulfoalkyl and carboxyalkyl,

?

R3 represents replacement of hydrogen, alkyl and aryl,

?

X1 represents an anionic counterion selected from bromide, chloride, iodide, tosylate, triflate, carbonate trifluoromethane, dodecyl benzosulfonate and tetrafluoroborate,

?

n represents 0 and 1,

?

m varies from 1 to 8.

2. Coating composition set according to claim 1, wherein said first composition of component further comprises binder resins that are transparent to radiation near infrared. 3. Coating composition set according to claim 2, wherein the binder resins are select from the group of polymers containing units monomeric derivatives of nitrocellulose, hydroxyalkylcellulose, styrene, carbonate, amide, urethane, acrylate, vinyl alcohol and ester, and mixtures thereof. 4. Coating composition set according to claim 3, wherein said second composition of component comprises crosslinked silicone polymers that have repetition units near infrared selected from crosslinked silicone polymer networks according to the formulas VIII, IX and X:

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Formula VIII

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Formula IX

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Formula X

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in the that

?

- (R4) 2 -Si-O- represents crosslinked polymeric polymer networks,

?

R4 represents substitution of methyl, ethyl and aryl of crosslinked polymeric polymer networks,

?

B represents repeating units that absorb near the infrared, which show strong absorption bands between 780 and 1200 nm. Repeating absorption units near infrared include indole derivatives, benz [e] indole, benz [cd] indole, benzothiazole, naphthiazole, benzoxazole, naphthoxazole, benzselenazole and naphthoselenazole, which can be represented according to formulas XI, XII and XIII:

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Formula XI

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Formula XII

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Formula XIII

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3. 4

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in the that

?

Z1 and Z2 represent enough atoms to form condensed, substituted or unsubstituted aromatic rings, such like phenyl and naphthyl,

?

D1 and D2 represent -O-, -S-, -Se-, -CH = CH, and -C (CH 3) 2 -,

?

R5 represents alkyl, alkyloxy, halide of alkyl, pyridine, alkyl pyridine and alkylthio,

?

R6 represents alkyl substitution, sulfonylalkyl and carboxyalkyl,

?

R7 represents replacement of hydrogen, alkyl and aryl,

?

R8 represents substitution of alkyl, benzyl, alkylamine, alkylsulfonic acid, acid alkylcarboxylic,

?

X2 represents an anionic counterion selected from bromide, chloride, iodide, tosylate, triflate, carbonate trifluoromethane, dodecyl benzosulfonate and tetrafluoroborate,

?

n represents 0 and 1,

?

m varies from 1 to 18.

5. Thermal printing plate without adequate water for near-infrared laser imaging, said printing plate comprising: (i) a substrate of support, and (ii) a top layer of composite material that comprises a coating composition set according to any of claims 1 to 4. 6. Thermal printing plate without water according to claim 5, wherein the support substrate is made of any sheet material, selected from materials that They consist of metal, plastic, composite and paper.