Waterless diazo planographic printing plates with epoxy-silane in undercoat and/or overcoat layers

Claim 2

A PRESENSITIZED PLANOGRAPHIC PRINTING PLATE CAPABLE OF BEING IMAGED COMPRISING A SUBSTRATE HAVING APPLIED TO AT LEAST ONE SURFACE THEREOF:

Claim 3

AS AN UNDERCOAT LAYER, A SENSITIZED COMPOSITION COMPRISING AN EPOXY-SILANE, A MONOMERIC OR PREPOLYMERIC EPOXIDE MATERIAL POLYMERIZABLE TO HIGHER MOLECULAR WEIGHTS THROUGH THE ACTION OF A CATIONIC CATALYST, AND, AS A CATALYST PRECURSOR, RADIATION-SENSITIVE AROMATIC DIAZONIUM SALT OF A COMPLEX HALOGENIDE WHICH DECOMPOSES UPON APPLICATION OF ENERGY TO RELEASE A LEWIS ACID EFFECTIVE TO INITIATE POLYMERIZATION AND INTERACTION OF SAID EPOXIDE AND EPOXY-SILANE AND

Claim 4

AS AN UNDERCOAT LAYER, A SENSITIZED COMPOSITION COMPRISING AN EPOXY-SILANE, A MONOMERIC OR PREPOLYMERIC EPOXIDE MATERIAL POLYMERIZABLE TO HIGHER MOLECULAR WEIGHTS THROUGH THE ACTION OF A CATIONIC CATALYST, AND, AS A CATALYST PRECURSOR, RADIATION-SENSITIVE AROMATIC DIAZONIUM SALT OF A COMPLEX HALOGENIDE WHICH DECOMPOSES UPON APPLICATION OF ENERGY TO RELEASE A LEWIS ACID EFFECTIVE TO INITIATE POLYMERIZATION AND INTERACTION OF SAID EPOXIDE AND EPOXY-SILANE AND

Claim 5

APPLYING TO A SUBSTRATE (A) AS AN UNDERCOAT LAYER A SENSITIZED COMPOSITION COMPRISING AN EPOXY-SILANE, A MONOMERIC OR PREPOLYMERIC EPOXIDE POLYMERIZABLE TO HIGHER MOLECULAR WIGHTS THROUGH THE ACTION OF A CATIONIC CATALYST AND, AS A CATALYST PRECUSOR, A RADIATION-SENSITIVE AROMATIC DIAZONIUM SALT OF A COMPLEX HALOGENIDE WHICH DECOMPSES UPON APPLICATION OF ENERGY TO RELEASE A LEWIS ACID EFFECTIVE INITIATE POLYMERIZATION AND INTERACTION OF SAID EPOXIDE AND EPOXY-SILANE AND (B) AS AN OVERCOAT LAYER A COMPOSITION COMPRISING AN ORGANOSILOXANE AND FROM 0 TO 50 PERCENT OF AN EPOXY-SILANE AS BASED ON THE TOTAL WEIGHT OF THE COMPONENTS IN THE OVERCOAT LAYER, WITH THE PROVISO THAT (1) WHEN SAID OVERCOAT LAYER COMPOSITION IS DEVOID OF EPOXU-SILANE, SAID UNDERCOAT LAYER COMPOSITION CONTAINS ABOUT 25 TO 75 PERCENT EPOXYSILANE AND ABOUT 15 TO ABOUT 40 PERCENT OF SAID CATALYST PRECURSOR, AND (2) WHEN SAID EPOXY-SILANE IS A COMPONENT OF SAID OVERCOAT LAYER COMPOSITION, SAID UNDERCOAT LAYER COMPOSITION CONTAINS ABOUT 1 TO ABOUT 20 PERCENT EPOXYSILANE AND ABOUT 0.5 TO ABOUT 10 PERCENT OF SAID CATLAYST PRECURSOR, ALL PERCENTS BEING BASED ON THE TOTAL WEIGHT OF SAID EPOXIDE MATERIAL IN SAID UNDERCOAT LAYER EXCEPT THE PERCENT OF SAID CATALYST PRECURSOR IN PROVISO (2) IS BASED ON THE TOTAL WEIGHT OF EPOXIDE MOIETY CONTAINING COMPOUNDS IN SAID UNDERCOAT LAYER SAID EPOXY-SILANE IN SAID LAYERS BEING SELECTED FROM COMPOUNDS HAVING THE GENERAL FORMULA OXIRANYL-X-SI(-O-R)(-O-R1)-Y WHEREIN EACH OF X, R AND R1 IS AN ALKYLENE, ALKOXY, ARYLENE, ALKARYLENE, ARALKYLENE, CARBALKOXY OR ETHER GROUP AND Y IS AN ALKOXKY OR EOPXY GROUP; AND SAID ORGANOSILOXANE BEING SILICONE ELASTOMER FORMED BY CURING AND OR POLYMERIZING SILICONE GUM;

Claim 6

APPLYING TO A SUBSTRATE (A) AS AN UNDERCOAT LAYER A SENSITIZED COMPOSITION COMPRISING AN EPOXY-SILANE, A MONOMERIC OR PREPOLYMERIC EPOXIDE POLYMERIZABLE TO HIGHER MOLECULAR WIGHTS THROUGH THE ACTION OF A CATIONIC CATALYST AND, AS A CATALYST PRECUSOR, A RADIATION-SENSITIVE AROMATIC DIAZONIUM SALT OF A COMPLEX HALOGENIDE WHICH DECOMPSES UPON APPLICATION OF ENERGY TO RELEASE A LEWIS ACID EFFECTIVE INITIATE POLYMERIZATION AND INTERACTION OF SAID EPOXIDE AND EPOXY-SILANE AND (B) AS AN OVERCOAT LAYER A COMPOSITION COMPRISING AN ORGANOSILOXANE AND FROM 0 TO 50 PERCENT OF AN EPOXY-SILANE AS BASED ON THE TOTAL WEIGHT OF THE COMPONENTS IN THE OVERCOAT LAYER, WITH THE PROVISO THAT (1) WHEN SAID OVERCOAT LAYER COMPOSITION IS DEVOID OF EPOXU-SILANE, SAID UNDERCOAT LAYER COMPOSITION CONTAINS ABOUT 25 TO 75 PERCENT EPOXYSILANE AND ABOUT 15 TO ABOUT 40 PERCENT OF SAID CATALYST PRECURSOR, AND (2) WHEN SAID EPOXY-SILANE IS A COMPONENT OF SAID OVERCOAT LAYER COMPOSITION, SAID UNDERCOAT LAYER COMPOSITION CONTAINS ABOUT 1 TO ABOUT 20 PERCENT EPOXYSILANE AND ABOUT 0.5 TO ABOUT 10 PERCENT OF SAID CATLAYST PRECURSOR, ALL PERCENTS BEING BASED ON THE TOTAL WEIGHT OF SAID EPOXIDE MATERIAL IN SAID UNDERCOAT LAYER EXCEPT THE PERCENT OF SAID CATALYST PRECURSOR IN PROVISO (2) IS BASED ON THE TOTAL WEIGHT OF EPOXIDE MOIETY CONTAINING COMPOUNDS IN SAID UNDERCOAT LAYER SAID EPOXY-SILANE IN SAID LAYERS BEING SELECTED FROM COMPOUNDS HAVING THE GENERAL FORMULA OXIRANYL-X-SI(-O-R)(-O-R1)-Y WHEREIN EACH OF X, R AND R1 IS AN ALKYLENE, ALKOXY, ARYLENE, ALKARYLENE, ARALKYLENE, CARBALKOXY OR ETHER GROUP AND Y IS AN ALKOXKY OR EOPXY GROUP; AND SAID ORGANOSILOXANE BEING SILICONE ELASTOMER FORMED BY CURING AND OR POLYMERIZING SILICONE GUM;

Claim 7

AS AN OVERCOAT LAYER, AN ABHESIVE COMPOSITION COMPRISING AN ORGANOSILOXANE AND FROM 0 TO 50 PERCENT OF AN EPOXYSILANE AS BASED ON THE TOTAL WEIGHT OF THE COMPONENTS IN THE OVERCOAT LAYER SAID EPOXY-SILANE IN SAID LAYERS BEING SELECTED FROM COMPOUNDS HAVING THE GENERAL FORMULA OXIRANYL-X-SI(-O-R)(-O-R1)-Y WITH THE PROVISO THAT (1) WHEN SAID OVERCOAT LAYER COMPOSITION IS DEVOID OF EPOXY-SILANE, SAID UNDERCOAT LAYER COMPOSITION CONTAINS ABOUT 25 TO ABOUT 75 PERCENT EPOXY-SILANE AND ABOUT 15 TO ABOUT 40 PERCENT OF SAID CATALYST PRECURSOR, AND (2) WHEN SAID EPOXY-SILANE IS A COMPONENT OF SAID OVERCOAT LAYER COMPOSITION, SAID UNDERCOAT LAYER COMPOSITION CONTAINS ABOUT 1 TO ABOUT 20 PERCENT EPOXY-SILANE AND ABOUT 0.5 TO ABOUT 10 PERCENT OF SAID CATALYST PRECURSOR, ALL PERCENTS BEING BASED ON THE TOTAL WEIGHT OF SAID EPOXIDE MATERIAL IN SAID UNDERCOAT LAYER EXCEPT THE PERCENT OF SAID CATALYST PERCURSOR IN PROVISO (2) IS BASED ON THE TOTAL WEIGHT OF EPOXIDE MOIETY CONTAINING COMPOUNDS IN SAID UNDERCOAT LAYER WHEREIN EACH OF X, R AND R1 IS AN ALKYKENE, ALKOXY, ARYLENE, ALAKARYLENE, ARALKYLENE, CARBALKOXY OR ETHER GROUP AND Y IS AN ALKOXY OR EPOXY GROUP; SAID UNDERCOAT LAYER BECOMING FIRMLY BONDED TO SAID OVERCOAT LAYER THROUGHINTRA- AND INTER-LAYER REACTION UPON EXPOSURE OF SAID COATED SUBSTRATE TO AN ENERGY SOURCE. SAID ORGANOSILOXANE BEING SILICONE ELASTOMER FORMED BY CURING AND OR POLYMERIZING SILICONE GUM; SAID UNDERCOAT LAYER BECOMING FIRMLY BONDED TO SAID OVERCOAT LAYER THROUGH INTRA- AND INTER-LAYER REACTION UPON EXPOSURE OF SAID COATED SUBSTRATE TO AN ENERGY SOURCE.

Claim 8

AS AN OVERCOAT LAYER, AN ABHESIVE COMPOSITION COMPRISING AN ORGANOSILOXANE AND FROM 0 TO 50 PERCENT OF AN EPOXYSILANE AS BASED ON THE TOTAL WEIGHT OF THE COMPONENTS IN THE OVERCOAT LAYER SAID EPOXY-SILANE IN SAID LAYERS BEING SELECTED FROM COMPOUNDS HAVING THE GENERAL FORMULA OXIRANYL-X-SI(-O-R)(-O-R1)-Y WITH THE PROVISO THAT (1) WHEN SAID OVERCOAT LAYER COMPOSITION IS DEVOID OF EPOXY-SILANE, SAID UNDERCOAT LAYER COMPOSITION CONTAINS ABOUT 25 TO ABOUT 75 PERCENT EPOXY-SILANE AND ABOUT 15 TO ABOUT 40 PERCENT OF SAID CATALYST PRECURSOR, AND (2) WHEN SAID EPOXY-SILANE IS A COMPONENT OF SAID OVERCOAT LAYER COMPOSITION, SAID UNDERCOAT LAYER COMPOSITION CONTAINS ABOUT 1 TO ABOUT 20 PERCENT EPOXY-SILANE AND ABOUT 0.5 TO ABOUT 10 PERCENT OF SAID CATALYST PRECURSOR, ALL PERCENTS BEING BASED ON THE TOTAL WEIGHT OF SAID EPOXIDE MATERIAL IN SAID UNDERCOAT LAYER EXCEPT THE PERCENT OF SAID CATALYST PERCURSOR IN PROVISO (2) IS BASED ON THE TOTAL WEIGHT OF EPOXIDE MOIETY CONTAINING COMPOUNDS IN SAID UNDERCOAT LAYER WHEREIN EACH OF X, R AND R1 IS AN ALKYKENE, ALKOXY, ARYLENE, ALAKARYLENE, ARALKYLENE, CARBALKOXY OR ETHER GROUP AND Y IS AN ALKOXY OR EPOXY GROUP; SAID UNDERCOAT LAYER BECOMING FIRMLY BONDED TO SAID OVERCOAT LAYER THROUGHINTRA- AND INTER-LAYER REACTION UPON EXPOSURE OF SAID COATED SUBSTRATE TO AN ENERGY SOURCE. SAID ORGANOSILOXANE BEING SILICONE ELASTOMER FORMED BY CURING AND OR POLYMERIZING SILICONE GUM; SAID UNDERCOAT LAYER BECOMING FIRMLY BONDED TO SAID OVERCOAT LAYER THROUGH INTRA- AND INTER-LAYER REACTION UPON EXPOSURE OF SAID COATED SUBSTRATE TO AN ENERGY SOURCE.

Claim 9

as an overcoat layer, an abhesive compisition comprising an organosiloxane and from 0 to 50 percent of an epoxy-silane as based on the total weight of the components in the overcoat layer said epoxy-silane in said layers being selected from compounds having the general formula

Claim 10

as an overcoat layer, an abhesive compisition comprising an organosiloxane and from 0 to 50 percent of an epoxy-silane as based on the total weight of the components in the overcoat layer said epoxy-silane in said layers being selected from compounds having the general formula

Claim 11

A presensitized printing plate as claimed in claim 1 wherein said catalyst precursor is 2,5-diethoxy-4-(p-tolylthio)-benzenediazonium hexafluorophosphate.

Claim 12

EXPOSING AT LEAST A PORTION OF SAID COATED SUBSTRATE TO AN ENERGY SOURCE THROUGH AN ARTICLE HAVING OPAQUE AND TRANSPARENT AREAS TO EFFECT SAID POLYMERIZATION AND INTERACTION AND TO RENDER THE EXPOSED AREAS OF SAID COATED SUBSTRATE INSOLUBLE AND

Claim 13

EXPOSING AT LEAST A PORTION OF SAID COATED SUBSTRATE TO AN ENERGY SOURCE THROUGH AN ARTICLE HAVING OPAQUE AND TRANSPARENT AREAS TO EFFECT SAID POLYMERIZATION AND INTERACTION AND TO RENDER THE EXPOSED AREAS OF SAID COATED SUBSTRATE INSOLUBLE AND

Claim 14

exposing at least a portion of said coated substrate to an energy source through an article having opaque and transparent areas to effect sAid polymerization and interaction and to render the exposed areas of said coated substrate insoluble and

Claim 15

exposing at least a portion of said coated substrate to an energy source through an article having opaque and transparent areas to effect sAid polymerization and interaction and to render the exposed areas of said coated substrate insoluble and

Claim 16

an overcoat layer comprising an organo-siloxane and from 0 to 50% of an epoxy-silane as based on the total weight of the components in the overcoat layer; with the proviso that (1) when said overcoat layer composition is devoid of epoxy-silane, said undercoat layer composition contains about 25 to about 75 percent epoxy-silane and about 15 to about 40 percent of said catalyst precursor, and (2) when said epoxy-silane is a component of said overcoat layer composition, said undercoat layer composition contains about 1 to about 20 percent epoxy-silane and about 0.5 to about 10 percent of said catalyst precursor, all percents being based on the total weight of said epoxide material in said undercoat layer except the percent of said catalyst precursor in proviso (2) is based on the total weight of epoxide moiety containing compounds in said undercoat layer and about 15 to 40 percent catalyst precursor, based on the weight of the epoxide material, when said overcoat layer as applied is devoid of epoxy-silane; said epoxy-silane in said layers being selected from compounds having the general formula

Claim 17

an overcoat layer comprising an organo-siloxane and from 0 to 50% of an epoxy-silane as based on the total weight of the components in the overcoat layer; with the proviso that (1) when said overcoat layer composition is devoid of epoxy-silane, said undercoat layer composition contains about 25 to about 75 percent epoxy-silane and about 15 to about 40 percent of said catalyst precursor, and (2) when said epoxy-silane is a component of said overcoat layer composition, said undercoat layer composition contains about 1 to about 20 percent epoxy-silane and about 0.5 to about 10 percent of said catalyst precursor, all percents being based on the total weight of said epoxide material in said undercoat layer except the percent of said catalyst precursor in proviso (2) is based on the total weight of epoxide moiety containing compounds in said undercoat layer and about 15 to 40 percent catalyst precursor, based on the weight of the epoxide material, when said overcoat layer as applied is devoid of epoxy-silane; said epoxy-silane in said layers being selected from compounds having the general formula

Claim 18

as an overcoat layer, an organosiloxane; said undercoat layer becoming firmly bonded to said overcoat layer through intra-and inter-layer reaction upon exposure of said coated substrate to an energy source.

Claim 19

as an overcoat layer, an organosiloxane; said undercoat layer becoming firmly bonded to said overcoat layer through intra-and inter-layer reaction upon exposure of said coated substrate to an energy source.

Claim 20

as an overcoat layer, an organosiloxane in admixture with from about 10 to 50% by weight of an epoxy-silane as based on the total weight of the components in the overcoAt layer, said epoxy-silane in said layers being selected from compounds having the general formula

Claim 21

as an overcoat layer, an organosiloxane in admixture with from about 10 to 50% by weight of an epoxy-silane as based on the total weight of the components in the overcoAt layer, said epoxy-silane in said layers being selected from compounds having the general formula

Claim 22

REMOVING SAID UNEXPECTED AREAS OF SAID COATED SUBSTRATE.

Claim 23

REMOVING SAID UNEXPECTED AREAS OF SAID COATED SUBSTRATE.

Claim 24

A presensitized printing plate as claimed in claim 1 wherein said epoxide material is selected from the group consisting of epoxy-novolacs and glycidyl ethers of bisphenol A.

Claim 25

removing said unexposed areas of said coated substrate.

Claim 26

removing said unexposed areas of said coated substrate.

Claim 27

A presensitized plate as claimed in claim 2 wherein said epoxy-silane is glycidoxypropyltrimethoxy silane.

Claim 28

A presensitized plate as claimed in claim 1 wherein said overcoat layer as applied is devoid of epoxy-silane.

Claim 29

A presensitized plate as claimed in claim 5 wherein said epoxy-silane present in said undercoat is glycidoxy-propyltrimethoxysilane.

Claim 30

A presensitized plate as claimed in claim 6 wherein said catalyst precursor is 2,5-diethoxy-4(p-tolylthio)-benzenediazonium hexafluorophosphate.

Claim 31

A presensitized plate as claimed in claim 1 wherein said overcoat layer comprises from about 10 to 50% by weight of said epoxy-silane.

Claim 32

A presensitized plate as claimed in claim 8 wherein said epoxy-silane is glycidoxypropyltrimethoxysilane.

Claim 33

A presensitized plate as claimed in claim 9 wherein said catalyst precursor is 2,5-diethoxy-4-(p-tolylthio) benzenediazonium hexafluorophosphate.

Claim 34

A presensitized plate as claimed in claim 1 wherein said substrate is metal, plastic or paper.

Claim 35

A presensitized printing plate capable of being imaged comprising a substrate having applied thereto:

Claim 36

A presensitized printing plate capable of being imaged comprising a substrate having applied thereto:

Claim 37

A presensitized printing plate capable of being imaged comprising a substrate having applied thereto:

Claim 38

A presensitized printing plate capable of being imaged comprising a substrate having applied thereto:

Claim 39

A positive working, planographic printing plate, suitable for accepting ink only in oleophilic areas and printing therefrom while rejecting ink in oleophobic non-printing areas, in the absence of dampening, which comprises: a base substrate having on at least one of its surfaces oleophilic printing areas and oleophobic non-printing areas; said oleophobic non-printing areas consisting of an abhesive, polymerized solvent-insoluble reaction product of

Claim 40

A positive working, planographic printing plate, suitable for accepting ink only in oleophilic areas and printing therefrom while rejecting ink in oleophobic non-printing areas, in the absence of dampening, which comprises: a base substrate having on at least one of its surfaces oleophilic printing areas and oleophobic non-printing areas; said oleophobic non-printing areas consisting of an abhesive, polymerized solvent-insoluble reaction product of

Claim 41

A planographic printing plate as claimed in claim 14 wherein said catalyst precursor is 2,5-diethoxy-4(p-tolylthio) benzene diazonium hexafluorophosphate.

Claim 42

A planographic printing plate as claimed in claim 14 wherein said substrate is metal, plastic or paper.

Claim 43

A planographic printing plate as claimed in claim 14 wherein said epoxide material is selected from the group consisting of epoxy-novolacs and glycidyl ethers of bisphenol A.

Claim 44

A planographic printing plate as claimed in claim 16 wherein said epoxy-silane is glycidoxypropyltrimethoxy silane.

Claim 45

A planographic printing plate as claimed in claim 14 wherein said overcoat layer comprises from about 10 to 50% by weight of said epoxy-silane.

Claim 46

A planographic printing plate as claimed in claim 19 wherein said epoxy-silane is glycidoxypropyltrimethoxysilane.

Claim 47

A planographic printing plate as claimed in claim 19 wherein said catalyst precursor is 2,5-diethoxy-4-(p-tolylthio) benzene diazonium hexaflourophosphate.

Claim 48

A planographic printing plate as claimed in claim 14 wherein said overcoat layer as applied is devoid of epoxy-silane.

Claim 49

A planographic printing plate as claimed in claim 22 wherein said epoxy-silane present in said undercoat is glycidoxypropyltrimethoxy silane.

Claim 50

A planographic printing plate as claimed in claim 23 wherein said catalyst precursor is 2,5-diethoxy-4-(p-tolyltio) benzene diazonium hexfluorophosphate.

Claim 51

A planographic printing plate as claimed in claim 14 in which the oleophilic printing areas consist of the bare base substrate.

Claim 52

A planographic printing plate as claimed in claim 14 in which the oleophilic printing areas consist of the cured undercoat layer.

Claim 55

A method as claimed in claim 27 wherein said energy source is electromagnetic radiation.

Claim 56

A method as claimed in claim 27 wherein said energy source is electron beam irradiation.

Claim 57

A method as claimed in claim 27 wherein said catalyst precursor is 2,5-diethoxy-4(p-tolylthio)-benzenediazonium hexafluorophosphate.

Claim 58

A method as claimed in claim 27 wherein said epoxide is selected from the group consisting of epxoy-novolacs and glycidyl ethers of bis-phenol A.

Claim 59

A method as claimed in claim 27 wherein said overcoat layer solution as applied is devoid of epxoy-silane.

Claim 60

A method as claimed in claim 27 wherein prior to the exposure to said energy source the coated substrate is permitted to react with atmospheric moisture.

Claim 61

A method as claimed in claim 27 wherein after exposure to said energy source but prior to removal of unexposed areas, the coated substrate is subjected to heat.

Claim 62

A method as claimed in claim 27 wherein said unexposed areas of the coated substrate are removed by a solvent or mixtures thereof.

Claim 63

A method as claimed in claim 27 wherein said overcoat layer solution contains from about 10 to about 50 percent by weight of said epoxy-silane.

Claim 64

A method as claimed in claim 36 wherein said epoxy-silane is glycidoxypropyltrimethoxysilane.

Claim 65

A method as claimed in claim 27 wherein said unexposed areas are removed employing a solvent which removes the organosiloxane but in which the epoxide material is insoluble.

Claim 66

A method as claimed in claim 38 wherein said solvent is cyclohexane.

Claim 67

A method as claimed in claim 38 wherein subsequent to removal of the organosiloxane, the coated substrate is exposed to an energy source to cure the epoxide material in the initially unexposed area.