Negative image diazography formulation with acid labile coupler, diazonium compound and carboxylic acid anhydride

Claim 2

A negative-working, light-sensitive diazography formulation comprising (i) at least one diazonium compound D capable of forming an organic azo dyestuff D--YOH or D--Y'OH, (ii) at least one acid labile blocked-coupler adapted to be converted in the presence of acid into an active azo-coupling species YOH or Y'OH, said blocked-coupler being chemically inert with respect to said diazonium compound D and having the structural formula Y--O--B, wherein Y--O-- is the residue of said active azo-coupling species YOH and further wherein the residue --O--B is an acid labile oxygen bridged blocking moiety B defining a radical selected from the group consisting of tertiary ether, acetal, ketal and MEM ether, (iii) at least one light-sensitive acid progenitor adapted to photolytically generate an acid species capable of unblocking said blocked-coupler Y--O--B to convert same into said active azo-coupling component YOH, or rearrangement derivative Y'OH thereof, and (iv) at least one carboxylic acid anhydride adapted to inactivate, when subjected to alkaline developing conditions, unreacted diazonium compound remaining in the unexposed portions of the formulation after imagewise exposure to light.

Claim 3

A negative-working, light-sensitive diazography formulation comprising (i) at least one light-sensitive salt of a diazonium compound D capable of forming an organic azo dyestuff D--YOH or D--Y'OH, said salt being adapted to photolytically generate an acid species capable of unblocking the below blocked-coupler Y--O--B (ii) to convert same into an active azo-coupling component YOH or Y'OH, (ii) at least one acid labile blocked-coupler adapted to be converted in the presence of said acid species into said active azo-coupling component YOH or rearrangement derivative Y'OH thereof, said blocked-coupler being chemically inert with respect to said salt of said diazonium compound D and having the structural formula Y--O--B, wherein Y--O-- is the residue of said active azo-coupling species YOH and further wherein the residue --O--B is an acid labile oxygen bridged blocking moiety B defining a radical selected from the group consisting of tertiary ether, acetal, ketal and MEM ether, and (iii) at least one carboxylic acid anhydride adapted to inactivate, when subjected to alkaline developing conditions, unreacted diazonium compound remaining in the unexposed portions of the formulation after imagewise exposure to light.

Claim 4

A negative-working, light-sensitive diazography formulation comprising (i) at least one light-sensitive salt of a diazonium compound D capable of forming an organic azo dyestuff D--YOH or D--Y'OH, said salt being adapted to photolytically generate an acid species capable of unblocking the below blocked-coupler Y--O--B (ii) to convert same into an active azo-coupling component YOH or Y'OH, (ii) at least one acid labile blocked-coupler adapted to be converted in the presence of said acid species into said active azo-coupling component YOH or rearrangement derivative Y'OH thereof, said blocked-coupler being chemically inert with respect to said salt of said diazonium compound D and having the structural formula Y--O--B, wherein Y--O-- is the residue of said active azo-coupling species YOH and further wherein the residue --O--B is an acid labile oxygen bridged blocking moiety B defining a radical selected from the group consisting of tertiary ether, acetal, ketal and MEM ether, and (iii) at least one carboxylic acid anhydride adapted to inactivate, when subjected to alkaline developing conditions, unreacted diazonium compound remaining in the unexposed portions of the formulation after imagewise exposure to light.

Claim 5

The diazography formulation as defined by claim 2 wherein said salt (i) is a diazo salt comprising a complex anion of a Lewis acid.

Claim 6

The diazography formulation as defined by claim 1 or 2 wherein said acid labile blocked-coupler has the structural formula: ##STR86## wherein each R, which may be the same or different, is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, aralkyl, alkaryl, aralkenyl, and alkenylaryl, and Y is aryl.

Claim 7

The diazography formulation as defined by claim 4 wherein each R is selected from the group consisting of alkyl and aryl.

Claim 8

The diazography formulation as defined by claim 1 or 2 wherein said acid labile blocked-coupler has the structural formula: ##STR87## wherein R 4 and R 5 , which may be the same or different, are selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, aralkyl, alkaryl, aralkenyl and alkenylaryl, R 5 may also be hydrogen, and Y is aryl.

Claim 9

The diazography formulation as defined by claim 6 wherein R 4 and R 5 are selected from the group consisting of alkyl and aryl.

Claim 10

The diazography formulation as defined by claim 1 or 2 wherein said acid labile blocked-coupler has the structural formula: ##STR88## wherein R 6 , R 7 and R 8 , which may be the same or different, are selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, aralkyl, alkaryl, aralkenyl and alkenylaryl, and Y is aryl.

Claim 11

The diazography formulation as defined by claim 8 wherein R 6 , R 7 and R 8 are selected from the group consisting of alkyl and aryl.

Claim 12

The diazography formulation as defined by claim 1 or 2 wherein said acid labile blocked-coupler has the structural formula: ##STR89## wherein each R 1 , R 2 and R 3 , which may be the same or different, is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, aralkyl, alkaryl, aralkenyl and alkenylaryl, Y is aryl, and A is any bridging linkage.

Claim 13

The diazography formulation as defined by claim 10 wherein each R 1 , R 2 and R 3 is selected from the group consisting of alkyl and aryl.

Claim 14

The diazography formulation as defined by claim 1 or 2 wherein said acid labile blocked-coupler has the structural formula: Y--O--CH.sub.2 --O--CH.sub.2 CH.sub.2 --OCH.sub.3 wherein Y is aryl.

Claim 15

The diazography formulation as defined by claim 1 or 2 wherein said acid labile blocked-coupler has the structural formula: ##STR90## wherein Y is aryl and A is any bridging linkage.

Claim 16

The diazography formulation as defined by claim 1 or 2 wherein said acid labile blocked-coupler is selected from the group consisting of 1-naphthyl triphenylmethyl ether; 1-methylcyclopentyl 1-naphthyl ether; 1-butoxy-1-(1-naphthoxy)ethane; t-butyl phenyl ether; 2-(1-naphthoxy)-2-methylbutane; 1-(1-butoxy)-1-(1-naphthoxy)ethane; 1,2-bis(5-t-butoxy-1-naphthyl)ethane; dibenzo(d,f)-2,2-dimethyl-1,3-dioxepine; dibenzo(d,f)-2-methyl-2-phenyl-1,3-dioxepine; dibenzo(d,f)-2,2-diphenyl-1,3-dioxepine; 2,2'-di(2-tetrahydropyranoxy)diphenyl; 2,3-isopropylidenedioxynaphthalene, t-butyl 1-naphthyl ether; 1-naphthyl 2-tetrahydropyranyl ether; benzo(e)-2-phenyl-1,3-dioxin; 1-t-butoxy-5-benzylnaphthalene; t-butyl (4-bromo-1-naphthyl) ether; dibenzo(d,f)-2-methyl-1,3-dioxepine; and β-methoxyethoxymethyl α-naphthyl ether.

Claim 17

The diazography formulation as defined by claim 1 or 2 wherein said acid labile blocked-coupler is t-butyl 1-naphthyl ether.

Claim 18

The diazography formulation as defined by claim 2 wherein said light-sensitive salt comprises an anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, pentachlorobismuthate, stannous chloride and chlorozincate.

Claim 19

The diazography formulation as defined by claim 16 wherein said anion is hexafluorophosphate.

Claim 20

The diazography formulation as defined by claim 1 or 2 wherein said carboxylic acid anhydride is selected from the group consisting of substituted and unsubstituted maleic, succinic, glutaric, isatoic, naphthoic, phthalic, mellitic, acetic, glycolic, benzoic and butyric anhydrides.

Claim 21

The diazography formulation as defined by claim 1 or 2 wherein said carboxylic acid anhydride is selected from the group consisting of substituted and unsubstituted maleic anhydrides.

Claim 22

The diazography formulation as defined by claim 1 or 2 wherein said carboxylic acid anhydride is 2,3-dimethylmaleic anhydride.

Claim 23

The diazography formulation as defined by claim 1 or 2 wherein said carboxylic acid anhydride is trimellitic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, or a mixture thereof.

Claim 24

The diazography formulation as defined by claim 14 wherein said carboxylic acid anhydride is selected from the group consisting of substituted and unsubstituted maleic, succinic, glutaric, isatoic, naphthoic, phthalic, mellitic, acetic, glycolic, benzoic and butyric anhydrides.

Claim 25

The diazography formulation as defined by claim 14 wherein said carboxylic acid anhydride is 2,3-dimethylmaleic anhydride, trimellitic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, or a mixture thereof.

Claim 26

The diazography formulation as defined by claim 2 wherein said acid labile blocked-coupler is t-butyl 1-naphthyl ether, said light-sensitive salt comprises an anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate pentachlorobismuthate, stannous chloride and chlorozincate, and said carboxylic acid anhydride is selected from the group consisting of substituted and unsubstituted maleic, succinic, glutaric, isatoic, naphthoic, phthalic, mellitic, acetic, glycolic, benzoic and butyric anhydrides.

Claim 27

The diazography formulation as defined by claim 24 wherein said anion is hexafluorophosphate and said carboxylic acid anhydride is 2,3-dimethylmaleic anhydride, trimellitic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, or a mixture thereof.

Claim 28

A light-sensitive diazotype photoreproduction material comprising a support member coated with the diazography formulation as defined by claim 1, 2, 3, 16, 17, 24 or 25.

Claim 29

A light-sensitive diazophotoreproduction material comprising a support member coated with the diazography formulation as defined by claim 14.

Claim 30

A light-sensitive diazophotoreproduction material comprising a support member coated with the diazography formulation as defined by claim 18.

Claim 31

The photoreproduction material as defined by claim 26, said support member being a film substrate.

Claim 32

The photoreproduction material as defined by claim 29, said diazography formulation including a resin matrix.

Claim 33

A negative-working diazography photoreproduction process comprising imagewise exposing the diazotype material as defined by claim 26 to light of a quality and quantity sufficient to photochemically liberate catalytic amounts of acid therefrom, thus unblocking coupler molecules, and thence developing said diazotype material under alkaline conditions such that active azo-coupling species couple with undecomposed diazonium compound in the light-struck areas to form azo dye while unreacted diazonium compound remaining in the areas not exposed to light is inactivated.

Claim 34

A negative-working diazography photoreproduction process comprising imagewise exposing the diazotype material as defined by claim 26 to light of a quality and quantity sufficient to photochemically liberate catalytic amounts of acid therefrom, thus unblocking coupler molecules, heating the thus-exposed diazotype material, and thence developing said diazotype material under alkaline conditions such that active azo-coupling species couple with undecomposed diazonium compound in the light-struck areas to form azo dye while unreacted diazonium compound remaining in the areas not exposed to light is inactivated.

Claim 35

The process as defined by claim 32 wherein the diazotype material is heated during development.

Claim 36

The diazography formulation as defined by claim 1 or 2, said acid labile blocked-coupler having the structural formula: ##STR91##

Claim 37

The diazography formulation as defined by claim 1 or 2, said acid labile blocked-coupler having the structural formula: ##STR92##

Claim 38

The diazography formulation as defined by claim 1 or 2, said acid labile blocked-coupler having the structural formula: ##STR93##

Claim 39

The diazography formulation as defined by claim 1 or 2, said acid labile blocked-coupler having the structural formula: ##STR94##

Claim 40

The diazography formulation as defined by claim 1 or 2, said acid labile blocked-coupler having the structural formula: ##STR95##

Claim 41

The diazography formulation as defined by claim 1 or 2, said acid labile blocked-coupler having the structural formula: ##STR96##

Claim 42

The diazography formulation as defined by claim 1 or 2, the diazonium compound/salt including a cation selected from the group consisting of p-chlorobenzenediazonium; 2,4-dichlorobenzenediazonium; 2,5-dichlorobenzenediazonium; 2,4,6-trichlorobenzenediazonium; p-methoxybenzenediazonium; o-methoxybenzenediazonium; 2-chloro-4-(dimethylamino)-5-methoxybenzenediazonium; 4-chloro-2,5-dimethoxybenzenediazonium; 2,4,5-triethoxy-4-biphenyldiazonium-[2,5-diethoxy-4-(p-ethoxyphenyl)benzenediazonium]; 2,5-dimethoxy-4'-methyl-4-biphenyldiazonium[2,5-dimethoxy-4-(p-tolyl)benzenediazonium]; 2,5-diethoxy-4-(phenylthio)benzenediazonium; 2,5-diethoxy-4-(p-tolylthio)qbenzenediazonium; p-morpholinobenzenediazonium; 2,5-dichloro-4-morpholinobenzenediazonium; 2,5-dimethoxy-4-morpholinobenzenediazonium; and 4-(dimethylamino)naphthalenediazonium.