Thermal recording method

Claim 2

A THERMAL RECORDING MEMBER USEFUL FOR FORMING A REVERSIBLE LATENT IMAGE BY HEATING WHICH IS CAPABLE, OF BEING DEVELOPED INTO A PERMANENT VISIBLE IMAGE, SAID RECORDING MEMBER, COMPRISING A SUPPORT HAVING THEREON A UNIFORM AND TRANSPARENT RECORDING LAYER COMPOSED OF A HEAT-SENSITIVE COMPOSITION WHICH COMPRISES A POLYMER COMPLEX INCLUDING A POLYMER MOIETY WHICH IS NORMALLY DYEABLE AT ROOM TEMPERATURE BUT WHICH, IN THE POLYMER COMPLEX, IS DYEABLE ONLY AFTER HEATING THE COMPLEX TO AN ELEVATED TEMPERATURE, WHEREIN SAID POLYMER COMPLEX IS A COMPLEX OF A POLYMER (A) AND A POLYMER (B), AND WHEREIN SAID POLYMER (A) IS A DYEABLE POLYMER SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS AND COPOLYMERS

Claim 3

A thermal recording member according to claim 1 wherein said polymer (A) is a homopolymer of one of said group, a copolymer of more than one of said group or a copolymer of one of said group with a different vinyl monomer.

Claim 4

A thermal recording member according to claim 2 wherein said different vinyl monomer is selected from the group consisting of methacrylates, acrylates, acrylamides, acrylonitrile, vinyl ethers, vinyl acetate, vinyl imidazoles and ethylene.

Claim 5

A thermal recording member accroding to claim 1 in which said polymer (A) is selected from the group consisting of homopolymers and copolymers of N-vinyl pyrrolidone, N-vinyl-3-methyl pyrrolidone, N-vinyl-5-methyl pyrrolidone, N-vinyl-3,3,5-trimethyl pyrrolidone, N-vinyl-3-benzylpyrrolidone, N-vinyl piperidone, N-vinyl-4-methyl piperidone, N-vinyl caprolactam, N-vinyl capryllactam, N-vinyl-3-morpholinone, N-vinyl thiopyrrolidone, N-vinyl-2 pyriodone, N-vinyl-2-oxazolidone, N-vinyl-5-methyl-2-oxazolidone, N-vinyl-5-ethyl-2-oxazolidone, N-vinyl-4-methyl-2-oxazolidone, N-vinyl-2-thio-oxazolidone, N-vinyl-2-mercaptobenzothiazole, N-vinyl imidazole, N-vinyl-2-methyl imidazole, N-vinyl-4-methyl imidazole, ethylene oxide, propylene oxide, methacrylamide, acrylamide, N-methyl acrylamide, N-n-butyl acrylamide, N-benzyl acrylamide, 2-vinylpyridine and 4-vinyl pyridine.

Claim 6

A thermal recording member according to claim 1 in which said polymer (B) is selected from the group consisting of polyesters obtained by reacting an aliphatic polyhydric carboxylic acid and diols, acid cellulose derivatives, an acid polyvinyl polymer, an acrylic acid polymer, a methacrylic acid polymer, an Alpha , Beta -unsaturated acid polymer, acid polyvinyl alcohol derivatives, cellulose ethers, a phenolic resin, a cresol-formaldehyde resin and a phenoxyacetic acidformaldehyde resin.

Claim 7

A thermal recording member according to claim 1, in which said polymer (B) is selected from the group consisting of homopolymers and copolymers of maleic anhydride, maleic anhydride mono-esters and maleic anhydride mono-amides.

Claim 8

A thermal recording member according to claim 1 in which said polymer (B) is selected from the group consisting of copolymers of (1) and Alpha , Beta -unsaturated acid selected from the group consisting of maleic anhydride, maleic anhydride mon-esters, maleic anhydride mono-amides, itaconic anhydride, citraconic anhydride and diester fumarate, and (2) a vinyl monomer selected from the group consisting of vinyl acetate, vinyl ethers, acrylamide, vinyl esters, ethylene and acrylic esters.

Claim 9

A thermal recording member according to claim 1 in which said polymer (B) is selected from the group consisting of methyl vinyl ether/maleic acid copolymers, methyl vinyl ether/maleic acid mono n-butyl ester copolymers, methyl vinyl ether/maleic acid mono-N-n-hexylamide copolymers, methyl vinyl ether/maleic acid mono-n-octyl ester copolymers, methyl vinyl ether/maleic acid mono-n-octadecyl ester copolymers, n-butyl vinyl ether/maleic acid mono-amide copolymers, n-butyl vinyl ether/maleic acid mono-N-i-propyl amide copolymers, methyl vinyl ether/maleic acid mono-N-methyl-N-octadecyl amide copolymers, n-butyl vinyl ether/maleic acid mono-N-methyl amide copolymers, n-butyl ether/maleic acid mono ethyl ester copolymers, vinyl acetate/maleic acid mon-ethyl ester copolymers, methyl cellulose hydrogen succinate, benzyl cellulose hydrogen succinate, p-sulfobenzene cellulose acetatE, ethyl hydroxyethyl cellulose, mono-ammonium salts of methyl vinyl ether/maleic acid copolymers, mono-N-methyl ammonium salts of methyl vinyl ether/maleic acid copolymers, hydroxyethyl cellulose, resol-type phenol formaldehyde resins and succinic acid monobenzyl esters.

Claim 10

A thermal recording member according to claim 1 in which the heat-sensitive composition further contains a proton acceptor or a proton donor.

Claim 11

A thermal recording member according to claim 9, in which the proton acceptor is selected from the group consisting of:

Claim 12

A thermal recording member according to claim 9 in which the proton donor is selected from the group consisting of FH, HCl, R-COOH, C6H5OH, C6H5NHCOCH3, RCONHR'', C2H5NHC2H5, RCONH2, H2O, Cl3CH, C6H5-NH-C6H5, (CH2)2NH, C6H5NH2 and C6H5CH2NH2, wherein R and R'' are each alkyl or aryl.

Claim 13

A thermal recording member according to claim 1 in which the heat-sensitive composition further contains an aliphatic or aromatic ketone which is non-volatile at room temperature.

Claim 14

A thermal recording member according to claim 1 in which the heat-sensitive composition further contains a member selected from the group consisting of Alpha -chloroanthraquinone, benzophenone, p-dimethyl-aminobenzaldehyde, 9-fluorene carboxylic acid, p-nitro phenol, Michler''s ketone, p-nitro phenyl acetate, p-benzoquinone, benzhydrol and benzoin.

Claim 15

A thermal recording member useful for forming a reversible latent image by heating which is capable of being developed into a permanent visible image, said recording member having a uniform and transparent heat-sensitive recording layer which comprises a polymer complex of a polymer (A) and a polymer (B); wherein said polymer (A) is selected from the group consisting of poly-N-vinyl pyrrolidone, N-vinyl pyrrolidone/vinyl acetate copolymers, poly-N-vinyl-5-methyl-2-oxazolidone, N-vinyl-5-methyl-2-oxazolidone/vinyl acetate copolymers, poly-N-vinyl piperidone, poly-N-vinyl caprolactam, poly-N-vinyl morpholinone, poly-N-vinyl-2-oxazolidone, polyn-N-vinyl imidazole, poly-4-vinyl pyridine, polyethylene oxide and poly-N-octyl pyrrolidone, and wherein said polymer (B) is selected from the group consisting of methyl vinyl ether/maleic acid copolymers, methyl vinyl ether/maleic acid mono-n-butyl ester copolymers, methyl vinyl ether/maleic acid mono-N-n-hexylamide copolymers, methyl vinyl ether/maleic acid mono-n-octyl ester copolymers, methyl vinyl ether/maleic acid mono-n-octadecyl ester copolymers, n-butyl vinyl ether/maleic acid mono-amide copolymers, n-butyl vinyl ether/maleic acid mono-N-i-propyl amide copolymers, methyl vinyl ether/maleic acid mono-N-methyl-N-octadecyl amide copolymers, n-butyl vinyl ether/maleic acid mono-N-methyl amide copolymers, n-butyl vinyl ether/maleic acid mono ethyl ester copolymers, vinyl acetate/maleic acid mono ethyl ester copolymers, methyl cellulose hydrogen succinate, benzyl cellulose hydrogen succinate, p-sulfobenzene cellulose acetate, ethyl hydroxy ethyl cellulose, mono-ammonium salts of methyl vinyl ether/maleic acid copolymers, mono-N-methyl ammonium salts of methyl vinyl ether/maleic acid copolymers, hydroxy ethyl cellulose, resol-type phenol formaldehyde resins and succinic acid monobenzyl ester.

Claim 16

A thermal recording member useful for forming a reversible latent image by heating which is capable of being developed into a permanent visible image, said recording member having a uniform and transparent heat-sensitive recording layer which comprises a polymer complex of a polymer (A) and a polymer (B); wherein said polymer (A) is selected from the group consisting of poly-N-vinyl pyrrolidone, N-vinyl pyrrolidone/vinyl acetate copolymers, poly-N-vinyl-5-methyl-2-oxazolidone, N-vinyl-5-methyl-2-oxazolidone/vinyl acetate copolymers, poly-N-vinyl piperidone, poly-N-vinyl caprolactam, poly-N-vinyl morpholinone, poly-N-vinyl-2-oxazolidone, polyn-N-vinyl imidazole, poly-4-vinyl pyridine, polyethylene oxide and poly-N-octyl pyrrolidone, and wherein said polymer (B) is selected from the group consisting of methyl vinyl ether/maleic acid copolymers, methyl vinyl ether/maleic acid mono-n-butyl ester copolymers, methyl vinyl ether/maleic acid mono-N-n-hexylamide copolymers, methyl vinyl ether/maleic acid mono-n-octyl ester copolymers, methyl vinyl ether/maleic acid mono-n-octadecyl ester copolymers, n-butyl vinyl ether/maleic acid mono-amide copolymers, n-butyl vinyl ether/maleic acid mono-N-i-propyl amide copolymers, methyl vinyl ether/maleic acid mono-N-methyl-N-octadecyl amide copolymers, n-butyl vinyl ether/maleic acid mono-N-methyl amide copolymers, n-butyl vinyl ether/maleic acid mono ethyl ester copolymers, vinyl acetate/maleic acid mono ethyl ester copolymers, methyl cellulose hydrogen succinate, benzyl cellulose hydrogen succinate, p-sulfobenzene cellulose acetate, ethyl hydroxy ethyl cellulose, mono-ammonium salts of methyl vinyl ether/maleic acid copolymers, mono-N-methyl ammonium salts of methyl vinyl ether/maleic acid copolymers, hydroxy ethyl cellulose, resol-type phenol formaldehyde resins and succinic acid monobenzyl ester.

Claim 17

A thermal recording member useful foR forming a reversible latent image by heating which is capable of being developed into a permanent visible image, said recording member having a uniform heat-sensitive recording layer which comprises a polymer complex of poly-N-vinyl pyrrolidone and a methyl vinyl ether/maleic acid mono-n-butyl ester copolymer.

Claim 18

A thermal recording member useful foR forming a reversible latent image by heating which is capable of being developed into a permanent visible image, said recording member having a uniform heat-sensitive recording layer which comprises a polymer complex of poly-N-vinyl pyrrolidone and a methyl vinyl ether/maleic acid mono-n-butyl ester copolymer.

Claim 19

A thermal recording method which comprises forming a reversible latent image by applying a thermal pattern to a recording member having a uniform and transparent heat-sensitive layer which contains a polymer complex of a polymer (A) and a polymer (B), said polymer (A) being selected from the group consisting of homopolymers and copolymers of N-vinyl lactams, N-vinyl cyclic carbamates, N-vinyl imidazoles, vinyl pyridines, alkylene oxides and acrylamides, and said polymer (B) being selected from the group consisting of polymers having a carboxylic acid radical, a sulfonic acid radical or an OH radical, and then contacting said heat-sensitive layer with a dye solution to convert said reversible latent image into a permanent visible image.

Claim 20

A thermal recording method which comprises forming a reversible latent image by applying a thermal pattern to a recording member having a uniform and transparent heat-sensitive layer which contains a polymer complex of a polymer (A) and a polymer (B), said polymer (A) being selected from the group consisting of homopolymers and copolymers of N-vinyl lactams, N-vinyl cyclic carbamates, N-vinyl imidazoles, vinyl pyridines, alkylene oxides and acrylamides, and said polymer (B) being selected from the group consisting of polymers having a carboxylic acid radical, a sulfonic acid radical or an OH radical, and then contacting said heat-sensitive layer with a dye solution to convert said reversible latent image into a permanent visible image.

Claim 21

A thermal recording method according to claim 16 in which said dye solution is an aqueous dye solution.

Claim 22

A thermal recording method according to claim 16 in which said dye is selected from the group consisting of triphenylmethane dyes, xanthene dyes, mono azo dyes, anthraquinone dyes and ketoimine type dyes.

Claim 23

A thermal recording method according to claim 16 in which said polymer (A) is selected from the group consisting of homopolymers and copolymers of N-vinyl pyrrolidone, N-vinyl-3-methyl pyrrolidone, N-vinyl-5-methyl pyrrolidone, N-vinyl-3,3,5-trimethyl pyrrolidone, N-vinyl-3-benzyl-pyrrolidone, N-vinyl piperidone, N-vinyl-4-methyl piperidone, N-vinyl caprolactam, N-vinyl capryllactam, N-vinyl-3-morpholinone, N-vinyl thiopyrrolidone, N-vinyl-2-pyridone, N-vinyl-2-oxazolidone, N-vinyl-5-methyl-2-oxazolidone, N-vinyl-5-ethyl-2-oxazolidone, N-vinyl-4-methyl-2-oxazolidone, N-vinyl-2-thiooxazolidone, N-vinyl-2-mercaptobenzothiazole, N-vinyl imidazole, N-vinyl-2-methyl imidazole, N-vinyl-4-methyl imidazole, ethylene oxide, propylene oxide, methacrylamide, acrylamide, N-methyl acrylamide, N-n-butyl acrylamide, N-benzyl acrylamide, 2-vinylpyridone and 4-vinyl pyridine.

Claim 24

A thermal recording method according to claim 16 in which said polymer (B) is selected from the group consisting of homopolymers and copolymers of maleic anhydride, maleic anhydride mono-esters and maleic anhydride mono-amides.

Claim 25

A thermal recording method according to claim 16 in which said polymer (B) is selected from the group consisting of copolymers of (1) an Alpha , Beta -unsaturated acid selected from the group consisting of maleic anhydride, maleic anhydride mono-esters, maleic anhydride mono-amides, itaconic anhydride, citraconic anhydride and diester fumarate, and (2) a vinyl monomer selected from the group consisting of vinyl acetate, vinyl ethers, acrylamide, vinyl esters, ethylene and acrylic esters.

Claim 26

A thermal recording method according to claim 16 in which said polymer (B) is selected from the group consisting of methyl vinyl ether/maleic acid copolymers, methyl vinyl ether/maleic acid mono-n-butyl ester copolymers, methyl vinyl ether/maleic acid mono-N-n-hexylamide copolymers, methyl vinyl ether/maleic acid mono-n-octyl ester copolymers, methyl vinyl ether/maleic acid mono-n-octadecyl ester copolymers, n-butyl vinyl ether/maleic acid mon-amide copolymers, n-butyl vinyl ether/maleic acid mono-N-i-propyl amide copolymers, methyl vinyl ether/maleic acid mono-N-methyl-N-octadecyl amide copolymers, n-butyl vinyl ether/maleic acid mono-N-methyl amide copolymers, n-butyl vinyl ether/maleic acid mono ethyl ester copolymers, vinyl acetate/maleic acid mono ethyl ester copolymers, methyl cellulose hydrogen succinate, benzyl ceLlulose hydrogen succinate, p-sulfobenzene cellulose acetate, ethyl hydroxy ethyl cellulose, mono-ammonium salts of methyl vinyl ether/maleic acid copolymers, mono-N-methyl ammonium salts of methyl vinyl ether/maleic acid copolymers, hydroxy ethyl cellulose, resol-type phenol formaldehyde resins and succinic acid monobenzyl ester.

Claim 27

A Thermal recording method which comprises applying a thermal pattern to a recording member having a uniform and transparent heat-sensitive layer which contains a polymer complex of poly-N-vinyl pyrrolidone and a vinyl ether/maleic acid mono ester copolymer.

Claim 28

A Thermal recording method which comprises applying a thermal pattern to a recording member having a uniform and transparent heat-sensitive layer which contains a polymer complex of poly-N-vinyl pyrrolidone and a vinyl ether/maleic acid mono ester copolymer.