High speed photothermographic materials containing tellurium compounds and methods of using same

A photothermographic material comprising a transparent support having on one side thereof, one or more photothermographic emulsion layers comprising:

• a. one or more preformed silver halides present in an amount of from about 0.005 to about 0.5 mole per mole of a non-photosensitive source of reducible silver ions,
• b. a non-photosensitive source of reducible silver ions that comprises one or more silver carboxylates of fatty acids having from 10 to 30 carbon atoms, said one or more silver carboxylates being present in an amount of from about 10 to about 50 weight % of the total dry weight of said emulsion layer(s),
• c. one or more hindered phenol reducing agents,
• d. one or more hydrophobic binders,
• e. a heteroaromatic mercapto compound, and
• f. one or more tellurium chemical sensitizers that are represented by the following Structure I or II:
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent the same or different chloro, bromo, SCN, S(C═S)ORa, S(C═S)SRa, or S(C═S)N(Ra)(Rb) groups, the multiple Ra, Rb, and R′groups are the same or different alkyl groups, the multiple L groups are the same or different ligands derived from a thiourea as represented in Structure IV, V, or VI below, m is 2, n is 4,
• wherein:
• in Structure IV, R1, R2, R3 and R4 are independently hydrogen, alkyl, cycloalkyl, allyl, alkenyl, alkynyl, aryl or heterocyclic groups, or R1 and R2 taken together, R3 and R5 taken together, R1 and R3 taken together or R2 and R4 taken together, can form a 5- to 7-membered heterocyclic ring,
• in Structure V, R1, R2, R3, R4 and R5 are independently hydrogen, alkyl, cycloalkyl, allyl, alkenyl, alkynyl, aryl or heterocyclic groups, or R3 and R5 taken together, R4 and R5 taken together, R1 and R3 taken together or R2 and R4 taken together, can form a substituted or unsubstituted 5- to 7-membered heterocyclic ring, and
• in Structure VI, R1, R2, R3, R4, R5, and R6 are independently hydrogen, alkyl, cycloalkyl, allyl, alkenyl, alkynyl, aryl or heterocyclic groups, or R3 and R6 taken together, R4 and R5 taken together, R1 and R3 taken together, R2 and R4 taken together, or R5 and R6 taken together, can form a substituted or unsubstituted 5- to 7-membered heterocyclic ring, and R7 is a divalent aliphatic or alicyclic linking group,
• said tellurium chemical sensitizer represented by Structure I or II being present in said material in an amount of from about 1×10−5 to about 0.01 mole per mole of total silver.

A method for preparing a photothermographic emulsion comprising the following steps, in order:

• A) providing a photothermographic emulsion comprising silver halide grains and a non-photosensitive source of reducible silver ions, and
• B) positioning one or more of the tellurium chemical sensitizers represented by Structure I or II shown below on or around said silver halide grains,
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra) (Rb), S(C═S)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb), S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═O)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6- or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, m is 0, 1, 2, or 4, and n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1, X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different.

A method of preparing a photothermographic emulsion comprising:

• A) providing silver halide grains,
• B) providing a photothermographic emulsion of said silver halide grains and a non-photosensitive source of reducible silver ions, and
• C) during or anytime after step A, chemically sensitizing said silver halide grains with a tellurium chemical sensitizer represented by Structure I or II shown below
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra)(Rb), S(C═S)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb), S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6- or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, m is 0, 1, 2, or 4, and n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1, X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different.

A photothermographic material comprising a support having thereon one or more layers comprising a binder and in reactive association:

• a. a photocatalyst,
• b. a non-photosensitive source of reducible silver ions,
• c. a reducing composition for said reducible silver ions, and
• d. a tellurium chemical sensitizer represented by the following Structure I or II:
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra)(Rb), S(CS)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb), S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═O)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6- or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, and m is 0, 1, 2, or 4, n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1, X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different, except than when m is 0 and n is 2, X1 cannot be two identical S(C═S)N(Ra)(Rb) groups.

A photothermographic material comprising a support having thereon one or more layers comprising a binder and in reactive association:

• a. a photocatalyst,
• b. a non-photosensitive source of reducible silver ions,
• c. a reducing composition for said reducible silver ions,
• d. a tellurium chemical sensitizer represented by the following Structure I or II:
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra)(Rb), S(C═S)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb)2, S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═O)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6- or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, m is 0, 1, 2, or 4, and n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1, X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different, and
• e. additional chemical sensitization achieved by oxidative decomposition of a spectral sensitizing dye.

A photothermographic material comprising a support having thereon one or more layers comprising a binder and in reactive association:

• a. a photocatalyst,
• b. a non-photosensitive source of reducible silver ions,
• c. a reducing composition for said reducible silver ions,
• d. a tellurium chemical sensitizer represented by the following Structure I or II:
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra)(Rb), S(C═S)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb), S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═O)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6-or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, m is 0, 1, 2, or 4, and n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1, X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different, and
• e. a heteroaromatic mercapto compound or a heteroaromatic disulfide compound in an amount of at least 0.0001 mole per mole of total silver.

A photothermographic material comprising a support having thereon one or more layers comprising a binder and in reactive association:

• a. a photocatalyst,
• b. a non-photosensitive source of reducible silver ions,
• c. a reducing composition for said reducible silver ions,
• d. a tellurium chemical sensitizer represented by the following Structure I or II:
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra)(Rb), S(C═S)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb), S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═O)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6- or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, m is 0, 1, 2, or 4, and n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1, X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different, and
• e. phthalazine or a phthalazine derivative.

A photothermographic material comprising a transparent support having thereon one or more layers one on side thereof comprising a binder and in reactive association:

• a. a photocatalyst,
• b. a non-photosensitive source of reducible silver ions,
• c. a reducing composition for said reducible silver ions, and
• d. a tellurium chemical sensitizer represented by the following Structure I or II:
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra)(Rb), S(C═S)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb)2, S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═O)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6- or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, m is 0, 1, 2, or 4, and n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1, X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different, and
• on the opposite side of said transparent support, an antihalation layer comprising one or more antihalation dyes.

A photothermographic material comprising a support having thereon one or more layers comprising a binder and in reactive association:

• a. a photocatalyst,
• b. a non-photosensitive source of reducible silver ions,
• c. a reducing composition for said reducible silver ions,
• d. a tellurium chemical sensitizer represented by the following Structure I or II:
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra)(Rb), S(C═S)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb)2, S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═O)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6- or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, m is 0, 1, 2, or 4, and n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1, X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different, and
• e. a co-developer.

A photothermographic material comprising a support having thereon one or more layers comprising a binder and in reactive association:

• a. a photocatalyst,
• b. a non-photosensitive source of reducible silver ions,
• c. a reducing composition for said reducible silver ions,
• d. a tellurium chemical sensitizer represented by the following Structure I or II:
• Te(L)m(X1)n (I)
• Pd(X2)2[Te(R′)2]2 (II)
• wherein X1 and X2 independently represent halo, OCN, SCN, S(C═S)N(Ra)(Rb), S(C═S)ORa, S(C═S)SRa, S(P═S)(ORa)(ORb)2, S(P═S)(Ra)(Rb), SeCN, TeCN, CN, SRa, ORa, N3, alkyl, aryl, or O(C═O)Ra groups, Ra and Rb are an alkyl, alkenyl, cycloalkyl, heterocycyl, or aryl group, or Ra and Rb taken together can form a 5-, 6- or 7-membered heterocyclic ring, L is a ligand derived from a neutral Lewis base, R′ is an alkyl or aryl group, m is 0, 1, 2, or 4, and n is 2 or 4 provided that when m is 0 or 2, n is 2 or 4, and when m is 1 or 4, n is 2, and further provided that multiple X1 X2, L, Ra, Rb, or R′ groups in the molecule can be the same or different, and
• e. additional chemical sensitization achieved by addition of a second chemical sensitizer that is represented by the following Structure IV, V, or VI:
• wherein:
• in Structure IV, R1, R2, R3 and R4 are independently hydrogen, alkyl, cycloalkyl, allyl, alkenyl, alkynyl, aryl or heterocyclic groups, or R1 and R2 taken together, R3 and R5 taken together, R1 and R3 taken together or R2 and R4 taken together, can form a 5- to 7-membered heterocyclic ring,
• in Structure V, R1, R2, R3, R4 and R5 are independently hydrogen, alkyl, cycloalkyl, allyl, alkenyl, alkynyl, aryl or heterocyclic groups, or R3 and R5 taken together, R4 and R5 taken together, R1 and R3 taken together or R2 and R4 taken together, can form a substituted or unsubstituted 5- to 7-membered heterocyclic ring, and
• in Structure VI, R1, R2, R3, R4, R5, and R6 are independently hydrogen, alkyl, cycloalkyl, allyl, alkenyl, alkynyl, aryl or heterocyclic groups, or R3 and R6 taken together, R4 and R5 taken together, R1 and R3 taken together, R2 and R4 taken together, or R5 and Rb taken together, can form a substituted or unsubstituted 5- to 7-membered heterocyclic ring, and R7 is a divalent aliphatic or alicyclic linking group.