Image forming materials and image forming process

Claim 2

In an image forming material comprising a support having thereon a layer composed of a Ge--S composition or a Ge--S--X composition, wherein X represents at least one element selected from the group consisting of Al, Si, Mg, Ti, V, Mn, Co, Ni, Sn, Zn, Pd, In, Se, Te, Fe, I, P and O, which undergoes a structural change capable of being detected optically, electrically or chemically upon exposure imagewise to light, in contact with a continuous or discontinuous layer of (a) a metal selected from the group consisting of Ag, Cu, Ge, Zn, Cd, Au, Pb, Al, Ga, In, Sn, V, Se, Cr, Fe, Tl, Bi, Mg, Mn, Co, Ni, Sb, Te and Pd or (b) a metal compound selected from the group consisting of halides of metals of Group IB, Group IVB or Group VIB of the Periodic Table, sulfides of metals of Group IB, Group IIB, Group IVB or Group VIII of the Periodic Table, and oxides of metals of Group IV, Group V or Group VI of the Periodic Table; wherein upon exposure to light said Ge--S or Ge--S--X composition layer interacts with said metal or metal compound containing layer and thereby forms a visible image which has a different hydrophilicity or hydrophobicity in the exposed areas than in the non-exposed areas; wherein the improvement comprises: said Ge--S or Ge--S--X composition layer has a thickness of at least about 300A, and said Ge--S composition or said Ge--S--X composition contains at least one element selected from the group consisting of Ag, Cu and Pb in an amount of more than two atoms of Ag, Cu and/or Pb based on 100 atoms of the Ge--S composition or the Ge--S--X composition.

Claim 3

The image forming material as set forth in claim 1, wherein said material additionally contains an organic compound in a state of contacting said Ge--S composition or said Ge--S--X composition layer and said metal or metal compound, said organic compound being a compound conventionally used in silver halide photographic chemistry as an antifogging agent, a sensitizing agent, a desensitizing agent, a developing agent, a dye, a pigment or a photochromic compound.

Claim 4

The image forming material as set forth in claim 1, wherein the amount of the Ag and/or Cu is 5 or more atoms based on 100 atoms of the Ge--S composition or the Ge--S--X composition and wherein the amount of the Pb is 10 or more atoms based on 100 atoms of the Ge--S composition or the Ge--S--X composition.

Claim 5

The image forming material as set forth in claim 1, wherein the amount of the Ag and/or Cu in the Ge--S composition having the formula GeS.sub.α is up to about (α-1)/(α+1)×200 and in the Ge--S--X composition having the formula GeS.sub.α X.sub.β is up to about (α-1)/(α+β+1)×200 and wherein the amount of the Pb in the Ge--S composition having the formula GeS.sub.α is up to about (α-1)/(α+1)×100 and in the Ge--S--X composition having the formula GeS.sub.α X.sub.β is up to about (α-1)/(α+β+1)×100, wherein in the above α is the atomic ratio of sulfur atoms to germanium atoms and β is the atomic ratio of X atoms to germanium atoms.

Claim 6

The image forming material as set forth in claim 4, wherein said Ag and/or Cu is present in an amount of about 80% of said amount as set forth in claim 5 and said Pb is present in an amount of about 80% of said amount set forth in claim 4.

Claim 7

The image forming material as set forth in claim 5, wherein the amount of Ag is up to 10 atoms, the amount of Cu is up to 10 atoms and the amount of Pb is up to 20 atoms, respectively, each based on 100 atoms of the Ge--S composition or the Ge--S--X composition.

Claim 8

The image forming material as set forth in claim 1, wherein the atomic ratio of the Ge to the S in the Ge--S composition or the Ge--S--X composition is 1≦S/Ge<16.

Claim 9

The image forming material as set forth in claim 1, wherein X is an element selected from the group consisting of Al, Si, I, P and O.

Claim 10

The image forming material as set forth in claim 1, wherein said continuous or discontinuous layer contains a halide of Ag, Cu or Pb or a sulfide of Ag, Cu, Pb or Se.

Claim 11

The image forming material as set forth in claim 1, wherein said continuous or discontinuous layer is a metal layer of Ag or Cu.

Claim 12

The image forming material as set forth in claim 2, wherein the amount of the Ag and/or Cu is 5 or more atoms based on 100 atoms of the Ge--S composition or the Ge--S--X composition and wherein the amount of the Pb is 10 or more atoms based on 100 atoms of the Ge--S composition or the Ge--S--X composition.

Claim 13

The image forming material as set forth in claim 2, wherein the amount of the Ag and/or Cu in the Ge--S composition having the formula GeS.sub.α is up to about (α-1)/(α+1)×200 and in the Ge--S--X composition having the formula GeS.sub.α X.sub.β is up to about (α-1)/(α+β+1)×200 and wherein the amount of the Pb in the Ge--S composition having the formula GeS.sub.α is up to about (α-1)/(α+1)×100 and in the Ge--S--X composition having the formula GeS.sub.α X.sub.β is up to about (α-1)/(α+β+1)×100, wherein in the above α is the atomic ratio of sulfur atoms to germanium atoms and β is the atomic ratio of X atoms to germanium atoms.

Claim 14

The image forming material as set forth in claim 12, wherein said Ag and/or Cu is present in an amount of about 80% of said amount as set forth in claim 16 and said Pb is present in an amount of about 80% of said amount set forth in claim 12.

Claim 15

The image forming material as set forth in claim 13, wherein the amount of Ag is up to 10 atoms, the amount of Cu is up to 10 atoms and the amount of Pb is up to 20 atoms, respectively, each based on 100 atoms of the Ge--S composition or the Ge--S--X composition.

Claim 16

The image forming material as set forth in claim 2, wherein the atomic ratio of the Ge to the S in the Ge--S compositon or the Ge--S--X composition is 1≦S/Ge<16.

Claim 17

The image forming material as set forth in claim 2, wherein X is an element selected from the group consisting of Al, Si, I, P and O.

Claim 18

The image forming material as set forth in claim 2, wherein said organic compound is a compound having at least one of a --SH moiety, a >C═S moiety, a --(S) n -- moiety wherein n is 1 to 6, a --SO 2 H moiety or a --SO 3 H moiety.

Claim 19

The image forming material as set forth in claim 2, wherein said organic compound is selected from the group consisting of Methylene Blue, Crystal Violet and Rhodamine B.

Claim 20

The image forming material as set forth in claim 17, wherein said organic compound is selected from the group consisting of (1) thioureas represented by the following formula: ##STR83## wherein R 1 , R 2 , R 3 and R 4 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms or a phenyl group, or wherein R 1 and R 2 or R 3 and R 4 may be bonded to form a 5-membered heterocyclic ring; (2) thiosemicarbazides and thiocarbazides represented by the following formulae: ##STR84## wherein R 1 , R 2 , R 3 and R 4 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or derivatives thereof; (3) dithiocarbamic acids represented by the following formula: ##STR85## wherein R 1 and R 2 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aralkyl group having 7 to 9 carbon atoms or a phenyl group; M represents a hydrogen atom or a n-valent metal ion; and n represents 1 or 2; (4) thiobenzophenones represented by the following formula: ##STR86## wherein R 1 and R 2 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms; an alkoxy grup having 1 to 5 carbon atoms, a dialkylamino group having 1 to 5 carbon atoms in each of the alkyl moieties thereof, a chlorine atom, a bromine atom or an iodine atom; (5) dithiolan; (6) a thiazole or a benzothiazole; (7) a thiadiazole; (8) a pyrrole or a benzopyrrole; (9) an imidazole or a benzimidazole; (10) a imidazoline; (11) a triazole or a benzotriazole; (12) a tetrazole; (13) a pyrimidine; and (14) a tetrazaindene.

Claim 21

The image forming material as set forth in claim 2, wherein said organic compound is selected from the group consisting of 1-phenyl-5-mercaptotetrazole, 3-methyl-4-phenyl-5-mercapto-1,2,4-triazole, 3,4-dimethyl-5-mercapto-1,2,4-triazole, 3-(p-caproamidophenyl)4-ethyl-5-mercapto-1,2,4-triazole, 3-n-undecyl-4-phenyl-5-mercapto-1,2,4-triazole, 1,5-dimercapto-3,7-diphenyl(1,2,4)triazolo(1,2,2) (1,2,4)triazole, 1-phenyl-2-mercaptoimidazole, 2-hexadecylthioimidazoline hydrobromide, 2-thioxo-4-oxothiazolidine, 2,5-dimercapto-1,3,4-thiadiazole, bismuthiol II, 2-ethylthio-4-methyl-6-hydroxypyrimidine, 2-mercapto-4-hydroxy-6-methyl pyrimidine, N,N,N',N'-tetramethyl-4,4'-diaminothiobenzophenone, sodium diethyldithiocarbamate, silver diethyldithiocarbamate, N,N,N',N'-tetramethyl-p-phenylene-diamine hydrochloride, monoethylurea, dimethylolthiourea, 4-phenylthiosemicarbazide, 2,5-di-(1,1-dimethylbutyl)hydroquinone and 1-(m-caproamidophenyl)-5-mercaptotetrazole.

Claim 22

A method for forming visible images having different hydrophilicity or hydrophobicity in the exposed areas than in the non-exposed areas which comprises exposing the image-forming material of claim 1 to light.

Claim 23

The method as set forth in claim 21, wherein said image forming material additionally contains an organic compound conventionally used in silver photographic chemistry as an antifogging agent, a sensitizing agent, a desensitizing agent, a developing agent, a dye, a pigment, or a photochromic compound in a state of contacting said Ge--S composition or said Ge--S--X composition layer and said metal or metal compound.

Claim 24

The method as set forth in claim 21 where in addition to exposing said material to light, said material is physically developed to thereby produce visible images having a high contrast.

Claim 25

The image forming material as set forth in claim 1 wherein said improvement comprises said Ge--S composition or said Ge--S--X composition containing silver in an amount of more than two atoms of silver based on one hundred atoms of the Ge--S composition or the Ge--S--X composition.

Claim 26

The image forming material as set forth in claim 1 wherein said improvement comprises said Ge--S composition or said Ge--S--X composition containing copper in an amount of more than two atoms of copper based on one hundred atoms of said Ge--S or said Ge--S--X composition.

Claim 27

The image forming material as set forth in claim 1 wherein said improvement comprises said Ge--S composition or said Ge--S--X composition containing lead in an amount of more than two atoms of lead based on one hundred atoms of said Ge--S or said Ge--S--X composition.

Claim 28

The image forming material as set foth in claim 25 wherein said material comprises a support having thereon a layer of Ge--S--P composition in contact with a layer of silver and said Ge--S--P composition contains copper.

Claim 29

The image forming material as set forth in claim 26 wherein said material comprises a support having thereon a Ge--S composition containing lead in contact with a layer of silver.

Claim 30

The image forming material as set forth in claim 1 comprising a support having thereon a layer of a Ge--S composition containing silver in contact with a silver metal layer.