The present invention is to provide a silver halide photographic light-sensitive material comprising a support having thereon a light-sensitive silver halide emulsion layer comprising a compound represented by Formula,

The present invention relates to a silver halide photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material or a photographic meterial), a mercapto compound, and a disulfide compound, and in more detail to a silver halide light-sensitive material, comprising said compound, which exhibits minimized fogging, and excellent pressure resistance, as well as excellent sensitivity.
Generally, various pressures are applied onto light-sensitive materials coated with silver halide emulsions. For example, sheet films such as graphic arts light-sensitive materials, and medical direct radiographic materials are manually handled which frequently results in being folded and curled. As noted above, when various pressures are applied onto photographic light-sensitive materials, silver halide grains are subjected to application of pressure through media such as gelatin as the binder of silver halide grains, and a plastic film as the support. When silver halide grains are subjected to application of pressure, variation of photographic performance results. Details are reported, for example, by K. B. Mather, J. Opt. Soc. Am., 38, 1054 (1948), P. Faelens and P. deSmet, Sci. et Ind. Phot., 24, No. 5, 178 (1954), P. Faelens, J. Phot. Sci., 2, 105 (1954), and others.
In addition, sought is further improvement of retaining performance of light-sensitive materials, particularly retardation of an increase in fogging during storage.
Camera light-sensitive materials are developed varying period of time from immediate to several months or one year after exposure. It is preferable that during such an elapse of time, fogging performance be maintained.
An objective of the present invention is to provide a silver halide photographic light-sensitive material, comprising mercapto compounds and disulfide compounds, which exhibits low fogging, excellent pressure resistance, and excellent sensitivity, and is to provide mercapto compounds as well as disulfide compounds.
The objective of the present invention has been achieved employing the embodiments below.
1. A silver halide photographic light-sensitive material comprising a support having thereon a light-sensitive silver halide emulsion layer comprising a compound represented by Formula,
Formula 1
Zxe2x80x94Sxe2x80x94X
wherein Z represents a group represented by Formula 1-2; X represents a hydrogen atom or Zxe2x80x94Sxe2x80x94,
wherein A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90N(xe2x86x92O)xe2x80x94, or xe2x95x90CR91xe2x80x94, in which R91 represents a substituent, and at least two of A1, A2, A3, A4, and A5 are respectively xe2x95x90N(xe2x86x92O)xe2x80x94and xe2x95x90CR91xe2x80x94.
2. The photographic material of item 1, wherein the compound represented by Formula 1 is selected from the group of compounds represented by Formula 6 to Formula 14,
wherein R61, R71, R81, and R91 each represent a substituent; m6 represents 1 to 4; m7 and m8 represent an integer of 0 to 4; m9 represents an integer of 0 to 3; when m6, m7, m8 and m9 are 2 or more, R61, R71, R81, and R91 may be a different substituent and may bond to each other to form a condensation ring; A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x80x94CR92, or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least two of A1, A2, A3, A4, and A5 represent xe2x95x90Nxe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least one represents xe2x95x90N(xe2x86x92O)xe2x80x94; and R92 represents a substituent; Ra and Rb each represent an electron attractive group and may be the same or different, and p and q each represent integer of 1 to 4; R11, R12, R13, an R14 each represent a substituent; m11 represents an integer of 1 to 4; m12 and m13 each represent an integer of 0 to 4; m14 represents an integer of 0 to 3; A1, A2, A3, A4, and A5 each are the same as each of Formula 9.
3. The photographic material of item 2, wherein the compound represented by Formula 1 is selected from the group of compounds represented by Formula 6 to Formula 10,
wherein R61, R71, R81, and R91 each represent a substituent; m6 represents an integer of 1 to 4; m7 and m8 represent 0 to 4; m9 represents an integer of 0 to 3; when m6, m7, m8 and m9 are 2 or more, R61, R71, R81, and R91 may be a different substituent and may bond to each other to form a condensation ring; A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90CRxe2x80x94, or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least two of A1, A2, A3, A4, and A5 represent xe2x95x90Nxe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least one represents xe2x95x90N(xe2x86x92O)xe2x80x94; and R92 represents a substituent;
wherein Ra and Rb each represent an electron attractive group and may be the same or different, and p and q each represent an integer of 1 to 4.
4. The photographic material of item 2, wherein the compound represented by Formula 1 is selected from the group of compounds represented by Formula 11 to Formula 14.
wherein R11, R12, R13, and R14 each represent a substituent; m11 represents an integer of 1 to 4; m12 and m13 each represent an integer of 0 to 4; m14 represents an integer of 0 to 3; and A1, A2, A3, A4, and A5 each are the same as each of Formula 9.
5. The photographic material of item 3, wherein each R61, R71, R81, and R91 in Formula 6 to Formula 9 represents a group which promotes adsorption onto silver halide grains.
6. The silver halide light-sensitive material of item 1,
wherein the compound is contained in an amount of 1xc3x9710xe2x88x927 to 1xc3x9710xe2x88x921 mole per mole of Ag.
7. The silver halide light-sensitive material of item 3, wherein the compound is represented by Formula 10,
wherein Ra and Rb each represent an electron attractive group and may be the same or different, and p and q each represent an integer of 1 to 4.
8. The photographic material of item 3, wherein the compound is represented by Formula 6,
wherein R61 represent a substituent and m6 represents an integer of 1 to 4, when m6 is 2 or more, R61 may be a different substituent and may bond to each other to form a condensation ring.
9. The photographic material of item 3, wherein the compound is represented by Formula 7,
wherein R71 represent a substituent and m7 represents an integer of 0 to 4, when m7 is 2 or more, R71 may be a different substituent and may bond to each other to form a condensation ring.
10. The silver halide light-sensitive material of item 3, wherein the compound is represented by Formula 8,
wherein R81 represent a substituent and m8 represents an integer of 0 to 4, when m8 is 2 or more, R81 may be a different substituent and may bond to each other to form a condensation ring.
11. The photographic material of item 3, wherein the compound is represented by Formula 9,
wherein A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90CRxe2x80x94, or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least two of A1, A2, A3, A4, and A5 represent xe2x95x90Nxe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least one represents xe2x95x90N(xe2x86x92O)xe2x80x94; and R92 represents a substituent;
12. The photographic material of item 1, wherein the emulsion is subjected to reduction sensitization.
13. The photographic material of item 3, wherein the emulsion contains a tabular silver halide grain.
14. A photographic material comprising a compound represented by Formulas 2 to 5, 6-2, and 7-2.
wherein X1 represents xe2x80x94NR21xe2x80x94 or xe2x80x94Oxe2x80x94; X2, X3, and X4 each represents xe2x95x90CR22xe2x80x94 or xe2x95x90Nxe2x80x94; both R21 and R22 represent a hydrogen atom or a substituent; X1, X2, X3, and X4 may form a condensation ring with each other, however, all of X1, X2, X3, and X4 are not a nitrogen atom; Y1, Y2, Y3, Y4, and Y5 each represent xe2x95x90Nxe2x80x94 or xe2x95x90CR31xe2x80x94, however, any one of Y1, Y3 and Y5 is not xe2x95x90Nxe2x80x94; Q represents a group of atoms necessary for forming a 5-membered or 6-membered heterocyclic ring comprising at least one of xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94N less than , xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94, or NR31COxe2x80x94, wherein R31 represents a hydrogen atom or a substituent; G represents an oxygen atom and a sulfur atom; W represents xe2x80x94Sxe2x80x94Sxe2x80x94C(xe2x95x90G)xe2x80x94 as well as a group of atoms necessary to form a 5-membered or 6-membered ring, and may have a substituent which may form a ring along with W; R62 represents an alkyl group having at least 2 carbon atoms, an aryl group, a cycloalkyl group, a hydroxy group, a carboxy group, a nitro group, a trifluoromethyl group, an amido group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbonyloxy group, a cyano group, a bromine atom, an iodine atom, a fluorine atom, an alkoxy group, an aryloxy group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an amino group, an alkylamino group, or a hydroxyamino group, m62 represents an integer of 1 to 4, and when m62 is at least 2, R62 may be a different group and may bond to each other to form a condensation ring; R72 represents a substituent, and m72 represents an integer of 1 to 4; R81 represents a substituent and m8 represents an integer of 0 to 4; A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90CR92xe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, at least two of A1, A2, A3, A4, and A5 represent xe2x95x90Nxe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least one represents xe2x95x90N(xe2x86x92O)xe2x80x94; and R91 and R92 each represent a substituent, and m9 represents an integer of 0 to 3.
The present invention will now be detailed.
In Formula 1, Z represents a group represented by Formula 1-2; X represents a hydrogen atom or Zxe2x80x94Sxe2x80x94; A1, A2, A3, A4, and A5 in Formula 1-2 each represent xe2x95x90Nxe2x80x94, xe2x95x90N(xe2x86x92O)xe2x80x94, or xe2x95x90CR91xe2x80x94, in which R91 represents a substituent, and at least two of A1, A2, A3, A4, and A5 are respectively xe2x95x90N(xe2x86x92O)xe2x80x94, and xe2x95x90CR91xe2x80x94, that means at least one of A1, A2, A3, A4, and A5 represents xe2x95x90N(xe2x86x92O)xe2x80x94, and at the same time at least one of the rest represents xe2x95x90CR91xe2x80x94. Substituents represented by R91 include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl group, and an oleyl group); a cycloalkyl group (for example, a cyclopropyl group and a cyclohexyl group); an aryl group (for example, a phenyl group, a p-tetradecanyloxyphenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group); a hydroxy group; a carboxy group; a nitro group; a trifluoromethyl group; an amido group (for example, an acetamide group and a benzamido group); a carbamoyl group (for example, a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group (for example, an ethyloxycarbonyl group and an isopropyloxycarbonyl group); an aryloxycarbonyl group (for example, a phenyloxycarbonyl group); a carbonyloxy group (for example, a methylcarbonyloxy group, a propylcarbonyloxy group, and a phenylcarbonyloxy group); a cyano group; a halogen atom (a chlorine atom, a bromine atom, a iodine atom, and a fluorine atom); an alkoxy group (for example, a methoxy group, and a butoxy group); an aryloxy group (for example, a phenoxy group); a sulfonyl group (for example, a methanesulfonyl group and a p-toluenesulfonyl group); a sulfonamido group (for example, a methanesulfonamido group, a dodecylsulfonamido group, and a p-toluenesulfonamido group); a sulfamoyl group (for example, a methylsulfamoyl group and a phenylsulfamoyl group); an amino group; an alkylamino group (for example, an ethylamino group, a dimethylamino group, and a hydroxyamino group). When there are at least two xe2x95x90CR91xe2x80x94, R91 may be different from each other, and a plurality of xe2x95x90CR91xe2x80x94 may bond to each other to form a condensation ring.
In Formula 2, X1 represents xe2x80x94NR21xe2x80x94 or xe2x80x94Oxe2x80x94; X2, X3, and X4 each represents xe2x95x90CR22xe2x80x94 or xe2x95x90Nxe2x80x94; both R21 and R22 represent a hydrogen atom or a substituent (for example, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group, and a cyclohexyl group; and an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group) may form a condensation ring with X1, X2, X3, and X4, and however, all of X1, X2, X3, and X4 are not xe2x95x90Nxe2x80x94.
In Formula 3, Y1, Y2, Y3, Y4, and Y5 each represent xe2x95x90Nxe2x80x94 or xe2x95x90CR31xe2x80x94 wherein R31 represent a hydrogen atom or a substituent (for example, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group, and a cyclohexyl group; and an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group. However, any one of Y1, Y3 and Y5 is not xe2x95x90Nxe2x80x94.
In Formula 4, Q represents a group of atoms necessary for forming a 5-membered or 6-membered heterocyclic ring comprising at least one of xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94N less than , xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94, or xe2x80x94NR31COxe2x80x94, wherein R31 represent a hydrogen atom or a substituent (for example, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group, and a cyclohexyl group; and an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group.
In Formula 5, G represents an oxygen atom and a sulfur atom, and W represents a group of atoms necessary to form a 5-membered or 6-membered ring along with xe2x80x94Sxe2x80x94Sxe2x80x94C(xe2x95x90G)xe2x80x94and may have a substituent which may form a ring along with W. Said rings include an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group. Said substituents include an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group and a cyclohexyl group; a hydroxy group; a carboxy group; a nitro group; a trifluoromethyl group; an amido group such as acetamido group, and a benzamido group; a carbamoyl group such as a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group such as an ethyloxycarbonyl group and an isopropyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; a carbonyloxy group such as a methyl carbonyloxy group, a propylcarbonyloxy group, and a phenylcarbonyloxy group; a cyano group; a halogen atom such as a chlorine atom, bromine atom, an iodine atom, and a fluorine atom; an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group; an aryloxy group such as a phenoxy group; a sulfonyl group such as a methanesulfonyl group and a p-toluenesulfonyl group; a sulfonamido group such as a methanesulfonamido group, a dodecylsulfonamido group, and a p-toluenesulfonamido group; a sulfamoyl group such as a methylsulfamoyl group and a phenylsulfamoyl group; an amino group; an alkylamino group such as an ethylamino group, dimethylamino group, and a hydroxyamino group.
In Formula 6, R61 represents a substituent. Said substituents include an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group, and a cyclohexyl group; an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group; an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group, a hydroxy group; a carboxy group; a nitro group; a trifluoromethyl group; an amido group such as acetamido group and a benzamido group; a carbamoyl group such as a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group, such as an ethyloxycarbonyl group and an isopropyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; a carbonyloxy group such as a methylcarbonyloxy group, a propylcarbonyloxy group, and a phenylcarbonyloxy group; a cyano group; a halogen atom such as a chlorine atom, bromine atom, an iodine atom, and a fluorine atom, an alkoxy group such as a methoxy group, an ethoxy group and a butoxy group; an aryloxy group such as a phenoxy group; a sulfonyl group such as a methanesulfonyl group and p-toluenesulfonyl group; a sulfonamido group such as a methanesulfonamido group, a dodecylsulfonamido group, and a p-toluenesulfonamido group; a sulfamoyl group such as a methylsulfamoyl group, and a phenylsulfamoyl group; an amino group; an alkylamino group such as an ethylamino group, dimethylamino group, and a hydroxyamino group. When m6 is 2 or more, R61 may be a different group and may combine with each other to from a condensation ring.
In Formula 6-2, R62 represents a substituent. Said substituents include an alkyl group having at least 2 carbon atoms such as an ethyl group, an isopropyl group, a cyclohexyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group; an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group; a hydroxy group; a carboxy group; a nitro group; a trifluoromethyl group; an amido group such as acetamido group and a benzamido group; a carbamoyl group such as a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group, such as an ethyloxycarbonyl group and an isopropyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; a carbonyloxy group such as a methylcarbonyloxy group, a propylcarbonyloxy group, and a phenylcarbonyloxy group; a cyano group; a halogen atom such as a chlorine atom, bromine atom, an iodine atom, and a fluorine atom; an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group; an aryloxy group such as a phenoxy group; a sulfonyl group such as a methanesulfonyl group and p-toluenesulfonyl group; a sulfonamido group such as a methanesulfonamido group, a dodecylsulfonamido group, and a p-toluenesulfonamido group; a sulfamoyl group such as a methylsulfamoyl group and a phenylsulfamoyl group, an amino group; an alkylamino group such as an ethylamino group, a dimethylamino group and a hydroxyamino group. When m62 is 2 or more, R62 may be a different group and may bond to each other to form a condensation ring.
In Formula 7, R71 represents the same as R61.
In Formula 7-2, R72 represents the same as R61.
In Formula 8, R81 represents the same as R61.
In Formula 9, R91 represents the same as R61.
In Formula 10, Ra and Rb each represent an electron attractive group which includes a carboxy group; a nitro group; a trifluoromethyl group; a carbamoyl group such as a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group such as an ethyloxycarbonyl group and an isopropyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; a cyano group; a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom; a sulfonyl group such as a methanesulfonyl group, and a p-toluenesulfonyl group; a carbonyloxy group such as a methylcarbonyloxy group and a propylcarbonyloxy group; an alkylcarbonyl group such as a methylcarbonyl group and a phenylcarbonyl group.
In Formula 11, R11 represents the same as R61.
In Formula 12, R12 represents the same as R61.
In Formula 13, R13 represents the same as R61.
In Formula 14, R14 represents the same as R61.
Agents which promote adsorption onto silver halide grains include groups derived from cyclic or chain thioethers (for example, dimethyl sulfide, methyl sulfide, methyl phenyl sulfide, and thiocrown ethers), groups derived from aliphatic mercaptans (for example, groups derived from methylmercaptan, and propylmercaptan), groups derived from aromatic mercaptans (for example, thiophenol, and thionaphthol), and, groups derived from cyclic or chain thioamides, groups derived from cyclic or chain thioureids, groups derived from heterocyclic mercaptans (when a nitrogen atom is adjacent to a carbon atom which is bonded to an xe2x80x94SH group, said groups are the same as cyclic thioamido groups which is in the relationship of tautomers, and the specific examples of said groups are the same as those listed above), groups derived from azoles capable of forming silver imide, groups derived from nitrogen-containing aromatic cyclic quaternary salts (for example, N-methylpyridinium salt, and N-ethylquinolium salt). Of these, preferred are groups derived from thioamide, thioureido, aromatic mercaptans, heterocyclic mercaptans or azoles capable of forming silver imide, but more preferred are groups derived from heterocyclic mercaptans or azoles capable of forming silver imide.
Specific examples of groups, derived from heterocyclic mercaptans and derived from azoles capable of forming silver imide, include those derived from heterocyclic mercaptans such as mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-oxadiazole, 2-mercapto-1,3,4-thisdiazole, 2-mercaptoimidazole, 2-mercapto-1,3-oxazole, 2-mercapto-1,3-thiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptopyridine, 2-mercaptopyrimidine, and mercaptotriazine, and derived from azoles capable of forming silver imide such as benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, tetraazaindene, indazole, and purine. Of these, preferred are groups derived from mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-oxadiazole, 2-mercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, 2-mercaptobenzozazole, 2-mercaptobenzothiazole, 2-mercaptopyrimidine, mercaptotriazine, benzotriazole, and triazole, however more preferred are groups derived form mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mwercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, benzotriazole, tetrazole, and still more preferably employed are groups derived from mercaptotetrazole, 2-mercapto-1,3,4-thiadiazole and benzotriazole Spefici examples of compounds of the present invention will now be illustrated below. However, the present invention is not limited to these examples.
Synthesis examples of the compounds of the present invention will now be described.
 less than Synthesis of Compound 6-2 greater than
5.0 g of Compound 6-2a were dissolved in 50 ml of dichloromethane, and 6.2 g of urea peroxide were added. The resulting mixture was cooled to 0xc2x0 C. and 13.2 g of trifluoroacetic anhydride were slowly added dropwise. The resulting mixture was stirred for 30 minutes as it was, and then heated to room temperature. When the reaction was completed, an aqueous sodium sulfite solution was added to decompose excess peroxides. The resulting mixture was poured into a 0.5 mole/liter aqueous hydrochloric acid solution. Subsequently, extraction was carried out utilizing dichloromethane, and the resulting extract was washed with an aqueous sodium hydrogencarbonate solution, and then dried utilizing magnesium sulfate. Then, solvents were removed under reduced pressure. The resulting suspension was washed with acetonitrile and filtered, whereby 4.5 g (a yield of 82 percent) of Compound 6-2b were obtained. The structure was identified utilizing NMR and mass spectra.
Then, 4.0 g of Compound 6-2b were dissolved in 50 ml of ethanol and 2.6 g of sodium hydrosulfide were added. The resulting mixture was heated to 100xc2x0 C. while stirring. After the completion of the reaction, the solvent was removed under reduced pressure, and the resulting residue was dissolved in water. The resulting solution was acidified utilizing acetic acid, whereby precipitates were formed. The resulting precipitates were collected by filtration, and 3.5 g (a yield of 89 percent) of Compound 6-2c was obtained. The structure was identified utilizing NMR and mass spectra.
Subsequently, 3.0 g of Compound 6-2c were subjected to suspension in water and then heated to 40xc2x0 C. Subsequently, 2.3 g of a 30 percent aqueous hydrogen peroxide solution were added dropwise while maintaining a temperature no higher than 50xc2x0 C. The reaction mixture was stirred at 45xc2x0 C. After setting aside the resulting reaction mixture over night in a refrigerator at 5xc2x0 C., crystals were collected employing filtration and then washed with chilled methanol, whereby 2.3 g (a yield of 78 percent) of Compound 6-2 were obtained. The structure was identified utilizing NMR and mass spectra.
 less than Synthesis of Compound 7-2 greater than
5.0 g of Compound 7-2a were dissolved in 50 ml of dichloromethane, and 6.3 g of urea peroxide were added. The resulting mixture was cooled to 0xc2x0 C. whereupon 13.2 g of trifluoroacetic anhydride were slowly added dropwise. The resulting mixture was stirred for 30 minutes as it was, and then heated to room temperature. When the reaction was completed, an aqueous sodium sulfite solution was added to decompose excess peroxides. The resulting mixture was poured into a 0.5 mole/liter aqueous hydrochloric acid solution. Subsequently, extraction was carried out utilizing dichloromethane, and the resulting extract was washed with an aqueous sodium hydrogencarbonate solution, and then dried utilizing magnesium sulfate. Solvents were then removed under reduced pressure. The resulting product was washed with acetonitrile and filtered, whereby 4.4 g (a yield of 80 percent) of Compound 7-2b were obtained. The structure was identified utilizing NMR and mass spectra.
Then, 4.0 g of Compound 7-2b were dissolved in 50 ml of ethanol and 2.6 g of sodium hydrosulfide were added. The resulting mixture was heated to 100xc2x0 C. while stirring. After the completion of the reaction, the solvent was removed under reduced pressure, and the resulting residue was dissolved in water. The resulting solution was acidified utilizing acetic acid, whereby precipitates were formed. The resulting precipitates were collected by filtration, and 2.9 g (a yield of 89 percent) of Compound 7-2c was obtained. The structured was identified utilizing NMR and mass spectra.
Subsequently, 2.0 g of Compound 7-2c were subjected to suspension in water and then heated to 40xc2x0 C. Subsequently, 2.0 g of a 30 percent aqueous hydrogen peroxide solution were added dropwise while maintaining a temperature no higher than 50xc2x0 C. The resulting mixture was stirred at 45xc2x0 C. After setting aside said resulting reaction mixture overnight in a refrigerator at 5xc2x0 C., crystals were collected employing filtration and then washed with chilled methanol, whereby 2.3 g (a yield of 80 percent) of Compound 7-2 were obtained. The structure was identified utilizing NMR and mass spectra.
 less than Synthesis of Compound 8-3 greater than
5.0 g of Compound 8-3a were dissolved in 50 ml of dichloromethane, and 5.8 g of urea peroxide were added. The resulting mixture was cooled to 0xc2x0 C. and 13.2 g of trifluoroacetic anhydride were slowly added dropwise. The resulting mixture was stirred for 30 minutes as it was, and then heated to room temperature. When the reaction was completed, an aqueous sodium sulfite solution was added to decompose excess peroxides. The resulting mixture was poured into a 0.5 mole/liter aqueous hydrochloric acid solution. Subsequently, extraction was carried out utilizing dichloromethane, and the resulting extract was washed with an aqueous sodium hydrogencarbonate solution, and then dried utilizing magnesium sulfate. Solvents were then removed under reduced pressure. The resulting product was washed with acetonitrile and filtered, whereby 4.6 g (a yield of 85 percent) of Compound 8-3b were obtained. The structure was identified utilizing NMR and mass spectra.
Then, 4.0 g of Compound 8-3b were dissolved in 50 ml of ethanol and 2.4 g of sodium hydrosulfide were added. While stirring, the resulting mixture was heated to 100xc2x0 C. After the completion of the reaction, the solvent was removed under reduced pressure, and the resulting residue was dissolved in water. The resulting solution was acidified utilizing acetic acid, whereby precipitates were formed. The resulting precipitates were collected by filtration, and 2.7 g (a yield of 68 percent) of Compound 8-3c was obtained. The structure was identified utilizing NMR and mass spectra.
Subsequently, 2.5 g of Compound 8-3c were subjected to suspension in water and then heated to 40xc2x0 C. Subsequently, 1.7 g of a 30 percent aqueous hydrogen peroxide solution were added dropwise while maintaining a temperature no higher than 50xc2x0 C. The resulting mixture was stirred while maintaining 45xc2x0 C. After setting aside the resulting reaction mixture overnight in a refrigerator at 5xc2x0 C., crystals were collected employing filtration and then washed with chilled methanol, whereby 2.1 g (a yield of 87 percent) of Compound 8-3 were obtained. The structure was identified utilizing NMR and mass spectra.
 less than Synthesis of Compound 9-1 greater than
5.0 g of Compound 9-la were dissolved in 50 ml of dichloromethane, and 8.6 g of urea peroxide were added. The resulting mixture was cooled to 0xc2x0 C. and 18.3 g of trifluoroacetic anhydride were slowly added dropwise. The resulting mixture was stirred for 30 minutes as it was, and then heated to room temperature. When the reaction completed, an aqueous sodium sulfite solution was added to decompose excess peroxides. The resulting mixture was poured into a 0.5 mole/liter aqueous hydrochloric acid solution. Subsequently, extraction was carried out utilizing dichloromethane, and the resulting extract was washed with an aqueous sodium hydrogencarbonate solution, and then dried utilizing magnesium sulfate. Then, any remaining solvents were removed under reduced pressure. The resulting product was washed with acetonitrile and filtered, whereby 4.8 g (a yield of 84 percent) of Compound 9-1b were obtained. The structure was identified utilizing NMR and mass spectra.
Then, 4.0 g of Compound 9-1b were dissolved in 50 ml of ethanol and 3.4 g of sodium hydrosulfide were added. The resulting mixture was heated to 100xc2x0 C. while stirring. After the completion of the reaction, the solvent was removed under reduced pressure, and the resulting residue was dissolved in water. The resulting solution was acidified utilizing acetic acid, whereby precipitates were formed. The resulting precipitates were collected by filtration, and 3.3 g (a yield of 85 percent) of Compound 9-1c were obtained. The structure was identified utilizing NMR and mass spectra.
Subsequently, 3.0 g of Compound 9-1c were subjected to suspension in water and then heated to 40xc2x0 C. Subsequently, 3.3 g of a 30 percent aqueous hydrogen peroxide solution were added dropwise while maintaining a temperature no higher than 50xc2x0 C. The resulting mixture was stirred while maintaining 45xc2x0 C. After setting aside the resulting reaction mixture over night in a refrigerator at 5xc2x0 C., crystals were collected employing filtration and then washed with chilled methanol, whereby 2.7 g (a yield of 91 percent) of Compound 9-1 were obtained. The structure was identified utilizing NMR and mass spectra.
It is possible to synthesize other compounds employing the same or analogous methods.
The added amount of the compounds represented by Formulas 1 through 14 of the present invention is not particularly limited. However, when added to light-sensitive silver halide emulsion layers, the added amount is preferably in the range from 1.0xc3x9710xe2x88x927 to 1.0xc3x9710xe2x88x921 mole per mole of AgI of the layer to be added, and is more preferably in the rang from 1.0xc3x9710xe2x88x926 to 5.0xc3x9710xe2x88x923 mole.
It is also possible to add the compounds represented by Formulas 1 through 14 of the present invention in the form of a solid or a solution. When added in the form of a solution, said compounds may be dissolved in water, in water-soluble solvents, or in mixtures thereof, and the resulting solution may be added. Or said compounds may be subjected to emulsion dispersion, and the resulting dispersion may then be added. When dissolved in water, it is possible to adjust the pH to a high or low value so as to enhance the solubility, and then the resulting solution may be added. Two or more compounds may also be employed in combination.
As reduction sensitization preferably employed in the present invention, it is possible to select any of the methods in which reducing agents, known in the art, are added to silver halide emulsions, in which silver halide grains are subjected to growth or ripening at a low pAg of 1 to 7, which is called silver digestion, or in which silver halide grains are subjected to growth or ripening at a high pH of 8 to 11, which is called high pH ripening. Further, two or more methods may be employed in combination. The light-sensitive materials including the compound represented by Formula 1 are resistive to latent-image regression.
A method, in which reduction sensitizers are added, is preferable one in the point in which it is possible to precisely control the level of reduction sensitization. Reduction sensitizers, known in the art, include stannous salts, amines, polyamine acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds, and borane compounds. In the present invention, it is possible to employ reduction sensitizers selected from those known in the art and to employ those in combination of two or more types. Preferable reduction sensitizers include stannous chloride, urea dioxide, and dimethylaminoborane. It is necessary to determine the added amount of reduction sensitizers, depending on the emulsion production conditions. However, the added amount is suitably in the range from 10xe2x88x927 to 10xe2x88x923 mole per mole of silver halide.
It is also possible to preferably employ ascorbic acid and derivatives thereof as the reduction sensitizers employed in the present invention. It is permissible to dissolve reduction sensitizers in water, alcohols, glycols, ketones, esters, or amides, and to add the resulting composition during grain formation, prior to or after chemical sensitization. Said reduction sensitizers may be added during any of the emulsion preparation processes. However, any method, in which addition is carried out during grain growth, is particularly preferred. Reduction sensitizers may also be previously charged into a reaction vessel. However, it is preferable that the addition is carried out at the optimal time during grain growth.
Further, reduction sensitizers may be added in advance to an aqueous water-soluble silver salt or water-soluble alkali halide solution, and grains may be formed employing these aqueous solutions.
Further, any method is preferred in which, along with grain formation, a reduction sensitizer solution is added several times after dividing said solution, or continuously added over a long period of time.
Silver halide grains incorporated into the silver halide emulsion, which has undergone reduction sensitization, preferably employed in the present invention, may have regular crystal structures such as cube, octahedron, tetradecahedron, or irregular crystal forms such as sphere and a tabular form. Of these structures, tabular grains are preferred. Grains having an optional ratio of (100) plane to (111) plane may also be employed. Further, grains having complexes of these crystal forms may be employed, and grains having various crystal forms may be mixed.
Tabular silver halide grains, as described in the present invention, refer to grains having one twin plane or at least two parallel twin planes. The aspect ratio of said grains is commonly 2 or more, and is preferably from 3 to 12.
In the present invention, the average grain diameter of silver halide grains is preferably from 0.2 to 10 xcexcm, is more preferably from 0.3 to 7.0 xcexcm, and is most preferably from 0.4 to 5.0 xcexcm.
In the present invention, employed as silver halide photographic emulsions may be optional emulsions such as polydispersed emulsions having a wide grain size distribution and monodispersed emulsions having a narrow grain size distribution. However, the monodispersed emulsions are preferably employed.
In the present invention, it is possible that in said silver halide photographic emulsions, optionally employed as silver halides may be silver iodobromide, silver iodochlorobromide, or silver iodochloride. However, silver iodobromide and silver iodochlorobromide are particularly preferred.
In the present invention, the average silver iodide content ratio of silver halide grains contained in the silver halide photographic emulsion is preferably from 1 to 40 mole percent, and is more preferably from 2 to 20 mole percent.
Preferably employed as silver halide grains incorporated into the silver halide photographic emulsion, which is preferably employed in the present invention, may be core/shell type grains. Said core/shell type grains, as described herein, refer to those comprised of a core, and a shell covering said core. Said shell is comprised of one or more layers. The silver iodide content ratio of said core and said shell is preferably different from each other.
It is possible to prepare the silver halide emulsion preferably employed in the present invention, employing various methods known in the art.
Namely, it is possible to employ a single-jet method, a double-jet method, a triple-jet method, or a fine silver halide grain supplying method, and combinations thereof. Further, it is possible to employ a method in combination in which the pH as well as the pAg in a liquid phase, in which silver halide is formed, is controlled while matching the growth rate of silver halide grains.
It is also possible to employ a seed emulsion to produce silver halide photographic emulsions. When said seed emulsion is employed, silver halide grains of said seed emulsion may have regular crystal structures such as a cube, octahedron and tetradecahedron, or irregular crystal forms such as a sphere or a tabular form. Of these grains, grains having an optional ratio of the (100) plane to the (111) plane may be employed. Further, grains having complexes of these crystal forms may also be employed, and grains having various crystal forms may be mixed. In the present invention, when said tabular silver halide grains are employed, silver halide grains in the employed seed emulsion are preferably those having a twin plane, and twinned silver halide grains having two parallel twin planes facing each other are particularly preferred.
In the present invention, if a seed emulsion is employed or not employed, it is possible to apply the methods known in the art to determine conditions for silver halide nucleation and ripening.
During the production of silver halide photographic emulsions, it is possible to employ silver halide solvents known in the art. Examples of said silver halide solvents include (a) organic thioethers described in U.S. Pat. Nos. 3,271,157, 3,531,289, and 3,574,628; Japanese Patent Publication Open to Public Inspection Nos. 54-1019, and 54-158917; and Japanese Patent Publication No. 58-30571; (b) thiourea derivatives described in Japanese Patent Publication Open to Public Inspection Nos. 53-82408, 55-29829, 57-77736 and others; (c) silver halide solvents having a thiocarbonyl group interposed between an oxygen or a sulfur atom and a nitrogen atom, as described in Japanese Patent Publication Open to Public Inspection No. 53-144319; (d) imidazoles described in Japanese Patent Publication Open to Public Inspection No. 54-100717; (e) sulfites; (f) thiocyanates; (g) ammonia; (h) ethylenediamines substituted by a hydroxyalkyl group, described in Japanese Patent Publication Open to Public Inspection No. 57-196228; (i) substituted mercaptotetrazoles described in Japanese Patent Publication Open to Public Inspection No. 57-202531; (j) water-soluble bromides; and (k) benzimidazole derivatives described in Japanese Patent Publication Open to Public Inspection No. 58-54333.
It is possible to apply any of an acidic emulsion method, a neutral emulsion method, and an ammonia emulsion method to the production of silver halide photographic emulsions.
In the production of silver halide photographic emulsions, halide ions and silver ions may be simultaneously mixed, or any one of them may be mixed with any others. Further, taking into account the critical growth rate of silver halide crystals, it is possible to add halide ions and silver ions successively, or simultaneously, while controlling the pAg and pH in the reaction vessel. The halide composition of silver halide grains may be varied utilizing a conversion method at any of the stages during the formation of silver halide.
In the production of silver halide photographic emulsions, during the nucleation process and/or the nucleus growth process of silver halide grains, employing at least one selected from a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including its complex salts), a rhodium salt (including its complex salts), an iron salt or other VIII group metal salts (including their complex salts), metal ions may be added so that said metal ions may be incorporated into the interior and the surface of silver halide grains.
In the present invention, it is possible to employ twinned silver halide crystals having two parallel twin planes facing each other, but in this case, the silver halide grain is preferably tabular. The twinned crystals, as described above, are silver halide crystals having at least one twin plane in one grain. The classification of twin crystal structures is described in detail in Klein and Moiser, Photographisches Korrespondenz, Volume 99, page 99 and Volume 100, page 57.
When tabular silver halide grains are employed in the present invention, at least 50 percent of the total projection area of silver halide grains incorporated into the silver halide emulsion subjected to reduction sensitization, which is preferably employed in the present invention, is preferably comprised of tabular silver halide grains, at least 60 percent of the same is more preferably comprised of tabular silver halide grains, and at least 80 percent is still more preferably comprised of tabular silver halide grains.
When tabular silver halide grains are employed in the present invention, the ratio of tabular silver halide grains having two twin planes parallel to the major plane is preferably at least 60 percent in terms of the number of silver halide grains, is more preferably at least 70 percent, and is still more preferably at least 80 percent.
During the production of silver halide emulsions, it is possible to employ materials capable of forming a protective colloid as the dispersion medium, and gelatin is preferably employed.
In the present invention, when gelatin is employed as the dispersing medium, it is possible to employ alkali processed gelatin, acid processed gelatin, or deionized gelatin. Methods for producing such gelatin is detailed in Arthur Veis, xe2x80x9cThe Macromolecular Chemistry of Gelatinxe2x80x9d, Academic Press, 1964, and others.
Further, listed as materials capable of functioning as forming protective colloid, other than gelatin, may be, for example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin, and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfuric acid ester; sugar derivatives such as sodium alginate; and starch derivatives; synthetic or semi-synthetic hydrophilic homopolymers and copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinyl imidazole or polyvinyl pyrazole.
Silver halide grains in silver halide photographic emulsions preferably possess dislocation lines in their interior. Positions, in which said dislocation lines are located, are not particularly limited. However, said dislocation lines are preferably located near the exterior surface, edges, or tops of silver halide grains. The ratio of positions, into which said dislocation lines are introduced, is preferably at least 50 percent with respect to the total silver amount of silver halide grains, and is more preferably from 60 to 80 percent. The ratio (by number) of silver halide grains having at least 5 dislocation lines per grain is preferably at least 30 percent, is more preferably at least 50 percent, and is still more preferably at least 80 percent. Further, in each case, the number of dislocation lines per grain is preferably at least 10, is more preferably at least 20, and is still more preferably at least 30.
During production of silver halide photographic emulsions, it is possible to employ oxidizing agents known in the photographic art. Listed as oxidizing agents are, for example, hydrogen peroxide (as an aqueous solution) and addition products thereof, such as H2O2, NaBO2, H2O2xe2x80x943H2O, 2Na2CO3xe2x80x943H2O2, Na4P2O7xe2x80x94H2O2, and 2Na2SO4xe2x80x94H2O2xe2x80x942H2O, and peroxyacid salts such as K2S2O3, K2C2O3, K4P2O3, K2[Ti (O)2C2O4]xe2x80x943H2O, peracetic acid, ozone, and thiosulfonic acid compounds.
During production of silver halide emulsions, reduction sensitization may be carried out in combination of said oxidizing agents.
During production of silver halide photographic emulsions, it is possible to carry out desalting during formation of silver halide grains, or after forming silver halide grains, for the purpose of preventing physical ripening or removing unnecessary salts. Desalting may be carried out, for example, employing the method described in Research Disclosure (hereinafter referred to as RD) Item 17643 Sect. II.
In order to remove unnecessary water-soluble salts from flocculated compositions or emulsions after physical ripening, a noodle washing method may be employed in which gelatin is gelled. Alternatively, it is possible to employ a flocculation method, employing inorganic salts, anionic surface active agents, anionic polymers (for example, polystyrene sulfonic acid), or gelatin derivatives (for example, acylated gelatin and carbamoyled gelatin).
Employed as other desalting methods may be desalting utilizing membrane separation described in xe2x80x9cKagaku Kogaku Binran (Handbook of Chemical Engineering)xe2x80x9d, 5th Edition, pages 924 to 954, edited by Kagakukogaku Kyokai and published by Maruzen, and others.
Methods described RD Volume 102 Item 10208 and Volume 131 Item 13122; Japanese Patent Publication Nos. 59-43727 and 62-27008; Japanese Patent Publication Open to Public Inspection Nos. 62-113137, 57-209823, 59-43727, 62-113137, 61-219948, 62-23035, 63-40137, 63-40039, 3-140946, 2-172816, 2-172817, and 4-22942, and others may be applicable to said membrane separation.
In the production of silver halide photographic emulsions, it is possible to select suitable conditions other than those described above while referring to Japanese Patent Publication Open to Public Inspection Nos. 61-6643, 61-14630, 61-112142, 62-157024, 62-18556, 63-92942, 63-151618, 63-163451, 63-220238, and 63-311244; RD Volume 365 Item 36544, Volume 367, Item 36736, and volume 391 Item 39121; and others.
Additives, which are employed to constitute color photographic materials employing silver halide emulsions, are described in RD Items 17643, 18716 and 308119. Tables 1 and 2 show reference sites of concerned compounds.
When light-sensitive color photographic materials are constituted employing silver halide emulsions, it is possible to employ various types of couplers. Specific examples of said couplers are described in the aforementioned RD. Table 3 shows reference sites of concerned couplers.
Additives, which are employed to constitute light-sensitive color materials employing silver halide emulsions may be added employing the dispersion method described in RD Item 308119 XIV. When light-sensitive color materials are constituted employing silver halide emulsions, it is possible to use supports described in RD Item 17643 page 28, RD Item 18716 pages 647 to 648, and RD Item 308119 XIX.
Light-sensitive color photographic materials, employing silver halide emulsions, may be provided with auxiliary layers such as filter layers or interlayers described in RD Item 308119 VII-K.
Light-sensitive color photographic materials, employing silver halide emulsions, may be constituted utilizing various layer configurations such as a conventional layer order, a reversed layer order or a unit constitution as described in RD Item 308119 VII-K.
Silver halide emulsions may be applied to various types of color photographic materials, represented by color negative film for general use or cinema use, color reversal film for slide or television applications, color paper, color positive film, and color reversal paper and various types of black-and-white light-sensitive materials such as monochromatic negative film, microfilm, and X-ray film.
Light-sensitive color photographic materials employing silver halide emulsions may be subjected to photographic processing employing conventional methods described in RD Item 17643 pages 28 to 29, RD Item 18716 page 615, and RD Item 308119 XIX.

Silver halide photographic light-sensitive material

Abstract: Formula 1

Abstract: wherein A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90N(xe2x86x92O)xe2x80x94, or xe2x95x90CR91xe2x80x94, in which R91 represents a substituent, and at least two of A1, A2, A3, A4, and A5 are respectively xe2x95x90N(xe2x86x92O)xe2x80x94 and xe2x95x90CR91xe2x80x94.


The present invention describes cyclopropylindole cytotoxic prodrugs of formulas (I), (II) and (III) as shown in the specification. The present invention is also directed to a method for the site-specific treatment of neoplastic diseases in a mammal which method includes the following steps: (i) administering to an afflicted mammal an effective amount of a targeting agent- enzyme donor peptide conjugate wherein the targeting agent is selected from the group of antibodies, monoclonal antibodies, adhesion molecules and tumor cell surface binding ligands; (ii) administering to the afflicted mammal an effective amount of an enzyme acceptor dimer thereby forming active enzymatic sites at a tumor cell surface; and (iii) administering to the afflicted mammal a therapeutically effective amount of an enzyme-activateable, cytotoxic pro-drug thereby releasing the cytotoxic drug at the tumor site.

(+)-cc-1065 (C. G. Chidester et. al., J. Amer. Chem. Soc., 103, 7629 (1981)) and the duocarmycins (Duocarmycin SA: M. Ichimura et al., J. Antibiot., 1990, 43, 1037; M. Ichimura et al., J. Antibiot., 1991, 44, 1045; Duocarmycin A, B.sub.1, B.sub.2, C.sub.1 and C.sub.2 : M. Ichimura et al., J. Antiobiot., 1988, 41, 1285; I. Takehashi et. al., J. Antiobiot., 1988, 41, 1915; T. Yasuzawa et. al., Chem. Pharm. Bull., 1988, 36, 3728; T. Ogawa et al., J. Antiobiot., 1989, 42, 1299; Pyrindamycin A and B: Ohba et al., J. Antiobiot., 1988, 41, 1515; S. Ishii et al., J. Antiobiot., 1989, 42, 1713) constitute exceptionally potent naturally occurring antitumor antibiotics, isolated from Streptomyces species that heve been shown to be related through their common participation in a characteristic minor grrove adenine N3 alkylation duplex DNA ( M. A. Warpehoski et. el., Chem. Res. Toxicol., 1988, 1, 315; L. Hurley et al., Acc. Chem. Res., 1986, 19, 230; D. L. Boger in Advances in Heterocylic Natural Product Synthesis, Vol. 2, W. H. Pearson; Ed., JAI Press, Greenwich, 1992, 1-188; D. L. Boger, Chemtracts: Org. Chem., 1991, 4, 329; R. S. Coleman and D. S. Boger in Studies in Natural Products Chemistry; Atyta-ur-Rahman, Ed., Elsevier, Amsterdam, 1989, Vol.3, 301; V. H. Rawal et. el., Heterocycl., 1987, 25, 701).
Since the disclosure of the structure of (+)-CC-1065, the agent and structural analogs have been the subject of continued synthetic as well as biological studies. Numerous synthetic analogs of CC-1065 and the duocarmycins have been synthesized incorporating deep-seated changes in the alkylating subunit with the intent of determining the fundamental structural features contributing to the polynucleootide recognition and funtional reactivity (D. L. Boger et al., Pure & Appl. Chem., 1993, 65, 1123; D. L. Boger et al., J. Amer. Chem. Coc., 992, 114, 9318; J. Amer. Chem., Soc., 1992, 114, 5487; D. L. Boger et al., Proc. Natl. Acad. Sci. USA, 1991, 88, 1431; D. L. Boger et al., Bioorg. & Med. Chem. Letts, 1991, 1, 55; J. Amer. Chem. Soc., 1992, 112, 5230; J. Org. Chem., 1990, 55, 5823; J. Org. Chem., 1989, 54, 1238; M. A. Warpehoski et al., J. Med. Chem., 1988, 31, 590). The cytotoxic potency of CC-1065 has been correlated with the alkylating activity and DNA-binding or DNA-interchelating activity of CC-1065. The two activities reside in two separate pads of the molecule. The alkylating activity is contained in the CPI unit A (cyclopropapyrroloindole unit) and the DNA-binding in the two subunits of the molecule.
CC-1065 is 100 to 1000-fold more cytotoxic than conventional cancer chemotherapeutic agents such as duanorubicin, vincristine and methotrexate (B. K. Bhuyan et al., Cancer Res., 1982, 42, 3532). Although CC-1065 showed moderate anti-tumor activity in vivo, it was not evaluated clinically because it caused delayed deaths in mice at therapeutic doses (J. P. McGovren et al., J. Antibiot., 1984, 37, 63; V. L. Reynolds et al., J. Antibiot., 1986, 39, 319). The synthesis of new analogs of CC-1065 that retain the high in vitro cytotoxicity of the parent drug without causing delayed lethality in mice have been reported (M. A. Warpehoski et al., J. Med. Chem., 1988, 31, 590-603). Adozelesin (U-73975) is one of many CC-1065 analogues with excellent broad-spectrum anti-tumor activity in vivo without causing delayed deaths (L.H. Li et al., Invest. New Drugs, 1991, 9, 137).
The high toxicity of CC-1065 and the related duocarmycins has prompted the synthesis of prodrug analogues. Ester and urethane analogs of the CPI phenol of the chloromethyl precursor to the cyclopropyl function typified by Carzelesin (U-80244) (FIG. 4) have proved to be more efficacious in vivo than the parent CPI drugs (L. H. Li et al., Cancer Res., 1992, 52, 4904). Hydrolysis of such esters or urethanes to reform the chloromethyl phenol compound must occur prior to the ring-closure reaction, in order to produce the DNA-reactive cyclopropyl keto compound. A similar prodrug strategy was recently reported for Duocarmycin B2 (H. Ogasawara et al., in Proceedings of the 85th Annual Meeting of the American Association for Cancer Research, Abstract 2325, p390, 1994).
The use of tumor specific antibodies to the targeted delivery of enzymes to the surface to tumor cells in combination with specific enzyme activated prodrugs has been employed in an effort to improve the therapeutic efficacy of a number of cytotoxic drugs. Prodrugs derived from etoposide and mitomycin C in combination with alkaline phosphatase antibody conjugates (P. D. Senter et al., Proc. Natl. Acad. Sci. USA. 1988, 85, 4842; P. D. Senter et al., Cancer Res. 1989, 49, 5789; H. J. Haisma et al., Cancer Immunol. Immunotherap., 1992, 34, 343); bifunctional alkylating agents and carboxypeptidase G2 (C. J. Springer et al., Eur. J. Cancer, 1991, 27 (11), 1361) and bacterial .beta.-glucuronidase (S. -M. Wang et al., Cancer Res., 1992, 52, 4484); vinca alkaloids and .beta.-lactamase (D. L. Meyer et al., Cancer Res., 1993, 53, 3956); and methoxtrexate and carboxypeptidase A (E. Haenseler et al., Biochemistry, 1992, 31, 891) have been reported in the recent literature. This antibody directed enzyme prodrug therapy, "ADEPT" approach has demonstrated efficacy both `in vivo` and in `in vivo` animal model studies. A glucuronide spacer prodrug derivative of doxorubicin has been employed together with a hymanized carcinoembryonic antigen-specific recombinant variable region fused to human .beta.-glucuronidase in an `in vivo` study with nude mice bearing human CEA expressing tumor zenografts. The two component fusion protein/prodrug system showed therapeutic effects superior to those of conventional chemotherapy (K. Bosslet et al., Cancer Res., 1994, 54, 2151).
Additionally, mAb-enzyme conjugates have been used for the site-specific formation of cytotoxic agents. The principle advantage of this approach compared to those involving the direct attachment of a cytotoxic agent to a mAb is that the targeted enzyme can greatly amplify the number of drug molecules delivered to each tumor cell. Furthermore, the cytotoxic effect may not be restricted to only those tumor cells that have bound the conjugate, since the drug is released extracellularly and may be able to migrate to neighboring tumor cells. The principle disadvantage lies in the approach's inherent complexity, since two separate agents and an appropriate time interval between their respective administrations are required for therapeutic efficacy.
Mab-enzyme conjugates can release a vast array of cytotoxins ranging from clinically approved anticancer drugs to highly potent agents that would have little chance for success in the clinic if given systemically. Several groups have demostrated that significant in vitro and in vivo antitumor activities can be obtained using this approach, and clinical studies are now underway. Further refinements in the technology, such as the use of recombinant fusion proteins comprises of relatively nonimmunogenic components, the development of prodrugs with optimal pharmacological distributions and minimal toxicities, and strategies to achieve high tumor to normal tissue conjugate ratios, may provide the basis for making this approach clinically useful.
The use of enzyme-acceptor and enzyme-donor polypeptides in enzyme complementation assays is described in U.S. Pat. No. 4,708,929. The prior art is silent on the use of this technology in the generation of cytotoxic agents by targeted enzymes.


A method of fabricating a plurality of optoelectronic components on a semiconductor substrate, each optoelectronic component comprising several layers grown in a reactor. Every layer is being grown under a predetermined individual pressure. The active layers of all the components are lying substantially at the same height. Control of the pressure in the reactor during growth allows the thickness of the layer grown to be constant or to vary over the substrate area.

Photonic integrated circuits (PIC) are semiconductor chips that include several optoelectronic components (e.g. semiconductor lasers, detectors, waveguides, FET devices, etc.). Such chips can be fabricated using various techniques that have been developed for the individual components. However, because each different component (e.g. a laser and a waveguide) requires a different layer structure, that is a stack of several layers having different thicknesses and compositions, the fabrication of PIC's using these known different techniques requires many processing and growth steps.
More advanced techniques have been disclosed in the literature that make it possible to grow the layers for the different components over the surface of a substrate in a single run. This can be done by controlling the lateral variations in the growth rate over the surface of the substrate, thereby to change the bandgap of the quantum wells in a controllable way laterally over the surface of the substrate. These advanced techniques include selective growth, shadow masked growth and non-planar growth using Metal Organic Chemical Vapour Deposition (MOCVD) growth in a reactor.
For growing high quality layers, the right growth conditions are chosen so as to obtain the best layers. The growth parameters include the temperature, pressure, gas flow.
Using the known techniques provides chips including several devices that consist each of a stack of several layers having different thicknesses and compositions. The composition within a few atomic layers can be changed by changing the gas that is switched to the MOCVD reactor.
As noted above, the growth rate can be controlled for each device over the surface of the substrate and this results in a complete integrated chip including devices in which the active layers are not lying at the same height. Such a structure has some disadvantages in that the coupling between different devices (e.g. a laser and a semiconductor waveguide) is not perfect and the overall surface is not planar.

Method of fabricating optoelectronic components


An apparatus and process for the rendering unintelligible of data stored on digital and analog recording media employs a means for embossing the media and a means for driving the media to traverse a path defined by the means for embossing. In one embodiment, the means for embossing includes knurled rollers that distort the surfaces of recording media passed therebetween. In one embodiment, the means for driving the recording media through the means for embossing includes a motor and at least one drive gear operatively associated with the means for embossing. The process for rendering recorded data unintelligible includes the steps of providing a means for embossing, providing a means for driving recording media through the means for embossing, and urging recording media through the means for embossing.

Compact discs, also known as CD's, are convenient, durable storage devices that are capable of holding large amounts of data. Information on a CD is typically recorded as a series of peaks and valleys located on a reflective metallic layer disposed within the disc itself.
The information stored on a CD is not directly readable by the human eye; a CD player is typically used to access data stored on a given CD. CD players use lasers to "read" CD's, gathering information about the peaks and valleys on the reflective layer of a given disc. This information is processed by an associated computer which then converts the information for use.
Since the data stored on a compact disc is not accessible directly and must be converted before use, it is possible to prevent retrieval of the stored information without physically destroying the entire disc. Altering the disc so as to prevent access to, and conversion, of the stored data will essentially prevent retrieval of the information stored on the disc. In other words, data stored on an "unreadable" disc is often irretrievable.
However, due to advances in technology, the definition of what it means for a disc to be "unreadable" is evolving. It is possible, for example, to retrieve data from very small regions of a damaged compact disc. Data recorded on a CD that is otherwise unreadable with typical CD players may often still be retrieved through the use of specialized machines. As a result, simply making a disc "non-playable" does not necessarily guarantee that the information on the disc is irretrievable. It is possible, by means of special laser reading devices, to retrieve information from small particles of compact discs. Particle size has to be reduced to 0.25 mm before this retrieval method is rendered useless.
To achieve secure destruction of the information on a compact disc, the disc must be altered so that no technology can be employed to access any of the information previously recorded on the disc. As used in this application, the term "secure" destruction of data refers to the destruction of data in a manner that makes the data irretrievable by any means. The irretrievability requirement is of particular importance to government-agencies, especially those agencies involved with issues of national security.
For archival purposes, it is often desirable to retain the disc and label in readable condition, even though destruction of the underlying data is desired. In many instances, the complete destruction of a disc containing sensitive information is not desirable. In some cases, it may be appropriate to keep discs from which no data may be recovered. In situations involving national security, for example, maintaining archives of discs that have been rendered unintelligible will help establish that certain discs have actually been rendered unintelligible, rather than stolen or misplaced. Without an archive of unintelligible, yet identifiable, discs, falsified records may incorrectly indicate that discs with sensitive information have been "destroyed," leading to possible information leaks. This type of archive requires a data destruction system that maintains the media labeling information, while rendering unintelligible the underlying data.
Several approaches have been explored in an attempt to achieve secure destruction of CD data. These approaches have included, among other things, the use of heat, chemical etching compounds, and standard abrasives. Unfortunately, none of these approaches has been adequate. Heating of CD's, for example, resulted in flaking of the information-containing layer. This flaking often produced loose pieces of the disc where the flake size was large enough to allow retrieval of information. Furthermore, chemical etching resulted in the production of noxious fumes which were sufficiently strong to be totally unacceptable in office environments. Abrasives, such as those used in conventional sanders, became so quickly loaded with removed debris that they were rendered useless after only a relatively-short period of use. In fact, early abrasives could not even securely destroy three CD's before the abrasive required replacement. Such a short life span is unacceptable.
Other approaches have used brushes or pads that contact a CD while the CD rotates. Several United States patents have been issued for these devices, as shown in U.S. Pat. Nos. 4,654,918; 4,662,025; and 4,709,437. However, none of the devices described in these patents is directed to the destruction of the information on the CD. They are merely directed to the cleaning of compact discs and, as such, do not accomplish the task of secure destruction.
A device for the secure destruction of CD data must irretrievably destroy the data on the disc without producing noxious fumes and must continue to operate over an extended period of time, having the capacity to destroy the information on more than three CD's.
Primitive abrasive systems that securely destroy the information on some types of CD's have recently been developed. Unfortunately, these abrasive systems are currently only suitable for destroying the information recording surfaces found on read-only CD's, which use aluminum recording surfaces. The abrasive systems used to destroy aluminum-surfaced discs are not satisfactory, however, for newer, recordable CD's which use gold recording surfaces. A new approach to securely destroy data stored on CD's having non-aluminum-based recording surfaces is required.
Thus, what is needed is a compact disc data destruction device that includes advantages of the known devices, while addressing the shortcomings they exhibit. The compact disc data destruction device should alter selected compact discs to destroy the data recorded on the disc so that recovery of the data is prevented. The device should also destroy the information on a compact disc while leaving the associated disc label in a legible format, so that the disc may be identified and accurately stored or discarded as needed. The device should also be clean to use and should not produce noxious fumes. The device should also be useable for an extended period of time, enabling destruction of data on many CD's, regardless of the type of material used for the disc information bearing surface. The device should also be economical and easy to use.

System for the secure destruction of compact disc data


An implantable anastomotic assembly, which is configured to be attached to cardiovascular tissue, includes a connection interface, a plurality of outer plates, and a plurality of connectors configured to extend between and interconnect the connection interface and the plurality of outer plates, respectively, according to various embodiments. An outer plate of the plurality of outer plates is configured to be engaged against the cardiovascular tissue before a respective connector of the plurality of connectors is interconnected between the connection interface and the outer plate of the plurality of outer plates, according to various embodiments.

Heart failure is a leading cause of death in developed countries. An estimated 100,000 Americans develop end-stage congestive heart failure each year with a one-year mortality of approximately 50%. There are many etiologies of heart failure. Treatment options depend on the underlying cause and consist of drug therapy, catheter based or surgical interventions for coronary artery disease, and catheter or surgical procedures for valve disease and other lesions. In the past, the only treatment for end-stage non-correctable heart failure was heart transplantation. Approximately 2,000 heart transplant procedures are done annually in the United States and approximately 5,000 are performed annually world-wide. At any given time, there are approximately 3,000 patients on the heart transplant waiting list in the United States. Consequently, demand for transplantation far outstrips the supply of donor hearts, and it is unlikely that this supply imbalance will improve. Because of the donor supply imbalance, practitioners have developed mechanical systems to support the circulation in patients with heart failure at imminent risk of death.
These systems are known as ventricular assist systems ("VAS") or more commonly as ventricular assist devices ("VAD"). A VAD implemented on the left side of the heart is referred to as a left ventricular assist device ("LVAD"), right side devices are referred to as right ventricular assist devices ("RVAD"s), and when applied to both sides of the heart these devices are referred to as "Bi-VAD"s. Initially, VAD therapy was limited to heart transplant candidates and was intended to buy time for these patients to survive to transplant and to improve their baseline health status going into transplant. This strategy is commonly referred to as Bridge to Transplant ("BTT"). As technology improved, VAD outcomes improved dramatically and VAD therapy was extended to the much larger population of heart failure patients who are not candidates for transplant. VAD treatment in the latter pool of patients with heart failure is referred to as Destination Treatment ("DT").
Conventional LVADs include pulsatile devices that create a pulsed flow and non-pulsatile devices that provide continuous flow. Most current LVADs are continuous flow devices. The smaller continuous flow LVADs are placed within the pericardial space and do not require an intra-abdominal pocket. These devices generally employ a separate component, called an apical cuff, that is first attached to the left ventricular apex, and the pumping device is then attached to the apical cuff. Most conventional apical cuffs consist of a rigid metal cylinder surrounded by a fabric sewing ring.
Conventional installation methods for apical cuffs generally involve attaching the apical cuff to the left ventricular apex with surgically placed sutures that are brought through the sewing ring on the apical cuff. For example, a practitioner may utilize a plurality of horizontal mattress double-armed pledgeted sutures placed from the epicardial surface of the left ventricular myocardium toward the sewing ring on the apical cuff. Each needle is passed through the heart and then up through the sewing ring. After all sutures are placed, the sutures are successively tied resulting in knots on the sewing ring. After the apical cuff is attached to the heart, a core of left ventricular muscle is removed in the center of the apical cuff and the pump is mechanically fastened to the apical cuff. This conventional method/practice of placing pledgeted sutures is time consuming, and imperfections may result in significant bleeding complications.

Ventricular assist assembly, system, and method

THE REGENTS OF THE UNIVERSITY OF COLORADO, A BODY CORPORATE


The invention disclosed provides a multi-fractionable tablet structure initially configurated in a unitary dosage while having readily severable sub-dosage units as components thereof. Score markings are positioned variously about the tablet such as along the top and bottom surfaces thereof. Additionally, score markings may appear along opposite vertical side surfaces of the tablet. Special placement of the score markings readily permits alternatively an accurate equal bisectional or trisectional fracture of the tablet as may be desired for patient consumption.

It is well known in the pharmaceutical art that tablets may be formed with a groove or score marking to facilitate breakage of the tablet into sub-dosage units. Typically, these tablets are configurated circularly with a transverse score marking disposed along the top surface of the tablet such that the tablet may be severed into half-sections. One example of such a tablet is that disclosed by Geller, in U.S. Pat. No. 3,883,647. Another example of a tablet having surface score lines and a circular configuration except severable into quarter-sections is the maltese-cross scored tablet disclosed by Languaer in U.S. Pat. No. 3,723,614.
Because of the inherent difficulties of breaking a grooved tablet into accurate predetermined parts, a variety of diverse attempts have been made in the prior art seeking tablet structures which are readily fractured into sub-dosage units by application of moderate manual pressure. One example of such an attempt is that disclosed by Kraus et al., in U.S. Pat. No. 3,336,200, where two half sections having a highly tapered top surface which join at a score line positioned along the diameter of the tablet. These diverse attempts to improve the convenience and accuracy of breaking a grooved tablet into predetermined parts have achieved limited success at best.
Inherently, the problem of breaking a grooved circular tablet resides in the hardness factor which results from tablet forming presses coupled with the small size configuration which does not allow for either ease of handling or breaking. A typical attempt to sever such circular tablet is by means of a sharp knife or related instrument which results more often than not, in facture of the tablet into undesired miniature pieces. In cases where the severing into two pieces is successful, the pressure which is required along the score marking frequently propels both sections from the initial location unless extreme care is used to contain the two pieces during the breaking operation.
In order to overcome the problem of breaking circular tablets because of the hardness factor and small size, prior art attempts have also been made to configurate oblong tablets having score lines disposed transversely along the top surface. One example of such a tablet is that disclosed by Zellers in U.S. Pat. No. 2,052,376. These oblong tablet configurations have also realized limited success in providing a solution to a readily, accurately severable unitary dosage tablet into sub-dosage units. Also, although tablets such as those disclosed by Zellers are oblong in appearance, the transverse cross-sectional configuration thereof is typically cylindrical. This configuration invites disadvantages associated with inclusion of sufficient amounts of active ingredients in a configuration which may be readily consumed without suffering patient discomfort.
One of the well recognized advantages of having a readily dividable tablet is that it permits the administration of a plurality of sub-dosage units thereby avoiding costs for specially preparing an individual tablet for each dosage unit.
It has now been found that by practice of the present invention, unitary dosage tablets may be prepared having specially disposed score markings which permit breakage of the unitary dosage tablet into multi-sectional sub-dosage units in a convenient, accurate manner. Thus, a number of the disadvantages inherent in prior art attempts to provide a solution to tablet breakage into accurate sub-dosage units which may be conveniently consumed by a patient have now been overcome by practice of the present invention.


The present invention is directed to a novel foamed polymer material for use as a dielectric in electric transmission lines. The foam dielectric of the present invention is obtained from extrusion of a polymer alloy and a supercritical fluid, especially carbon dioxide. Specifically, the foam polymer dielectric is made by:

Conventional coaxial cable comprises a core containing an inner conductor and a dielectric, and a conductive sheath surrounding the core, wherein the sheath serves as an outer conductor. The dielectric is positioned between the inner conductor and outer conductor.
Other transmission lines belong to the class of striplines and its derivatives such as the coplanar line and the microstripline. This class is characterized by a single conductor and one or more ground planes or grounded lines in a planar configuration. The signal travels through the dielectric space defined by these different lines and planes. The dielectric may be homogeneous or consist of different materials, including air.
Various polymeric materials have been used as the primary dielectric material in transmission lines.
One common type of dielectric is polyolefin foam. However, this dielectric is disadvantageous in that dissipation in the dielectric results in signal attenuation. The dielectric losses are a function of the dissipation factor of the polymer, the density of the foam, and the frequency of the signal.
Recently, improvements have been made in polymer foam technology allowing for improved properties of foam which may be used as a dielectric in transmission lines. For example, the MuCell® process of Trexel, Inc. achieves a uniform cell structure having a very small cell size, not more than 100 μm, and frequently not more than 60 μm. The MuCell® process for making microcellular foam is disclosed in U.S. Pat. No. 5,866,053 ("Park"), herein incorporated by reference. In this process, an extrusion system is used to provide the foamed material. The extrusion system involves a supplying plastic pellets which are melted, and also a blowing agent. Specifically, Park uses a supercritical fluid, such as carbon dioxide in the supercritical state, as the blowing agent, to foam a single polymer. In the extruder, the supercritical fluid (carbon dioxide) is dissolved into the molten plastic. The resulting material is then foamed in an expansion stage where a thermodynamic instability is caused by a rapid pressure drop.
In more detail, Park describes an extrusion system for providing a foamed plastic polymer, where a polymer is supplied to an extruder for movement through a rotating screw member. The material is placed in a molten state, and a blowing agent, such as a supercritical fluid, is introduced into the extruder at a selected pressure so that a two-phase mixture of the molten material and the blowing agent is formed. The blowing agent is then diffused into and dissolved in the molten material to form a single-phase solution, which is forwarded from a solution formation area to a nucleation device. Thermodynamic instability is induced through a rapid pressure drop. In a preferred embodiment, a pressure drop greater than 0.9 GPa/s occurs in the nucleation device to nucleate microcells in the solution. A further shaping device, e.g., a die, can be used to produce a foamed material of a desired shape. For further information regarding this process, see <http://www.trexel.com/descript.html>.
By using a polymer alloy which demonstrates high melt strength, superior electric dissipation properties and a glass transition temperature outside the temperature range of −40° C. to 100° C., the low-density foamed dielectric of the present invention is both thermally stable over an extended temperature range and results in extremely low signal attenuation.
U.S. Pat. No. 6,037,545 ("Fox"), herein incorporated by reference, describes a coaxial cable with a foam dielectric. The polymer alloy of the polymer foam is described as a blend of high- and low-density polyethylene. Further, a blowing agent is used in combination with an exothermic nucleating agent, such as azodicarbonamide and an endothermic nucleating agent, such as sodium carbonate/citric acid. The foams described in Fox have densities of between 0.22 g/cm3 and 0.17 g/cm3. However, the foam dielectric of Fox is disadvantageous because foam densities below 0.17 g/cm3 may suffer structural instability and cannot be readily achieved.
The present invention, which uses a combination of a polymer alloy and a supercritical fluid foaming agent, by comparison, can achieve a density as low as about 0.02 g/cm3. In a preferred embodiment of the present invention, the foamed dielectric has a density of from about 0.02 g/cm3 to about 0.20 g/cm3. This translates into superior attenuation properties while preserving favorable structural properties.

Microcellular foam dielectric for use in transmission lines

Abstract: (1) feeding a polymer alloy into an extruder and heating the polymer alloy,

Abstract: (2) feeding a supercritical fluid into the extruder,

Abstract: (3) mixing the polymer alloy and the supercritical fluid,

Abstract: (4) exiting the polymer alloy and the supercritical fluid from the extruder, and

Abstract: (5) passing the polymer alloy and the supercritical fluid through a crosshead.

Abstract: The foam dielectric of the present invention may be used in coaxial transmission lines. In this embodiment, an inner conductor is surrounded by the foam dielectric, which is further surrounded by a second conductor. Stripline and microstripline transmission lines may also be manufactured using the disclosed foam dielectric.


An actuator for a locking mechanism, which locks a shiftable lever in a locked position or a released position. The actuator includes a lock member which is shiftable between a locking position and an unlocking position for causing the lever to be locked in position or to be released from said locking position. A drive mechanism continuously forces the lock member toward said locking position. A drive mechanism causes a rotatable cam to rotate a predetermined distance in a preselected direction. The rotatable cam positions the lock member in the locking position or the unlocking position. The cam is specially designed to permit the lock member in the lock position, to be shifted to the unlocking position against the action of the drive mechanism. The drive mechanism includes a motor for rotating the cam in a predetermined direction, and a control circuit for controlling the power supply to a motor, in order to control the rotational phase angle of the cam.

1. Field of the Invention
The present invention generally relates to an actuator for use in a locking mechanism. More particularly, this invention relates to a shift lock actuator for a shift lever in a vehicle automatic transmission mechanism, and to a drive control circuit.
2. Description of the Related Art
Locking actuators used in vehicles have several applications such as in the automatic transmission mechanism or doors. A conventional actuator includes a motor, a feed screw which in capable of rotating in the forward and backward, a nut which cooperates with the feed screw, a lock bar which is shiftable between a locking position and an unlocking position, and a control circuit for controlling the rotation of the motor.
This actuator however, requires a stopper for holding the lock bar in the locking position or the unlocking position, and a limit switch, for detecting the lock bar position. This conventional design renders the construction of the actuator more complicated, and increases its size. Furthermore, when the lock bar abuts the stopper, a sound is produced, and the stop position of the lock bar varies as a result of the bouncing reaction of the lock bar.
It has been a design objective to cause the shift lock actuator in an automatic transmission mechanism, more difficult to unlock in an emergency situation. Such a design would involve a complex mechanical structure and control circuit.
Because of the need to control the rotation of the motor, the conventional actuator requires a complex control circuit, similar to the one disclosed in the Japanese Unexamined Patent Publication No. 2-38146. In this control circuit, an output circuit supplies current to the motor, and includes a bridge circuit having four transistors. This bridge circuit complicates the control circuit, and increases the size of the shift lock actuator.

Shift lock actuator and control circuit therefor


A transmission/engine control (1) for a motor vehicle with an automatic transmission (2) having a warning apparatus (3) for a disturbance of a signal transmission from an electrical position recognition apparatus (4) of a selection lever (5) which acts on the regulating device of the automatic transmission, via an electronic transmission control. The warning apparatus (3) has the purpose of notifying the driver that no further change in the direction of travel can be executed and the warning apparatus (3) coacts with a program module of a transmission independent processing unit (6) which, upon occurrence of the disturbance of the signal transmission, initiates an emergency operating mode of the automatic transmission (2) and determines a vehicle speed which is less than a specified threshold value. The processing unit (6) communicates a maximum allowable motor torque and/or a maximal allowable motor speed of rotation to a program module of a motor control (7). Alternatively, the warning apparatus (3) can provide a signal to a control apparatus (10) of a vehicle brake system for the activation of the brake system or signal to a locking apparatus (12) to lock the selection lever in its existing position, or the warning apparatus can provide the driver with an optical or an acoustic advisory indication.

The invention concerns a transmission/engine control for a motor vehicle with an automatic transmission in accord with such a control more closely defined in the generic concept of the present patent.
As taken from the state of the technology in the known transmission control for an automatic transmission of a motor vehicle that possesses an electrical circuitry, the placement of gear ratio position is initiated by the options of a driver. The driver accomplishes this by means of activating a gear selection lever, wherein the position of the lever is detected by a position recognition apparatus which sends a corresponding signal to an electronic transmission control.
Should a disturbance occur in a signal transmission along the signal pathway between the gear selection lever and the control of the automatic transmission, then an emergency operating mode is activated in order to allow the automatic transmission to run a hydraulic emergency program. A disturbance can come about through a dropout of a data bus of a Controller Area Network (hereinafter, xe2x80x9cCANxe2x80x9d) or in the failure of an electronic control device, such as the electronic transmission control.
In the case of a disturbance, as a result of the then activated emergency operating mode, no further alteration of the driving program in the automatic transmission is possible, except for stopping the motor. Normally, one gear stage becomes hydraulically fixed in an emergency operating mode. It is impossible for the driver to change this situation by manipulating the position of the gear selection lever since, firstly, the electro-hydraulic actuator for the clutch control can no longer be regulated electrically and, secondly, the electrical position recognition impulses can no longer be transmitted.
The latter, relating to the position recognition apparatus, is especially problematic in the case of an automatic transmission with an exclusively electrical connection between the gear selection lever and the transmission.
For example, DE-OS 196 43 812 describes a parking-block system for an automatic transmission in which the gear selection lever is completely uncoupled and the control demands of the lever are exclusively taken over by the electronic transmission control.
DE-PS 44 22 257 describes a gear selection apparatus for an automatic transmission wherein the stages xe2x80x9cDxe2x80x9d, xe2x80x9cNxe2x80x9d, and xe2x80x9cRxe2x80x9d are exclusively shifted in by an electric motor which is controlled by an electronic transmission regulatory apparatus. In this arrangement, only in the gear selection stage xe2x80x9cPxe2x80x9d would the mechanical-hydraulic coaction between the gear selection lever and the transmission be initiated.
If, by the occurrence of a disturbance of the signal transmission, a gear position for forward travel is shifted, and the driver, by means of the gear selection lever, gives the command for change to a reverse gear, this shifting order cannot be transmitted to the transmission control and carried out and the vehicle, upon starting from rest, disadvantageously travels forward contrary to the expectation of the driver.
In order to alert the driver that the automatic transmission is in the emergency mode, as advised by the state of the technology, the instrument board of the motor vehicle is provided with a warning element or a light signal to indicate such disturbance. Further, another known procedure is to notify the driver of an activation of the emergency mode by the extinguishing of a normally illuminated display of the gear selection position display on the instrument board or elsewhere, which is in electrical communication with the electronic transmission control.
However, this arrangement is disadvantageous because these warning displays only indicate a general emergency condition so that the driver can come to a false conclusion about carrying out a change in the direction of driving.
This can lead to a situation wherein, after a driver""s movement of a gear selection lever to change the travel direction of the vehicle from a xe2x80x9cFORWARDxe2x80x9d gear selection to xe2x80x9cREVERSExe2x80x9d, the vehicle itself moves in a xe2x80x9cfalsexe2x80x9d direction upon starting.
Upon a strong activation of the gas pedal, the motor vehicle can then run into an obstruction in the vicinity since, in such an occurrence, the reaction time in which the driver has available to evaluate the situation can be too short to avoid an accident by subsequent activation of the vehicle brake. Thus, the present invention has the purpose of making available a transmission/engine control for a motor vehicle with an automatic transmission and an electrical position recognition of the placement of gear selection lever with which, in the case of a disturbance of the signal transmission between the gear selection lever and transmission and in an activated emergency mode, the danger of accident by undesired starting from rest in a xe2x80x9cfalsexe2x80x9d direction is avoided, or at least a start of motion with only a low acceleration is possible.
In accord with the invention, this purpose is achieved with a transmission/engine control as discussed below.
When the invented transmission/engine control is constructed, assurance is advantageously given that in the case of a disturbance of a signal transmission from the electrical position recognition apparatus of the gear selection lever to the control means of the automatic transmission, by means of which a disturbance in a direction of travel change can no longer be carried out, and only a slow startup of the motor vehicle is possible.
This is of particular advantage, if the driver of the motor vehicle is of the opinion that he has effected a change in a direction of travel by means of activation of the gear selection lever whereby the fact is that, because of the disturbance, no change of the existing gear stage occurred. With the achievement in accord with the invention, namely, the motor vehicle does not travel with its entire available motor capacity, but only with a lesser motor capacity, so the driver has sufficient time and is able to avoid damage to his motor vehicle.
Alternative to this, the transmission/engine control can be so designed that with this achievement of the purpose of the invention, in a simple manner assurance can be given that in the case of a disturbance of the signal transmission from the electrical position recognition apparatus of the gear selection lever to the regulatory means of the automatic transmission, by which no change in the direction of travel is possible, a driver can start up from still stand with the motor vehicle, having no acceleration, or with only a reduced acceleration, that is, the vehicle speed, in what is for him a xe2x80x9cfalsexe2x80x9d direction.
By means of the activation of the vehicle brakes, in an advantageous manner, an accident can be avoided. To accomplish this, the vehicle brakes can be activated by a processing unit, independent of the transmission, in such a manner that a startup of the motor vehicle is in general prevented, or is possible only at a very slow speed.
With the invented achieving of the purpose of the invention which, in itself alone, or in combination with one of the achievements, provision can be made to achieve the advantage that the driver of a motor vehicle can be advised, through the blocked gear selection lever, that a change in the direction of the travel by means of a change of the gear selection in the automatic transmission is not possible. This would indicate that forward travel, subsequent to reverse travel, is not possible. This invented advantage provides the driver with a clear, and unmistakable announcement, that a change of the travel direction is not possible.
An optical or acoustic advisory display presents a constructive, simple and economical advantage of the invention which can be installed on the instrument panel.
In a development of the transmission/engine control, it can be provided that the warning apparatus is at least activated for a specific time of application.
To accomplish this, advantageously the driver is first signaled that a disturbance is in force and a travel directional change of the motor vehicle is not possible. After expiration of the time of application, the motor related or brake related operational intervention can, in part, be rescinded by the warning so that a larger vehicle mobility is made available and a limited continuation of travel to a repair station is assured. This travel would take place in a hydraulic emergency mode of the automatic transmission without markedly increasing the safety risks to the driver.
Further advantages and improvements of the invention arise with the aid of the drawing, showing a sketch schematically based on the described embodiment.

Transmission/engine control system for a motor vehicle with automatic transmission