JPS63220137A - Silver halide photographic emulsion for direct positive - Google Patents
Silver halide photographic emulsion for direct positiveInfo
- Publication number
- JPS63220137A JPS63220137A JP5445187A JP5445187A JPS63220137A JP S63220137 A JPS63220137 A JP S63220137A JP 5445187 A JP5445187 A JP 5445187A JP 5445187 A JP5445187 A JP 5445187A JP S63220137 A JPS63220137 A JP S63220137A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- halide photographic
- photographic emulsion
- emulsion
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 41
- 239000000839 emulsion Substances 0.000 title claims abstract description 39
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 32
- 239000004332 silver Substances 0.000 title claims abstract description 32
- 229940090898 Desensitizer Drugs 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 7
- QPFYXYFORQJZEC-FOCLMDBBSA-N Phenazopyridine Chemical class NC1=NC(N)=CC=C1\N=N\C1=CC=CC=C1 QPFYXYFORQJZEC-FOCLMDBBSA-N 0.000 abstract description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 abstract description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000370 acceptor Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 150000002344 gold compounds Chemical class 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical class N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- ZXQHSPWBYMLHLB-BXTVWIJMSA-M 6-ethoxy-1-methyl-2-[(e)-2-(3-nitrophenyl)ethenyl]quinolin-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC2=CC(OCC)=CC=C2[N+](C)=C1\C=C\C1=CC=CC([N+]([O-])=O)=C1 ZXQHSPWBYMLHLB-BXTVWIJMSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920006186 water-soluble synthetic resin Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/485—Direct positive emulsions
- G03C1/48515—Direct positive emulsions prefogged
- G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
囚 産業上の利用分野
本発明は直接ポジ用ハロゲン化銀写真乳剤に関するもの
であり、更に詳しくは新規な有機減感剤により高感度化
された直接ポジ用ハロゲン化銀写真乳剤に関するもので
ある。[Detailed Description of the Invention] Industrial Field of Application The present invention relates to a direct positive silver halide photographic emulsion, and more particularly to a direct positive silver halide photographic emulsion that has been made highly sensitive with a novel organic desensitizer. It concerns photographic emulsions.
（Ｂｌ 従来技術及びその問題点
直接ポジ像はある糧のハロゲン化銀写真乳剤を用いて得
る事ができる。例えば、米国特許第３，５０１．３０７
号明細書に記載さｎている様に、カブリを与えたハロゲ
ン化銀と電子受容体を含有するハロゲン化銀写真乳剤が
ある。この種のハロゲン化銀写真乳剤の高感度化のため
にはカブラセ剤や電子受容体の選択が重要であり、又、
分光増感の技術も用いられている。電子受容体として利
用されるものはピナクリプトール・イエローに代表され
る減感色素又はバラコートに代表さｎる有機減感剤が使
わｎる。しかしながら、低感度のものが多くハロゲン化
銀写真乳剤の低カブリ、高感度化を総合的に満足する化
合物は少ない。(Bl Prior Art and Its Problems Direct positive images can be obtained using certain silver halide photographic emulsions. For example, U.S. Pat. No. 3,501,307
As described in the specification, there is a silver halide photographic emulsion containing fogged silver halide and an electron acceptor. In order to increase the sensitivity of this type of silver halide photographic emulsion, selection of the fogging agent and electron acceptor is important.
Techniques of spectral sensitization have also been used. As electron acceptors, desensitizing dyes such as pinacryptol yellow or organic desensitizers such as balakote are used. However, many of them have low sensitivity, and there are few compounds that comprehensively satisfy the requirements for low fog and high sensitivity of silver halide photographic emulsions.
（０発明の目的
本発明者等は高感度で低カブリの直接ポジ用ハロゲン化
銀写真乳剤を製造するため鋭意研究を重ねた結果、この
目的を満す有機減感剤を得る事に成功した。したかって
、本発明の目的は、電子受答体として′＃現な壱機減感
剤を用いる墨によって、高感度かつ低カブリの直接ポジ
用ハロゲン化鋏写真乳剤を提供することにある。(0 Purpose of the Invention The present inventors have conducted extensive research to produce a direct positive silver halide photographic emulsion with high sensitivity and low fog, and as a result, have succeeded in obtaining an organic desensitizer that satisfies this purpose. Therefore, it is an object of the present invention to provide a halogenated scissors photographic emulsion for direct positive use with high sensitivity and low fog using ink using a modern desensitizer as an electron acceptor.
（ＩＪ）発明の構放
本発明において用いられるｉ′ｒ現な有機減感剤は一般
式〔■〕又は（ＩＩ）で表わされるピリジウム塩である
。(IJ) Explanation of the Invention The organic desensitizer used in the present invention is a pyridium salt represented by the general formula [■] or (II).
Ｘ−Ｘ−
（１） （ｎ）
式中Ｒ１〜Ｒ８は同じでも異なっていてもよく、そｎぞ
ｎ水素、アルキル基を示し、几とＲ，ＲとＲ″、Ｒ８ト
Ｒ４、ｎ ＩＩ トＲ＠、又はＲ’とＲ” でペンセフ
環又は複素環を形成していてもよい。X-X- (1) (n) In the formula, R1 to R8 may be the same or different, and each represents hydrogen or an alkyl group, R and R, R and R'', R8 and R4, and n II R@, or R' and R'' may form a pensef ring or a heterocycle.
几は置換さｒていてもよい（例えばスルホ基）アルキル
基を表わす。又、Ｘ−はアニオンであり、ハライドアニ
オンスルホ酸アニオン、パークロレイト、テトラフロロ
ボレート等を表わす。几represents an alkyl group which may be substituted (for example, a sulfo group). Further, X- is an anion, and represents a halide anion, sulfonic acid anion, perchlorate, tetrafluoroborate, or the like.
次に本発明で使用される有機減感剤の代表的な例をあげ
る。Next, typical examples of organic desensitizers used in the present invention will be given.
【１） ０、Ｈ，１− （６） 。、 （η Ｎ ０３Ｈ１ ０、Ｈ９ Ｎ ０、）Ｊ。[1] 0, H, 1- (6). , (η N 03H1 0, H9 N 0,)J.
本発明で用いられるシアノピリジウム塩はシアノピリジ
ン類とアルキル化剤の反応で容易に合成できる。合成例
を用いて、その詳細を述べる。The cyanopyridium salt used in the present invention can be easily synthesized by reacting cyanopyridines and an alkylating agent. The details will be described using a synthesis example.
く２−シアノ−Ｎ−エチルピリジニウム・アイオダイド
の合成〉
２−シアノピリジン３Ｉとヨウ化エチルｌｏｄを８時間
加熱還流後した０放冷後析晶をＰ取し、エーテルで洗浄
後乾燥したＯ
ｍｐ １６８℃（ｄｅｃ） 収音２．５ＪＴく４−
シアノ−Ｎ−エチルピリジニウム−アイオダイドの合成
〉
４−シアノピリジン２９とヨウ化エチル８Ｉ１１／を８
時間加熱還流した。放冷後析晶を戸数し、エーテルで洗
った後乾燥した。Synthesis of 2-cyano-N-ethylpyridinium iodide> 2-cyanopyridine 3I and ethyl iodide were heated under reflux for 8 hours. After cooling, the precipitated crystals were collected, washed with ether, and dried. 168℃ (dec) Sound pickup 2.5JT 4-
Synthesis of cyano-N-ethylpyridinium-iodide> 4-cyanopyridine 29 and ethyl iodide 8I11/8
The mixture was heated to reflux for an hour. After cooling, the precipitated crystals were separated, washed with ether, and dried.
ｍｐ １４３〜１４５° 収量３．７ｇ本発明で
使用される他の減感剤も上記合成例に準じて容易に合成
する事ができる。mp 143-145° Yield 3.7g Other desensitizers used in the present invention can also be easily synthesized according to the above synthesis example.
本発明においては、公知の方法で上記の減感剤をハロゲ
ン化銀写真乳剤に添加することができる。In the present invention, the desensitizer described above can be added to the silver halide photographic emulsion by a known method.
例えば、メタノール、エタノール、インプロパツール、
ピリジン、ジメチルホルムアミド、アセトン、水等の単
独または混合した溶媒の溶液として添加することができ
る。また、超音波分散を用いて、乳剤中に加えることも
できる。For example, methanol, ethanol, improper tool,
It can be added as a solution in a solvent such as pyridine, dimethylformamide, acetone, water, etc. alone or in combination. It can also be added to the emulsion using ultrasonic dispersion.
本発明において用いられる減感剤の添加量は、ハロゲン
化銀写真乳剤の種々の因子によって変化するが、好まし
くはｌＸｌ０−”２Ｘ１０−”ｍｏｌｅ／ｍｏｌｅ Ａ
ｇの範囲である。The amount of the desensitizer used in the present invention varies depending on various factors of the silver halide photographic emulsion, but is preferably 1X10-"2X10-"mole/mole A
g range.
乳剤への減感剤の添加は、乳剤製造のどの段階でも行え
るが、塗布直前に行うのが特に好ましい。Although the desensitizer can be added to the emulsion at any stage of emulsion production, it is particularly preferred to add it immediately before coating.
本発明に用いられるハロゲン化銀写真乳剤には、塩化銀
、臭化銀、塩臭化銀、沃化銀、塩沃臭化銀、または沃臭
化銀乳剤がある。Silver halide photographic emulsions used in the present invention include silver chloride, silver bromide, silver chlorobromide, silver iodide, silver chloroiodobromide, and silver iodobromide emulsions.
高感度の直接ポジ用ハロゲン化銀写真乳剤を得るために
は、８０モル％以上の臭化物を含むハロゲン化銀写真乳
剤が好ましい。In order to obtain a highly sensitive direct positive silver halide photographic emulsion, a silver halide photographic emulsion containing 80 mol % or more of bromide is preferred.
本発明において用いられるハロゲン化銀写真乳剤には、
単分散のもの、単分散でないものの両方が含まれるが、
単分散のものの方がより好ましい。The silver halide photographic emulsion used in the present invention includes:
It includes both monodisperse and non-monodisperse,
Monodisperse ones are more preferable.
また、本発明に用いらｎるハロゲン化銀写真乳剤の晶癖
は、立方体のものでも、正八面体のものでもよいが、立
方体のものの方がより好ましい。Further, the silver halide photographic emulsion used in the present invention may have a cubic crystal habit or a regular octahedral crystal habit, but a cubic crystal habit is more preferable.
また、本発明に用いられるハロゲン化銀写真乳剤の粒子
は、規則正しいものが好ましい。Furthermore, the grains of the silver halide photographic emulsion used in the present invention are preferably regular.
本発明には、ハロゲン化銀結晶内部に自由電子を捕獲す
る核を有し、表面に化学カブリ剤でカブリを与えらした
乳剤を用いてもよい。この型の乳剤の製造は、例えは、
米国特許第３．３６７．７７８号、同第３，６３２，３
４０号、同第３，７０９，６８９号の各明細書に記載さ
れている。In the present invention, an emulsion having a nucleus for capturing free electrons inside a silver halide crystal and whose surface is fogged with a chemical fogging agent may be used. The production of this type of emulsion is, for example,
U.S. Patent No. 3,367,778, U.S. Patent No. 3,632,3
No. 40 and No. 3,709,689.
本発明に用いられるハロゲン化銀写真乳剤は光または、
化学カブリ剤によりかぶらされる。The silver halide photographic emulsion used in the present invention is
Fogged by chemical fogging agents.
化学的にカブリを賦与する方法には、例えば、アントワ
ン・オート−（Ａｎｔｏｉｎｅ Ｈａｕｔｏｔ）および
アンリ・ンーブニル（Ｈｅｎｒｊ ５ａｕｂｅｎｊｅｒ
）によりシアンセ・アンダストリー・フォトグラフイン
ク（５ｃｉｅｎｃｅ ｅｔ Ｉｎｄｕａｔｒｉｅｓ Ｐ
ｈｏｔｏｇｒａｐｈｉｑｕｅ ） ２８巻５７〜６５頁
（１９５７年発行）に記載された化学増感の方法を用い
ると好ましい結果が得らｎるＯ
本発明に用いられるノ・ロゲン化銀写真乳剤は還元剤に
より、カブリを与えることができる。Methods of chemically imparting fog include, for example, those described by Antoine Hautot and Henri Aubenjer.
) by Ciense Industries Photography Inc.
Favorable results can be obtained by using the chemical sensitization method described in Vol. 28, pp. 57-65 (published in 1957). It can give fog.
還元剤の具体例としては、塩化第一錫、二酸化チオ尿素
、ホルマリン、ヒドラジンおよびその誘導体、アミンボ
ラン等かある。Specific examples of reducing agents include stannous chloride, thiourea dioxide, formalin, hydrazine and its derivatives, and amineborane.
本発明に用いられるハロゲン化銀写真乳剤は金化合物に
よっても、カブリを与えることかできる。The silver halide photographic emulsion used in the present invention can also be fogged by a gold compound.
金化合物の具体例としては、例えば塩化金酸、塩化金酸
カリウム、チオ硫酸金カリラム等がある。Specific examples of the gold compound include chloroauric acid, potassium chloroaurate, potassium thiosulfate, and the like.
本発明に用いられるハロゲン化銀写真乳剤は還乳剤と銀
よりも負電位の金属化合物とを組み合せることによって
も、カブリを与えることができる。The silver halide photographic emulsion used in the present invention can also be fogged by combining a reducing emulsion with a metal compound having a more negative potential than silver.
銀電位よりも負電位の金属化合物の具体例としては、前
述の金化合物の他に、塩化白金酸カリウム等の白金化合
物、ヘキサクロロイリジウム酸カリウム等のイリジウム
化合物が用いられる。As specific examples of metal compounds having a potential more negative than silver potential, in addition to the above-mentioned gold compounds, platinum compounds such as potassium chloroplatinate and iridium compounds such as potassium hexachloroiridate are used.
更に上記の方法と、チオ硫酸ナトリウムやアリルチオ尿
素等の含硫増感剤、または、チオシアン酸カリウム等の
チオシアン酸化合物を併用することにより、ハロゲン化
銀写真乳剤をかぶらせることもできる。Furthermore, a silver halide photographic emulsion can be fogged by using the above method in combination with a sulfur-containing sensitizer such as sodium thiosulfate or allylthiourea, or a thiocyanic acid compound such as potassium thiocyanate.
本発明において用いられる保護コロイドとしては、例え
ばゼラチン、アルブミン、寒天、アラビアゴム、アルギ
ン酸等の天然物、ポリビニルアルコール、ポリビニルピ
ロリドン、セルロースエーテル等の如き水溶性合成樹脂
等が挙げられる。Examples of the protective colloid used in the present invention include natural products such as gelatin, albumin, agar, gum arabic, and alginic acid, and water-soluble synthetic resins such as polyvinyl alcohol, polyvinylpyrrolidone, and cellulose ether.
本発明においては、安定剤、増白剤、紫外線吸収剤、硬
膜剤、界面活性剤、防腐剤、可塑剤、マット化剤等の各
種添加剤をハロゲン化銀；真乳剤に含ませることかでき
る〇
本発明において用いられる支持体としては、例えばポリ
エチレンテレフタレート、セルロースアセテート等の樹
脂フィルム、合成紙、耐水紙等が挙げられる。また、プ
ラスチックがラミネートされた紙も使用することができ
る。これらの支持体上に必要に応じて、公知の方法によ
り下引層を設けることもできる。In the present invention, various additives such as stabilizers, brighteners, ultraviolet absorbers, hardeners, surfactants, preservatives, plasticizers, and matting agents may be included in the silver halide; true emulsion. Examples of the support used in the present invention include resin films such as polyethylene terephthalate and cellulose acetate, synthetic paper, and waterproof paper. Paper laminated with plastic can also be used. If necessary, a subbing layer can be provided on these supports by a known method.
本発明の直接ポジ用ハロゲン化銀写真乳剤を塗布した感
光材料は、公知の現像、定着、漂白等の各処理浴、ある
いは、これらが組み合わされた処理浴により処理される
。The light-sensitive material coated with the direct positive silver halide photographic emulsion of the present invention is processed using known processing baths such as development, fixing and bleaching, or a combination of these processing baths.
本発明の特徴は、新規な有機減感剤を電子受容体として
用いて、高感度の直接ポジ用ハロゲン化銀写真乳剤が得
られる点にある。A feature of the present invention is that a highly sensitive direct positive silver halide photographic emulsion can be obtained by using a novel organic desensitizer as an electron acceptor.
以下、本発明を実施例に基づいて詳細に説明するが、も
ちろん本発明がこｎに限定されるものではない。Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is of course not limited thereto.
（匂実施例
実施例
コントロール・ダブル・ラン法を用いて、沃臭化銀乳剤
（ヨード２モル％）を調製した。この原乳剤は晶癖が立
方体で、平均粒子サイズ０．２５ｍで、平均粒子サイズ
の３０％以内に９５重量％の粒子を含む単分散乳剤であ
った。沈でん、水洗後セラチンを加え、ｐＨを８．０、
ＰＡｇを５．０に調整し、塩化金酸カリウム２ ”Ｆ
／ ｍｄｅＡｇを加え、６０℃で２時間かぶらせた。そ
の後ＰＡｇを８．５、ｐＨを５．０に調整して試料分を
分割し、減感剤をハロゲン化銀１モル当り、表１に示す
ように添加し、？ｉ！Ｉ！膜剤と界面活性剤を加え、下
引加工したポリエチレンをラミネートとした紙支持体上
に硝酸銀に換算して、３．７１７ｍ”の塗布量で塗布し
た。乾燥後者試料を適当な大きさに裁断し、０．１５の
濃度差のあるウェッジを通して露光した後、コタ′ツク
社処方Ｄ−７２現像液を用いて２０℃で９０秒間現像し
、酸性定着液を用いて定着した後、水洗し、乾燥した。(Odor Example) A silver iodobromide emulsion (2 mol % iodine) was prepared using the control double run method. This raw emulsion had a cubic crystal habit, an average grain size of 0.25 m, and an average It was a monodispersed emulsion containing 95% by weight of particles within 30% of the particle size. After precipitation and water washing, ceratin was added and the pH was adjusted to 8.0.
Adjust PAg to 5.0 and add potassium chloroaurate 2”F.
/ mdeAg was added and the mixture was heated at 60°C for 2 hours. Thereafter, the PAg was adjusted to 8.5 and the pH to 5.0, the sample was divided, and a desensitizer was added per mole of silver halide as shown in Table 1. i! I! A coating amount of 3.717 m'' in terms of silver nitrate was applied onto a paper support laminated with subbed polyethylene to which a film agent and a surfactant were added.The dried latter sample was cut into appropriate sizes. After exposing the film to light through a wedge with a density difference of 0.15, it was developed at 20°C for 90 seconds using Kotatsuku's D-72 developer, fixed using an acidic fixer, and then washed with water. Dry.
濃度測定の結果、表１を得た。As a result of concentration measurement, Table 1 was obtained.
表中の８は、光学濃度０．７５のところで測定した値で
あり、バラコート（化合物Ａ）を添加した値を１．０と
した相対値で表わした０又、Ｄｌｍは最低′ＩＩ４度を
表わしている。8 in the table is the value measured at an optical density of 0.75, and is expressed as a relative value with the value with Baraquat (compound A) added as 1.0. It represents.
化合物Ａ
Ｂｒ
表１
■
［
■
（Ｆ） 発明の効果
表１から明らかな様に、本発明に用いられた有機減感剤
は秀れており、最低濃度も小さいという特徴がある。又
、増感色素との併用により、さらに高い増感性が期待で
きる。Compound A Br Table 1 ■ [ ■ (F) Effects of the Invention As is clear from Table 1, the organic desensitizer used in the present invention is excellent and has the characteristic of having a low minimum concentration. In addition, even higher sensitization can be expected by using it in combination with a sensitizing dye.
従って、本発明の有機減感剤を電子受容体として、利用
する事により高感度な直接ポジ用ハロゲン化銀写真感光
材料を得る事ができる。Therefore, by using the organic desensitizer of the present invention as an electron acceptor, a highly sensitive direct positive silver halide photographic light-sensitive material can be obtained.
Claims (1)
剤を、少なくとも１種含有する事を特徴とする直接ポジ
用ハロゲン化銀写真乳剤。 ▲数式、化学式、表等があります▼〔 I 〕▲数式、化
学式、表等があります▼〔II〕 〔式中Ｒ＾１〜Ｒ＾８は同じでも異なっていてもよく、
それぞれ水素、アルキル基、を示し、Ｒ＾１とＲ＾２、
Ｒ＾２とＲ＾３、Ｒ＾３とＲ＾４又はＲ＾５とＲ＾６、
Ｒ＾７とＲ＾８でベンゼン環、又は複素環を形成してい
てもよい。Ｒはアルキル基を表わす。 また、Ｘ＾−はアニオンを表わす。〕(1) A direct positive silver halide photographic emulsion containing at least one organic desensitizer represented by the general formula (I) or (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I]▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] [In the formula, R^1 to R^8 may be the same or different,
R^1 and R^2 each represent hydrogen and an alkyl group,
R^2 and R^3, R^3 and R^4 or R^5 and R^6,
R^7 and R^8 may form a benzene ring or a heterocycle. R represents an alkyl group. Moreover, X^- represents an anion. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5445187A JPS63220137A (en) | 1987-03-09 | 1987-03-09 | Silver halide photographic emulsion for direct positive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5445187A JPS63220137A (en) | 1987-03-09 | 1987-03-09 | Silver halide photographic emulsion for direct positive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63220137A true JPS63220137A (en) | 1988-09-13 |
Family
ID=12971055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5445187A Pending JPS63220137A (en) | 1987-03-09 | 1987-03-09 | Silver halide photographic emulsion for direct positive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63220137A (en) |
-
1987
- 1987-03-09 JP JP5445187A patent/JPS63220137A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH10206995A (en) | Silver halide photographic sensitive material | |
| US4521508A (en) | Silver halide photographic light-sensitive materials | |
| US3765901A (en) | Spectral sensitization of light-sensitive silver halide emulsions | |
| US3541089A (en) | Method of preparing chain-substituted trimethine indole dyestuffs | |
| US3573920A (en) | Fine grain silver halide emulsions containing novel dye combinations | |
| US3408196A (en) | Sensitization of silver halide emulsion with labile selenium formed in situ | |
| US3563754A (en) | Photographic process | |
| JPS63220137A (en) | Silver halide photographic emulsion for direct positive | |
| JPS61277947A (en) | Silver halide photographic sensitive material | |
| JPS60239737A (en) | Silver halide photosensitive material | |
| JPS63220135A (en) | Silver halide photographic emulsion for direct positive | |
| JP2873852B2 (en) | Silver halide photographic material | |
| JPH037931B2 (en) | ||
| US3752673A (en) | Silver halide emulsion containing a merocyanine dye | |
| US5077190A (en) | Process for spectral sensitization of a silver halide emulsion | |
| JP2604240B2 (en) | Silver halide photographic material | |
| JPS62222243A (en) | Silver halide photographic sensitive material | |
| JPS63220133A (en) | Silver halide photographic emulsion for direct positive | |
| JPS63253349A (en) | Silver halide photographic emulsion for direct positive | |
| JPH0629944B2 (en) | Photographic material that can be handled under white light | |
| JPS63243937A (en) | Direct positive silver halide photographic emulsion | |
| JPS63220134A (en) | Silver halide photographic emulsion for direct positive | |
| JPH06230507A (en) | Silver halide photographic sensitive material | |
| JPS63220136A (en) | Silver halide photographic emulsion for direct positive | |
| JPS6052417B2 (en) | photographic material |