JPH0360419B2 - - Google Patents
Info
- Publication number
- JPH0360419B2 JPH0360419B2 JP10929383A JP10929383A JPH0360419B2 JP H0360419 B2 JPH0360419 B2 JP H0360419B2 JP 10929383 A JP10929383 A JP 10929383A JP 10929383 A JP10929383 A JP 10929383A JP H0360419 B2 JPH0360419 B2 JP H0360419B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- dye
- heat
- photosensitive material
- 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.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- -1 silver halide Chemical class 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004442 acylamino group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims 2
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 125000004149 thio group Chemical group *S* 0.000 claims 1
- 239000000975 dye Substances 0.000 description 21
- 239000010410 layer Substances 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000011161 development Methods 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- WVKWKEWFTVEVCF-UHFFFAOYSA-N 2h-benzotriazole-4-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=NNN=C12 WVKWKEWFTVEVCF-UHFFFAOYSA-N 0.000 description 2
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- PIEZJBSAYXLSPM-UHFFFAOYSA-N O1CCCC1.C(=C)(Cl)Cl Chemical compound O1CCCC1.C(=C)(Cl)Cl PIEZJBSAYXLSPM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 1
- 125000004657 aryl sulfonyl amino group Chemical group 0.000 description 1
- MCARFLPZFIHKIF-UHFFFAOYSA-N azane;2h-benzotriazole-4-sulfonic acid Chemical compound [NH4+].[O-]S(=O)(=O)C1=CC=CC2=NNN=C12 MCARFLPZFIHKIF-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- ICPGNGZLHITQJI-UHFFFAOYSA-N iminosilver Chemical class [Ag]=N ICPGNGZLHITQJI-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
- G03C1/49854—Dyes or precursors of dyes
-
- 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
-
- 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
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/40—Development by heat ; Photo-thermographic processes
- G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
- G03C8/4033—Transferable dyes or precursors
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
〔産業上の利用分野〕
本発明は熱現像カラー感光材料に関し、特に、
熱現像によつて拡散性色素を放出又は形成する色
素供与物質を含有する新規な熱現像カラー拡散転
写画像を得る感光材料に関する。
〔従来技術〕
従来から知られている感光性ハロゲン化銀を使
用する写真法は感光性、階調性および画像保存性
等において他の写真法に勝るものであり、最も広
く実用化されてきた写真法である。
しかしながら、この方法においては現像、定着
および水洗などの処理工程に湿式処理法を用いる
ために、処理に時間と手間がかかり、また処理薬
品による人体への影響が懸念されたり、或いは処
理室や作業者に対する上記薬品による汚染が心配
されたり、更には廃液による公害の発生への配慮
といつた多くの問題点が存在している。従つて感
光性ハロゲン化銀を用いかつ乾式処理が可能であ
る感光材料の開発が望まれていた。
上記乾式処理写真法に関しては多くの提案が行
なわれているが、なかでも現像工程を熱処理で行
ない得る熱現像感光材料は上記要望に適つた感光
材料として注目を集めている。
この様な熱現像感光材料については、例えば特
公昭43−4921号および同43−4924号公報にその記
載があり、有機銀塩、ハロゲン化銀および還元剤
から成る感光材料が開示されている。
かかる熱現像感光材料に改良を加え、種々の方
法によつて色画像を得る試みがなされている。
例えば米国特許第3531286号、同第3761270号お
よび同第3764328号等の各明細書中に芳香族第１
級アミン現像主薬の酸化体とカプラーとの反応に
よつて色画像を形成させる熱現像カラー感光材料
が開示されている。
また、リサーチ・デイスクロージヤー15108号
および第15127号には、スルホンアミドフエノー
ル或いはスルホンアミドアニリンの誘導体現像主
薬の酸化体とカプラーとの反応によつて色画像を
形成させる熱現像カラー感光材料が開示されてい
る。しかし、これらの方法においては、熱現像後
露光部に還元銀の像と色画像とが同時に生ずるた
め、色画像が濁るという問題点があつた。なお、
この問題点を解決する方法として、銀像を液体処
理により取り除くか、色素のみを他の層、例えば
受像層を有する受像シートに転写する方法がある
が、未反応物と色素を区別して色素のみを転写す
ることは容易でないという問題点を有している。
また、リサーチ・デイスクロージヤー16966号
に色素部を有する有機イミノ銀塩を用い、熱現像
によつて露光部でイミノ基を遊離させ、溶剤を用
いて転写紙としての受像層上に色画像を形成させ
る熱現像カラー感光材料が開示されている。しか
し、この方法では光の当つていない部分での色素
の遊離を抑制することが困難であり、鮮明な色画
像を得ることができないという問題点を有してい
る。
また、特開昭52−105821号、同52−105822号、
第56−50328号各公報、米国特許第4235957号明細
書、リサーチ・デイスクロージヤー14448号、同
15227号および同18137号等に感熱銀色素漂白法に
よつてポジの色画像を形成させる熱現像カラー感
光材料が開示されている。しかし、この方法にお
いては、色素の漂白を速めるための活性化剤を含
むシートを重ねて加熱するなどの余分な工程と写
真構成材料が必要であり、かつ得られた色画像が
長期の保存中に、共存する遊離銀などによつて
徐々に還元、漂白されるという問題点を有してい
る。
また、米国特許第3180732号、同第3985565号お
よび同第4022617号の各明細書中並びにリサー
チ・デイスクロージヤー12533号にロイコ色素を
利用して色画像を形成させる熱現像カラー感光材
料が開示されている。しかし、この方法ではロイ
コ色素を安定に写真感光材料に内蔵することは困
難で、保存時に徐々に着色するという問題点を有
している。
更にまた、特開昭57−179840号公報には、色素
放出助剤および拡散性色素を放出する還元性色素
供与物質を用いて色画像を形成させる熱現像カラ
ー感光材料が開示されている。しかし、この方法
では、色素放出助剤を用いることが必須要件であ
り、この色素放出助剤とは所謂塩基もしくは塩基
のプレカーサーである。このように塩基もしくは
塩基プレカーサーを用いる技術では、有機銀塩酸
化剤を用いる熱現像感光材料においては塩基の存
在によつてカブリが増し、最高濃度が低くなると
いう問題点を有している。
更にまた、特開昭57−186744号公報には、熱現
像により拡散性色素を放出する色素供与物質を用
いて色画像を得る熱現像カラー感光材料が開示さ
れている。しかし、該公報に記載の色素供与物質
の例示化合物は重層塗布時または熱現像時におけ
る層間の移動が完全に止められているとはいい難
く、そのために色濁りを生じやすいという欠点を
有している。
〔発明の目的〕
そこで、本発明の目的は、新規なカラー画像形
成方法が可能である熱現像カラー感光材料を提供
することにあり、かつこれまでの公知の感光材料
が有していた問題点を解決することを目的とす
る。
即ち、本発明の目的は新規な色素供与物質を含
有する熱現像カラー感光材料を提供するにある。
本発明の他の目的は、簡単な熱現像操作によつ
て鮮明なカラー画像を得ることができる熱現像カ
ラー感光材料を提供するにある。
本発明の更に他の目的は、露光前に長期間にわ
たり保存（以下、生保存という）しても高い濃度
のカラー画像を得ることができる熱現像カラー感
光材料を提供することにある。
本発明の更に他の目的は、カブリの発生が低
く、高い最高濃度が得られる熱現像カラー感光材
料を提供することにある。
本発明の更に他の目的は、色濁りの少ない鮮明
なカラー画像を得ることができる熱現像カラー感
光材料を提供することにある。
〔発明の要旨〕
前記目的を達成する本発明に係る熱現像カラー
感光材料は、支持体上に少なくとも(a)ハロゲン化
銀、(b)有機銀塩、(c)還元剤、(d)バインダーおよび
(e)色素供与物質を含有する写真構成層を有する熱
現像カラー感光材料において、該色素供与物質が
下記一般式〔Ｉ〕で表わされる重合可能な化合物
から生成されるポリマーであることを特徴とす
る。
一般式〔〕
式中、Ｒは水素原子またはメチル基を表し、Ｊ
は−Ｏ−、
[Industrial Field of Application] The present invention relates to a heat-developable color photosensitive material, and in particular,
The present invention relates to a photosensitive material from which a novel heat-developable color diffusion transfer image can be obtained, which contains a dye-providing substance that releases or forms a diffusible dye upon heat development. [Prior art] The conventionally known photographic method using photosensitive silver halide is superior to other photographic methods in terms of photosensitivity, gradation, image preservation, etc., and has been the most widely put into practical use. It is a photographic method. However, since this method uses wet processing for processing steps such as development, fixing, and water washing, processing is time-consuming and labor-intensive, and there are concerns that the processing chemicals may affect the human body, or the processing room and work area may be affected. There are many problems, such as concerns about contamination of people by the above-mentioned chemicals, and further consideration of pollution caused by waste liquid. Therefore, it has been desired to develop a photosensitive material that uses photosensitive silver halide and can be dry processed. Many proposals have been made regarding the above-mentioned dry processing photographic method, and among them, heat-developable photosensitive materials in which the developing step can be carried out by heat treatment are attracting attention as photosensitive materials that meet the above-mentioned requirements. Such heat-developable photosensitive materials are described in, for example, Japanese Patent Publication Nos. 43-4921 and 43-4924, which disclose photosensitive materials comprising an organic silver salt, silver halide, and a reducing agent. Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, in US Pat. No. 3,531,286, US Pat. No. 3,761,270, and US Pat.
A heat-developable color photosensitive material is disclosed in which a color image is formed by a reaction between an oxidized product of an amine developing agent and a coupler. Furthermore, Research Disclosure No. 15108 and No. 15127 disclose a heat-developable color photosensitive material in which a color image is formed by the reaction of an oxidized product of a sulfonamide phenol or sulfonamide aniline derivative developing agent with a coupler. has been done. However, in these methods, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a problem that the color image becomes cloudy. In addition,
To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as an image receiving sheet having an image receiving layer. The problem is that it is not easy to transfer. In addition, using an organic imino silver salt having a dye part in Research Disclosure No. 16966, the imino group is liberated in the exposed area by heat development, and a color image is transferred onto the image-receiving layer as a transfer paper using a solvent. A heat-developable color photosensitive material is disclosed. However, this method has the problem that it is difficult to suppress the release of dye in areas not exposed to light, and it is not possible to obtain clear color images. Also, JP-A-52-105821, JP-A No. 52-105822,
No. 56-50328, U.S. Patent No. 4235957, Research Disclosure No. 14448,
No. 15227 and No. 18137, etc., disclose heat-developable color photosensitive materials in which a positive color image is formed by a heat-sensitive silver dye bleaching method. However, this method requires extra steps and photographic construction materials, such as stacking and heating sheets containing activators to speed up the bleaching of the dyes, and the resulting color images do not survive long-term storage. Another problem is that it is gradually reduced and bleached by coexisting free silver and the like. Further, in the specifications of U.S. Patent No. 3180732, U.S. Patent No. 3985565, and U.S. Patent No. 4022617, as well as Research Disclosure No. 12533, heat-developable color photosensitive materials are disclosed that utilize leuco dyes to form color images. ing. However, this method has the problem that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. Furthermore, JP-A-57-179840 discloses a heat-developable color photosensitive material in which a color image is formed using a dye-releasing aid and a reducing dye-providing substance that releases a diffusible dye. However, in this method, it is essential to use a dye release aid, and this dye release aid is a so-called base or a precursor of a base. As described above, the technique using a base or a base precursor has the problem that in a heat-developable photosensitive material using an organic silver salt oxidizing agent, the presence of the base increases fog and lowers the maximum density. Furthermore, JP-A-57-186744 discloses a heat-developable color photosensitive material in which a color image is obtained using a dye-providing substance that releases a diffusible dye upon heat development. However, the exemplified compounds of the dye-providing substances described in this publication cannot be said to completely prevent interlayer movement during multilayer coating or heat development, and therefore have the disadvantage that color turbidity tends to occur. There is. [Object of the Invention] Therefore, an object of the present invention is to provide a heat-developable color photosensitive material that enables a new color image forming method, and which solves the problems that conventionally known photosensitive materials have. The purpose is to solve the problem. That is, an object of the present invention is to provide a heat-developable color photosensitive material containing a novel dye-providing substance. Another object of the present invention is to provide a heat-developable color photosensitive material capable of producing clear color images through a simple heat-developing operation. Still another object of the present invention is to provide a heat-developable color photosensitive material that can provide a color image with high density even when stored for a long period of time (hereinafter referred to as raw storage) before exposure. Still another object of the present invention is to provide a heat-developable color photosensitive material that exhibits low fogging and provides a high maximum density. Still another object of the present invention is to provide a heat-developable color photosensitive material that can produce clear color images with little color turbidity. [Summary of the Invention] The heat-developable color photosensitive material according to the present invention that achieves the above object comprises at least (a) silver halide, (b) organic silver salt, (c) reducing agent, and (d) binder on a support. and
(e) A heat-developable color light-sensitive material having a photographic constituent layer containing a dye-providing substance, characterized in that the dye-providing substance is a polymer produced from a polymerizable compound represented by the following general formula [I]. do. General formula [] In the formula, R represents a hydrogen atom or a methyl group, and J
is -O-,
【式】【formula】
【式】または単なる結合手を表し、ＰはCp
との関係において−Ｏ−、−Ｓ−、
[Formula] or simply represents a bond, P is -O-, -S-,
【式】【formula】
一般式〔〕において、
構成部分の代表的な例としては、下記のものが
挙げられる。
一般式〔〕におけるCpは熱現像によつて形
成される還元剤が酸化体と反応して拡散性の色素
を供与することのできる有機基であつて、例えば
下記一般式〔〕〜〔〕で表されるものが挙げ
られる。
In the general formula [], Representative examples of the constituent parts include the following. Cp in the general formula [] is an organic group that can provide a diffusible dye when the reducing agent formed by heat development reacts with the oxidant, and for example, in the following general formulas [] to [] The following are listed.
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
式中、R1、R2、R3およびR4はそれぞれ水素原
子、ハロゲン原子、アルキル基、シクロアルキル
基、アリール基、アルコキシ基、アリールオキシ
基、アラルキル基、アシル基、アシルアミノ基、
アルコキシアルキル基、アリールオキシアルキル
基、Ｎ置換カルバモイル基、アルキルアミノ基、
アリールアミノ基、アシルオキシ基、アシルオキ
シアルキル基、シアノ基の中から選ばれた置換基
を表す。これらの置換基はさらにアルキル基、ア
リール基、水酸基、カルボキシル基、スルホ基、
シアノ基、ニトロ基、スルフアモイル基、カルバ
モイル基、アシルアミノ基、アルキルスルホニル
アミノ基、アリールスルホニルアミノ基、アルコ
キシ基、アリールオキシ基、アシル基、アラルキ
ル基等で置換されていてもよい。
還元剤と有機銀塩との反応によつて生じた酸化
体が上記一般式〔〕〜〔〕の有機基と反応し
て拡散性色素を放出する形態には、大きく分けて
２通りあり、一つは色素を形成するタイプ（色素
形成型）であり、他の一つはあらかじめ一般式
〔〕〜〔〕の活性点部分に離脱可能な基を介
して色素を結合させておき、この色素を拡散させ
るタイプ（色素放出型）である。前者のような色
素形成型の場合はｎは１であり、ＰはCpの活性
点に結合している。一方、後者のようにあらかじ
め色素を分子中に結合させる色素放出型の場合は
ｎは１であり、Ｐは活性点以外の置換基もしくは
活性点以外の部位に結合している。そのとき色素
(D)と活性点とを結合する離脱可能な基としては、
−Ｏ−、−Ｓ−、[Formula] In the formula, R 1 , R 2 , R 3 and R 4 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, an acylamino group ,
Alkoxyalkyl group, aryloxyalkyl group, N-substituted carbamoyl group, alkylamino group,
Represents a substituent selected from an arylamino group, an acyloxy group, an acyloxyalkyl group, and a cyano group. These substituents further include alkyl groups, aryl groups, hydroxyl groups, carboxyl groups, sulfo groups,
It may be substituted with a cyano group, nitro group, sulfamoyl group, carbamoyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxy group, aryloxy group, acyl group, aralkyl group, etc. There are roughly two ways in which the oxidant produced by the reaction between the reducing agent and the organic silver salt reacts with the organic groups of the above general formulas [] to [] to release the diffusible dye. One is a type that forms a dye (pigment-forming type), and the other is a type in which a dye is bonded in advance to the active site of the general formula [] to [] via a detachable group. It is a diffusion type (dye-releasing type). In the case of the former pigment-forming type, n is 1, and P is bound to the active site of Cp. On the other hand, in the case of a dye-releasing type in which a dye is bonded into the molecule in advance like the latter, n is 1, and P is bonded to a substituent other than the active site or a site other than the active site. At that time, the dye
The detachable group that connects (D) and the active site is:
-O-, -S-,
【式】【formula】
本発明に係る熱現像カラー感光材料は、色素供
与物質として上記一般式〔〕で表される化合物
から生成されるポリマーを用いることを特徴とす
るものであつて、重層塗布後および熱現像時にあ
らかじめ決められた層からの流出を抑制すること
により、生保存性が良好であり、カブリ濃度の低
い、かつ最高濃度値が高い鮮明なカラー画像を簡
単な操作により得ることができる。
〔実施例〕
以下、実施例によつて本発明を更に詳しく説明
する。
実施例 １
16.9ｇの硝酸銀を純水200mlに溶解し、29％の
アンモニア水35mlを加える。別に20.1ｇの４−ス
ルホベンゾトリアゾールを純水50mlに溶解する。
室温撹拌下に４−スルホベンゾトリアゾールの水
溶液をアンモニア性硝酸銀水溶液に加え30分撹拌
し、生成した４−スルホベンゾトリアゾール銀ア
ンモニウム塩を取、水洗することによつて、
21.5ｇの４−スルホベンゾトリアゾールアンモニ
ウム塩を得る。該４−スルホベンゾトリアゾール
銀アンモニウム塩16.2ｇに３％ポリビニルピロリ
ドン水溶液150mlを加え24時間ボールミルにより
分散して分散液を作成した（これを分散液−と
する。）。
次に、Ｎ−〔４−（Ｎ，Ｎ−ジエチルアミノ）−
２−メチルフエニル〕スルフアミン酸ナトリウム
7.6ｇ及び本発明のポリマー（Ｐ−１）20ｇに３
％ポリビニルピロリドン水溶液200mlを加え、24
時間ボールミルにより分散して分散液を得た（こ
れを分散液−とする。）。
分散液−で用いた本発明のポリマー（Ｐ−
１）に代えて、本発明のポリマー（Ｐ−２）20ｇ
を用いた以外は、同様に操作を行ない、分散液を
得た（これを分散液−とする。）。
６％ゼラチン水溶液20mlと３％ポリビニルピロ
リドン水溶液50mlを混合した水溶液を撹拌しつ
つ、以下の成分を順々に添加して塗布液を作成し
た。
（成分−１） 分散液− 30ml
（成分−２） 分散液− 40ml
（成分−３） 臭化銀乳剤（乳剤１Kg中にゼラチ
ン60ｇと銀0.35モルを含む、平均粒径0.06μｍ
の立方体乳剤に、３，3′−ジ−（γ−スルホプ
ロピル）−９−メチル−チアジカルボシアニン
ナトリウム塩を銀１モル当り４×10-4モル添加
した乳剤） 10ml
（成分−４） ３％３−アミノ−５−メルカプト
−１，２，４−トリアゾール水溶液 2.5ml
（成分−５） Ｎ，Ｎ−ジメチルウレア ５ｇ
この塗布液をポリエチレンテレフタレートベー
ス上に１m2当り銀量が0.60ｇになるように塗布し
て第１層を設けた。
次に、６％ゼラチン水溶液20mlと６％ポリビニ
ルピロリドン水溶液50mlを混合した水溶液を第１
層の上に塗布して中間層を設けた。
次に、６％ゼラチン水溶液20mlと３％ポリビニ
ルピロリドン水溶液50mlを混合した水溶液を撹拌
しつつ以下の成分を順々に添加して塗布液を作成
した。
（成分−１） 分散液− 30ml
（成分−２） 分散液− 40ml
（成分−３） 臭化銀乳剤（乳剤１Kg中にゼラチ
ン60ｇと銀0.35モルを含む、平均粒径0.06μｍ
の立方体乳剤に、３，3′−ジ−（γ−スルホプ
ロピル）−５，5′−ジフエニル−９−エチルカ
ルボシアニンナトリウム塩を銀１モル当り４×
10-4モル添加した乳剤） 10ml
（成分−４） ３％３−アミノ−５−メルカプト
−１，２，４−トリアゾール水溶液 2.5ml
（成分−５） Ｎ，N′−ジメチルウレア ５ｇ
この塗布液を中間層の上に塗布して第２層を設
けた。
以上の操作によつて感光材料(A)を作成した。
また比較として以下の操作を行なつた。
分散液−で用いた本発明のポリマー（Ｐ−
１）に代えて下記に示す比較化合物−を20ｇ用
いた以外は同様に操作を行ない分散液を得た（こ
れを分散液−とする。）。
また分散液−で用いた本発明のポリマー（Ｐ
−１）に代えて下記に示す比較化合物−を20ｇ
用いた以外は同様に操作を行ない分散液を液た
（これを分散液−とする。）。
更に第１層を設けた塗布液の（成分−２）分散
液−に代えて分散液−を40ml、第２層を設け
た塗布液の（成分−２）分散液−に代えて分散
液−を40ml用いた以外は全く同様にして感光材
料(B)を作成した。
この様にして作製した感光材料(A)及び(B)にステ
ツプウエツジを通してそれぞれ白色光、赤色光及
び緑色光の露光を与えた（1600CMS（カンデラ・
メートル・秒））。
次に受像紙と重ね合せて160℃、30秒間加熱し
て現像後受像紙を剥離した。
尚、ここで用いた受像紙は写真用バライタ紙上
に10％塩化ビニリデン−テトラヒドロフラン溶液
を用いて乾燥膜厚50μｍとなるように塗布したも
のである。
その結果を表−１、−２、−３に示し
た。
The heat-developable color photosensitive material according to the present invention is characterized in that it uses a polymer produced from the compound represented by the above general formula [] as a dye-providing substance, and is prepared in advance after multilayer coating and during heat development. By suppressing outflow from a predetermined layer, a clear color image with good storage stability, low fog density, and high maximum density value can be obtained by simple operations. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Dissolve 16.9 g of silver nitrate in 200 ml of pure water and add 35 ml of 29% aqueous ammonia. Separately, 20.1 g of 4-sulfobenzotriazole was dissolved in 50 ml of pure water.
By adding an aqueous solution of 4-sulfobenzotriazole to an ammoniacal silver nitrate aqueous solution while stirring at room temperature and stirring for 30 minutes, the produced 4-sulfobenzotriazole silver ammonium salt was taken and washed with water.
21.5 g of 4-sulfobenzotriazole ammonium salt are obtained. 150 ml of a 3% polyvinylpyrrolidone aqueous solution was added to 16.2 g of the 4-sulfobenzotriazole silver ammonium salt and dispersed in a ball mill for 24 hours to prepare a dispersion (this will be referred to as a dispersion). Next, N-[4-(N,N-diethylamino)-
Sodium 2-methylphenylsulfamate
3 to 7.6 g and 20 g of the polymer (P-1) of the present invention
Add 200ml of polyvinylpyrrolidone aqueous solution, 24%
A dispersion liquid was obtained by dispersing with a ball mill for a time (this will be referred to as a dispersion liquid). Polymer of the present invention (P-
In place of 1), 20 g of the polymer (P-2) of the present invention
A dispersion liquid was obtained by carrying out the same operation except for using . (This is referred to as a dispersion liquid.) A coating solution was prepared by adding the following components in order to a mixed aqueous solution of 20 ml of 6% gelatin aqueous solution and 50 ml of 3% polyvinylpyrrolidone aqueous solution while stirring. (Component-1) Dispersion - 30ml (Component-2) Dispersion - 40ml (Component-3) Silver bromide emulsion (1 kg of emulsion contains 60 g of gelatin and 0.35 mol of silver, average particle size 0.06 μm)
10 ml (component-4) of a cubic emulsion in which 4 x 10 -4 mol of 3,3'-di-(γ-sulfopropyl)-9-methyl-thiadicarbocyanine sodium salt was added per mol of silver. 3% 3-amino-5-mercapto-1,2,4-triazole aqueous solution 2.5ml (Component-5) N,N-dimethylurea 5g This coating solution was coated on a polyethylene terephthalate base at a silver content of 0.60g per 1m2 . The first layer was provided by applying the following coating. Next, an aqueous solution of 20 ml of 6% gelatin aqueous solution and 50 ml of 6% polyvinylpyrrolidone aqueous solution was added to the first layer.
An intermediate layer was provided by coating on top of the layer. Next, a coating solution was prepared by adding the following components in order to a mixed aqueous solution of 20 ml of 6% gelatin aqueous solution and 50 ml of 3% polyvinylpyrrolidone aqueous solution while stirring. (Component-1) Dispersion - 30ml (Component-2) Dispersion - 40ml (Component-3) Silver bromide emulsion (1 kg of emulsion contains 60 g of gelatin and 0.35 mol of silver, average particle size 0.06 μm)
3,3'-di-(γ-sulfopropyl)-5,5'-diphenyl-9-ethylcarbocyanine sodium salt was added to a cubic emulsion of 4x per mole of silver.
10 ml (component - 4) 3% 3-amino-5-mercapto-1,2,4-triazole aqueous solution 2.5 ml (component-5) N,N'-dimethylurea 5 g This coating solution was applied on top of the intermediate layer to provide a second layer. A photosensitive material (A) was prepared by the above operations. The following operations were also performed for comparison. Polymer of the present invention (P-
A dispersion was obtained by carrying out the same procedure except that 20 g of the comparative compound shown below was used in place of 1) (this is referred to as a dispersion). In addition, the polymer of the present invention (P
-20g of the comparative compound shown below in place of -1)
A dispersion liquid was prepared by carrying out the same procedure except for using the same method (this is referred to as a dispersion liquid). Furthermore, 40 ml of the dispersion liquid was added instead of the dispersion liquid (component-2) of the coating liquid that provided the first layer, and the dispersion liquid was added instead of the dispersion liquid (component-2) of the coating liquid that provided the second layer. A photosensitive material (B) was prepared in exactly the same manner except that 40 ml of the material was used. The photosensitive materials (A) and (B) thus prepared were exposed to white light, red light, and green light, respectively, through a step wedge (1600 CMS (candela)).
meters/seconds)). Next, it was stacked with image-receiving paper and heated at 160° C. for 30 seconds, and after development, the image-receiving paper was peeled off. The image receiving paper used here was a photographic baryta paper coated with a 10% vinylidene chloride-tetrahydrofuran solution to a dry film thickness of 50 .mu.m. The results are shown in Tables-1, -2, and -3.
【表】
上記表中DYは青色光に対して反射濃度で測定
し、DMは緑色光に対して反射濃度で測定した最
高濃度である。
表−２、−３から明らかなように、本発明
のポリマーを用いて作成した感光材料Ａは比較用
感光材料Ｂに較べて色濁りの少ないすぐれた性能
を有していることがわかる。
実施例 ２
下記の感光材料(C)、(D)、(E)および(F)を用意し
た。
感光材料(C)
実施例１の感光材料(A)の第１層の成分２として
用いた分散液−中の本発明のポリマー（Ｐ−
１）の代わりに、本発明のポリマー（Ｐ−６）の
ラテツクス50mlを用い第１層を塗布し、さらにそ
の上に12％ゼラチン水溶液20mlと12％ポリビニル
ピロリドン水溶液50mlを混合した水溶液を保護層
として塗布した。
感光材料(D)
上記感光材料(C)の（Ｐ−６）の代わりに、本発
明のポリマー（Ｐ−７）のラテツクス70mlを用い
第１層および感光材料(C)と同じ組成の保護層を塗
布した。
感光材料(E)
実施例１の感光材料(A)の第１層の成分２の分散
液−中の本発明のポリマー（Ｐ−１）の代わり
に、下記構造式の比較化合物−を20ｇ用いた以
外は実施例１と同様に第１層及び保護層を塗布し
た。
感光材料(F)
上記感光材料(E)の比較化合物−の代わりに、
比較化合物−を用いて第１層及び保護層を塗布
した。
このようにして作成した感光材料(C)、(D)、(E)お
よび(F)にステツプウエツジを通してそれぞれ白色
光で1600CMS（カンデラ・メートル・秒）の露光
を与えた。次に実施例１で用いたものと同じ受像
紙を重ね合わせて160℃、30秒間加熱して現像後
受像紙を剥離した。
一方、これらの感光材料を温度50℃、相対湿度
50％の強制劣化条件下に24時間放置した後、同様
に露光、現像した。
受像紙上に得られた結果を表に示す。濃度の
数値は得られたシアンのネガ像を赤色光に対して
反射濃度で測定した。比感度は感光材料(C)の劣化
前の感度を100とした時の相対感度を示している。[Table] In the above table, D Y is the reflection density measured for blue light, and D M is the highest density measured for green light. As is clear from Tables 2 and 3, it can be seen that the photosensitive material A prepared using the polymer of the present invention has superior performance with less color turbidity compared to the comparative photosensitive material B. Example 2 The following photosensitive materials (C), (D), (E) and (F) were prepared. Photosensitive material (C) Polymer of the present invention (P-
Instead of 1), a first layer is applied using 50 ml of latex of the polymer (P-6) of the present invention, and then a protective layer is applied on top of the aqueous solution of 20 ml of 12% gelatin aqueous solution and 50 ml of 12% polyvinylpyrrolidone aqueous solution. It was applied as. Photosensitive material (D) In place of (P-6) in the above photosensitive material (C), 70 ml of latex of the polymer (P-7) of the present invention was used as the first layer and a protective layer having the same composition as the photosensitive material (C). was applied. Photosensitive material (E) In place of the polymer (P-1) of the present invention in the dispersion of component 2 in the first layer of the photosensitive material (A) of Example 1, 20 g of a comparative compound having the following structural formula was added. The first layer and the protective layer were applied in the same manner as in Example 1 except that the first layer and the protective layer were coated. Photosensitive material (F) Instead of the comparative compound of the above photosensitive material (E),
A first layer and a protective layer were applied using the comparative compound. The light-sensitive materials (C), (D), (E) and (F) thus prepared were each exposed to white light at 1600 CMS (candela-meter-seconds) through a step wedge. Next, the same image-receiving paper used in Example 1 was layered and heated at 160° C. for 30 seconds, and after development, the image-receiving paper was peeled off. On the other hand, these photosensitive materials are heated at a temperature of 50℃ and relative humidity.
After being left under 50% forced deterioration conditions for 24 hours, it was exposed and developed in the same manner. The results obtained on receiver paper are shown in the table. The density value was determined by measuring the reflection density of the obtained cyan negative image against red light. The specific sensitivity indicates the relative sensitivity when the sensitivity of the photosensitive material (C) before deterioration is set as 100.
【表】
表からも明らかなように、本発明のポリマー
を用いた感光材料(C)および(D)は比較化合物を用い
た感光材料(E)および(F)に較べ、生保存性が非常に
良好であることがわかる。これは色素供与物質が
ポリマー化されているために、強制劣化の条件で
も同一層内に固定化されているためと考えられ
る。他方、(E)および(F)においては強制劣化条件で
色素供与物質が保護層の方へ移動してしまつたた
めと思われる。[Table] As is clear from the table, the photosensitive materials (C) and (D) using the polymer of the present invention have much better storage stability than the photosensitive materials (E) and (F) using the comparative compound. It can be seen that the results are good. This is thought to be because the dye-donating substance is polymerized and thus remains fixed in the same layer even under forced deterioration conditions. On the other hand, in (E) and (F), this seems to be because the dye-donating substance migrated toward the protective layer under forced deterioration conditions.
Claims (1)
銀、(b)有機銀塩、(c)還元剤、(d)バインダーおよび
(e)色素供与物質を含有する写真構成層を有する熱
現像カラー感光材料において、該色素供与物質が
下記一般式〔Ｉ〕で表わされる重合可能な化合物
から生成されるポリマーであることを特徴とする
熱現像カラー感光材料。 一般式〔〕 （式中、Ｒは水素原子またはメチル基を表し、Ｊ
は−Ｏ−、【式】【式】 【式】または単なる結合手を表し、ＰはCp との関係において−Ｏ−、−Ｓ−、
【式】【式】 【式】−Ｎ＝Ｎ−、（Cp）−NHCO −、（Cp）−NHSO2−、（Cp）−Ｏ−SO2−または
二価の含窒素複素環基を表し、Ｙはアルキレン
基、アリーレン基、またはアルキル基、アリーレ
ン基を含み且つオキシ基、イミノ基、カルボニル
基、オキシカルボニル基、カルバモイル基、チオ
基、スルホニル基、スルフアモイル基の少なくと
も一つを含む二価の基を表し、ｍは０または１、
ｎは１をを表し、Cpはイエロー、マゼンタまた
はシアンの各色素供与残基を表す。 但し、Cpが である場合は、Ｐは−Ｓ−であることはない。 尚、Rxは無置換もしくは置換アニリノ基、ア
シルアミノ基またはウレイド基を表し、Arは無
置換または置換フエニル基を表す。）[Scope of Claims] 1 At least (a) photosensitive silver halide, (b) organic silver salt, (c) reducing agent, (d) binder, and
(e) A heat-developable color light-sensitive material having a photographic constituent layer containing a dye-providing substance, characterized in that the dye-providing substance is a polymer produced from a polymerizable compound represented by the following general formula [I]. A heat-developable color photosensitive material. General formula [] (In the formula, R represents a hydrogen atom or a methyl group, and J
represents -O-, [formula] [formula] [formula] or a simple bond, and P represents -O-, -S-,
[Formula] [Formula] [Formula] -N=N-, (C p )-NHCO -, (C p )-NHSO 2 -, (C p )-O-SO 2 - or divalent nitrogen-containing heterocycle Y represents an alkylene group, an arylene group, or an alkyl group, an arylene group, and at least one of an oxy group, an imino group, a carbonyl group, an oxycarbonyl group, a carbamoyl group, a thio group, a sulfonyl group, and a sulfamoyl group. represents a divalent group containing m is 0 or 1,
n represents 1, and C p represents a yellow, magenta or cyan dye-donating residue. However, if C p , then P cannot be -S-. In addition, R x represents an unsubstituted or substituted anilino group, an acylamino group or a ureido group, and A r represents an unsubstituted or substituted phenyl group. )
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10929383A JPS602950A (en) | 1983-06-20 | 1983-06-20 | Heat developable color photosensitive material |
| DE19843422455 DE3422455A1 (en) | 1983-06-20 | 1984-06-16 | Thermally developable light-sensitive colour-photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10929383A JPS602950A (en) | 1983-06-20 | 1983-06-20 | Heat developable color photosensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS602950A JPS602950A (en) | 1985-01-09 |
| JPH0360419B2 true JPH0360419B2 (en) | 1991-09-13 |
Family
ID=14506499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10929383A Granted JPS602950A (en) | 1983-06-20 | 1983-06-20 | Heat developable color photosensitive material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS602950A (en) |
| DE (1) | DE3422455A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6161158A (en) * | 1984-08-31 | 1986-03-28 | Konishiroku Photo Ind Co Ltd | Heat developing color photosensitive material |
| JPS6161157A (en) * | 1984-08-31 | 1986-03-28 | Konishiroku Photo Ind Co Ltd | Heat developing color photosensitive material |
| JPS61148447A (en) * | 1984-12-24 | 1986-07-07 | Konishiroku Photo Ind Co Ltd | Heat developable color photosensitive material |
| JPS61175637A (en) * | 1985-01-30 | 1986-08-07 | Konishiroku Photo Ind Co Ltd | Heat-developable color photosensitive material |
| JPS61177451A (en) * | 1985-02-01 | 1986-08-09 | Konishiroku Photo Ind Co Ltd | Thermodeveloping color sensitive material |
| JPS61210351A (en) * | 1985-03-15 | 1986-09-18 | Konishiroku Photo Ind Co Ltd | Heat developable color photosensitive material |
| JPS625238A (en) * | 1985-06-29 | 1987-01-12 | Konishiroku Photo Ind Co Ltd | Heat developable photosensitive material |
| JPH061364B2 (en) * | 1985-11-22 | 1994-01-05 | コニカ株式会社 | Photothermographic material |
| EP0236508A4 (en) * | 1985-09-17 | 1989-06-13 | Konishiroku Photo Ind | Thermally developable photographic material. |
| JPS62121452A (en) * | 1985-11-20 | 1987-06-02 | Konishiroku Photo Ind Co Ltd | Heat developable photosensitive material |
| JPS6298351A (en) * | 1985-10-24 | 1987-05-07 | Konishiroku Photo Ind Co Ltd | Heat developable photosensitive material |
| JP2597908B2 (en) | 1989-04-25 | 1997-04-09 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
| US5424268A (en) * | 1994-05-13 | 1995-06-13 | Polaroid Corporation | Imaging medium and process |
-
1983
- 1983-06-20 JP JP10929383A patent/JPS602950A/en active Granted
-
1984
- 1984-06-16 DE DE19843422455 patent/DE3422455A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE3422455A1 (en) | 1984-12-20 |
| JPS602950A (en) | 1985-01-09 |
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