JPS6292943A - Image forming method - Google Patents
Image forming methodInfo
- Publication number
- JPS6292943A JPS6292943A JP23387185A JP23387185A JPS6292943A JP S6292943 A JPS6292943 A JP S6292943A JP 23387185 A JP23387185 A JP 23387185A JP 23387185 A JP23387185 A JP 23387185A JP S6292943 A JPS6292943 A JP S6292943A
- Authority
- JP
- Japan
- Prior art keywords
- dye
- acid
- layer
- photosensitive
- image
- 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
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- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Chemical class 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007529 inorganic bases Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical class ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PWXJULSLLONQHY-UHFFFAOYSA-N phenylcarbamic acid Chemical class OC(=O)NC1=CC=CC=C1 PWXJULSLLONQHY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 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
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 239000002689 soil Substances 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- 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
- G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は感光材料を加熱により色素画像を形成する画像
形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an image forming method for forming a dye image by heating a photosensitive material.
（従来の技術）
ハロゲン化銀を用いる写真法は、他の写真法たとえば電
子写真やノアゾ写真法に比べて、感度や階調調節などの
写真特性にすぐれているので、従来から最も広範に用い
られてきた。近年になってハロゲン化銀を用いた感光材
料の画像形成処理法を従来の現像液等による湿式処理か
ら、加熱等による乾式処理にかえることにより簡易で迅
速に画像を得ることのできる技術が開発されてきた。(Prior art) Photography using silver halide has been the most widely used method since it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and noazo photography. I've been exposed to it. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. It has been.
熱現像感光材料は当該技術分野では公知であり熱現像感
光材料とそのプロセスについては、たとえば写真工学の
基礎（１９７９年コロナ社発行）の５５３頁５５５頁、
１９７８年４月発行映像情報４０頁、ネゾレツツ、「フ
ォトグラフィーとりプログラフイーのハンドブック」第
７版（Ｎｅｂ−１ｅｔｔｓ％Ｈａｎｄｂｏｏｋ ｏｆ
Ｐｈｏｔｏｇｒａｐｈｙ ａｎｄ Ｒｅｐｒｏｇｒａ−
ｐｈｙ ７ ｔｈ Ｅａ、 ）ヴアン・ノストランド・
ラインホールト１ 力ｙ ノｅニー （Ｖａｎ Ｎｏ５
ｔｒａｎｄ ＲｅｉｎｈｏｌｄＣｏｍｐａｎｙ ）の３
２〜３３頁、米国特許第３．１５２゜９０４号、第３，
３０１，６７８号、第３，３９２，０２０号第３，４５
７，０７５号、英国特許第１，１３１，１０８号、１，
１６７，７７７号および、リサーチディスクロージャー
誌１９７８年６月号９〜１５被−ノ（ＲＤ−１７０２９
）に記載されている。Heat-developable photosensitive materials are well known in the art, and for information on heat-developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979), p. 553, p. 555;
Published in April 1978, video information page 40, Nezolets, "Handbook of Photography and Programming" 7th edition (Neb-1etts% Handbook of
Photography and Reprogra-
phy 7 th Ea, ) Van Nostrand
Reinhold 1 force y noe knee (Van No5
trand Reinhold Company) 3
pp. 2-33, U.S. Patent No. 3.152°904, No. 3,
No. 301,678, No. 3,392,020 No. 3,45
No. 7,075, British Patent No. 1,131,108, 1,
No. 167,777 and Research Disclosure Magazine June 1978 Issue No. 9-15 (RD-17029)
)It is described in.
また加熱によりカラー像を得る種々の方法が例えばりサ
ーチディスクロージャー誌１９７８年５月号５４〜５８
ベーノ（ＲＤ−１６９６６号）、同１９７６年４月号３
０〜３２ページ（ＲＤ−１４４３３号）、米国特許第３
，９８５，６５５号、同４．４６３，０７９号、同４，
４７４，８６７号、同４，４７８．９２７号、同４，５
０７，３８０号、同４．５００゜６２６号、同４，４８
３，９１４号等に提案されている。これらはいずれも加
熱によって色素を生成もしくは放出させ色素の像様分布
を形成させるものであり、短時間で色素の像様分布が得
られる特徴がある。Also, various methods of obtaining color images by heating are described, for example, in Search Disclosure Magazine, May 1978 issue, 54-58.
Beno (RD-16966), April 1976 issue 3
Pages 0-32 (RD-14433), U.S. Patent No. 3
, No. 985,655, No. 4.463,079, No. 4,
No. 474,867, No. 4,478.927, No. 4,5
No. 07,380, No. 4.500゜626, No. 4,48
No. 3,914, etc. All of these produce or release dyes by heating to form an image-like distribution of the dye, and are characterized by the ability to obtain an image-like distribution of the dye in a short period of time.
（発明が解決しようとする問題点）
しかしながら、加熱現像によって高い色素濃度を得よう
とすると一般にカプリも上昇し、画像識別性（ディスク
リミネーション）の高い写真を得ることが困難であった
。また、現像、転写条件の変動、すなわち、温度・時間
の変動に対して画像識別性が悪化するという問題があっ
た。また、特開昭５９−２１８４４３号等には少量の水
の存在下で加熱して可動性色素の像様分布を形成する方
法が開示されているが、この方法では水が存在している
ため加熱終了後も感光材料の温度が下がりにくく、過現
像が生じ易いという問題があった。(Problems to be Solved by the Invention) However, when attempting to obtain a high dye density by heat development, capri generally increases, making it difficult to obtain photographs with high image discrimination. Furthermore, there is a problem in that image distinguishability deteriorates due to fluctuations in development and transfer conditions, that is, fluctuations in temperature and time. In addition, Japanese Patent Application Laid-open No. 59-218443 discloses a method of forming an image-like distribution of mobile dye by heating in the presence of a small amount of water, but in this method, since water is present, There is a problem in that the temperature of the photosensitive material is difficult to lower even after heating is completed, and overdevelopment is likely to occur.
従って、本発明の目的は、色素画像濃度の最低濃度が低
（、かつ最高濃度の高い画像を得る方法を提供すること
にある。本発明の別の目的は、現像、転写条件の変動に
対しても良好な画像識別性を与える方法を提供すること
にある。本発明の更に別の目的は、少量の水の存在下で
加熱して可動性色素の像様分布を形成する方法における
過現像によるカブリの上昇を防止する方法を提供するこ
とにある。Therefore, an object of the present invention is to provide a method for obtaining an image with a low minimum dye image density (and a high maximum density). It is another object of the present invention to provide a method for producing image-wise distribution of mobile dyes by heating in the presence of a small amount of water. It is an object of the present invention to provide a method for preventing an increase in fog due to.
（問題点を解決するための手段）
本発明の目的は、支持体上に少（とも感光性ハロゲン化
銀、バインダーおよび色素供与性物質を含む感光材料を
像様露光後、または像様露光と同時に水の存在下で加熱
し、可動性色素の像様分布を形成する画像形成方法にお
いて、前記可動性色素の像様分布を形成する反応系に酸
性成分を化学的に関与させることを特徴とする画像形成
方法により達成される。(Means for Solving the Problems) An object of the present invention is to coat a light-sensitive material containing a small amount (at least a light-sensitive silver halide, a binder, and a dye-providing substance) on a support after or simultaneously with imagewise exposure. An image forming method in which an imagewise distribution of a mobile dye is formed by heating in the presence of water at the same time, characterized in that an acidic component is chemically involved in the reaction system that forms an imagewise distribution of the mobile dye. This is achieved by an image forming method.
本発明において、前記可動性色素の像様分布を形成する
反応系に酸性成分を化学的に関与させるとは、具体的に
はその反応系を含む層に水を与えたときに測定される一
値（材料の表面に２０μｌ／−の水を与え、平板ガラス
電極、例えば東亜電波社製Ｇ５−１６５Ｆを用いて測定
することができる。）を低くすることを意味する。従っ
て本発明で言う酸性成分は、これが水の中に存在すると
き酸性を示すことができるものが好ましく、例えば酸性
化合物として知られているものが好ましく用いられる。In the present invention, chemically involving an acidic component in the reaction system that forms the imagewise distribution of the mobile dye means, specifically, the amount of water measured when water is applied to the layer containing the reaction system. It means to lower the value (which can be measured by applying 20 μl/− of water to the surface of the material and using a flat glass electrode, for example, G5-165F manufactured by Toa Denpa Co., Ltd.). Therefore, the acidic component referred to in the present invention is preferably one that can exhibit acidity when present in water, and for example, those known as acidic compounds are preferably used.
本発明において好ましい酸性成分の存在量は上記の方法
で測定した一値が８．５以下、より好ましくは３〜７の
範囲になるに十分な量である。In the present invention, the preferred amount of the acidic component present is an amount sufficient so that the single value measured by the above method is 8.5 or less, more preferably in the range of 3 to 7.
本発明において使用される酸性成分は、有機酸、無機酸
あるいはこれらを発生しうろ化合物のいずれでもよい。The acidic component used in the present invention may be an organic acid, an inorganic acid, or a compound that generates these acids.
有機酸としては脂肪族モノカルボン酸類、例えは、カシ
ロン酸、カプリル酸、・ξルミチン酸、ステアリン酸、
ヘゾタデカン酸、ベヘン酸、フェニル酢酸など、脂肪族
不飽和モノカルボ／酸類、例えば、クロトン酸、プロピ
オール酸など、脂肪族ポリカルボン酸類、例えば酒石酸
、アジピン酸、ニトリロジプロピオン酸など、芳香族ま
たは複素環モノあるいはポリカルボン酸類、例えば、安
息香酸、ナフトエ酸、フタル酸、ｍ −トＩＪル酢酸、
０−１− ＩＪル酢酸、ｍ−クロロフェニル６［、ｐ−
メトキシフェニル酢酸、ニコチン酸、キノリン酸など、
酸性水酸基を有する酸類、例えば、フェノールなど、脂
肪族または芳香族スルホン酸類、例エバ、メタンスルホ
ン酸、ベンゼンスルホン酸、トルエンスルホン酸、メン
チレンスルホン酸すと、アミノ酸類、例えば、グリ７ン
、グルタミン酸、アスパラギン酸、システィン、シスチ
ン、トリフトファ／、トレオニン、ゾロリン、ヒト９０
キシゾロリン、リシン、ロイ７ンなど、アミノ酸鰐導体
、例えばグルタチオンなどのベプチ１あるいは各種蛋白
質など、校素環式化合物、例えば・ぐルビノル酸、尿酸
など、等が挙げられる。これら有機酸の中では、酸解離
定数（ｐｋａ）が９以下であるものが好ましい。無機酸
としては、不揮発性の酸が好ましく、例えば、トリポリ
りん酸、ｅロリン酸。Examples of organic acids include aliphatic monocarboxylic acids, such as casillonic acid, caprylic acid, ξlumitic acid, stearic acid,
Aliphatic unsaturated monocarbo/acids such as hezotadecanoic acid, behenic acid, phenylacetic acid, etc., aliphatic polycarboxylic acids such as crotonic acid, propiolic acid, aromatic or heterocyclic acids such as tartaric acid, adipic acid, nitrilodipropionic acid, etc. Mono- or polycarboxylic acids, such as benzoic acid, naphthoic acid, phthalic acid, m-triacetic acid,
0-1- IJ ruacetic acid, m-chlorophenyl 6[, p-
Methoxyphenylacetic acid, nicotinic acid, quinolinic acid, etc.
Acids having an acidic hydroxyl group, such as phenol, aliphatic or aromatic sulfonic acids, such as EVA, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, menthylenesulfonic acid, amino acids, such as glycine, Glutamic acid, aspartic acid, cysteine, cystine, tritiffa/, threonine, zoroline, human 90
Examples include xyzololine, lysine, leucine, etc., amino acid conductors such as glutathione and various proteins, and cyclic compounds such as glubinolic acid, uric acid, and the like. Among these organic acids, those having an acid dissociation constant (pka) of 9 or less are preferred. As the inorganic acid, nonvolatile acids are preferred, such as tripolyphosphoric acid and e-rophosphoric acid.
リン酸など、等がある。その他の酸性成分として、酸性
白土などの化合物が挙げられる。There are phosphoric acid, etc. Other acidic components include compounds such as acid clay.
本発明においては、可動性色素の必要量が形成あるいは
放出されてから前記反応系に酸性成分を化学的に関与さ
せることが望ましい。In the present invention, it is desirable to chemically involve the acidic component in the reaction system after the required amount of mobile dye has been formed or released.
そのための手段としては、特に限定されないが、９：］
えば現俄のための加熱によって融解して拡散する常温で
は固体の酸性成分を感光材料および／土たは色素固定材
料の構成層に添加しておく方法がちる。この方法に使用
しうる酸性成分としては、前述した酸性成分のうち分子
量が３００以下で、融点が４０℃以上、好ましくは５０
°Ｃ以上の化合′吻が挙げられる。Means for this purpose are not particularly limited, but 9:]
For example, there is a method in which an acidic component, which is solid at room temperature and melts and diffuses when heated, is added to the constituent layers of the light-sensitive material and/or clay or dye-fixing material. Among the acidic components mentioned above, the acidic components that can be used in this method include those having a molecular weight of 300 or less and a melting point of 40°C or higher, preferably 50°C or higher.
Examples include compound temperatures above °C.
また、別の手段としては、熱現像処理温度でも拡散しな
い酸性成分の層を感光材料および／土たは色素固定材料
に設けておき、拡散してくる塩基をこの層で中和する方
法がある。この方法に使用しうる酸性成分としては、分
子量が３００を越える化合物が好ましく、例示した分子
量３００以下の化合物の誘導体なども包含される。また
、ｐｋａ９以下の酸性基（もしくは加水分解して酸性基
を与える前駆体）をふくむ化合物が好ましく、さらに好
ましくは米国特許第３．３３６２．８１９号に記載され
ているオレイン酸のような高級脂肪酸、米国ｌ特許３，
３６２，８１９号に記載されているアクリル酸、メタア
クリル酸もしくはマレイン酸の重合体とその部分エステ
ルまたはその酸無水物、仏国特許２，２９０，６９９号
に記載されているアクリル酸とアクリル酸エステルの共
重合体、米国特許４．１３９，３８３号やリサーチディ
スクローノで−Ｎｏ、 １６１０２ （１９７７）に
記載されているようなラテックス型酸性ポリマーを挙げ
ることができる。Another method is to provide a layer of acidic components that do not diffuse even at heat development processing temperatures on the photosensitive material and/or soil or dye fixing material, and neutralize the base that diffuses with this layer. . The acidic component that can be used in this method is preferably a compound with a molecular weight of more than 300, and also includes derivatives of the exemplified compounds with a molecular weight of 300 or less. In addition, compounds containing an acidic group (or a precursor that hydrolyzes to give an acidic group) having a pka of 9 or less are preferred, and higher fatty acids such as oleic acid described in U.S. Pat. No. 3,3362,819 are more preferred. , U.S. Patent 3,
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides described in French Patent No. 362,819; acrylic acid and acrylic acid described in French Patent No. 2,290,699; Examples include copolymers of esters and latex-type acidic polymers as described in US Pat. No. 4,139,383 and Research Disc. No. 16102 (1977).
その他米国特許４，０８８，４９３号、特開昭５２−１
５３．７３９号、同５３−１，０２３号、同５３−４，
５４０号、同５３−４５４１号、同５３−４．５４２号
に記載されているものも使用できる。Other U.S. Patent No. 4,088,493, Japanese Unexamined Patent Publication No. 52-1
No. 53.739, No. 53-1,023, No. 53-4,
Those described in No. 540, No. 53-4541, and No. 53-4.542 can also be used.
酸性ポリマーの具体例としてはエチレン、酢酸ビニル、
ビニルメチルエーテルのビニル七ツマ−と無水マレイン
酸との共重合体およびそのｎ −７’チル半エステル、
ブチルアクリレートとアクリル酸トの共重合物、セルロ
ースアセテートハイドロジエンフタレート等がある。Specific examples of acidic polymers include ethylene, vinyl acetate,
A copolymer of vinyl methyl ether and maleic anhydride, and its n-7'-thyl half ester;
Copolymers of butyl acrylate and acrylic acid, cellulose acetate hydrogen phthalate, etc.
また別の手段としては加熱により酸を放出する化合物（
酸ブレカーサ−）を用いる方法がある。Another method is to use compounds that release acids when heated (
There is a method using an acid breaker.
この酸ブレカーサ−としては特開昭６０−１０８８３７
号や特願昭５９−４８３０５号に記載のオキシムエステ
ル類、特願昭５９−８５８３４号、同５９−８５８３６
号、同６０−１３７１７４号に記載のロッセン転移によ
り酸全放出する化合物などが挙げられる。具体的には、
ＯＣＲ５８ＣＨ５
ＯＣｌｉ 。As this acid breaker, JP-A-60-108837
Oxime esters described in Japanese Patent Application No. 59-48305, Japanese Patent Application No. 59-85834 and Japanese Patent Application No. 59-85836
No. 60-137174, compounds which release all of the acid through Rossen rearrangement, and the like. Specifically, OCR58CH5 OCli.
などを挙げることができる。etc. can be mentioned.
本発明においては、上記酸性成分は、塩基および／−！
たけ塩基プレカーサーを感光材料もしくけ色素固定材料
に内蔵させる場合には塩基および／または塩基ブレカー
サ−全顎えない方の材料の構成層へ導入するのが好まし
い。特に、色素固定材料に塩基および／または塩基プレ
カーサーを内蔵させ、感光材料の最下層に上記酸性成分
、好ましくは、常温では固体であり融点が５０℃以上の
該拡散性化合物および／または該耐拡散性の化合物？導
入することが好ましい。一方、後述するように難溶性金
属化合物（ａ）とこの化合物（ａ）の金属イオンと錯形
成反応する化合物（ｂ）を感光材料と色素固定材料に分
けて添加しておき、両材料を重ね合わせて加熱現象して
塩基を発生させる手段を採用した場合は、前記の酸性成
分である拡散性化合物や耐拡散性の化合物は感光材料、
色素固定材料のいずれに加えてもよい。In the present invention, the acidic component is a base and/-!
When a base precursor is incorporated into a light-sensitive material or a dye-fixing material, it is preferable to introduce the base and/or the base breaker into a constituent layer of the material that does not contain the whole base. In particular, the dye-fixing material incorporates a base and/or a base precursor, and the acidic component described above is added to the bottom layer of the photosensitive material, preferably the diffusible compound and/or the diffusion-resistant compound that is solid at room temperature and has a melting point of 50°C or higher. A sexual compound? It is preferable to introduce it. On the other hand, as described later, a poorly soluble metal compound (a) and a compound (b) that reacts with the metal ions of this compound (a) to form a complex are added separately to the light-sensitive material and the dye fixing material, and the two materials are layered together. When a method of generating a base through a heating phenomenon is adopted, the above-mentioned acidic components such as diffusible compounds and diffusion-resistant compounds are used in photosensitive materials,
It may be added to any dye fixing material.
酸性成分を感光材料および／または色素固定材料の構成
層に導入するには、バインダー中に微粒子にして分散含
有させるのが好ましい。具体的には特願昭６０−１６５
３４９号に記載の固体分散法を利用して分散することが
〒きる。また、融点が１００℃以下のものについては、
加熱・融解した状態マゼラチンと界面活性剤の水溶液と
高速で攪拌し、ゼラチン分散物を得ることも可能である
。In order to introduce the acidic component into the constituent layers of the photographic material and/or the dye-fixing material, it is preferable to disperse the acidic component in the form of fine particles in the binder. Specifically, the patent application 1986-165
It can be dispersed using the solid dispersion method described in No. 349. In addition, for those with a melting point of 100℃ or less,
It is also possible to obtain a gelatin dispersion by stirring heated and melted magelatin and an aqueous solution of a surfactant at high speed.
本発明の好ましい画像形成方法においては、感光材料を
像様露光後または像様露光と同時に水ならびに塩基およ
び／−！たけ塩基プレカーサーの存在下〒加熱し、可動
性色素の像様分布を形成する。In a preferred image forming method of the present invention, a light-sensitive material is exposed to water, a base and/or a base and/or after or simultaneously with imagewise exposure. Heating in the presence of a bamboo base precursor forms an imagewise distribution of mobile dye.
本発明に用いられる塩基および／または塩基プレカーサ
ーは感光材料および／または色素固定材料に内蔵できる
。また、本発明において使用される水に溶解させた状態
でも使用することもできる。The base and/or base precursor used in the present invention can be incorporated into the light-sensitive material and/or the dye-fixing material. Moreover, it can also be used in a state dissolved in the water used in the present invention.
本発明における水の量は、感光材料および色素固定材料
の全塗布膜の１量の少なくとも０．１倍、好ましくは全
塗布膜の重量の０．１倍ないし全塗布膜の最大膨潤体積
に相当する水の重量の範囲内であり、さらに好ましくは
全塗布膜の重量の０．１倍ないし全塗布膜の最大膨潤体
積に相当する水の重量から全塗布膜の重量を差引いた量
の範囲内である。The amount of water in the present invention is at least 0.1 times the amount of the total coating film of the photosensitive material and dye fixing material, preferably 0.1 times the weight of the total coating film to the maximum swelling volume of the total coating film. within the range of the weight of water, more preferably within the range of 0.1 times the weight of the entire coating film to the weight of water corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film. It is.
膨潤時の膜の状態は不安定であり、条件によっては局所
的ににじみを生ずるおそれがありこれを避けるには感光
材料と色素固定材料の全塗布膜の最大膨潤時の体積に相
当する水の量以下が好ましいの１ある。The state of the film during swelling is unstable, and depending on the conditions, local bleeding may occur.To avoid this, add water equivalent to the maximum swelling volume of the entire coated film of the photosensitive material and dye fixing material. It is preferable that the amount is less than or equal to the amount.
しかし本発明の効果は前記の量より水が多いところ↑も
、上記の欠点が生じるのみフ、その効果が発揮される点
〒は望ましい範囲の水の量の場合と同じフある。However, the effect of the present invention is that even when the amount of water is greater than the above-mentioned amount, the above-mentioned disadvantages occur, but the effect is exhibited in the same way as when the amount of water is within the desired range.
本発明では加熱による現像を利用し、水は単に画像状に
分布した色素を移動させるために存在させるものである
から、現像液をフィルムユニットの中で展開し、常温付
近ｆ現像を起こさせるいわゆるカラー拡散転写法におけ
る現像時の膜中の−よりずっと低い声で現像を行うこと
ができる。−を高くするとカブリが著しく増大しかえっ
て不都合である。したがって現像および色素移動のだめ
の加熱の際の膜°の−は１２以下が好ましく、１１以下
中性声まｆがさらに好ましい。In the present invention, development by heating is used, and water is present simply to move the dye distributed in an image. Therefore, the developer is developed in the film unit and the so-called development is carried out at around room temperature. Development can be carried out with a much lower tone than that in the film during development in the color diffusion transfer method. If - is increased, fog will increase significantly, which is even more inconvenient. Therefore, during development and heating of the dye transfer tank, the film angle is preferably -12 or less, more preferably 11 or less with a neutral f.
本発明において塗布膜を形成するバインダーは水転写が
可能なものならなんでもよく、また塗布膜は感光性ハロ
ゲン化銀、色素供与性物質、媒染剤、高沸点有機溶媒な
どを含みうるが、このような添加物があっても本発明は
同様に成立する。In the present invention, the binder forming the coating film may be any binder that can be water-transferred, and the coating film may contain photosensitive silver halide, a dye-donating substance, a mordant, a high-boiling organic solvent, etc. Even if additives are present, the present invention is similarly applicable.
最大膨潤体積は、用いる水の中に測定するべき塗布膜を
もつ感光材料または固定材料を浸漬させ、十分膨潤した
ところで顕微鏡等で断面の長さを測定して膜厚を求め、
問題にしている感光材料または色素固定材料の塗布膜の
面積を乗じれば求めることができる。The maximum swelling volume is determined by immersing the photosensitive material or fixed material with the coating film to be measured in the water used, and once it has swelled sufficiently, measuring the length of the cross section with a microscope etc. to determine the film thickness.
It can be determined by multiplying by the area of the coating film of the photosensitive material or dye fixing material in question.
膨潤度の測定法は、ホトグラフィック サイエンス エ
ンジニアリンク１６巻４４９頁（１９７２年発行）に記
載がある。The method for measuring the degree of swelling is described in Photographic Science Engineering Link, Vol. 16, p. 449 (published in 1972).
ゼラチン膜の膨潤度は硬膜の程度によって著しく変ｒヒ
するが、最大膨潤時の膜厚が乾燥膜厚の２倍ないし６倍
になるように硬膜の程度を調節するのが通常１ある。The degree of swelling of a gelatin film varies significantly depending on the degree of hardening, but the degree of hardening is usually adjusted so that the film thickness at maximum swelling is 2 to 6 times the dry film thickness. .
上記の水は色素固定材料に供給してもよいし、感光材料
に供給してもよい。また色素固定材料と感光材料の両者
に供給してもよい。The above water may be supplied to the dye fixing material or to the photosensitive material. Further, it may be supplied to both the dye fixing material and the photosensitive material.
本発明において、水はどのような方法によシ供ｆｆ１−
Ｊれてもよい。たとえば、細孔からジェットとして噴出
させてもよいし、ウェッブローラーで濡らしてもよい。In the present invention, water can be supplied by any method.ff1-
It's okay to be J. For example, it may be ejected as a jet from pores, or it may be wetted with a web roller.
また水の入ったポットを押しつぶす形式で用いてもよく
、これらの方法および他の方法により制約されるもの１
はない。まだ結晶水やマイクロカプセルとして材料中に
内蔵させておいてもよい。It may also be used in the form of crushing a pot filled with water; however, restrictions imposed by these methods and other methods 1
There isn't. It may still be incorporated into the material as crystal water or microcapsules.
本発明〒用いられる水とは、いわゆる１純水”に限らず
、広く慣習的に使われる意味での水を含む。また、純水
とメタノール、ＤＭＦ、アセトン、ジイソブチルケトン
などの低沸点溶媒との混合溶媒〒もよい。さらに、後述
の画像形成促進剤、親水性熱溶剤等を含有させた液でも
よい。The water used in the present invention is not limited to so-called 1-pure water, but includes water in the widely customary sense.Also, pure water and low boiling point solvents such as methanol, DMF, acetone, and diisobutyl ketone are used. A mixed solvent may also be used.Furthermore, a liquid containing an image formation accelerator, a hydrophilic heat solvent, etc., which will be described later, may also be used.
水金外部から供給する場合には、感光要素および／又は
色素固定要素に一定量を供給することが均一な画像を得
るためには必要であるが、後述するように膜の最大膨潤
量以下の少量の水を与える場合には材料表面におけるハ
ジキ膜中への水の浸透のムラ等によシ画像ムラが生じや
すい。そのためその水に界面活性剤を含ませ材料表面に
おける水のひろがシを改良してもよい。When water is supplied from outside, it is necessary to supply a certain amount to the photosensitive element and/or dye fixing element in order to obtain a uniform image, but as described below, When a small amount of water is applied, image unevenness tends to occur due to uneven penetration of water into the repellent film on the surface of the material. Therefore, the water may contain a surfactant to improve the spread of water on the surface of the material.
本発明で用いられる界面活性剤は写真業界および一般に
湿潤剤、濡れ剤として知られている界面活性剤を用いる
ことができる。これらの界面活性剤は多数の公知文献た
とえば界面活性剤便覧、界面活性剤科学シリーズ（マー
チ／・ジエイ・シック編集、マーセル・デツカ−社 １
９６７年）（５ｕｒｆａｃｔａｎｔ ５ｃｉｅｎｃｅ
５ｅｒｔｅｓ （Ｅｄｉｔｅｄ ｂｙＭａｒｔｉｎ
Ｊ、５ｃｈｉｃｋ ＊ Ｍａｒｃｅｌ Ｄｅｋｋｅｒ
Ｉｎｃ。As the surfactant used in the present invention, surfactants known in the photographic industry and generally as wetting agents and wetting agents can be used. These surfactants are described in many well-known documents such as Surfactant Handbook, Surfactant Science Series (edited by March/J. Schick, Marcel Detzker & Co., vol. 1).
967) (5urfactant 5science
5ertes (Edited by Martin
J, 5chick *Marcel Dekker
Inc.
１９６７））等に記載されている。界面活性剤には陽イ
オン性、陰イオン性、両性、非イオン性の区別があるが
、後述の要件を満たすもの１あれば、すべて用いること
が可能である。界面活性剤は２種以上を併用してもよい
。1967)). There are three types of surfactants: cationic, anionic, amphoteric, and nonionic, but any surfactant can be used as long as it satisfies the requirements described below. Two or more surfactants may be used in combination.
本発明で用いられる界面活性剤の量は界面活性剤の種類
によって異なるが水溶液の表面張力が４０ ｄｙｎｅ
７ｃｍ以下になる添加量が望ましい。The amount of surfactant used in the present invention varies depending on the type of surfactant, but the surface tension of the aqueous solution is 40 dyne.
It is desirable that the amount added be 7 cm or less.
本発明に用いられる塩基としては、アルカリ金属、アル
カリ土類金属または４級アルキルアンモニウムの水酸化
物、炭酸塩、重炭酸塩、ホウ酸塩、第２および第３リン
酸塩、キノリン酸塩、メタホウ酸塩等の無機塩基：脂肪
族アミン類、芳香族アミン類、複素環状アミ、７類、ア
ミジン類、環状アミジン類、グアニジン類、環状グアニ
ジン類等の有機塩基およびそれらの炭酸塩、重炭酸塩、
ホウ酸塩、第２および第３リン酸塩等が挙げられる。The bases used in the present invention include hydroxides, carbonates, bicarbonates, borates, secondary and tertiary phosphates, quinolates of alkali metals, alkaline earth metals or quaternary alkylammoniums, Inorganic bases such as metaborates: organic bases such as aliphatic amines, aromatic amines, heterocyclic amides, 7-class amidines, cyclic amidines, guanidines, cyclic guanidines, and their carbonates and bicarbonates salt,
Examples include borates, secondary and tertiary phosphates, and the like.
また本発明に用いられる塩基プレカーサーとしては前記
有機塩基のプレカーサーが挙げられる。Further, examples of the base precursor used in the present invention include precursors of the organic bases described above.
ここでいう塩基プレカーサーとは熱分解、電解等によム
塩基性成分を放出するものである。たとえばトリクロロ
酢酸、シアノ酢酸、アセト酢酸、α−スルホニル酢酸な
どの熱分解性有機酸と前記有機塩基との塩、米国特許第
４，０８８，４９６号に記載の２−カルダキシ力ルポキ
サミドとの塩などが挙げられる。その他英国特許第９９
８，９４５号、米国特許第３，２２０，８４６号、特開
昭５０−２２６２５号等に記載の塩基プレカーサーを用
いることができる。The base precursor referred to herein is one that releases a basic component by thermal decomposition, electrolysis, or the like. For example, salts of thermally decomposable organic acids such as trichloroacetic acid, cyanoacetic acid, acetoacetic acid, and α-sulfonylacetic acid with the above-mentioned organic bases, salts of 2-cardoxylic rupoxamide described in U.S. Pat. No. 4,088,496, etc. can be mentioned. Other British Patent No. 99
Base precursors described in US Pat. No. 8,945, US Pat. No. 3,220,846, JP-A-50-22625, etc. can be used.
また電解により塩基を発生させる化合物として次のもの
を挙げることが〒きる。たとえば、電解酸化が用いられ
る化合物として各種脂肪酸塩を挙げることができる。こ
の反応によってアルカリ金属やグアニジン類、アミジン
類等の有機塩基の炭酸塩を極めて効率良く得ることがで
きる０また電解還元が用いられる化合物としては、ニト
ロ化合物、ニトロン化合物、ニトリル類、アゾ化合物、
アゾキシ化合物等が挙げられ、これら化合物の還元によ
υアミン類、ヒドラジン類等の塩基が生成される。また
、ｐ−アミノフェノール類、ｐ−７二二レンジアミン類
、ヒドラジン類は塩基として使用されるだけでなく、直
接色画像形成物質として使用〒きる。In addition, the following compounds can be mentioned as compounds that generate bases by electrolysis. For example, various fatty acid salts can be mentioned as compounds for which electrolytic oxidation is used. Through this reaction, carbonates of alkali metals and organic bases such as guanidines and amidines can be obtained extremely efficiently.Compounds for which electrolytic reduction is used include nitro compounds, nitrone compounds, nitriles, azo compounds,
Examples include azoxy compounds, and bases such as υamines and hydrazines are produced by reduction of these compounds. In addition, p-aminophenols, p-7 22-diamines, and hydrazines are not only used as bases, but can also be used directly as color image-forming substances.
また、種々の無機塩共存下〒の水の電解によジアルカリ
成分を生成させることも利用フきる。It is also possible to generate dialkali components by electrolysis of water in the coexistence of various inorganic salts.
上記の他に、塩基を発生させる方法が各種あり、いずれ
も有効である。たとえば、前記した難溶性金属化合物お
よびこの難溶性金属化合物を構成する金属イオンと錯形
成反応しうる化合物（錯形成化合物）の混合により塩基
を発生きせる方法がある。難溶性金属化合物としては、
例えば、亜鉛、アルミニウム、バリウム、カルシウム等
の炭酸、リン酸、ホウ酸などとの塩、それらの水酸化物
、あるいはそれらの酸化物等が挙げられる。錯形成化合
物については、例えばニー・イー・マーチル、アール、
エム・スミス（Ａ、Ｅ、 Ｍａｒｔｅｌｌ 、 Ｒ，Ｍ
。In addition to the above, there are various methods of generating bases, all of which are effective. For example, there is a method in which a base is generated by mixing the above-mentioned sparingly soluble metal compound and a compound (complex-forming compound) capable of forming a complex with the metal ions constituting the sparingly soluble metal compound. As poorly soluble metal compounds,
Examples include salts of zinc, aluminum, barium, calcium and the like with carbonic acid, phosphoric acid, boric acid, etc., their hydroxides, and their oxides. Regarding complex-forming compounds, see, for example, N. E. Martill, R.
M. Smith (A, E, Martell, R, M
.
Ｓｍ１ｔｈ）共著、クリティカル スタビリテイ コン
スタンツ（Ｃｒ１ｔｉｃａｌ ５ｔａｂｉｌｉｔｙ Ｃ
ｏｎ５ｔａｎｔｓ ）第１〜５巻、ブレナムブレス（Ｐ
ｌｅｎｕｍ Ｐｒｅｓｓ ）に詳述されている。具体的
には、アミンリン酸類、カルダン酸類（（モノ、ジ、ト
リまたはテトラカルメン酸化合物、およびそれらに更に
、フォスフォノ、ヒドロキシ、オキソ、エステル、アミ
ド、アルコキシ、メルカプト、アルキルチオ、フォスフ
イノ、アミノ、イミノなどの置換基で置換された化合物
）、例えばイミノジ酢酸およびその訪導体、アニリンカ
ルボン酸類、ピリジンカル設ン酸類など）、ヒドロキサ
ム酸類、ポリアクリレート類、ポリリン酸類などの化合
物、および好ましくは、それら化合物の塩（例えば、ア
ルカリ金属、グアニジン類、アミジン類、４級アンモニ
ウムなどとの塩）などが挙げられる０
上記、難溶性金属化合物と錯形成化合物は、感光材料と
色素固定材料に別々に添加するのが有利である。Sm1th) co-author, Critical Stability Constance (Crltical 5tability C)
on5tants) Volumes 1-5, Blenheim Breath (P
lenum Press). Specifically, amine phosphoric acids, cardanic acids (mono, di, tri, or tetracarmenic acid compounds, and in addition to these, phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, phosphino, amino, imino, etc.) (e.g., iminodiacetic acid and its derivatives, anilinecarboxylic acids, pyridinecarboxylic acids, etc.), hydroxamic acids, polyacrylates, polyphosphoric acids, and preferably salts of these compounds. (For example, salts with alkali metals, guanidines, amidines, quaternary ammonium, etc.) The above-mentioned sparingly soluble metal compounds and complex-forming compounds should be added separately to the photosensitive material and the dye fixing material. It's advantageous.
塩基および／または塩基プレカーサーは単独でも２種以
上組み合わせても使用することができる。The base and/or base precursor can be used alone or in combination of two or more.
本発明に用いられる塩基および／または塩基プレカーサ
ーの量は、広い範囲を用いることができる。感光層およ
び／または色素固定層中に使用する場合には、塗布膜を
重量換算して各々５０重量％以下で用いるのが適当であ
り、さらに好ましくは、０．０１重量％から４０重量％
の範囲が有用受ある。また塩基および／または塩基プレ
カーサーは、水に溶解させて使用することもでき、この
場合には、０．００５ ＋ｎｏｌｅ／Ａ’ Ａいし２モ
ル／ｌの濃度が好ましく、特に０．０５ ｍｏ ｌｅ／
ｅないし１モル／ｌの濃度が好ましい。The amount of base and/or base precursor used in the present invention can vary widely. When used in the photosensitive layer and/or dye fixing layer, it is appropriate to use the coating film in an amount of 50% by weight or less, more preferably 0.01% to 40% by weight.
There is a range of useful information. The base and/or base precursor can also be used dissolved in water, in which case a concentration of 0.005 + nole/A'A to 2 mol/l is preferred, particularly 0.05 mol/l.
Concentrations of between e and 1 mol/l are preferred.
本発明〒は加熱をするが、水という溶媒全比較的多く含
んフいるため感光材料の最高一度は感光材料中の水溶液
（添加された水に各種添加剤が溶解したもの）の沸点に
より決まる。最低温度は５０℃以上が好ましい。水の沸
点は常圧下１は１００℃１あり、１００℃以上に加熱す
ると水の蒸発により、水分がなくなることがあるので、
水不透過性の材料↑Ｉ祭光材料の表面を覆ったり、高温
高圧の水蒸気を供給するのは好ましい。この場合には水
溶液の沸点も上昇するから感光材料の温度も上昇し有利
である。っ
加熱手段は、単なる熱板、アイロン、熱ローラ−、カー
メンやチタンホワイトなどを利用した発熱板またはその
類似物であってよい。Although heating is performed in the present invention, since the solvent, water, is contained in a relatively large amount, the maximum temperature of the photosensitive material is determined by the boiling point of the aqueous solution (various additives dissolved in the added water) in the photosensitive material. The minimum temperature is preferably 50°C or higher. The boiling point of water is 100 degrees Celsius under normal pressure, and when heated above 100 degrees Celsius, the water may disappear due to evaporation.
It is preferable to cover the surface of the water-impermeable material ↑I or to supply high-temperature and high-pressure water vapor. In this case, since the boiling point of the aqueous solution also rises, the temperature of the photosensitive material also rises, which is advantageous. The heating means may be a simple heating plate, an iron, a heating roller, a heating plate using carmen or titanium white, or the like.
本発明では、前記の水好ましくはならびに塩基および／
または塩基プレカーサーの存在下に感光材料を加熱し可
動性の色素の像様分布を形成する工程の後で、感光材料
から色素固定層へ前記可動性の色素を転写することもで
きるが、前記の可動性の色素の像様゛分布を形成するだ
めの加熱と同時に可動性の色素を色素固定層へ転写する
方式において本発明の効果は特に顕著に奏せられる。そ
のために、本発明に用いられる感光材料は、支持体上に
少なくとも感光性ハロゲン化銀、必要に応じて有機銀塩
酸化剤、必要に応じて還元剤、色素供与性物質、場合に
応じて酸性成分およびバインダーを含む感光層（１）を
有する感光要素と、（１）層で形成された可動性の色素
を受けとめることのできる色素固定層（ＩＩ） ｋ有す
る色素固定要素より構成される。In the present invention, the water preferably and the base and/or
Alternatively, after the step of heating the photosensitive material in the presence of a base precursor to form an imagewise distribution of the mobile dye, the mobile dye can be transferred from the photosensitive material to the dye fixing layer. The effects of the present invention are particularly noticeable in a system in which the mobile dye is transferred to the dye fixing layer at the same time as heating is performed to form an imagewise distribution of the mobile dye. For this purpose, the photosensitive material used in the present invention is prepared by disposing on a support at least a photosensitive silver halide, an organic silver salt oxidizing agent if necessary, a reducing agent if necessary, a dye-donating substance, and an acidic compound if necessary. It is composed of a photosensitive element having a photosensitive layer (1) containing components and a binder, and a dye fixing element having a dye fixing layer (II) capable of receiving the mobile dye formed by layer (1).
上述の感光層（Ｉ）と色素固定層（ｎ）とは、同一の支
持体上に形成してもよいし、また別々の支持体上に形成
することもフきる。色素固定層（ＩＩ）と、感光層（１
）とはひきはがすこともできる。たとえば、像様露光後
均一加熱現像し、その後、色素固定層（ＩＩ）または感
光層をひきはがすことが１きる。The above-mentioned photosensitive layer (I) and dye fixing layer (n) may be formed on the same support, or may be formed on separate supports. A dye fixing layer (II) and a photosensitive layer (1)
) can also be torn off. For example, after imagewise exposure, uniform heat development can be carried out, and then the dye fixing layer (II) or the photosensitive layer can be peeled off.
また感光層（Ｉ）を支持体上に塗布した感光要素と、固
定層（ＩＩ） ’？支持体上に塗布した固定要素とを別
々に形成させた場合には、感光要素に像様露光して固定
要素を重ね水好ましくはならびに塩基および／または塩
基ブレカーサ−の存在下１均一加熱することにより可動
性色素を固定層（Ｉｔ）に移すことができる。Furthermore, a photosensitive element having a photosensitive layer (I) coated on a support and a fixed layer (II)'? If the fixing element coated on the support is formed separately, the photosensitive element is imagewise exposed, the fixing element is superimposed, and the fixing element is heated uniformly in the presence of water, preferably a base and/or a base breaker. allows the mobile dye to be transferred to the fixed layer (It).
色素固定層（Ｉ［）は、色素固定のため、たとえば色素
媒染剤を含むことがフきる。媒染剤としては種々の媒染
剤を用いることができ、特に有用なものはポリマー媒染
剤！ある。媒染剤の他に塩基、塩基ブレカーサ−など、
および熱溶剤を含んフもよい。特に感光層（１）と色素
固定層（ＩＩ）とが別の支持体上に形成されている場合
には、塩基、塩基ブレカーサ−を固定層（Ｉ［）に含ま
せることは特に有用フある。The dye fixing layer (I[) may contain, for example, a dye mordant for dye fixation. Various mordants can be used as mordants, and polymer mordants are particularly useful! be. In addition to mordants, bases, base breaker, etc.
It may also contain a hot solvent. In particular, when the photosensitive layer (1) and the dye fixing layer (II) are formed on different supports, it is particularly useful to include a base or a base breaker in the fixing layer (I[). .
感光要素と色素固定要素とが別個の支持体上に形成され
る形態には大別して２つあり、一方は剥離型フあり他方
は剥離不要型１ある。前者の剥離型の場合には画像露光
後、感光要素の塗布面と色素固定要素の塗布面とを重ね
合せ、転写画像形成後は速やかに感光要素を色素固定要
素から剥離する。最終画像が反射型フあるか透過型フあ
るかによって、色素固定要素の支持体は不透明支持体か
透明支持体かを選択できる。また必要に応じて白色反射
層を塗設してもよい。後者の剥離不要型の場合には感光
要素中の感光層と色素固定要素中の色素固定層との間に
白色反射層が介在することが必要であり、この白色反射
層は感光要素、色素固定要素のいずれに塗設されていて
もよい。色素固定要素の支持体は透明支持体１あること
が必要！ある。There are two types of forms in which the photosensitive element and the dye-fixing element are formed on separate supports: one is a peelable type and the other is a peelable type. In the former peel-off type, after image exposure, the coated surface of the photosensitive element and the coated surface of the dye-fixing element are overlapped, and after the transfer image is formed, the photosensitive element is immediately peeled off from the dye-fixing element. Depending on whether the final image is a reflection type or a transmission type, the support of the dye fixing element can be selected as an opaque support or a transparent support. Further, a white reflective layer may be coated if necessary. In the case of the latter type that does not require peeling, it is necessary to have a white reflective layer interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element. It may be painted on any of the elements. The support for the dye fixing element must have one transparent support! be.
以下、色素固定要素が感光要素と別の支持体上にある場
合、感光要素を感光材料と、また色素固定要素を色素固
定材料ということがある。Hereinafter, when the dye-fixing element is on a support separate from the photosensitive element, the photosensitive element may be referred to as a photosensitive material, and the dye-fixing element may be referred to as a dye-fixing material.
感光要素と色素固定要素とが同一の支持体に塗設される
形態の代表的なものは、転写画像の形成後、感光要素を
受像要素から剥離する必要のない形態〒ある。この場合
には、透明または不透明の支持体上に感光層、色素固定
層と白色反射層とが積層される。好ましい態様としては
、例えば、透明支持体／感光層／白色反射層／色素固定
層／、透明支持体／色素固定層／白色反射層／感光層な
どを挙げることができる。A typical configuration in which the photosensitive element and the dye-fixing element are coated on the same support is a configuration in which there is no need to peel the photosensitive element from the image-receiving element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred embodiments include, for example, transparent support/photosensitive layer/white reflective layer/dye fixing layer/transparent support/dye fixing layer/white reflective layer/photosensitive layer.
感光要素と色素固定要素とが同一の支持体上に塗設され
る別の代表的形態には、例えば特開昭５６−６７８４０
、カナダ特許第６７４，０８２号、米国特許第３，７３
０，７１８号に記載されている如く、感光要素の一部ま
たは全部を色素固定要素から剥離する形態があり、適当
な位置に剥離ｊ−が塗設されているものを挙げることが
１きる。Another typical form in which a photosensitive element and a dye fixing element are coated on the same support includes, for example, Japanese Patent Application Laid-Open No. 56-67840.
, Canadian Patent No. 674,082, U.S. Patent No. 3,73
As described in No. 0,718, there is a form in which part or all of the photosensitive element is peeled off from the dye fixing element, and one example is one in which a release j- is coated at an appropriate position.
感光要素と色素固定要素が同一支持体上にある場合、単
に感光材料ということが以下ではある。When the light-sensitive element and the dye-fixing element are on the same support, they will simply be referred to as light-sensitive materials in the following.
感光要素および／または色素固定要素は、導電性の発熱
体層を有する形態であってもよく、この層に通電するこ
とにより加熱することもできる。The photosensitive element and/or the dye fixing element may have a conductive heat generating layer, and can be heated by passing electricity through this layer.
本発明に使用し得るハロゲン化銀は、塩化銀、臭化銀、
あるいは塩臭化銀、塩沃化銀、塩沃臭化銀のいずれ↑も
よい。Silver halides that can be used in the present invention include silver chloride, silver bromide,
Alternatively, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide are all suitable.
具体的には特願昭５９−２２８５５１号の３５頁〜３６
頁、米国特許４，５００，６２６号第５０欄、リサーチ
・ディスクロージャー誌１９７８年６月号９頁〜１０頁
（ＲＤ１７０２９）等に記載されているハロゲン化銀乳
剤のいずれもが使用フきる。Specifically, pages 35 to 36 of Japanese Patent Application No. 59-228551.
Any of the silver halide emulsions described in U.S. Pat.
ハロゲン化銀乳剤は未後熟のまま使用してもよいが通常
は化学増感して使用する。通常型感光材料用乳剤で公知
の硫黄増感法、還元増感法貨金属増感法などを単独また
は組合わせて用いることが１きる。これらの化学増感を
含窒素腹素壌化合物の存在下１行うこともできる（特開
昭５８−１２６５２６号、同５８−２１５６４４号）。Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, well-known sulfur sensitization methods, reduction sensitization methods, metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing compounds (JP-A-58-126526, JP-A-58-215644).
本発明で使用するハロゲン化銀乳剤は、主として潜像が
粒子表面に形成される表面潜像型であっても、粒子内部
に形成される内部潜像型であってもよい。内部潜像型乳
剤と造核剤とを組合わせた直接反転乳剤を使用すること
もマきる。The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. It is also possible to use a direct reversal emulsion which is a combination of an internal latent image type emulsion and a nucleating agent.
本発明において使用される感光性ハロゲン化銀の塗設量
は、銀換算１■ないし１０９／ｒｎ２の範囲である。The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 to 109/rn2 in terms of silver.
本発明においては、感光性ハロゲン化銀と共に、有機金
属塩を酸化剤として併用することもできる。In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.
この場合、感光性ハロゲン化銀と有機金属塩とは接触状
態もしくは接近した距離にあることが必要ｔある。In this case, it is necessary that the photosensitive silver halide and the organic metal salt be in contact with each other or at a close distance.
このような有機金属塩の中、有機銀塩は、特に好ましく
用いられる。Among such organic metal salts, organic silver salts are particularly preferably used.
上記の有機銀塩酸化剤を形成するのに使用し得る有機化
合物としては、特願昭５９−２２８５５１号の３７頁〜
３９頁、米国特許４，５００，６２６号第５２欄〜第５
３欄等に記載の化合物がある。また特願昭５８−２２１
５３５号記載のフェニルグロビオール酸銀などのアルキ
ニル基を有するカルボン酸の銀塩も有用である。Examples of organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include Japanese Patent Application No. 59-228551, page 37-
Page 39, U.S. Pat. No. 4,500,626, columns 52-5.
There are compounds listed in column 3, etc. Also, the patent application 1986-221
Also useful are silver salts of carboxylic acids having alkynyl groups, such as silver phenylglobiolate described in No. 535.
以上の有機銀塩は、感光性ハロゲン化銀１モルあたり、
０．０１ないし１０モル、好ましくは０．０１ないし１
モルを併用することができる。感光性ノ・ロゲン化銀と
有機銀塩の塗布量合計は銀換算で５０■ないし１０ｊｉ
／ｍ２が適描である。The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 to 10 ji in terms of silver.
/m2 is a suitable drawing.
本発明に用いられるハロゲン化銀は、メチン色素類その
他によって分光増感されてもよい。用いラレる色素には
、シアニン色素、メロシアニン色素、複合シアニン色素
、複合メロシアニン色素、ホロポーラ−シアニン色素、
ヘミシアニン色素、スチリル色素およびヘミオキンノー
ル色素が包含される。The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes,
Included are hemicyanine dyes, styryl dyes and hemioquinol dyes.
具体的には、特開昭５９−１８０５５０号、同６０−１
４０３３５号、リサーチ・ディスクロージャー誌１９７
８年６月号１２〜１３頁（ＲＤ１７０２９）等に記載の
増感色素や、特開昭６０−１１１２３９号、特願昭６０
−１７２９６７号等に記載の熱脱色性の増感色素が挙げ
られる。Specifically, Japanese Patent Publication Nos. 59-180550 and 60-1
No. 40335, Research Disclosure Magazine 197
The sensitizing dyes described in June 1988 issue, pages 12-13 (RD17029), JP-A-60-111239, Japanese Patent Application No. 1983
Examples include heat-decolorizable sensitizing dyes described in Japanese Patent No. 172,967 and the like.
これらの増感色素は単独に用いてもよいが、それらの組
合わせを用いてもよく、増感色素の組合わせは特に、強
色増感の目的でしばしば用いられる０
増感色素とともに、それ自身分光増感作用をもたない色
素あるいは可視光を実質的に吸収しない物質！あって、
強色増感を示す物質と乳剤中に含んでもよい（例えば米
国特許２，９３３，３９０号、同３，６３５，７２１号
、同３，７４３，５１０号、同３．６１５，６１３号、
同３，６１５，６４１号、同３．６１７，２９５号、同
３，６３５，７２１号に記載のもの）。These sensitizing dyes may be used alone or in combinations thereof, and combinations of sensitizing dyes are particularly suitable for use with 0 sensitizing dyes, which are often used for the purpose of supersensitization. A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light! There it is,
The emulsion may contain a substance exhibiting supersensitization (for example, U.S. Pat. Nos. 2,933,390, 3,635,721, 3,743,510, 3,615,613,
3,615,641, 3,617,295, and 3,635,721).
これらの増感色素を乳剤中に添加する時期は化学熟成時
もしくはその前後１もよいし、米国特許第４，１８３，
７５６号、同第４，２２５，６６６号に従ってハロゲン
比銀粒子の核形成前後でもよい。These sensitizing dyes may be added to the emulsion during chemical ripening or before or after chemical ripening.
No. 756 and No. 4,225,666 may be used before or after nucleation of halogen ratio silver particles.
添加量は一般にハロゲン化銀１モル当たり１０−８ない
し１０−２モル程度である。The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.
次に色素供与性物質について説明する。Next, the dye-donating substance will be explained.
本発明に使用することのできる色素供与性物質の例とし
て、まず、現像薬と反応しうるカプラーを挙げることが
〒きる。このカプラーを利用する方式は、銀塩と現像薬
との酸化還元反応によって生じた現像薬の酸化体がカプ
ラーと反応して色素を形成するものであり、多数の文献
に記載されている。このカプラーは４当量カプラーでも
、２当量カプラー１もよい。また、耐拡散基を脱離基に
持ち、現像薬の酸化体との反応によシ拡散性色素を生成
する２当量カプラーも好ましい。現像薬およびカプラー
の具体例は・ジエームズ著「ザ セオリー オプ ザ
フォトグラフィック プロセス」第４版（Ｔ、 Ｈ，Ｊ
ａｍｅａ″″Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ ｔｈｅ Ｐ
ｈｏｔ。Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. This method using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. This coupler may be a 4-equivalent coupler or a 2-equivalent coupler 1. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and produce a diffusible dye upon reaction with an oxidized developer. Specific examples of developers and couplers can be found in ``The Theory Op.
Photographic Process” 4th edition (T, H, J
amea""The Theory of the P
Hot.
ｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ ” ） ２９１〜３
３４頁、および３５４〜３６１頁、特開昭５８−１２３
５３３号、同５８−１４９０４６号、同５８−１４９０
４７号、同５９−１１１１４８号、同５９−１２４３９
９号、同５９−１７４８３５号、同５９−２３１５３９
号、同５９−２３１５４０号、同６０−２９５０号、同
６０−２９５１号、同６０−１４２４２号、同６０−２
３４７４号、同６０−６６２４９号等に詳しく記載され
ている。291~3
34 pages and 354-361 pages, JP-A-58-123
No. 533, No. 58-149046, No. 58-1490
No. 47, No. 59-111148, No. 59-12439
No. 9, No. 59-174835, No. 59-231539
No. 59-231540, No. 60-2950, No. 60-2951, No. 60-14242, No. 60-2
It is described in detail in No. 3474, No. 60-66249, etc.
また、有機銀塩と色素を結合した色素銀化合物も色素供
与性物質の例に挙げることができる。色素銀化合物の具
体例はリサーチ・ディスク口−ジャー誌１９７８年５月
号、５４〜５８頁（ＲＤ−１６９６６）等に記載されて
いる。Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds are described in Research Disc-Jar, May 1978 issue, pages 54-58 (RD-16966).
また、熱現像銀色素漂白法に用いられるアゾ色素も色素
供与性物質の例に挙げることができる。Furthermore, azo dyes used in heat-developable silver dye bleaching methods can also be cited as examples of dye-donating substances.
アゾ色素の具体例および漂白の方法は米国特許第４．２
３５，９５７号、リサーチ・ディスクロー・ジャー誌、
１９７６／４４月号、３０〜３２頁（ＲＤ−１４４３３
）等に記載されている。また、米国特許第３，９８５，
５６５号、同４，０２２，６１７号等に記載されている
ロイコ色素も色素供与性物質の例に挙げることが！きる
。Specific examples of azo dyes and bleaching methods are disclosed in U.S. Patent No. 4.2.
No. 35,957, Research Disclosure Magazine,
1976/44 issue, pages 30-32 (RD-14433
) etc. Also, U.S. Patent No. 3,985,
The leuco dyes described in No. 565 and No. 4,022,617 can also be cited as examples of dye-donating substances! Wear.
また、別の色素供与性物質の例として、画像状に拡散性
色素を放出乃至拡散する機能を持つ化合物を挙げること
ができる。この型の化合物は次の一般式［ＬＩ〕で表わ
すことが〒きる。Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula [LI].
（Ｄｙｅ−Ｘ）ｎ−Ｙ （Ｌ［）Ｄｙｅは色素基
、一時的に短波化された色素基または色素前動体層を表
わし、Ｘは単なる結合または連結基１［わし、Ｙは画像
状に潜像を有する感光性銀塩に対応または逆対応して（
Ｄｙｅ−Ｘ）ｎ−Ｙフ表わされる化合物の拡散性に差を
生じさせるか、または、Ｄｙｅを放出し、放出されたＤ
ｙｅと（Ｄｙｅ −Ｘ ）ｎ−ｙとの間に拡散性におい
て差を生じさせるような性質を有する基を表わし、ｎは
１ｔたは２を表わし、ｎが２の時、２つのＤｙｅ −Ｘ
は同−寸も異なっていてもよい。(Dye-X)n-Y (L[)Dye represents a dye group, a temporarily shortened dye group or a dye premotor layer, Corresponding or inversely to a photosensitive silver salt with a latent image (
Dye-X) n-Y causes a difference in the diffusivity of the expressed compound or releases the
Represents a group having the property of causing a difference in diffusivity between ye and (Dye -X)ny, where n represents 1t or 2, and when n is 2, two Dye -X
may be the same or different in size.
一般式［：Ｌ［，１１？表わされる色素供与性物質の具
体例としては、例えば、ハイドロキノン系現像薬と色素
成分を連結した色素現像薬が、米国特許第３．１３４，
７６４号、同第３，３６２，８１９号、同第３．５９７
，２００号、同第３，５４４，５４５号、同第３．４８
２，９７２号等に記載されている。また、分子内求核置
換反応によシ拡散性色素を放出させる物質が、特開昭５
１−６３，６１８号等に、イソオキサシロン環の分子内
巻き換え反応によシ拡散性色素を放出させる物質が、特
開昭４９−１１１，６２８号等に記載されている。これ
らの方式はいずれも現像の起こらなかった部分で拡散性
色素が放出または拡散する方式であり、現像の起こった
ところｆは色素は放出も拡散もしない。General formula [:L[,11? As a specific example of the dye-donating substance expressed, for example, a dye developer in which a hydroquinone-based developer and a dye component are linked is described in U.S. Patent No. 3.134,
No. 764, No. 3,362,819, No. 3.597
, No. 200, No. 3,544,545, No. 3.48
No. 2,972, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction was published in JP-A No. 5
JP-A No. 1-63,618, etc., and JP-A-49-111,628, etc., disclose substances that release diffusible dyes through an intramolecular rewinding reaction of isoxacilone rings. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and in the area f where development has occurred, the dye is neither released nor diffused.
また、別の方式としては、色素放出性化合物を色素放出
能力のない酸化体型にして還元剤もしくはその前駆体と
共存させ、現像後、酸化されずに残った還元剤によシ還
元して拡散性色素を放出させる方式も考案されており、
そこに用いられる色素供与性物質の具体例が、特開昭５
３−１１０，８２７号、同５４−１３０，９２７号、同
５６−１６４，３４２号、同５３−３５，５３３号に記
載されている。Another method is to make the dye-releasing compound into an oxidized form without dye-releasing ability, coexist with a reducing agent or its precursor, and after development, the remaining unoxidized reducing agent reduces and diffuses. A method of releasing sex pigments has also been devised,
A specific example of the dye-donating substance used therein is
It is described in No. 3-110,827, No. 54-130,927, No. 56-164,342, and No. 53-35,533.
一方、現像の起こった部分で拡散性色素を放出させる物
質として、拡散性色素を脱離基に持つカノラーと現像薬
の酸化体との反応によシ拡散性色素を放出させる物質が
、英国特許第１，３３０，５２４号、特公昭４８−３９
，１６５号、英国特許第３．４４３，９４０号等に記載
されている。On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a canoler having a diffusible dye as a leaving group and an oxidized form of a developer has been patented in the UK. No. 1,330,524, Special Publication No. 48-39
, No. 165, British Patent No. 3,443,940, etc.
また、これらのカラー現像薬を用いる方式では現像薬の
酸化分解物による画像の汚染が深刻な問題となるためこ
の問題を改良する目的で、現像薬を必要としない、それ
自身が還元性を持つ色素放出性化合物も考案されている
。その代表例はたとえば、米国特許第３，９２８，３１
２号、同第４，０５３，３１２号、同第４，０５５，４
２８号、同第４，３３６，３２２号、特開昭５９−６５
８３９号、同５９−６９８３９号、同５３−３８１９号
、同５１−１０４，３４３号、リサーチ・ディスクロー
ジャー誌１７４６５号、米国特許第３，７２５，０６２
号、同第３．７２８，１１３号、同第３．４４３，９３
９号、特開昭５８−１１６，５３７号、同５７−１７９
８４０号、米国特許第４，５００，６２６号等に記載さ
れている色素供与性物質１ある。In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer is a serious problem. Dye-releasing compounds have also been devised. A typical example is, for example, U.S. Patent No. 3,928,31
No. 2, No. 4,053,312, No. 4,055,4
No. 28, No. 4,336,322, JP-A-59-65
No. 839, No. 59-69839, No. 53-3819, No. 51-104,343, Research Disclosure No. 17465, U.S. Patent No. 3,725,062
No. 3.728,113, No. 3.443,93
No. 9, JP-A-58-116,537, JP-A No. 57-179
No. 840, US Pat. No. 4,500,626, and the like.
本発明に用いうる色素供与性物質の具体例としては前述
の米国特許第４，５００，６２６号の第２２欄〜第４４
欄に記載の化合物を挙げることができるが、なか１も前
記米国特許に記載の化合物（１）〜（３）、（１０）〜
（１３）、（１６）〜（１９）、（２８）〜（３０）、
（３３）〜（３５）、（３８）〜（４０）、（４２）〜
（６４）が好ましい。また特願昭５９−２４６４６８号
の８０〜８７頁に記載の化合物も有用１ある。Specific examples of dye-providing substances that can be used in the present invention include those described in columns 22 to 44 of the aforementioned U.S. Pat. No. 4,500,626.
Among them, compounds (1) to (3) and (10) to which are described in the above US patent can be mentioned.
(13), (16) to (19), (28) to (30),
(33) ~ (35), (38) ~ (40), (42) ~
(64) is preferred. Compounds described on pages 80 to 87 of Japanese Patent Application No. 59-246468 are also useful.
上記の色素供与性化合物および以下に述べる画像形成促
進剤などの疎水性添加剤は米国特許第２．３２２，０２
７号記載の方法などの公知の方法により感光材料の層中
に導入することができる。この場合には、特開昭５９−
８３１５４号、同５９ 。Hydrophobic additives such as the dye-providing compounds described above and the imaging promoters described below are described in U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 7. In this case, JP-A-59-
No. 83154, 59.
−１７８４５１号、同５９−１７８４５２号、同５９−
１７８４５３号、同５９−１７８４５４号、同５９−１
７８４５５号、同５９−１７８４５７号などに記載のよ
うな高沸点有機溶媒を、必要に応じて沸点５０℃〜１６
０℃の低沸点有機溶媒と併用して、用いることが〒きる
。-178451, 59-178452, 59-
No. 178453, No. 59-178454, No. 59-1
No. 78455, No. 59-178457, etc., a high boiling point organic solvent may be used as necessary at a boiling point of 50°C to 16°C.
It can be used in combination with a low boiling point organic solvent at 0°C.
高沸点有機溶媒の量は用いられる色素供与性物質１ｇに
対して１０ｇ以下、好ましくは５ｇ以下である。The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing substance used.
また特公昭５１−３９８５３号、特開昭５１−５９９４
３号に記載されている重合物による分散法も使用ｔきる
。Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used.
水に実質的に不溶な化合物の場合には、前記方法以外に
・々イングー中に微粒子にして分散含有させることがで
きる。In the case of a compound that is substantially insoluble in water, in addition to the above-mentioned method, it can be dispersed and contained in fine particles in the ingu.
疎水性物質を親水性コロイに分散する際には、種々の界
面活性剤を用いることができ、それらの界面活性剤とし
ては特開昭５９−１５７６３６号の第（３７）〜（３８
）頁に界面活性剤として挙げたものを使うことができる
。When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used.
) can be used as surfactants listed on page 1.
本発明においては感光材料中に還元性物質を含有させる
のが望ましい。還元性物質としては一般に還元剤として
公知なものの他、前記の還元性を有する色素供与性物質
も含まれる。また、それ自身は還元性を持たないが現像
過程で求核試薬や熱の作用によυ還元性を発現する還元
剤プレカーサーも含まれる。In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducing properties but exhibit υ-reducing properties through the action of nucleophiles and heat during the development process.
本発明に用いられる還元剤の例としては、米国特許４，
５００，６２６号の第４９〜５０欄、同４．４８３，９
１４号の第３０〜３１欄、特開昭６０−１４０３３５号
の第（１７）〜（１８）頁、特開昭６０−１２８４３８
号、同６０−１２８４３６号、同６０−１２８４３９号
、同６０−１２８４３７号等に記載の還元剤が利用でき
る。また、特開昭５６−１３８，７３６号、同５７−４
０，２４５号、米国特許第４，３３０，６１７号等に記
載されている還元剤プレカーサーも利用できる。Examples of reducing agents used in the present invention include U.S. Pat.
No. 500,626, columns 49-50, 4.483,9
No. 14, columns 30-31, JP-A-60-140335, pages (17)-(18), JP-A-60-128438
No. 60-128436, No. 60-128439, No. 60-128437, etc. can be used. Also, JP-A-56-138,736, JP-A No. 57-4
Reducing agent precursors such as those described in US Pat. No. 0,245 and US Pat. No. 4,330,617 can also be used.
米国特許第３，０３９，８６９号に開示されているもの
のような種々の現像薬の組合せも用いることができる。Combinations of various developers can also be used, such as those disclosed in US Pat. No. 3,039,869.
本発明に於いては還元剤の添加量は銀１モルに対して０
．０１〜２０モル、特に好ましくは０．１〜１０モルで
ある。In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol.
本発明において感光材料には画像形成促進剤を用いるこ
とが１きる。画像形成促進剤には銀塩酸化剤と還元剤と
の酸化還元反応の促進、色素供与性物質からの色素の生
成または色素の分解あるいは拡散性色素の放出等の反応
の促進および、感光材料層から色素固定層への色素の移
動の促進等の機能があり、物理化学的な機能からは前記
の塩基または塩基プレカーサー、求核性化合物、高沸点
有機溶媒（オイル）、熱溶剤、界面活性剤、銀または銀
イオンと相互作用を持つ化合物等に分類される。ただし
、これらの物質群は一般に複合機能を有しており、上記
の促進効果のいくつかを合せ持つのが常である。これら
の詳細については特許１１５５９−２１３９７８号の６
７〜７１頁に記載されている。In the present invention, an image formation accelerator can be used in the light-sensitive material. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. It has the function of promoting the movement of the dye from the dye to the dye fixed layer, and from the physicochemical function, it has the above-mentioned base or base precursor, nucleophilic compound, high boiling point organic solvent (oil), thermal solvent, and surfactant. It is classified as a compound that interacts with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details on these, see Patent No. 11559-213978-6.
It is described on pages 7-71.
本発明においては、現像時の処理温度および処理時間の
変動に対し、常に一定の画像を得る目的で種々の現像停
止剤を併用することが〒きる。In the present invention, various development stoppers may be used in combination for the purpose of always obtaining a constant image despite fluctuations in processing temperature and processing time during development.
ここでいう現像停止剤とは、適正現像後、塩基と反応し
て膜中の塩基濃度を下げ現像を停止する化合物または銀
および銀塩と相互作用して現像を抑制する化合物〒ある
。具体的には、加熱により共存する塩基と置換反応を起
す親電子化合物があり、その例は特願昭５９−８５８３
６号に記されている。The term "development stopper" as used herein refers to a compound that reacts with a base to reduce the base concentration in the film and stop development after proper development, or a compound that inhibits development by interacting with silver and silver salts. Specifically, there are electrophilic compounds that cause a substitution reaction with a coexisting base when heated; an example of this is disclosed in Japanese Patent Application No. 59-8583
It is written in No. 6.
また加熱によりメルカプト化合物を放出する化合物も有
用１あシ、例えば特願昭５９−１９０１７３号、同５９
−２６８９２６号、同５９−２４６４６８号、同６０−
２６０３８号、同６０−２２６０２号、同６０−２６０
３９号、同６０−２４６６５号、同６０−２９８９２号
、同５９−１７６３５０号、に記載の化合物がある。Compounds that release mercapto compounds when heated are also useful, for example, Japanese Patent Application No. 190173/1983;
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
There are compounds described in No. 39, No. 60-24665, No. 60-29892, and No. 59-176350.
また本発明においては感光材料に現像の活性化と同時に
画像の安定化を図る化合物を用いることができる。好ま
しく用いられる具体的化合物については米国特許第４，
５００，６２６号の第５１〜５２欄に記載されている。Further, in the present invention, a compound that activates the development and stabilizes the image can be used in the photosensitive material. For specific compounds preferably used, see U.S. Patent No. 4,
No. 500,626, columns 51-52.
本発明においては種々のカプリ防止剤を使用することが
できる。カプリ防止剤としては、アゾール類、特開昭５
９−１６８４４２号記載の窒素を含むカルはン酸類およ
びリン酸類、あるいは特開昭５９−１１１，６３６号記
載のメルカグト化合物およびその金属塩、昭和６０年１
０月１４日付特許出願（Ｂ）（特許出願人；富士写真フ
ィルム株式会社）に記載されているアセチレン化合物類
などが用いられる。Various anti-capri agents can be used in the present invention. As anti-capri agents, azoles, JP-A-5
Nitrogen-containing carnic acids and phosphoric acids described in No. 9-168442, or mercagut compounds and metal salts thereof described in JP-A-59-111,636, published in 1985.
Acetylene compounds described in patent application (B) dated October 14th (patent applicant: Fuji Photo Film Co., Ltd.) are used.
本発明においては、感光材料に必要に応じて画像調色剤
を含有することができる。有効な調色剤の具体例につい
ては特願昭５９−２６８９２６号９２〜９３頁に記載の
化合物がある。In the present invention, the photosensitive material may contain an image toning agent if necessary. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92-93.
本発明の感光材料のバインダーは、単独〒あるいは組合
わせて用いることができる。このバインダーには親水性
のものを用いることができる。親水性バインダーとして
は、透明か半透明の親水性バインダーが代表的↑めり、
例えばゼラチン、ゼラチン誘導体等のタン・ぐり質、セ
ルロース誘導体や、デンプン、アラビヤゴム等の多糖類
のような天然物質と、ポリビニルピロリドン、アクリル
アミド重合体等の水溶性のポリビニル化合物のような合
成重合物質を含む。他の合成重合物質には、ラテックス
の形〒用いられ、写真材料の寸度安定性を増加させる分
散状ビニル化合物がある。The binders for the photosensitive material of the present invention can be used alone or in combination. A hydrophilic binder can be used for this binder. Transparent or translucent hydrophilic binders are typical examples of hydrophilic binders.
For example, natural substances such as gelatin, pulp such as gelatin derivatives, cellulose derivatives, polysaccharides such as starch and gum arabic, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers are used. include. Other synthetic polymeric materials include dispersed vinyl compounds that are used in latex form to increase the dimensional stability of photographic materials.
本発明においてバインダーは１ ｍ２ｈｆｃす２０ 、
ｐ以下の塗布量″’ｅ、Ｂす、好ましくは１０９以下さ
らに好ましくは７ｇ以下が適当″Ｉ？ある。In the present invention, the binder is 1 m2hfc20,
Appropriate amount of coating is less than 10g, preferably less than 10g, more preferably less than 7g. be.
バインダー中に色素供与性物質などの疎水性化合物と共
に分散される高沸点有機溶媒とバインダーとの比率はバ
インダー１−ｇに対して溶媒１ ｃｃ以下、好ましくは
０．５ ｃｃ以下、さらに好ましくは０．３ｃｃ以下が
適当〒ある。The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 cc or less of solvent per 1 g of binder, preferably 0.5 cc or less, more preferably 0. .3cc or less is suitable.
本発明の写真感光材料および色素固定材料には、写真乳
剤層その他のバインダ一層に無機または有機の硬膜剤を
含有してよい。The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other binder layer.
硬膜剤の具体例は、特願昭５９−２６８９２６号明細書
９４頁ないし９５頁や特開昭５９−１５７６３６号第（
３８）頁に記載のものが挙げられ、これらは単独または
組合わせて用いることができる。Specific examples of hardening agents can be found in Japanese Patent Application No. 59-268926, pages 94 to 95, and Japanese Patent Application Laid-open No. 59-157636 (
Examples include those described on page 38), and these can be used alone or in combination.
本発明における感光材料および場合によって用いられる
色素固定材料に使用される支持体は、処理温度に耐える
ことの１きるものである。一般的な支持体としては、ガ
ラス、紙、重合体フィルム、金属およびその類似体が用
いられるばかシでなく、特願昭５９−２６８９２６号明
細書の９５頁〜９６頁に支持体として挙がっているもの
が使用できる。The supports used in the light-sensitive materials and optionally used dye-fixing materials in the present invention are those that can withstand processing temperatures. Commonly used supports include glass, paper, polymer films, metals, and their analogues; You can use what you have.
本発明マ使用する感光材料の中に着色している色素供与
性物質を含有する場合には、さらにイラジェーション防
止やハレーション防止物質、あるいは各種の染料を感光
材料に含有させることはそれ程必要↑はないが、特願昭
５９−２６８９２６号９７〜９８頁や米国特許４，５０
０，６２６号の第５５欄（４１〜５２行）に例示された
文献に記載されているフィルター染料や吸収性物質等を
含有させることができる。When the light-sensitive material used in the present invention contains a colored dye-donating substance, it is necessary to further contain an irradiation-preventing substance, an anti-halation substance, or various dyes↑ Although there is no
Filter dyes, absorbent substances, etc. described in the literature exemplified in column 55 (lines 41 to 52) of No. 0,626 can be contained.
イエロー、マゼンタ、シアンの３原色を用いて、色度図
内の広範囲の色を得るために、本発明に用いられる感光
要素は、少なくとも３層のそれぞれ異なるスペクトル領
域に感光性を持つハロゲン化銀乳剤層を有する必要があ
る。In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta and cyan, the light-sensitive element used in the present invention comprises at least three layers of silver halide, each sensitive to a different spectral region. It is necessary to have an emulsion layer.
互いに異なるスペクトル領域に感光性を持つ少なくとも
３つの感光性ハロゲン化銀乳剤層の代表的な組合せとし
ては、特開昭５９−１８０５５０号に記載のものがある
。A typical combination of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions is described in JP-A-59-180550.
本発明に用い゛られる感光材料は、必要に応じて同一の
スペクトル領域に感光性を持つ乳剤層を乳剤の感度によ
って２層以上に分けて有していてもよい。The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.
本発明に用いられる感光材料は、必要に応じて、熱現像
感光材料として知られている各種添加剤や、感光層以外
の層、例えば静電防止層、導電層、保循層、中間層、Ａ
Ｈ層、剥離層、マット層等を含有することができる。各
種添加剤としては、リサーチ・ディスクロージャー誌１
９７８年６月号の９頁ないし１５頁（ＲＤ１７０２９）
、特願昭５９−２０９５６３号などに記載されている添
加剤、例えば可塑剤、鮮鋭度改良用染料、ＡＨ染料、増
感色素、マット剤、界面活性剤、螢光増白剤、紫外線吸
収剤、スベリ防止剤、酸化防止剤、退色防止剤等の添加
剤がある。The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials, layers other than the photosensitive layer, such as an antistatic layer, a conductive layer, a circulation layer, an intermediate layer, A
It can contain an H layer, a release layer, a matte layer, etc. For various additives, see Research Disclosure Magazine 1.
June 978 issue, pages 9 to 15 (RD17029)
, additives described in Japanese Patent Application No. 59-209563, etc., such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, and ultraviolet absorbers. There are additives such as anti-slip agents, antioxidants, and anti-fading agents.
特に、保護層には、接着防止のために有機、無機のマッ
ト剤を含ませるのが通常１ある。また、この保護層には
媒染剤、Ｕｖ吸収剤を含ませてもよい。保護層および中
間層はそれぞれ２層以上から構成されていてもよい。In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and a UV absorber. Each of the protective layer and the intermediate layer may be composed of two or more layers.
また中間層には、退色防止や混色防止のための還元剤、
Ｕｖ吸収剤、ＴｌＯ２などの白色顔料を含ませてもよい
。白色顔料は感度を上昇させる目的で中間層のみならず
乳剤層に添加してもよい。In addition, the intermediate layer contains a reducing agent to prevent color fading and color mixing.
UV absorbers, white pigments such as TlO2 may also be included. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.
感光材料または色素固定材料は、加熱現像もしくは色素
の拡散転写のだめの加熱手段としての導電性の発熱体層
を有する形態であってもよい。The photosensitive material or dye fixing material may have a conductive heating layer as a heating means for heat development or dye diffusion transfer.
この場合の透明または不透明の発熱要素は、抵抗発熱体
として従来公知の技術を利用して作ることができる。The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements.
抵抗発熱体としては、半導性を示す無機材料の薄膜を利
用する方法と導電性微粒子をバインダーに分散した有機
物薄膜を利用する方法とがある。As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder.
これらの方法に利用フきる材料は、特願昭５９−１５１
８１５号明細書等に記載のものを利用できる０
本発明に用いられる色素固定材料は媒染剤を含む層を少
なくとも１ｊ−有しｔおり、色素固定層が表面に位置す
る場合、必要に応じて、さらに保護層を設けることがで
きる。Materials that can be used in these methods are disclosed in Japanese Patent Application No. 59-151.
The dye fixing material used in the present invention has at least 1 layer containing a mordant, and when the dye fixing layer is located on the surface, if necessary, Furthermore, a protective layer can be provided.
色素固定材料の層構成、バインダー、添加剤、媒染剤添
加層の設置位置などは特願昭５９−２６８９２６号明細
書の６２頁９行〜６３頁１８行の記載およびそこに引用
された特許明細書に記載のものが本願にも適用ｔきる。The layer structure of the dye-fixing material, the location of the binder, additives, mordant addition layer, etc. are described in Japanese Patent Application No. 59-268926, page 62, line 9 to page 63, line 18, and the patent specifications cited therein. What is described in the above can also be applied to the present application.
本発明に用いられる色素固定材料は前記の層の他に必要
に応じて剥離層、マット剤層、カール防止層などの補助
層を設けることが〒きる。In addition to the above-mentioned layers, the dye fixing material used in the present invention may be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary.
上記層の１つまたは複数の層には、色素移動を促進する
ための塩基および／または塩基ブレカーサ−、親水性熱
溶剤、色素の退色を防ぐための退色防止剤、Ｕｖ吸収剤
、スベリ剤、マット剤、酸化防止剤、寸度安定性を増加
させるための分散状ビニル化合物、螢光増白剤等を含ま
せてもよい。One or more of the above layers may include a base and/or base breaker to promote dye transfer, a hydrophilic heat solvent, an anti-fading agent to prevent fading of the dye, a UV absorber, a slip agent, A matting agent, an antioxidant, a dispersed vinyl compound for increasing dimensional stability, a fluorescent whitening agent, etc. may be included.
これらの添加剤の具体例は特願昭５９−２０９５６３号
の１０１頁〜１２０頁に記載されている。Specific examples of these additives are described on pages 101 to 120 of Japanese Patent Application No. 59-209563.
上記層中のバインダーは親水性のものが好ましく、透明
か、半透明の親水性コロイドが代表的ｆある。具体例に
は前記の感光材料の所〒挙げたバインダーが用いられる
。The binder in the layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical examples. Specific examples include the binders listed above for the photosensitive materials.
本発明における画像受像層としては、熱・現像カラー感
光材料に使用する色素固定層があり、通常便用される媒
染剤の中から任意に選ぶことが！きるが、それらの中１
も特にポリマー媒染剤が好ましい。ここ１ポリマー媒染
剤とは、三級アミノ基を含むポリマー、含窒素複素環部
分を有するポリマー、およびこれらの４級カチオン基金
含むイリマー等フある。The image-receiving layer in the present invention includes a dye-fixing layer used in heat-developable color photosensitive materials, and any mordant can be selected from commonly used mordants! I can do it, but one of them
Polymer mordants are also particularly preferred. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, and an irimer containing a quaternary cation group thereof.
この具体例については特願昭５９−２６８９２６号９８
〜１００頁や米国特許４，５００，６２６号の第５７〜
６０欄に記載されている。Regarding this specific example, please refer to Japanese Patent Application No. 59-268926.
~Page 100 or No. 57 of U.S. Patent No. 4,500,626~
It is stated in column 60.
本発明においては熱現像感光層、保護ノ１、中間層、下
塗層、パック層その他の層の塗布法は米国特許４，５０
０，６２６号の第５５〜５６欄に記載の方法が適用〒き
る。In the present invention, the method of coating the heat-developable photosensitive layer, protective layer 1, intermediate layer, undercoat layer, pack layer, and other layers is disclosed in U.S. Pat.
The method described in columns 55-56 of No. 0,626 can be applied.
熱現像感光材料へ画像を記録するための画像露光の光源
としては、可視光をもきむ幅射線金用いることができ、
例えば特願昭５９−２６８９２６号の１００頁や米国特
許４，５００，６２６号の第５６欄に記載の光源音用い
ることができる。As a light source for image exposure to record an image on a heat-developable photosensitive material, a beam beam that emits visible light can be used.
For example, the light source sound described in Japanese Patent Application No. 59-268926, page 100 and U.S. Pat. No. 4,500,626, column 56 can be used.
（実施例）
以下、本発明の具体的実施例を示し、本発明をさらに詳
細に説明する。(Examples) Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail.
実施例１ ベンゾトリアゾール銀乳剤の作り方について述べる。Example 1 This article describes how to make benzotriazole silver emulsion.
ゼラチン２８ｇとベンゾトリアゾール１３．２Ｉを水３
００ゴに溶解した。この溶液を４０℃に保ち攪拌した。28g of gelatin and 13.2I of benzotriazole in 33g of water
It was dissolved in 00g. This solution was kept at 40°C and stirred.
この溶液に硝酸銀１７ｇを水１００ｄに溶かした液を２
分間〒加えた。Add 17 g of silver nitrate dissolved in 100 d of water to this solution.
Added minutes.
このベンゾトリアゾール銀乳剤のｐＨ’に調整し、沈降
させ、過剰の塩を除去した。その後、−を６．３０に合
わせ、収１４００ｇのベンゾトリアゾール銀乳剤を得た
。The pH' of this benzotriazole silver emulsion was adjusted and sedimented to remove excess salt. Thereafter, - was adjusted to 6.30 to obtain 1400 g of benzotriazole silver emulsion.
第５層と第１層用のハロゲン化銀乳剤の作り方をのべる
。This article describes how to make silver halide emulsions for the 5th and 1st layers.
良く攪拌しているゼラチン水溶液（水ｉｏｏ。A well-stirred gelatin aqueous solution (water ioo.
ｄ中にゼラチン２０．９と塩化ナトリウム３．１含み、
７５℃に保温したもの）に塩化ナトリウムと臭化カリウ
ムを含有している水溶液５ＱＱｄと硝酸銀水溶液（水６
００＃Ｉｔに硝酸銀０．５９モルを溶解させたもの）を
同時に４０分間にわたって等流量で添加した。このよう
にして、平均粒子サイズ０．４０μｍの単分散立方体塩
臭化銀乳剤（臭素５０モル％）を調製した。d contains 20.9 gelatin and 3.1 sodium chloride,
Aqueous solution 5QQd containing sodium chloride and potassium bromide (kept at 75°C) and silver nitrate aqueous solution (water 6
0.59 mol of silver nitrate dissolved in 00#It) was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (50 mol % of bromine) with an average grain size of 0.40 μm was prepared.
水洗、脱塩後、チオ硫酸す） ＩＪウム５を夕と４−ヒ
ドロキシ−６−メチル−１＋３．３ａ＋７−チトラザイ
ンデン２０■を添加して、６０′Ｃ↑化学増感を行なっ
た。乳剤の収量は６００ｇでめった。After washing with water and desalting, chemical sensitization at 60'C was carried out by adding 5 ml of thiosulfate and 20 ml of 4-hydroxy-6-methyl-1+3.3a+7-titrazaindene. The yield of emulsion was 600 g.
次に、第３層用のハロゲン化銀乳剤の作り方をのべる。Next, we will explain how to make a silver halide emulsion for the third layer.
良く偉拌しているゼラチン水溶液（水１０００ｄ中にゼ
ラチン２０ｇと塩化ナトリウム３Ｉを含み、７５℃に保
温したもの）に塩化ナトリウムと臭化カリウムを含有し
ている水・溶液６００ ｍｌと硝酸銀水溶液（水５ＱＱ
ｍ／に硝酸銀０．５９モルを溶解させたもの）を同時に
４０分間にわたって等流量１添加した。このようにして
、平均粒子サイズ０．３５μｍの単分散立方体塩臭化銀
乳剤（臭素８０モル％）を調製した。Add 600 ml of an aqueous solution containing sodium chloride and potassium bromide to a well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3I of sodium chloride in 1000 d of water and keep warm at 75°C) and an aqueous silver nitrate solution ( Water 5QQ
0.59 mol of silver nitrate dissolved in m/m/ml) was simultaneously added in an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.
水洗、脱塩後、チオ硫酸ナトリウム５ｒｎ９と４−ヒド
ロキシ−６−メチル−１，３，３ａ＋７−チトラザイン
デン２０〜を添加して、６０℃で化学増感を行なった２
、乳剤の収量は６００ｇであった。After washing with water and desalting, sodium thiosulfate 5rn9 and 4-hydroxy-6-methyl-1,3,3a+7-titrazaindene 20~ were added to perform chemical sensitization at 60°C.
The yield of emulsion was 600 g.
次に、色素供与性物質のゼラチン分散物の作υ方につい
て述べる。Next, a method for preparing a gelatin dispersion of a dye-donating substance will be described.
イエローの色素供与性物質（Ａ） （ｒ ５．９ 、界
面活性剤トシて、コハク酸−２−エチル−ヘキシルエス
テルスルホン酸ンーダ０．５，９．トリイソノニルフォ
スフェート１０．ｐｔ−秤量し、酢酸エチル３０ｍ／を
加え、約６０℃に加熱溶解させ、均一な溶液とした。こ
の溶液と石灰処理ゼラチンの１０％溶液１００ｇとを攪
拌混合した後、ホモジナイザー１１０分間、１１０００
０ｒｐにて分散した。この分散液をイエローの色素供与
性物質の分散物と言う。Yellow dye-donating substance (A) (r 5.9, surfactant, succinic acid 2-ethyl-hexyl ester sulfonate 0.5,9. triisononyl phosphate 10.pt) was weighed. , 30 m/ethyl acetate was added and dissolved by heating at about 60°C to obtain a homogeneous solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was heated with a homogenizer for 110 minutes at 11,000 ml.
Dispersion was performed at 0 rpm. This dispersion is called a yellow dye-providing substance dispersion.
マゼンタの色素供与性物質（Ｂ）を使う事と高沸点溶媒
としてトリクレジルフォスフェートｅ ７．５ｙ使う以
外は、上記方法により同様にしてマゼンタの色素供与性
物質の分散物を作った１）イエローの色素分散物と同様
にして、シアンの色素供与性物質（Ｃ）を使い作った。A dispersion of a magenta dye-donating substance was prepared in the same manner as described above, except that the magenta dye-donating substance (B) was used and tricresyl phosphate e 7.5y was used as a high boiling point solvent 1) A cyan dye-providing substance (C) was used in the same manner as the yellow dye dispersion.
酸性成分のゼラチン分散物を次のようにして作った。A gelatin dispersion of acidic ingredients was prepared as follows.
１０％ゼラチン水溶液１００ｇ、界面活性剤とシテコハ
ク酸−２−エチルヘキシルエステルスルホン酸ソーダ０
．５ｇ、水１００ゴを加熱混合し、９０℃に保つ。100g of 10% gelatin aqueous solution, surfactant and 2-ethylhexyl citesuccinate sulfonate sodium 0
．． Heat and mix 5 g and 100 g of water and keep at 90°C.
次にベヘン酸２０ｇを上記水溶液に加え、粉末が融解し
てから、ホモジナイザーを用い１０分間、１０．０００
ｒｐｍｆ分散しながら分散液の温度を２０℃ま〒冷却
し、ベヘン酸のゼラチン分散物を得た。Next, 20 g of behenic acid was added to the above aqueous solution, and after the powder had melted, it was heated using a homogenizer for 10 minutes at 10.000 g.
The temperature of the dispersion liquid was cooled to 20° C. while performing rpmf dispersion to obtain a gelatin dispersion of behenic acid.
またステアリン酸のゼラチン分散物も同様の方法で作っ
た。A gelatin dispersion of stearic acid was also prepared in a similar manner.
これらにより、次表のような多層構成のカラー感光材料
を作った。Using these materials, a color photosensitive material with a multilayer structure as shown in the following table was prepared.
色素供与性物質
（Ａｌ
（Ｂ）
Ｈ
Ｈ
（Ｄ−３）
ｆ
２Ｈ５
次に受像層を有する色素固定材料の作り方について述べ
る。Dye-donating substance (Al (B) H H (D-3) f 2H5 Next, a method for producing a dye-fixing material having an image-receiving layer will be described.
下記構造のポリマー９ｆを水１３０ゴに溶解し、１０％
石灰処理ゼラチン５０ｖ１デキストラン（平均分子量５
９０００ ）ｓ ｔおよび炭酸グアニジン４．５ｆと均
一に混合した。この混合液を二酸化チタンを分散したポ
リエチレンでラミネートした紙支持体上に５５μｍのウ
ェット膜厚に均一に塗布した。Polymer 9f with the following structure was dissolved in 130 g of water, and 10%
Lime-processed gelatin 50v1 dextran (average molecular weight 5
9000 ) s t and 4.5 f of guanidine carbonate. This mixed solution was uniformly applied to a wet film thickness of 55 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed.
更にこの上にゼラチン硬膜剤Ｈ−１を１．５ｆ。Furthermore, add 1.5 f of gelatin hardener H-1 on top of this.
Ｈ−２を０，５２および水１３（ＩＪおよび１０％石灰
処理ゼラチン７０Ｆを均一に混合した。この混合液を上
記塗布物上に２０μｍのウェット膜となるよう均一に塗
布した。この試料を乾燥して色素固定材料とした。0.52 of H-2 and 13 of water (IJ) and 10% lime-treated gelatin 70F were uniformly mixed. This mixed solution was evenly applied onto the above coating material to form a wet film of 20 μm. This sample was dried. It was used as a dye fixing material.
ゼラチン硬膜剤
（Ｈ−１） ：
ＣＩ（２＝ＣＩＩ−８Ｏ２ＣＨ２ＣＯＮ）ＩＣＨ２ＣＨ
２ＮＨＣＯＣＨ２Ｓ０２ＣＨ−ＣＩ（２（ＩＩ−２）Ｉ
ＣＩ Ｉ、、 ＝ＣＨ−８ｏ２ｃｉＩ２ＣＯＮ）ＩＣＨ
２ＣＨ２ＣＨ２Ｎｌ（ＣＯＣＨ２Ｓｏ２ ＧトＣＨ２上
記多層構成のカラー感光材料にタングステン電球を用い
、連続的に濃度が変化しているＧ、 Ｒ。Gelatin hardener (H-1): CI (2=CII-8O2CH2CON)ICH2CH
2NHCOCH2S02CH-CI(2(II-2)I CI I,, =CH-8o2ciI2CON)ICH
2CH2CH2Nl (COCH2So2 G to CH2) G and R whose density changes continuously using a tungsten light bulb as the color photosensitive material with the above multilayer structure.
ＩＲ三色分解フィルター（Ｇは５００〜６００ｎｍ、Ｒ
は６００〜７００ｎｍの〕９ンドノξスフイルター、
ＩＲは７００ｎｍ以上透過のフィルターを用い構成した
を通して、５００ルツクスで１秒露光した。IR three-color separation filter (G is 500-600 nm, R
is a 600-700nm] 9-nine ξ filter,
IR was exposed at 500 lux for 1 second through a filter configured to transmit at least 700 nm.
この露光済みの感光材料の乳剤面に２０ ｍｌ／ｒｒ？
の水をワイヤー・々−で供給し、その後色素固定材料と
膜面が接するように重ね合せた。吸水した膜の温度が９
０〜９５℃となるように温度調整したヒートローラーを
用い、２０秒間または２５秒間加熱した後色素固定材料
を感光材料からひきはが１と、固定材料上にＧ、Ｒ，Ｉ
Ｒの三色分解フィルターに対応してイエロー（２）、マ
ゼンタ（至）、シアン（Ｃ７の鮮明な像が得られた。各
色の最高濃度（Ｄｍａｘ ）と最低濃度（Ｄｍｉｎ ）
をマクベス反射濃度計（ＲＤ−５１９）を用いて測定し
たところ表１に示すような結果を得た。20 ml/rr on the emulsion side of this exposed photosensitive material?
of water was supplied through a wire, and then the dye-fixing material and the membrane surface were placed on top of each other so that they were in contact with each other. The temperature of the membrane that absorbed water was 9
After heating for 20 or 25 seconds using a heat roller whose temperature is adjusted to 0 to 95°C, remove the dye fixing material from the photosensitive material and place G, R, I on the fixing material.
Corresponding to the R three-color separation filter, clear images of yellow (2), magenta (to), and cyan (C7) were obtained.The maximum density (Dmax) and minimum density (Dmin) of each color.
When measured using a Macbeth reflection densitometer (RD-519), the results shown in Table 1 were obtained.
表−１に示したように、本発明の感光材料（Ｂ）および
（Ｃ）は比較試料例）に較べて２０秒加熱にお−・て、
高Ｄｍａｘ １低Ｄｍｉｎの画像識別性の良好な画像が
得られ、また加熱時間を５秒間長くしてもかぶりの増加
が少なく画像識別性が良好で、高い現像停止効果を有す
ることがわかる。As shown in Table 1, the photosensitive materials (B) and (C) of the present invention had a higher temperature when heated for 20 seconds than the comparative sample example).
It can be seen that an image with high Dmax and 1 low Dmin and good image discrimination was obtained, and even if the heating time was increased by 5 seconds, there was little increase in fog, and the image discrimination was good, and the film had a high development stopping effect.
代理人弁理士（８１０７）佐々木 清 隆（ほか２名）Representative Patent Attorney (8107) Kiyotaka Sasaki (and 2 others)
Claims (1)
よび色素供与性物質を含む感光材料を像様露光後、また
は像様露光と同時に水の存在下で加熱し、可動性色素の
像様分布を形成する画像形成方法において、前記可動性
色素の像様分布を形成する反応系に酸性成分を化学的に
関与させることを特徴とする画像形成方法。A photosensitive material containing at least a photosensitive silver halide, a binder, and a dye-providing substance on a support is heated in the presence of water after or simultaneously with imagewise exposure to obtain an imagewise distribution of the mobile dye. An image forming method comprising chemically involving an acidic component in a reaction system that forms an imagewise distribution of the mobile dye.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23387185A JPS6292943A (en) | 1985-10-19 | 1985-10-19 | Image forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23387185A JPS6292943A (en) | 1985-10-19 | 1985-10-19 | Image forming method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6292943A true JPS6292943A (en) | 1987-04-28 |
Family
ID=16961876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23387185A Pending JPS6292943A (en) | 1985-10-19 | 1985-10-19 | Image forming method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6292943A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6022673A (en) * | 1997-09-11 | 2000-02-08 | Fuji Photo Film Co., Ltd. | Image forming method |
-
1985
- 1985-10-19 JP JP23387185A patent/JPS6292943A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6022673A (en) * | 1997-09-11 | 2000-02-08 | Fuji Photo Film Co., Ltd. | Image forming method |
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