JP2906178B2 - Photothermographic materials for black and white image formation - Google Patents
Photothermographic materials for black and white image formationInfo
- Publication number
- JP2906178B2 JP2906178B2 JP27254290A JP27254290A JP2906178B2 JP 2906178 B2 JP2906178 B2 JP 2906178B2 JP 27254290 A JP27254290 A JP 27254290A JP 27254290 A JP27254290 A JP 27254290A JP 2906178 B2 JP2906178 B2 JP 2906178B2
- Authority
- JP
- Japan
- Prior art keywords
- dye
- black
- image
- silver
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- -1 silver halide Chemical class 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 42
- 239000004332 silver Substances 0.000 claims description 38
- 229910052709 silver Inorganic materials 0.000 claims description 38
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- 239000010410 layer Substances 0.000 description 58
- 238000000034 method Methods 0.000 description 35
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- 238000011161 development Methods 0.000 description 32
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- 239000000243 solution Substances 0.000 description 32
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- 230000007935 neutral effect Effects 0.000 description 12
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- 239000000123 paper Substances 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
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- 239000002243 precursor Substances 0.000 description 6
- 230000001235 sensitizing effect Effects 0.000 description 6
- 150000003378 silver Chemical class 0.000 description 6
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 6
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- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
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- 150000007857 hydrazones Chemical class 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
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- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
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- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- XOIYZMDJFLKIEI-UHFFFAOYSA-N (hydroxysulfonimidoyl)oxybenzene Chemical compound NS(=O)(=O)OC1=CC=CC=C1 XOIYZMDJFLKIEI-UHFFFAOYSA-N 0.000 description 1
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- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
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- 150000002513 isocyanates Chemical class 0.000 description 1
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- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
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- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 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
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229940036565 thiouracil antithyroid preparations Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000016776 visual perception Effects 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は黒白画像形成用熱現像感光材料に関し、特に
黒色画像の安定性が改善された黒白画像形成用熱現像感
光材料に関する。Description: FIELD OF THE INVENTION The present invention relates to a photothermographic material for forming black-and-white images, and more particularly to a photothermographic material for forming black-and-white images having improved black image stability.
現像工程を加熱によって行う熱現像処理は公知であ
り、黒白画像及びカラー画像を得るものが知られてい
る。又、熱現像により得られた画像を感光材料から画像
受像層に転写する、いわゆる転写型の熱現像感光材料も
広く知られている。A heat development process in which a development process is performed by heating is known, and a process for obtaining a black-and-white image and a color image is known. Also, a so-called transfer type photothermographic material which transfers an image obtained by heat development from a photosensitive material to an image receiving layer is widely known.
熱現像により黒白画像を得る方法としては、3M社の
「ドライシルバー」という商品名の熱現像型の感光材料
により代表される、銀により黒白画像を形成する熱現像
感光材料が市販されているが、このようなシステムは未
現像のハロゲン化銀が処理後も感光材料中に残存してお
り、プリント画像の保存性に大きな問題を抱えている。As a method of obtaining a black-and-white image by thermal development, a heat-developable photosensitive material that forms a black-and-white image with silver, which is represented by a heat-developable photosensitive material having a trade name of “Dry Silver” by 3M, is commercially available. However, in such a system, undeveloped silver halide remains in the photosensitive material even after processing, and there is a serious problem in the storability of a printed image.
即ち、現像済みのプリントを長期間保存した場合、未
現像のハロゲン化銀が光や熱により、黒化してしまう、
いわゆるプリントアウトにより白地の汚染が生じる。又
この方法は銀を回収することができない点が資源の再利
用の面から問題である。That is, when a developed print is stored for a long time, undeveloped silver halide is blackened by light or heat.
So-called printouts cause white background contamination. In addition, this method is problematic in that silver cannot be recovered in terms of resource recycling.
このような問題を解決する手段としてハロゲン化銀が
銀に還元される際に、この反応に対応して可動性色素を
生成又は放出し、該可動性色素を感光材料から色素受像
層に拡散転写させて黒白画像とする方法が提案されてい
る。As a means for solving such a problem, when silver halide is reduced to silver, a movable dye is generated or released in accordance with this reaction, and the movable dye is diffused and transferred from the photosensitive material to the dye receiving layer. A method has been proposed in which a black-and-white image is obtained.
例えば特開昭60−66249号には拡散性黒色色素を放出
する色素供与物質を用いて黒白画像を得る拡散転写型熱
現像感光材料を開示している。この方式によれば、前記
白地部における処理後の画像の保存安定性が改良される
がニュートラリティという点からみた時の厳密な意味で
の黒色画像が安定に得られないという問題がある。For example, Japanese Unexamined Patent Publication No. Sho 60-66249 discloses a diffusion transfer type photothermographic material which obtains a black-and-white image using a dye-providing substance which emits a diffusible black dye. According to this method, the storage stability of the processed image in the white background portion is improved, but there is a problem that a black image in a strict sense from the viewpoint of neutrality cannot be stably obtained.
又、例えばイエロー、マゼンタ及びシアン色素供与物
質を有する熱現像感光材料を用いて黒白画像を形成する
方法も知られているが、この場合、黒色画像のイエロ
ー、マゼンタ、シアンの色素画像のバランスを維持する
ことで、ニュートラルの安定性を確保していることから
画像品質として特にニュートラルの再現性が重要であ
る。Further, for example, a method of forming a black-and-white image using a photothermographic material having a yellow, magenta, and cyan dye-donating substance is also known. In this case, the balance of the yellow, magenta, and cyan dye images of the black image is adjusted. Maintaining the neutral stability ensures that neutral reproducibility is particularly important as image quality.
例えば最高濃度域にて黒色を合わせた場合に、低〜中
濃度域でのニュートラルのバランスが壊れたり、感光材
料の硬膜条件や保存条件又は処理条件が変化した場合に
おいても、ニュートラルの再現性が崩れたりしないよう
にすることが重要である。For example, when the black color is adjusted in the highest density range, the neutral balance in the low to middle density range is broken, and even when the hardening condition, storage condition, or processing condition of the photosensitive material changes, the neutral reproducibility It is important that they do not collapse.
特に黒色画像の再現においては青、緑、赤の各々の濃
度が僅か（例えば0.01程度）ずれただけでも画像全体の
ニュートラリティに与える影響は極めて大きく、この方
式においては、３つの色バランスを安定化させることが
特に強く要請される。In particular, in the reproduction of a black image, even a slight (for example, about 0.01) shift in the density of each of blue, green, and red has an extremely large effect on the neutrality of the entire image. It is particularly strongly required to make
特開昭60−162251号においては、得られた色素画像の
色について10度視野XYZ系における３刺激値から求めら
れるa*、b*の範囲を規定することによりニュートラルの
再現性が改良されるという記載がある。In JP-A-60-162251, the reproducibility of neutral is improved by defining the range of a * and b * obtained from tristimulus values in a 10-degree visual field XYZ system for the color of the obtained dye image. There is a description.
ところがこれによると、ある条件下にて求められた
a*、b*の値を有する感光材料を用いた場合でもその感光
材料の硬膜条件や依存条件（例えば保存時の温度、湿
度）が変化したり、現像条件（例えば現像温度、現像時
の湿度、現像機の圧力）等が変化した場合には満足でき
るニュートラルが得られないという問題が生じてくる。However, according to this, under certain conditions
Even when a photosensitive material having the values of a * and b * is used, the hardening conditions and the dependent conditions (for example, temperature and humidity during storage) of the photosensitive material change, and the developing conditions (for example, developing temperature, If the humidity or the pressure of the developing machine changes, a problem arises that a satisfactory neutral cannot be obtained.
上記のような問題に対して、本発明の目的は低濃度域
から高濃度域までの全領域において、黒色色調の再現性
が改善され、しかも感光材料の保存或は処理条件の変化
に対して安定した黒色画像を与えることのできる黒白画
像形成用熱現像感光材料を提供することである。In view of the above problems, an object of the present invention is to improve the reproducibility of black tones in all regions from a low-density region to a high-density region. An object of the present invention is to provide a photothermographic material for forming a black-and-white image capable of giving a stable black image.
本発明の上記目的は、支持体上にバインダー、感光性
ハロゲン化銀乳剤及びイエロー、マゼンタ、シアン色素
供与物質を有する黒白画像形成用熱現像感光材料におい
て、イエロー、マゼンタ、シアンの各色素供与物質から
形成もしくは放出される色素の分子量の最大のものに対
する最小のものの分子量の比率が0.75以上であることを
特徴とする黒白画像形成用熱現像感光材料により達成さ
れる。尚、上記分子量比率は好ましくは0.8以上、更に
好ましくは0.85以上である。The object of the present invention is to provide a black-and-white image forming photothermographic material having a binder, a photosensitive silver halide emulsion and a yellow, magenta, and cyan dye-providing material on a support, wherein each of the yellow, magenta and cyan dye-providing materials is provided. This is achieved by a photothermographic material for forming a black-and-white image, wherein the ratio of the molecular weight of the minimum dye to the maximum of the molecular weight of the dye formed or released from is not less than 0.75. In addition, the molecular weight ratio is preferably 0.8 or more, and more preferably 0.85 or more.
本発明の熱現像感光材料（以下、熱現感材と略する）
はイエロー、マゼンタ及びシアンの各色素画像から黒色
画像を形成するものであって、本発明においては各々の
色素の分子量を特定の比率の範囲内に抑えることが、黒
色色素画像の保存安定性、及び、熱現像条件変化におけ
る色調の安定化に必要である。即ち、各々の色調を与え
る色素の中で、最大分子量を有する色素の分子量（Ma）
と最低分子量を有する色素の分子量（Mb）の比、即ちΓ
＝Mb/Maが0.75以上で有ることが必要である。Photothermographic material of the present invention (hereinafter abbreviated as heat-sensitive material)
Is to form a black image from each of the yellow, magenta and cyan dye images, in the present invention, to keep the molecular weight of each dye within a specific ratio range, the storage stability of the black dye image, Also, it is necessary for stabilizing the color tone when the heat development conditions change. That is, among the dyes giving each color tone, the molecular weight (Ma) of the dye having the maximum molecular weight
And the molecular weight (Mb) of the dye having the lowest molecular weight, ie, Γ
= Mb / Ma needs to be 0.75 or more.
Γが0.75未満の時には本発明の効果即ち、黒色画像の
色調の安定化が得られない。好ましくはΓは0.8以上で
ある。特に好ましくは0.85以上である。When Γ is less than 0.75, the effect of the present invention, that is, the color tone of a black image cannot be stabilized. Preferably Γ is 0.8 or more. Particularly preferably, it is 0.85 or more.
本発明の熱現感材は、イエロー、マゼンタ及びシアン
色素がそれぞれ２種以上の色素を用いることによっても
可能である。この時、各々の色素画像の分子量は色素が
色素供与物質から化学量論的に放出される場合には、色
素供与物質の併用しているモル比を用いて以下に示され
る式によって与えられる。The heat-sensitive material of the present invention can also be obtained by using two or more dyes each for the yellow, magenta and cyan dyes. At this time, when the dye is stoichiometrically released from the dye-donor, the molecular weight of each dye image is given by the following formula using the molar ratio of the dye-donor used together.
ここで、Mkは各々の色素の分子量を表し、rkは各々の
色素供与物質のモル比を表す。又、色素画像が還元剤の
酸化体と色素供与物質のカップリング方式により形成さ
れる画像形成方法において、還元剤が２種以上併用され
る場合には形成される色素の平均分子量は以下の式によ
り求められる。 Here, Mk represents the molecular weight of each dye, and rk represents the molar ratio of each dye donor. Further, in an image forming method in which a dye image is formed by a coupling method of an oxidized form of a reducing agent and a dye-providing substance, when two or more reducing agents are used in combination, the average molecular weight of the formed dye is represented by the following formula: Required by
ここでMk′は各々の還元剤から形成される色素の分子
量を表し、rk′は熱現感材が含有する還元剤のモル比を
表す。 Here, Mk 'represents the molecular weight of the dye formed from each reducing agent, and rk' represents the molar ratio of the reducing agent contained in the heat-sensitive material.
更に、色素が還元剤の酸化体と色素供与物質のカップ
リング反応により形成される場合で、色素供与物質が実
質的に同一の色相を与える複数（ｘ個）の色素供与物質
からなり、又還元剤が２種以上の複数（ｙ個）の還元剤
からなる場合においては以下の式により与えられる。Further, when the dye is formed by a coupling reaction between an oxidized form of a reducing agent and a dye-donating substance, the dye-donating substance comprises a plurality (x) of dye-providing substances giving substantially the same hue. When the agent is composed of two or more kinds (y) of reducing agents, it is given by the following formula.
ここでMpqはｐ番目の色素供与物質とｑ番目の還元剤
から形成される色素の分子量を表し、kqはｑ番目の感還
元剤のモル比を表し、Cuはｕ番目の色素供与物質のモル
比を表す。 Here, Mpq represents the molecular weight of the dye formed from the p-th dye-donating substance and the q-th reducing agent, kq represents the molar ratio of the q-th reducing agent, and Cu represents the molar ratio of the u-th dye-donating substance. Represents the ratio.
本発明の熱現感材においては、上記３つのMi（ｉ＝Y,
M,C）のうち最大分子量Maと最低分子量Mbの比Γ＝Mb/Ma
が0.75以上であることがニュートラルの安定化のために
必須であり、これ以下の場合全濃度域におけるニュート
ラルの安定性、感光材料の長期保存時、感光材料や受像
材料の構成層の硬膜度或は熱現像条件の変動に対する安
定性が得られなくなる。In the heat-sensitive material of the present invention, the above three Mi (i = Y,
M, C) Ratio of maximum molecular weight Ma to minimum molecular weight Mb Γ = Mb / Ma
Of 0.75 or more is essential for neutral stabilization; below this, the stability of the neutral over the entire concentration range, and the hardness of the constituent layers of the photosensitive material and image receiving material during long-term storage of the photosensitive material Alternatively, stability against fluctuations in heat development conditions cannot be obtained.
本発明に用いられる色素供与物質としては、例えば特
開昭62−44737号、同62−129852号、同62−169158号、
特願平１−200859号に記載されている拡散性の色素を形
成するカプラー、例えば特開昭61−88254号記載のロイ
コ色素、或は例えば、米国特許4,235,957号に記載の熱
現像色素漂白法に用いられる、アゾ色素等が挙げられ
る。好ましくは拡散性色素を形成又は放出する色素供与
物質が用いられ、特に好ましくはカップリング反応によ
り拡散性色素を形成する化合物が好ましい。As the dye-providing substance used in the present invention, for example, JP-A-62-44737, JP-A-62-129852, JP-A-62-169158,
Couplers capable of forming diffusible dyes described in Japanese Patent Application No. 1-200859, such as the leuco dyes described in JP-A-61-88254, or the thermal developing dye bleaching method described in, for example, U.S. Pat. No. 4,235,957. And azo dyes and the like. A dye-providing substance that forms or emits a diffusible dye is preferably used, and a compound that forms a diffusible dye by a coupling reaction is particularly preferable.
以下、本発明で好ましく用いられる拡散性色素を形成
又は放出する色素供与物質について説明する。Hereinafter, a dye-providing substance that forms or releases a diffusible dye that is preferably used in the present invention will be described.
拡散性色素を形成もしくは放出する色素供与物質は、
感光性ハロゲン化銀及び／又は有機銀塩の還元反応に対
応もしくは逆対応し、拡散性の色素を形成又は放出でき
るものであればよく、ネガ型の色素供与物質とポジ型の
色素供与物質がある。Dye-providing substances that form or release diffusible dyes are:
Any material capable of forming or releasing a diffusible dye that corresponds to or reversely reacts with the reduction reaction of the photosensitive silver halide and / or organic silver salt may be used, and a negative dye-donor and a positive dye-donor may be used. is there.
ネガ型色素供与物質としては、例えば、米国特許4,46
3,079号、同4,439,513号、特開昭59−60434号、同59−6
5839号、同59−71046号、同59−87450号、同59−88730
号、同59−123837号、同59−124329号、同59−165054
号、同59−165055号等の各明細書に記載されている還元
性の色素放出化合物が挙げられる。As negative dye-donating substances, for example, U.S. Pat.
Nos. 3,079 and 4,439,513, JP-A-59-60434, and 59-6
No. 5839, No. 59-71046, No. 59-87450, No. 59-88730
Nos. 59-123837, 59-124329, 59-165054
And reducing dye-releasing compounds described in the respective specifications such as JP-A No. 59-165055 and the like.
別のネガ型の色素供与物質としては、例えば米国特許
4,474,867号、特開昭59−12431号、同59−48765号、同5
9−174834号、同59−159159号、同59−231040号、特開
平１−185630号等の各明細書に記載されているカップリ
ング型色素形成化合物が挙げられる。Another negative-type dye-providing substance is, for example, a US patent
4,474,867, JP-A-59-12431, JP-A-59-48765, and
Coupling type dye-forming compounds described in each specification such as JP-A Nos. 9-174834, 59-159159, 59-231040, and JP-A-1-185630.
カップリング型の色素形成化合物の更に別の好ましい
ネガ型色素供与物質としては、次の一般式（イ）で示さ
れるものである。Still another preferred negative dye-providing substance of the coupling type dye-forming compound is represented by the following general formula (A).
式中、Cpは還元剤の酸化体とカップリング反応して拡
散性の色素を形成することができるカプラー残基を表
し、Ｊは還元剤の酸化体と反応するCpの活性位と結合し
ている２価の有機基を表し、Ｂはバラスト基を表す。こ
こで言うバラスト基とは、熱現像中に色素供与物質を非
拡散化させる基であり、例えば炭素原子数８以上、好ま
しくは12以上を有する基、ポリマー鎖或は分子の性質に
より非拡散化機能を有する基（例えば水が存在しない熱
現像におけるスルフォ基など）を言う。バラスト基の最
も好ましいものはポリマー鎖である。 In the formula, Cp represents a coupler residue capable of forming a diffusible dye by coupling reaction with an oxidized form of a reducing agent, and J bonding to an active site of Cp reacting with the oxidized form of a reducing agent. Represents a divalent organic group, and B represents a ballast group. The term "ballast group" as used herein means a group which makes a dye-donating substance non-diffusible during thermal development. For example, a group having 8 or more, preferably 12 or more carbon atoms, a non-diffusible substance due to the nature of a polymer chain or molecule. A group having a function (for example, a sulfo group in thermal development in the absence of water). Most preferred of the ballast groups are polymer chains.
バラスト基としてポリマー鎖を有するカップリング型
色素供与物質としては、一般式（ロ）で表せられる単量
体から誘導されるポリマー鎖を有するものが好ましい。As the coupling type dye-providing substance having a polymer chain as a ballast group, a substance having a polymer chain derived from a monomer represented by the general formula (b) is preferable.
式中、Cp,Jは一般式（イ）で定義されたものと同じで
あり、Ｙはアルキレン基、アリーレン基又はアラルキレ
ン基を表し、ｌは０又は１を表し、Ｚは２価の有機基を
表し、Ｌはエチレン性不飽和基又はエチレン性不飽和基
を有する基を表す。 In the formula, Cp and J are the same as those defined in the general formula (A), Y represents an alkylene group, an arylene group or an aralkylene group, 1 represents 0 or 1, and Z represents a divalent organic group. L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.
一般式（イ）及び（ロ）で表されるカップリング型の
色素形成化合物の具体例としては、例えば、特開昭59−
124339号、同59−181345号、同60−2950号、同61−5794
3号、同61−59336号、特願平１−200859号、米国特許4,
631,251号、同4,650,748号、同4,656,124号の各明細書
に記載されたものがあるが、特に米国特許4,656,124
号、同4,631,251号及び同4,650,748号の各明細書に記載
されたポリマー型色素供与物質が好ましい。Specific examples of the coupling type dye-forming compounds represented by the general formulas (a) and (b) include, for example,
124339, 59-181345, 60-2950, 61-5794
No. 3, 61-59336, Japanese Patent Application No. 1-200859, U.S. Pat.
631,251, 4,650,748, and 4,656,124, and in particular, U.S. Pat.
And the polymer type dye-providing substances described in the specifications of JP-A Nos. 4,631,251 and 4,650,748 are preferred.
ポジ型の色素供与物質としては、例えば、特開昭59−
55430号、同59−165054号、同59−154445号、同59−116
655号、同59−124327号、同59−152440号、同64−13546
号等の各公報に記載された化合物がある。Examples of the positive dye-donating substance include, for example, JP-A-59-1984.
55430, 59-165054, 59-154445, 59-116
No. 655, No. 59-124327, No. 59-152440, No. 64-13546
There are compounds described in each gazette such as No.
上記色素供与物質のうち、イエロー色素供与性物質の
少なくとも１種、マゼンタ色素供与性物質の少なくとも
１種、及びシアン色素供与性物質の少なくとも１種をハ
ロゲン化銀を含有する感光性層中又は隣接層中に含有さ
せられる。好ましくは上記３種の色素強制物質が同一層
中に含有させられ、更に好ましくはハロゲン化銀粒子を
含有する同一の感光性層に含有させられる。Among the above dye-providing substances, at least one of a yellow dye-providing substance, at least one of a magenta dye-providing substance, and at least one of a cyan dye-providing substance are contained in or adjacent to a photosensitive layer containing silver halide. Contained in the layer. Preferably, the above three dye forcing substances are contained in the same layer, and more preferably, they are contained in the same photosensitive layer containing silver halide grains.
各々の色素供与物質の黒色画像を得るために必要とさ
れる量は、各色素の分子モル吸光係数（ε）を参考に、
最適なニュートラルが得られるように実験的に決められ
る。The amount required to obtain a black image of each dye-donor is determined by referring to the molecular molar extinction coefficient (ε) of each dye,
It is determined experimentally so as to obtain the optimum neutral.
ここでの黒色画像とは、JIS Z8729の「L*a*b*表色系
及びL*u*v*表色系による物体色の表示方法」に記載の方
法に従ってJIS Z8720に規定された標準光Ｃの下で求め
た10度視野XYZ系における三刺激値から求められるa*，b
*がa*＝５〜−10、b*＝５〜−10の範囲にある画像のこ
とをいうが、好ましくはa*＝３〜−５、b*＝３〜−５で
ある色を示す。The black image here is a standard defined in JIS Z8720 according to the method described in `` L * a * b * color system and L * u * v * color system display method of object color '' in JIS Z8729. A * , b obtained from tristimulus values in a 10-degree visual field XYZ system obtained under light C
* Is a * = 5-10, b * = is refers to an image in the range of 5 to-10, preferably an a * = 3-5, b * = Color is 3-5 .
上記色素供与物質から生成又は放出される画像色素と
しては例えば以下のものがある。Examples of image dyes produced or released from the above dye-providing substances include the following.
上記色素供与物質を熱現像感光材料の写真構成層に含
有させる方法としては、ジブチルフタレート、ジオクチ
ルフタレート或はトリクレジルフォスフェート等の公知
の高沸点有機溶剤を用いて、親水性コロイド溶液中に乳
化分散する方法、アルカリ性の親水性コロイド水溶液中
に溶解した後、酸で中和して分散する方法、及び親水性
コロイド水溶液中で公知の手段により機械的に固体状に
分散する方法など、公知の方法から適宜選択して用いる
ことができる。 As a method for incorporating the dye-providing substance into the photographic constituent layer of the photothermographic material, a known high-boiling organic solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate is used, and the hydrophilic colloid solution is used. Known methods such as a method of emulsifying and dispersing, a method of dissolving in an aqueous solution of an alkaline hydrophilic colloid and then neutralizing and dispersing with an acid, and a method of mechanically dispersing a solid in an aqueous solution of a hydrophilic colloid by a known means. Can be appropriately selected from the methods described above.
本発明の熱現像感光材料に用いられる、感光性ハロゲ
ン化銀としては従来公知のものを使用することができ、
例えば、塩化銀、臭化銀、沃臭化銀、塩臭化銀、塩沃臭
化銀を用いることができる。As the photosensitive silver halide used in the photothermographic material of the present invention, conventionally known photosensitive silver halides can be used,
For example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide can be used.
これらのハロゲン化銀は粒子内部から表面まで均一な
組成を有するもの、内部と表面で組成が異なるいわゆる
コア／シェル型或はステップ状もしくは連続的に組成が
変化している多層構造からなるハロゲン化銀であっても
よい。These silver halides have a uniform composition from the inside to the surface of the grain, a so-called core / shell type having a different composition between the inside and the surface, or a multilayered structure in which the composition changes stepwise or continuously. It may be silver.
又、ハロゲン化銀の形状は立方体、球形、８面体、12
面体、14面体等の明確な晶癖を有するもの又はそうでな
いもの等を用いることができる。又、例えば特開昭58−
111933号、同58−111934号、リサーチ・ディスクロージ
ャー22,534号に記載されているような、２つの平行する
結晶面を有し、かつ、これらの結晶面は各々他の結晶面
よりも面積が大きい粒子であって粒子の直径対厚さの比
が約5:1以上の平板状ハロゲン化銀も用いることができ
る。The shape of silver halide is cubic, spherical, octahedral, 12
Those having a clear crystal habit such as a tetrahedron, a tetrahedron, or the like can be used. In addition, for example,
Nos. 111933, 58-111934, and Research Disclosure 22,534, which have two parallel crystal planes, and each of these crystal planes has a larger area than the other crystal planes. However, tabular silver halide grains having a diameter to thickness ratio of about 5: 1 or more can also be used.
更に、例えば米国特許2,592,250号、同3,220,613号、
同3,271,257号、同3,317,322号、同3,511,622号、同3,5
31,291号、同3,447,927号、同3,761,266号、同3,703,58
4号、同3,736,140号、同3,761,276号、特開昭50−8524
号、同50−38525号、同52−15661号、同55−127549号等
に記載されている粒子表面が予めカブラされていない内
部潜像型ハロゲン化銀乳剤も用いることができる。Further, for example, U.S. Pat.Nos. 2,592,250 and 3,220,613,
3,271,257, 3,317,322, 3,511,622, 3,5
31,291, 3,447,927, 3,761,266, 3,703,58
No. 4, No. 3,736,140, No. 3,761,276, JP-A-50-8524
Nos. 50-38525, 52-15661, 55-127549, etc. can also be used.
又、感光性ハロゲン化銀はその粒子形成段階におい
て、イリジウム、金、ロジウム、鉄、鉛等の金属イオン
種を適当な塩の形で添加することができる。The photosensitive silver halide may be added with a metal ion species such as iridium, gold, rhodium, iron, or lead in a suitable salt form at the stage of grain formation.
上記感光性ハロゲン化銀乳剤の粒径は約0.02〜２μｍ
であり、好ましくは約0.05μｍ〜0.5μｍである。The photosensitive silver halide emulsion has a particle size of about 0.02 to 2 .mu.m.
And preferably about 0.05 μm to 0.5 μm.
本発明において、感光性ハロゲン化銀の調製方法とし
て感光性銀塩形成成分を後述の有機銀塩と共存させ、有
機銀塩の一部を感光性ハロゲン化銀の一部に変換させて
を形成させることもできる。In the present invention, as a method for preparing a photosensitive silver halide, a photosensitive silver salt-forming component is made to coexist with an organic silver salt described later, and a part of the organic silver salt is converted into a part of the photosensitive silver halide to form a photosensitive silver halide. It can also be done.
感光性ハロゲン化銀乳剤は公知の増感剤（例えば、活
性ゼラチン、無機硫黄、チオ硫酸ナトリウム、二酸化チ
オ尿素、塩化金酸ナトリウム等）でハロゲン化銀粒子表
面を化学増感することができる。The photosensitive silver halide emulsion can be chemically sensitized on the surface of silver halide grains with a known sensitizer (eg, active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate, etc.).
化学増感は、含窒素ヘテロ環化合物或はメルカプト基
含有ヘテロ環化合物の存在下に行うことも可能である。Chemical sensitization can also be performed in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.
更に感光性ハロゲン化銀は公知の分光増感色素によ
り、青、緑、赤、赤外光へ分光増感を施すことができ
る。代表的な増感色素としては、シアニン、メロシアニ
ン、３核又は４核シアニン、ホロポーラーシアニン、ス
チリル、ヘミシアニン、オキソノール等が挙げられる。
これらの増感色素の使用量はハロゲン化銀１モル当たり
１μmol〜1mol、好ましくは10μmol〜0.1molである。増
感色素はハロゲン化銀乳剤のどの過程において添加して
もよく、具体的にはハロゲン化銀粒子形成時、可溶性塩
類の除去時、化学増感開始前、化学増感時、或は化学増
感終了以降のいずれであってもよい。Further, the photosensitive silver halide can be subjected to spectral sensitization to blue, green, red and infrared light by a known spectral sensitizing dye. Representative sensitizing dyes include cyanine, merocyanine, trinuclear or tetranuclear cyanine, holopolar cyanine, styryl, hemicyanine, oxonol and the like.
The use amount of these sensitizing dyes is 1 μmol to 1 mol, preferably 10 μmol to 0.1 mol per 1 mol of silver halide. The sensitizing dye may be added in any step of the silver halide emulsion. Specifically, at the time of forming silver halide grains, at the time of removing soluble salts, before the start of chemical sensitization, at the time of chemical sensitization, or at the time of chemical sensitization. It may be any time after the end of feeling.
これらの感光性ハロゲン化銀及び感光性銀塩形成成分
は感光材料１m2当たり約0.01〜50g、好ましくは0.1〜10
gの範囲で用いられる。These light-sensitive silver halide and light-sensitive silver salt forming components are used in an amount of about 0.01 to 50 g, preferably 0.1 to 10 g per m 2 of the light-sensitive material.
Used in the range of g.
本発明の熱現像感光材料には、必要に応じて感度の上
昇や、現像性の向上を目的として、公知の有機銀塩を用
いることができる。In the photothermographic material of the present invention, a known organic silver salt can be used for the purpose of increasing sensitivity and improving developability, if necessary.
本発明において用いることのできる有機銀塩は、例え
ば、特開昭53−4921号、同49−52626号、同52−141222
号、同53−36224号、同53−37626号、同53−36224号、
同53−37610号等の各公報並びに米国特許3,330,633号、
同3,794,496号、同4,105,451号等の各公報に記載されて
いる長鎖脂肪族カルボン酸の銀塩やヘテロ環を有するカ
ルボン酸の銀塩、（例えばベヘン酸銀、α−（１−フェ
ニルテトラゾールチオ）酢酸銀等）、或は特公昭44−26
582号、同45−12700号、同45−18416号、同45−22815
号、特開昭52−137321号、同58−118638号、同58−1186
39号、米国特許4,123,274号等の公報に記載されている
イミノ基を有する化合物の銀塩がある。更に、特開昭61
−249044号記載のアセチレン銀等も用いることができ
る。Organic silver salts that can be used in the present invention include, for example, JP-A-53-4921, JP-A-49-52626, and JP-A-52-141222.
No. 53-36224, No. 53-37626, No. 53-36224,
Nos. 53-37610 and U.S. Pat.No. 3,330,633,
Nos. 3,794,496, 4,105,451, etc., silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocyclic ring (for example, silver behenate, α- (1-phenyltetrazolethiol) ) Silver acetate, etc.), or Japanese Patent Publication No. 44-26
No. 582, No. 45-12700, No. 45-18416, No. 45-22815
No., JP-A-52-137321, JP-A-58-118638, JP-A-58-1186
No. 39, U.S. Pat. No. 4,123,274, and the like, there is a silver salt of a compound having an imino group. In addition, JP
Acetylene silver described in JP-A-249044 can also be used.
中でもイミノ基を有する化合物の銀塩が好ましく、特
にベンゾトリアゾール及びその誘導体の銀塩（例えばベ
ンゾトエイアゾール銀、５−メチルベンゾトリアゾール
銀等）が特に好ましい。Among them, silver salts of compounds having an imino group are preferable, and silver salts of benzotriazole and its derivatives (for example, silver benzotoeazole, silver 5-methylbenzotriazole, etc.) are particularly preferable.
上記有機銀塩は、単独でも２種以上併用して用いるこ
ともでき、これらの調製はゼラチンのごとき親水性コロ
イド水溶液中で調製し、可溶性塩類を除去してそのまま
の形で使用することも、又有機銀塩を単離して機械的に
固体微粒子に粉砕・分散して使用することもできる。有
機銀塩の使用量は感光材料１m2当たり0.01〜20g、好ま
しくは0.1〜50gの範囲である。The above-mentioned organic silver salts can be used alone or in combination of two or more kinds.These preparations can be prepared in an aqueous solution of hydrophilic colloid such as gelatin, and can be used as it is by removing soluble salts. Further, the organic silver salt can be isolated and mechanically pulverized and dispersed into solid fine particles for use. The amount of the organic silver salt used is in the range of 0.01 to 20 g, preferably 0.1 to 50 g, per m 2 of the light-sensitive material.
本発明の熱現像感光材料に用いられる還元剤は、現像
機構や色素形成乃至放出機構により熱現像感光材料用と
して従来公知のものの中から適切なものを選択して使用
される。ここで言う還元剤には、熱現像時に還元剤を放
出する還元剤プレカーサーも含まれる。As the reducing agent used in the photothermographic material of the present invention, an appropriate one is selected from conventionally known photothermographic materials according to the developing mechanism and the dye formation / release mechanism. The reducing agent referred to herein includes a reducing agent precursor that releases the reducing agent during thermal development.
本発明に用いることのできる、還元剤としては、例え
ば、米国特許3,351,286号、同3,761,270号、同3,764,32
8号、同3,342,599号、同3,719,492号明細書、リサーチ
・ディスクロージャー12,146号、同15,108号、同15,127
号、及び特開昭56−27132号、同53−135628号、同57−7
9035号に記載のｐ−フェニレンジアミン系及び、ｐ−ア
ミノフェノール系現像主薬、リン酸アミドフェノール系
現像主薬、スルホンアミドアニリン系現像主薬、及びヒ
ドラゾン系現像主薬、フェノール類、スルホンアミドフ
ェノール類、ポリヒドロキシベンゼン類、ナフトール
類、ヒドロキシビスナフチル類、メチレンビスフェノー
ル類、アスコルビン酸類、１−アリール−３−ピラゾリ
ドン類、ヒドラゾン類、及び上記種々の還元剤のプレカ
ーサー類がある。As the reducing agent that can be used in the present invention, for example, U.S. Patent Nos. 3,351,286, 3,761,270, and 3,764,32
No. 8, No. 3,342,599, No. 3,719,492, Research Disclosure No. 12,146, No. 15,108, No. 15,127
And JP-A-56-27132, JP-A-53-135628, and JP-A-57-7
No. 9035, p-phenylenediamine-based and p-aminophenol-based developing agents, phosphate amidophenol-based developing agents, sulfonamidoaniline-based developing agents, and hydrazone-based developing agents, phenols, sulfonamidophenols, poly There are hydroxybenzenes, naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various reducing agents.
又、色素供与物質が還元剤を兼ねることもできる。 Further, the dye-providing substance can also serve as a reducing agent.
特に好ましい還元剤は、特開昭56−146133号及び同62
−227141号記載のＮ−（ｐ−Ｎ′,N′−ジアルキルアミ
ノ）フェニルスルファミン酸塩及びその誘導体である。Particularly preferred reducing agents are described in JP-A-56-146133 and JP-A-62-146133.
And N- (p-N ', N'-dialkylamino) phenylsulfamate and derivatives thereof described in JP-A-227141.
還元剤は２種以上同時に用いてもよく、又還元剤の使
用量は、感光材料１m2当たり、0.01〜100ミリモルの範
囲で使用される。Two or more reducing agents may be used simultaneously, and the amount of the reducing agent used is in the range of 0.01 to 100 mmol per 1 m 2 of the light-sensitive material.
本発明の熱現像感光材料には色素の転写促進その他の
目的で、熱溶剤を用いることができる。熱溶剤は熱現像
時に液状化し熱現像や色素の熱転写を促進する作用を有
する化合物であり、常温では固体状態であることが好ま
しい。In the photothermographic material of the present invention, a thermal solvent can be used for the purpose of accelerating the transfer of the dye and other purposes. The thermal solvent is a compound which is liquefied during thermal development and has an action of promoting thermal development and thermal transfer of a dye, and is preferably in a solid state at normal temperature.
本発明で用いることのできる熱溶剤としては、例えば
米国特許3,347,675号、同3,667,959号、同3,438,776
号、同3,666,477号、リサーチ・ディスクロージャー（N
o.17643号、特開昭51−19525号、同53−24829号、同53
−60223号、同58−118640号、同58−198038号、同59−2
29556号、同59−68730号、同59−84236号、同60−19125
1号、同60−232547号、同60−14241号、同61−52643
号、同62−78554号、同62−42153号、同62−44737号、
同63−53548号、同63−161446号、特開平１−224751
号、同２−863号等の各公報に記載された化合物が挙げ
られる。Examples of the thermal solvent that can be used in the present invention include, for example, U.S. Patent Nos. 3,347,675, 3,667,959, and 3,438,776.
No. 3,666,477, Research Disclosure (N
o.17643, JP-A-51-19525, JP-A-53-24829, and JP-A-53-24829
-60223, 58-118640, 58-198038, 59-2
29556, 59-68730, 59-84236, 60-19125
No. 1, No. 60-232547, No. 60-14241, No. 61-52643
No. 62-78554, No. 62-42153, No. 62-44737,
JP-A 63-53548, JP-A 63-161446, JP-A 1-222475
And the compounds described in JP-A Nos. 2-863 and the like.
具体的には、尿素誘導体（ジメチル尿素、フェニル尿
素等）、アミド誘導体（例えばアセトアミド、ステアリ
ルアミド、ベンズアミド、ｐ−トリアミド、ｐ−アセト
キシエトキシベンズアミド、ｐ−ブタノイルオキシエト
キシベンズアミド等）、スルホンアミド誘導体（例え
ば、ｐ−トリエンスルホンアミド等）、多価アルコール
類（例えば、1,6−ヘキサンジオール、ペンタエリスリ
トール、ポリエチレングリコール等）が好ましく用いら
れる。Specifically, urea derivatives (dimethylurea, phenylurea, etc.), amide derivatives (eg, acetamide, stearylamide, benzamide, p-triamide, p-acetoxyethoxybenzamide, p-butanoyloxyethoxybenzamide, etc.), sulfonamide derivatives (For example, p-trienesulfonamide and the like) and polyhydric alcohols (for example, 1,6-hexanediol, pentaerythritol, polyethylene glycol and the like) are preferably used.
上記熱溶剤の中でも特に水不溶性固体熱溶剤が好まし
く用いられ、そのような具体例としては、例えば、特開
昭62−136645号、同62−139545号、同63−53548号、同6
3−161446号、特開平１−224751号、同２−863号、同２
−120739号、同２−123354号等に記載されている化合物
が挙げられる。Among the above-mentioned thermal solvents, a water-insoluble solid thermal solvent is particularly preferably used. Specific examples of such thermal solvents include, for example, JP-A Nos. 62-136645, 62-139545, 63-53548, and 6
3-161446, JP-A-1-224751, JP-A-2-863, JP-A-2-86
And compounds described in JP-A-1203939 and JP-A-2-123354.
上記熱溶剤は、感光性ハロゲン化銀乳剤層、中間層、
保護層、受像部材の受像層等任意の層中に添加すること
ができ、又その添加量は通常バインダーに対して、10重
量％〜500重量％、より好ましくは30重量％〜300重量％
である。The thermal solvent is a photosensitive silver halide emulsion layer, an intermediate layer,
It can be added to any layer such as a protective layer and an image receiving layer of an image receiving member, and the amount of addition is usually from 10% by weight to 500% by weight, more preferably from 30% by weight to 300% by weight, based on the binder.
It is.
本発明の熱現像感光材料に用いることのできるバイン
ダーとしては、ポリビニルブチラール、ポリ酢酸ビニ
ル、エチルセルロース、ポリメタアクリレート、ポリビ
ニルアルコール、ポリビニルピロリドン、ゼラチン、フ
タル化ゼラチン等のゼラチン誘導体、セルロース誘導
体、タンパク質、デンプン、アラビアゴム等の合成或は
天然の高分子物質等があり、これらは単独で、或は２種
以上併用して用いることができる。特にゼラチン又はそ
の誘導体と、ポリビニルピロリドン又はポリピニルアル
コール等の親水性ポリマーとを併用することが好まし
く、特に好ましくはゼラチンとポリビニルピロリドンの
混合バインダーが用いられる。As the binder that can be used in the photothermographic material of the present invention, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives, proteins, There are synthetic or natural polymer substances such as starch and gum arabic, and these can be used alone or in combination of two or more. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polypinyl alcohol, and it is particularly preferable to use a mixed binder of gelatin and polyvinylpyrrolidone.
バインダーの使用量は通常支持体１m2当たり、0.05g
〜50gであり、好ましくは0.2g〜20gである。The amount of the binder used is usually 0.05 g per 1 m 2 of the support.
5050 g, preferably 0.2 g-20 g.
本発明の熱現像感光材料に使用される硬膜剤は、通常
のハロゲン化銀写真感光材料のゼラチン膜を硬膜するの
に用いられる多くの化合物を使用することができる。例
えばメタンスルホン酸系化合物、エポキシ系化合物、エ
チレンイミン系化合物、2,6−ジクロロ−ｓ−トリアジ
ン系化合物、マレイン酸イミド系化合物、活性ビニル系
化合物、カルボジイミド系化合物、イソシアナート系化
合物、Ｎ−メチロール系化合物、イソオキサゾール系化
合物、或はクロム明バン、硫酸ジルコニウム等の無機硬
膜剤を挙げることができる。As the hardener used in the photothermographic material of the present invention, many compounds used for hardening a gelatin film of a usual silver halide photographic material can be used. For example, methanesulfonic acid-based compounds, epoxy-based compounds, ethyleneimine-based compounds, 2,6-dichloro-s-triazine-based compounds, maleic imide-based compounds, active vinyl-based compounds, carbodiimide-based compounds, isocyanate-based compounds, N- Examples thereof include a methylol-based compound, an isoxazole-based compound, and an inorganic hardener such as chromium ban or zirconium sulfate.
本発明においては特に熱現像時に写真性能への悪影響
の少ない活性ビニル系化合物及びエポキシ系化合物が好
ましく用いられ、中でも特にビニルスルホン系化合物及
びエポキシ系化合物が特に好ましい。In the present invention, an active vinyl compound and an epoxy compound having little adverse effect on photographic performance during thermal development are preferably used, and a vinyl sulfone compound and an epoxy compound are particularly preferable.
硬膜剤の使用量は通常ゼラチン1g当たり0.001g〜0.2g
であり、特に好ましくは0.005〜0.1gである。又、熱現
像感光材料の硬膜剤として600％以下になるような添加
量にすることが好ましい。（ここでいう硬膜度とは、熱
現像感光材料を25℃の純水に３分間浸し、表面に付着し
た余分な水分を除いた後の吸水量（W1）を熱現像感光材
料のバインダー量（W2）で割った値を100倍したもの、
即ち で表される。） 本発明の熱現像感光材料には、上記以外に、必要に応
じて、各種添加剤を添加することができる。The amount of hardener used is usually 0.001 g to 0.2 g per 1 g of gelatin
And particularly preferably 0.005 to 0.1 g. Further, it is preferable to add the hardening agent of the photothermographic material so that the amount becomes 600% or less. (Here, the hardness is defined as the water absorption (W 1 ) of a photothermographic material after immersing the photothermographic material in pure water at 25 ° C. for 3 minutes to remove excess water adhering to the surface. 100 times the value divided by the amount (W 2 ),
That is It is represented by Various other additives can be added to the photothermographic material of the present invention, if necessary, in addition to the above.
本発明において使用することのできる現像促進剤とし
ては、例えば特開昭59−177550号、同59−111636号、同
59−124333号、同61−72233号、同61−236548号、特開
平１−152454号記載の化合物が有用であり、又、特開昭
61−159642号、特開平１−104645号、特願平−１−1107
67号記載の現像促進剤放出化合物、或は、特開平１−10
4645号記載の電気陰性度が４以上の金属イオンも用いる
ことができる。Examples of the development accelerator that can be used in the present invention include JP-A-59-177550, JP-A-59-111636, and JP-A-59-111636.
The compounds described in JP-A-59-124333, JP-A-61-72233, JP-A-61-236548 and JP-A-1-152454 are useful.
No. 61-156842, JP-A-1-104645, Japanese Patent Application No. 1-1107
No. 67, or a development accelerator releasing compound described in JP-A No. 1-10
Metal ions having an electronegativity of 4 or more described in No. 4645 can also be used.
本発明において使用することのできるカブリ防止剤と
しては、例えば米国特許3,645,739号明細書に記載され
ている高級脂肪酸、特公昭47−11113号記載の第２水銀
塩、特開昭51−47419号記載のＮ−ハロゲン化物、米国
特許3,700,457号、及び特開昭51−50725号、特願平１−
69994号、同１−104271号に記載のメルカプト化合物放
出性の化合物、同49−125016号記載のアリールスルホン
酸、同51−47419号記載のカルボン酸リチウム塩、英国
特許1,455,271号及び特開昭50−101019号記載の酸化
剤、同53−19825号記載のスルフィン酸類及びチオスル
ホン酸類、同51−3223号記載のチオウラシル類、同51−
26019号記載の硫黄、同51−42529号、同51−81124号、
及び同55−93149号記載のジスルフィド類及びポリスル
フィド類、同51−57435号記載のロジン或はジテルペン
類、同51−104338号記載のカルボキシル基又はスルホン
酸基を有するポリマー酸、米国特許4,138,265号記載の
チオゾリチオン、特開昭54−51821号、同55−142331
号、米国特許4,137,079号記載のトリアゾール類、特開
昭55−140883号記載のチオスルフィン酸エステル類、特
開昭59−46641号、同59−57233号、同59−57234号記載
のジ−又はトリ−ハロゲン化物、特開昭59−111636号記
載のチオール化合物、同60−198540号及び同60−227255
号記載のハイドロキノン誘導体、等が挙げられる。更に
別の好ましいカブリ防止剤としては、特開昭62−78554
号に記載の親水性基を有するカブリ防止剤、特開昭62−
121452号記載のポリマーカブリ防止剤、特開昭62−1234
56号記載のバラスト基を有するカブリ防止剤が挙げられ
る。又、特願平１−161239号記載の無呈色カプラーも好
ましく用いられる。Examples of the antifoggant which can be used in the present invention include higher fatty acids described in U.S. Pat. No. 3,645,739, mercury salts described in JP-B-47-11113, and JP-A-51-47419. N-halide, U.S. Patent No. 3,700,457, and JP-A-51-50725,
Nos. 69994 and 1-104271, compounds capable of releasing mercapto compounds, arylsulfonic acids described in 49-125016, lithium carboxylate salts described in 51-47419, British Patent 1,455,271 and JP-A-50 Oxidizing agents described in -101019, sulfinic acids and thiosulfonic acids described in 53-19825, thiouracils described in 51-3223 and 51-223.
26019 described sulfur, 51-42529, 51-81124,
And disulfides and polysulfides described in JP-A-55-93149, rosin or diterpenes described in JP-A-51-57435, a polymer acid having a carboxyl group or a sulfonic acid group described in JP-A-51-104338, U.S. Pat. Thiozolithion, JP-A-54-51821, JP-A-55-142331
No. 4,137,079, thiosulfinic acid esters described in JP-A-55-140883, JP-A-59-46641, JP-A-59-57233, and di- or JP-A-59-57234. Tri-halides, thiol compounds described in JP-A-59-111636, JP-A-60-198540 and JP-A-60-227255
And the like. Still another preferred antifoggant is described in JP-A-62-78554.
Fogging inhibitor having a hydrophilic group described in
Polymer antifoggant described in 121452, JP-A-62-1234
An antifoggant having a ballast group described in No. 56 is exemplified. Further, the colorless coupler described in Japanese Patent Application No. 1-161239 is also preferably used.
本発明において使用することのできる塩基プレカーサ
ーとしては加熱により脱炭酸して塩基性化合物を放出す
る化合物（グアニジントリクロロ酢酸等）、分子内求核
置換反応により分解してアミン類を放出する化合物、及
び水に難溶な塩基性金属化合物（水酸化亜鉛等）とこれ
を形成する金属イオンとで錯形成可能な化合物（ピコリ
ン酸等）との反応により塩基を放出する塩基プレカーサ
ー技術などが挙げられ、具体的には、例えば、特開昭56
−130745号、同59−157537号、同59−166943号、同59−
180537号、同59−174830号、同59−195237号、同62−10
8249号、同62−174745号、同62−187847号、同63−9794
2号、同63−96159号、特開平１−68746号等の各公報に
記載されている。Examples of the base precursor that can be used in the present invention include compounds that decarboxylate by heating to release a basic compound (such as guanidine trichloroacetic acid), compounds that decompose by an intramolecular nucleophilic substitution reaction to release amines, and A base precursor technology that releases a base by a reaction between a basic metal compound (such as zinc hydroxide) that is hardly soluble in water and a compound (such as picolinic acid) that can form a complex with a metal ion that forms the compound; Specifically, for example,
-130745, 59-157537, 59-166943, 59-
Nos. 180537, 59-174830, 59-195237, 62-10
No. 8249, No. 62-174745, No. 62-187847, No. 63-9794
No. 2, No. 63-96159, and JP-A-1-68746.
本発明の熱現像感光材料には上記した以外の各種の公
知の写真用添加剤を用いることができ、例えば、ハレー
ション防止染料、コロイド銀、蛍光増白剤、硬膜剤、帯
電防止剤、界面活性剤、無機及び有機のマット剤、退色
防止剤、紫外線吸収剤、白地色調調整剤等を含有するこ
とができる。これらについては具体的にはRD（リサーチ
・ディスクロージャー）誌No.17029号、同No.29963号、
特開昭62−135825号、及び同64−13546号の各公報に記
載されている。Various known photographic additives other than those described above can be used in the photothermographic material of the present invention. Examples thereof include an antihalation dye, colloidal silver, a fluorescent brightener, a hardener, an antistatic agent, and an interface. An activator, an inorganic or organic matting agent, an anti-fading agent, an ultraviolet absorber, a white color tone adjusting agent and the like can be contained. These are specifically described in RD (Research Disclosure) Magazine Nos. 17029 and 29963,
These are described in JP-A-62-135825 and JP-A-64-13546.
これらの各種添加剤は感光性層のみならず、中間層、
下引き層、保護層或はバッキング層等任意の構成層中に
適宜添加することができる。These various additives are used not only for the photosensitive layer, but also for the intermediate layer,
It can be appropriately added to any constituent layer such as an undercoat layer, a protective layer or a backing layer.
本発明の熱現像感光材料に用いられる支持体として
は、例えばガラス、ポリプロピレンフィルム、セルロー
スアセテートフィルム、ポリエチレンテレフタレートフ
ィルム、ポリエチレンナフタレートフィルム等の透明又
は不透明の合成プラスチックフィルム、アート紙、キャ
ストコート紙、バライタ紙等の各種コート紙、ポリエチ
レン樹脂被覆紙、更にこれらの各種支持体上に電子線硬
化性樹脂組成物を塗布・硬化させた支持体等が挙げられ
る。As the support used in the photothermographic material of the present invention, for example, glass, polypropylene film, cellulose acetate film, polyethylene terephthalate film, transparent or opaque synthetic plastic film such as polyethylene naphthalate film, art paper, cast coated paper, Examples include various coated papers such as baryta paper, polyethylene resin-coated papers, and supports obtained by applying and curing an electron beam-curable resin composition on these various supports.
本発明の熱現像感光材料は、（ａ）感光性ハロゲン化
銀乳剤、（ｂ）色素供与物質、（ｃ）バインダーを含有
し、更に（ｄ）有機銀、（ｅ）還元剤を含有することが
好ましい。これらは単一の写真構成層中に含まれていて
もよく、又２層以上からなる層に分割して添加されるこ
ともできる。具体的には、（ａ），（ｂ），（ｃ），
（ｄ）の成分を一つの層に添加し、（ｅ）をこれに隣接
する層に添加したり、或は、（ａ），（ｃ），（ｄ），
（ｅ）を単一の層に添加し、（ｂ）を他層に添加するこ
ともできる。The photothermographic material of the present invention contains (a) a photosensitive silver halide emulsion, (b) a dye-providing substance, (c) a binder, and further contains (d) organic silver, and (e) a reducing agent. Is preferred. These may be contained in a single photographic component layer, or may be added separately in two or more layers. Specifically, (a), (b), (c),
The component (d) is added to one layer, and (e) is added to an adjacent layer, or (a), (c), (d),
(E) can be added to a single layer and (b) can be added to another layer.
又、感光性層は２つ以上の感光性層から構成されるこ
ともでき、それぞれ低感度層及び高感度層とすることも
できる。Further, the photosensitive layer can be composed of two or more photosensitive layers, and can be a low-sensitivity layer and a high-sensitivity layer, respectively.
本発明の熱現像感光材料には、感光性層の他に下引き
層、中間層、保護層、フィルター層、バッキング層、剥
離層等の非感光性層を任意に設けることができる。The photothermographic material of the invention may optionally have a non-photosensitive layer such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer, in addition to the photosensitive layer.
中でも保護層を有する熱現感材において本発明の硬化
が大きく、中でも保護層のバインダーが0.1〜1.0g/m2、
特に0.1〜0.8g/m2の時に特に大きな効果を得ることがで
きる。Among them, the curing of the present invention is large in the heat-sensitive material having a protective layer, and the binder of the protective layer is 0.1 to 1.0 g / m 2 ,
Particularly when the amount is 0.1 to 0.8 g / m 2 , a particularly large effect can be obtained.
本発明の熱現像感光材料から黒白画像を得るために受
像部材が用いられる。An image receiving member is used to obtain a black-and-white image from the photothermographic material of the present invention.
受像部材は支持体とこの上に設けられた色素受容能を
有する受像層とから構成されるが、支持体自身が色素受
容能のある受像層を兼ねることもできる。The image receiving member is composed of a support and an image receiving layer having a dye receiving ability provided thereon, but the support itself can also serve as an image receiving layer having a dye receiving ability.
受像層はそれを構成するバインダー自身が色素受容能
を有する場合と、色素を受容し得る媒染剤がバインダー
中に含有されている場合とに大きく分けられる。The image receiving layer is roughly classified into a case where the binder itself has a dye receiving ability and a case where a mordant capable of receiving a dye is contained in the binder.
バインダーが色素受容能を有する場合、好ましく用い
られる物質は、ガラス転移温度が約40℃以上、約250℃
以下のポリマーで形成されているものが好ましく、具体
的には、「ポリマーハンドブック セカンド、エデイッ
ション」（ジョイ・ブランドラップ、イー・エイチ・イ
ンマーガット編）ジョン ウィリー アンド サンズ出
版｛Polymer Handbook 2nd.ed.（J.Brandrup,E.H.Immer
gut編）John Wiley ＆ Sons｝に記載されているガラス
転移温度が約40℃以上の合成ポリマーが有用であり、一
般的には、ポリマーの分子量として、2,000〜200,000程
度のものが有用である。これらのポリマーは単独でも２
種以上を併用してもよく、又２種以上の繰り返し単位を
有する共重合性のポリマーであってもよい。When the binder has a dye-accepting ability, a substance preferably used has a glass transition temperature of about 40 ° C. or more, about 250 ° C.
Polymers formed of the following polymers are preferred. Specifically, "Polymer Handbook Second Edition" (Joy Brand Wrap, edited by EH Inmargat), John Willy and Sons Publishing Co., Ltd. @ Polymer Handbook 2nd.ed. J. Brandrup, EHImmer
gut) Synthetic polymers having a glass transition temperature of about 40 ° C. or higher described in John Wiley & Sons II are useful, and generally those having a molecular weight of about 2,000 to 200,000 are useful. These polymers can be used alone or
More than one kind may be used in combination, or a copolymerizable polymer having two or more kinds of repeating units may be used.
具体的にはポリ塩化ビチル、ポリエステル、ポリカー
ボネート、ポリ塩化ビニリデン、ポリエーテル等が挙げ
られ、特に特開昭59−223425号記載のポリ塩化ビニル及
び同60−19138号記載のポリカーボネートが好ましい。Specific examples include polyvinyl chloride, polyester, polycarbonate, polyvinylidene chloride, and polyether, and polyvinyl chloride described in JP-A-59-223425 and polycarbonate described in JP-A-60-19138 are particularly preferred.
又、受像層がバインダー中に媒染剤を含有する受像部
材において、媒染剤としては、３級アミン又は４級アン
モニウム塩を含むポリマーが好ましく用いられ、例えば
米国特許3,709,690号明細書及び、特開昭64−13546号公
報等に記載の化合物が挙げられる。又、これらの媒染剤
を保持するのに用いられるバインダーとしては、例えば
ゼラチンやポリビニルアルコール等の親水性バインダー
が好ましく用いられる。Further, in the image receiving member in which the image receiving layer contains a mordant in a binder, as the mordant, a polymer containing a tertiary amine or a quaternary ammonium salt is preferably used. For example, US Pat. Compounds described in JP 13546 gazette and the like can be mentioned. As a binder used for holding these mordants, a hydrophilic binder such as gelatin or polyvinyl alcohol is preferably used.
上記媒染剤をバインダー中に有する受像層と似た形
で、色素受容能を有する疎水性ポリマーラテックスを親
水性バインダー中に分散してなる色素受容層も本発明で
用いることができる。A dye receiving layer obtained by dispersing a hydrophobic polymer latex having dye receiving ability in a hydrophilic binder in a similar manner to the image receiving layer having the mordant in the binder can also be used in the present invention.
本発明の受像部材は支持体上に単一の受像層が設けら
れた場合であってもよく、又複数の構成層が塗設されて
いてもよく、この場合、この全てが色素受像層であるこ
とも、又構成層の一部のみが受像層であることもでき
る。The image-receiving member of the present invention may be a case where a single image-receiving layer is provided on a support, or a plurality of constituent layers may be coated, and in this case, all of the layers are dye image-receiving layers. In some cases, only a part of the constituent layers may be the image receiving layer.
受像部材が受像層とは別に支持体を有する時、受像部
材の支持体としては、透明支持体、反射支持体のいずれ
であってもよい。具体的には、例えば、ポリエチレンフ
タレート、ポリカーボネート、ポリスチレン、ポリ塩化
ビニル、ポリプロピレン、及びこれらの支持体中に硫酸
バリウム、炭酸カルシウム、二酸化チタン等の白色顔料
を添加した支持体、アート紙、キャストコート紙、バラ
イタ紙、紙支持体上に白色顔料を含有する熱可塑性樹脂
（ポリエチレン等）を被覆した積層紙、布類、ガラス、
アルミニウム等の金属箔等を用いることができる。ま
た、支持体上に顔料を含んで電子線硬化性樹脂組成物を
塗布・硬化させた支持体、及び、第２種拡散反応性を有
する反射支持体なども本発明の受像部材の支持体とし
て、用いることができる。When the image receiving member has a support separately from the image receiving layer, the support of the image receiving member may be any of a transparent support and a reflective support. Specifically, for example, polyethylene phthalate, polycarbonate, polystyrene, polyvinyl chloride, polypropylene, and a support obtained by adding a white pigment such as barium sulfate, calcium carbonate, and titanium dioxide to the support, art paper, cast coat Paper, baryta paper, laminated paper, cloth, glass, coated with a thermoplastic resin (eg, polyethylene) containing a white pigment on a paper support,
A metal foil such as aluminum can be used. Further, a support obtained by applying and curing an electron beam-curable resin composition containing a pigment on a support, and a reflective support having a second type diffusion reactivity are also examples of the support of the image receiving member of the present invention. , Can be used.
本発明の受像部材に公知の各種添加剤を添加すること
ができる。そのような添加剤としては、例えば、汚染防
止剤、紫外線吸収剤、蛍光増白剤、画像安定剤、現像促
進剤、カブリ防止剤、pH調節剤（酸及び酸プレカーサ
ー、塩基プレカーサー等）、熱溶剤、有機フッ素系化合
物、油滴、界面活性剤、硬膜剤、マット剤及び各種金属
イオン等が挙げられる。Various known additives can be added to the image receiving member of the present invention. Such additives include, for example, antifouling agents, ultraviolet absorbers, fluorescent whitening agents, image stabilizers, development accelerators, antifoggants, pH regulators (acid and acid precursors, base precursors, etc.), heat Examples thereof include solvents, organic fluorine compounds, oil droplets, surfactants, hardeners, matting agents, and various metal ions.
本発明の熱現像感光材料は、感光材料の感色性に適し
た公知の露光手段に依って露光されることができる。The photothermographic material of the invention can be exposed by a known exposure means suitable for the color sensitivity of the photosensitive material.
用いることのできる露光光源としては、タングステン
ランプ、ハロゲンランプ、キノセンランプ、水銀灯、CR
T光源、FO−CRT光源、発光ダイオード、レーザー光源
（例えばガスレーザー、色素レーザー、YAGレーザー、
半導体レーザー等）等を単独或は複数組み合わせて用い
ることができる。又、半導体レーザーとSHG素子（第２
高調波発生素子）とを組み合わせた光源も用いることが
できる。その他、電子線、Ｘ線、γ線、α線等によって
励起された蛍光体から放出される光に依っても露光され
ることができる。Exposure light sources that can be used include tungsten lamps, halogen lamps, quinocene lamps, mercury lamps, and CR lamps.
T light source, FO-CRT light source, light emitting diode, laser light source (for example, gas laser, dye laser, YAG laser,
Semiconductor laser) or the like can be used alone or in combination. In addition, semiconductor lasers and SHG devices (second
A light source combined with a harmonic generation element) can also be used. In addition, exposure can be performed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like.
露光時間は１画面を１回の露光で行うか、或は１画素
毎にデジタル的に露光を行うかで異なるが、前者の場
合、通常0.001秒〜10秒であり、又、後者においては１
画素当たり10-8〜10-2秒の範囲で行われる。The exposure time varies depending on whether one screen is exposed by one exposure or whether exposure is performed digitally for each pixel. In the former case, the exposure time is usually 0.001 to 10 seconds.
This is done in the range of 10 -8 to 10 -2 seconds per pixel.
露光する際には、必要に応じて、色フィルターを用い
て、露光光源の色温度調整を行うこともでき、又レーザ
ー等によりスキャナー露光を行うこともできる。At the time of exposure, the color temperature of the exposure light source can be adjusted using a color filter, if necessary, or scanner exposure can be performed using a laser or the like.
本発明の熱現像感光材料は、像様露光後又は露光と同
時に、好ましくは70〜200℃、更に好ましくは90〜170℃
で好ましくは１〜180秒間、更に好ましくは２〜120秒間
加熱現像され、色素画像が形成される。拡散性色素の受
像部材への転写は熱現像時に、受像部材の受像層面を感
光材料の感光層側に密着させることにより、熱現像と同
時に行ってもよく、又、熱現像後に受像部材を感光材料
に密着させて色素を転写させてもよく、更に、水を供給
した後、感光材料と受像部材とを密着させてもよい。又
露光前に70〜160℃の範囲で感光材料を予備加熱した
り、特開昭60−143338号及び同61−162041号に記載され
ている様に、現像直前に、感光材料と受像部材の少なく
とも一方を80〜120℃の温度範囲で予備加熱することも
できる。The photothermographic material of the present invention is preferably after imagewise exposure or simultaneously with exposure, preferably 70 to 200 ° C, more preferably 90 to 170 ° C.
For 1 to 180 seconds, more preferably 2 to 120 seconds, to form a dye image. The transfer of the diffusible dye to the image receiving member may be performed simultaneously with the heat development by bringing the image receiving layer surface of the image receiving member into close contact with the photosensitive layer side of the photosensitive material during the thermal development, or the image receiving member may be exposed after the heat development. The dye may be transferred in close contact with the material, and further, after supplying water, the photosensitive material and the image receiving member may be closely attached. Further, the photosensitive material is preheated at a temperature of 70 to 160 ° C. before exposure, or as described in JP-A-60-143338 and JP-A-61-162041, immediately before the development, At least one of them can be preheated in a temperature range of 80 to 120 ° C.
本発明の熱現像感光材料を熱現像する際には、公知の
加熱手段を適用することができ、例えば、加熱されたヒ
ートブロックや面ヒータに接触させたり、熱ローラや熱
ドラムに接触させる方式、高温に維持された雰囲気中を
通過させる方式、高周波加熱方式を用い、或は、感光材
料又は受像部材の裏面にカーボンブラック層の様な発熱
導電性物質を設け、通電することにより生ずるジュール
熱を利用する方式などを適用することができる。When the photothermographic material of the present invention is thermally developed, a known heating means can be applied, for example, a method of contacting with a heated heat block or a surface heater, or a method of contacting with a heat roller or a heat drum. A method of passing through an atmosphere maintained at a high temperature, a high-frequency heating method, or a heat-generating conductive substance such as a carbon black layer provided on the back surface of a photosensitive material or an image receiving member, and the Joule heat generated by applying a current. For example, a method that uses the method can be applied.
熱現像時における加熱パターンは特に制限はなく、一
定温度で行う方法、現像初期を高温状態で行い現像後半
を低温状態で行う方法、或はこの逆の方法、更には３ス
テップ以上に温度領域を変化させる方法や連続的に温度
を変化させる方式等任意の方法で行うことができる。The heating pattern at the time of thermal development is not particularly limited, a method of performing at a constant temperature, a method of performing the initial development at a high temperature and performing the latter half of the development at a low temperature, or a converse method, and further, a temperature range of three or more steps. Any method such as a method of changing the temperature or a method of continuously changing the temperature can be used.
以下、本発明の具体的実施例を説明する。しかし当然
のことながら本発明は以下の実施例により限定されるも
のではない。Hereinafter, specific examples of the present invention will be described. However, needless to say, the present invention is not limited by the following examples.
尚、各実施例に用いた感光色素、添加剤の構造式及び
表は末尾に一括して記載した。The structural formulas and tables of the photosensitive dyes and additives used in each example are collectively described at the end.
実施例−１ （１）沃臭化銀乳剤（Em−１）の調製 以下に示す５種類の溶液を用いて、沃臭化銀乳剤（Em
−１）を調製した。種乳剤には、沃化銀含有率２モル
％、平均粒径（同体積の立方体の一辺の長さ。以下の記
載でも同様）0.09μｍの沃臭化銀乳剤（SE−１）を用い
た。Example-1 (1) Preparation of silver iodobromide emulsion (Em-1) A silver iodobromide emulsion (Em-1) was prepared using the following five types of solutions.
-1) was prepared. As the seed emulsion, a silver iodobromide emulsion (SE-1) having a silver iodide content of 2 mol% and an average grain size (length of one side of a cube having the same volume; the same applies to the following description) was used. .
（溶液Ａ−１） オセインゼラチン 0.45g ポリイソプロピレン・ポリエチレン オキシド・ジコハク酸エステル ナトリウム塩・10％メタノール溶液 5.0ml 28％アンモニア水 29ml 種乳剤（SE−１） 0.071モル相当量 イオン交換水 1750ml （溶液Ｂ−１） オセインゼラチン 5.0g KBr 200.0g KI 5.8g イオン交換水で 500mlに仕上げる （溶液Ｃ−１） AgNO3 246.3g 28％アンモニア水 200.9ml イオン交換水で 414mlに仕上げる （溶液Ｄ−１） 50％KBr水溶液 pAg調整必要量 （溶液Ｅ−１） 56％酢酸水溶液 pH調整必要量 40℃において、特開昭57−92523号、同57−92524号に
示される混合撹拌機を用いて、（溶液Ａ−１）に（溶液
Ｂ−１）と（溶液Ｃ−１）を同時混合法によって等流量
で添加した。(Solution A-1) Ossein gelatin 0.45 g Polyisopropylene / polyethylene oxide / disuccinate sodium salt / 10% methanol solution 5.0 ml 28% ammonia water 29 ml Seed emulsion (SE-1) 0.071 mol equivalent ion-exchanged water 1750 ml (Solution B-1) Ossein gelatin 5.0g KBr 200.0g KI 5.8g Finish to 500ml with ion exchange water (Solution C-1) 246.3g AgNO 3 280.9% ammonia water 200.9ml Finish to 414ml with ion exchange water (Solution D) -1) Required amount of pAg adjustment for 50% KBr aqueous solution (Solution E-1) Required amount of pH adjustment for 56% acetic acid aqueous solution At 40 ° C, using a mixing stirrer disclosed in JP-A-57-92523 and JP-A-57-92524. Then, (Solution B-1) and (Solution C-1) were added to (Solution A-1) at the same flow rate by the simultaneous mixing method.
同時混合中のpHは8.0に一定に保ち、それぞれ流量可
変のローラーチューブポンプにより（溶液Ｅ−１）の流
量を変えながら制御した。During the simultaneous mixing, the pH was kept constant at 8.0, and the control was performed while changing the flow rate of (Solution E-1) by using a roller tube pump having a variable flow rate.
pAgは（溶液Ｂ−１）と（溶液Ｃ−１）の添加を開始
する時点では8.8に調整し、その後（溶液Ｂ−１）の添
加量に比例して連続的に変化させ、（溶液Ｂ−１）と
（溶液Ｃ−１）の添加終了時には9.3となるように制御
した。pAgの制御は流量可変のローラーチューブポンプ
により（溶液Ｄ−１）の流量を変化させて行った。The pAg was adjusted to 8.8 at the start of the addition of (Solution B-1) and (Solution C-1), and then continuously changed in proportion to the amount of (Solution B-1). -1) and (Solution C-1) were controlled to 9.3 at the end of addition. The pAg was controlled by changing the flow rate of (Solution D-1) using a roller tube pump with a variable flow rate.
（溶液Ｂ−１）と（溶液Ｃ−１）の添加は、小粒子発
生の無い、許容最大速度（臨界速度）で行い、（溶液Ｃ
−１）296mlが添加されたところで、4.5×10-7モルのヘ
キサクロロイリジウム（IV）酸カリウム（K2IrCl6）を
水溶液として添加した。(Solution B-1) and (Solution C-1) are added at the maximum allowable speed (critical speed) without generation of small particles.
-1) When 296 ml had been added, 4.5 × 10 -7 mol of potassium hexachloroiridate (IV) (K 2 IrCl 6 ) was added as an aqueous solution.
更に（溶液Ｂ−１）と（溶液Ｃ−１）の添加を続け、
（溶液Ｃ−１）がすべて添加された時点で終了した。続
いて、（溶液Ｄ−１）と（溶液Ｅ−１）により、pAg＝1
0.4、pH＝6.0に調整し、常法により脱塩水洗を行った。
その後、オセインゼラチン45.65gを含有する水溶液中に
分散した後、イオン交換水で総量を1200mlに調整し、更
に（溶液Ｄ−１）と（溶液Ｅ−１）を用いて、40℃にお
いてpAgを8.5、pAgを5.8に調整した。このようにして得
られた乳剤（Em−１）は、沃化銀含有率２モル％の沃臭
化銀乳剤であり、平均粒径0.25μｍの単分散乳剤である
ことが判った。Further, the addition of (Solution B-1) and (Solution C-1) is continued,
The process was completed when (Solution C-1) was completely added. Subsequently, pAg = 1 by (solution D-1) and (solution E-1).
The solution was adjusted to 0.4 and pH = 6.0, and washed with desalinated water by a conventional method.
Then, after dispersing in an aqueous solution containing 45.65 g of ossein gelatin, the total amount was adjusted to 1200 ml with ion-exchanged water, and further, using (Solution D-1) and (Solution E-1), pAg Was adjusted to 8.5 and pAg to 5.8. The emulsion (Em-1) thus obtained was a silver iodobromide emulsion having a silver iodide content of 2 mol%, and was found to be a monodisperse emulsion having an average grain size of 0.25 μm.
得られた沃臭化銀粒子の形状はほぼ立方体であるが、
角や辺にやや丸みを帯びたものであった。The shape of the obtained silver iodobromide grains is almost cubic,
The corners and sides were slightly rounded.
（２）赤感光性乳剤の調製 Em−1 300mlを52℃に保温して撹拌し、後記増感色素
（ａ）50mg及び後記増感色素（ｂ）100mgをそれぞれ１
％メタノール溶液として添加し、その10分後に15μmol
のチオ硫酸ナトリウムを0.1％水溶液として添加し、更
に、60分後に塩化金酸（0.05％水溶液として）10μmol
とチオシアン酸アンモニウム（0.1％水溶液）20μmolを
添加した。更に52℃に保温して撹拌した状態で最適時間
熟成を続けた後、40℃に降温し、４−ヒドロキシ−６−
メチル−1,3,3a,7−テトラザインデン（HMT）250mg、１
−フェニル−５−メルカプトテトラゾール（PMT）5mg及
び下記のカブリ防止剤ST−１の25mgを５％メタノール溶
液として添加し、イオン交換水で全量を540mlにした。(2) Preparation of red-sensitive emulsion 300 ml of Em-1 was kept warm at 52 ° C. and stirred, and 50 mg of the sensitizing dye (a) and 100 mg of the sensitizing dye (b) described below were added in 1 part each.
% Methanol solution, and after 10 minutes, 15 μmol
Of sodium thiosulfate as a 0.1% aqueous solution, and after 60 minutes, 10 μmol of chloroauric acid (as a 0.05% aqueous solution)
And 20 μmol of ammonium thiocyanate (0.1% aqueous solution). After further aging for an optimum period of time while keeping the temperature at 52 ° C and stirring, the temperature was lowered to 40 ° C and 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene (HMT) 250 mg, 1
5 mg of -phenyl-5-mercaptotetrazole (PMT) and 25 mg of the following antifoggant ST-1 were added as a 5% methanol solution, and the total amount was made up to 540 ml with ion-exchanged water.
（３）有機銀乳剤の調製 50℃に保温したフェニルカルバモイルゼラチン10％水
溶液中に、特開昭57−92523号、同57−92524号に記載さ
れた混合撹拌機を用いて、アンモニア性硝酸銀水溶液及
びベンゾトリアゾール（ベンゾトリアゾールに対して02
モルのアンモニア水含有）の同時混合により調製し、添
加終了後のpHを低下させて、凝集・脱塩して針状結晶
（巾0.1〜0.3μｍ、長さ0.5〜２μｍ）を得た。(3) Preparation of Organic Silver Emulsion In a 10% aqueous solution of phenylcarbamoyl gelatin kept at 50 ° C, an aqueous solution of ammonium silver nitrate was mixed using a mixing stirrer described in JP-A-57-92523 and JP-A-57-92524. And benzotriazole (02 for benzotriazole
The mixture was prepared by simultaneous mixing of aqueous ammonia, and after completion of the addition, the pH was lowered, and the mixture was aggregated and desalted to obtain needle-like crystals (width 0.1 to 0.3 μm, length 0.5 to 2 μm).
（４）熱溶剤分散液の調製 後記熱溶剤−1 25gを0.04gの界面活性剤−１を含有す
る0.5％ポリビニルピロリドン（PVP）100ml中にアルミ
ナボールミルで分散し、120mlとした。(4) Preparation of Dispersion of Hot Solvent 125 g of the following hot solvent was dispersed in 100 ml of 0.5% polyvinylpyrrolidone (PVP) containing 0.04 g of surfactant-1 using an alumina ball mill to make 120 ml.
（５）色素供与物質分散液の調製 表２に示した下記色素供与物質（VC、MC及びCCの混合
物）合成10g、下記色汚染防止剤（Ｗ−１）2.4gを酢酸
エチル200mlとDOP（ジ−（２−エチルヘキシル）フタレ
ート）10.0gに溶解し、界面活性剤−１の５重量％水溶
液60mlと４％ゼラチン水溶液720mlを混合し、超音波ホ
モジナイザーで乳化分散し、酢酸エチルを減圧除去した
後、イオン交換水で全量を795mlに調整し、色素供与物
質分散液を得た。(5) Preparation of Dye Donor Dispersion 10 g of the following dye donor (mixture of VC, MC and CC) shown in Table 2 and 2.4 g of the following color stain inhibitor (W-1) were added to 200 ml of ethyl acetate and DOP ( Dissolved in 10.0 g of di- (2-ethylhexyl) phthalate), 60 ml of a 5% by weight aqueous solution of surfactant-1 and 720 ml of a 4% gelatin aqueous solution were mixed, emulsified and dispersed by an ultrasonic homogenizer, and ethyl acetate was removed under reduced pressure. Thereafter, the total amount was adjusted to 795 ml with ion-exchanged water to obtain a dye-donating substance dispersion.
（６）熱現像感光材料の作製 上記調整した有機銀塩分散液、ハロゲン化銀乳剤、色
素供与物質分散液、熱溶剤分散液、及び還元剤水溶液を
使用して、表−１に示す熱現像感光材料を作製した。
（添加量は特に記載のない限り、熱現像感光材料１m2当
たりの量で示した。） 以下、各熱現像感光材料において、各々の色素供与物
質の比率は、それぞれ即試料で最適なニュートラルが得
られるような比率をあらかじめ求めておき、その比率で
使用した。(6) Preparation of Photothermographic Material The above-prepared organic silver salt dispersion, silver halide emulsion, dye-donor dispersion, hot solvent dispersion, and aqueous reducing agent solution were subjected to heat development shown in Table 1. A photosensitive material was produced.
(The amount of addition was shown per 1 m 2 of the photothermographic material unless otherwise specified.) Hereinafter, in each photothermographic material, the ratio of each dye-providing substance was determined to be the optimum neutral value for each sample immediately. The ratio that could be obtained was determined in advance and used at that ratio.
塗布は、両面下引き層を塗設した支持体上にバッキン
グ層−１とバッキング層−２を同時に塗布乾燥を行い、
更にその反対側に、第１〜第３層を同時塗布を行い、そ
の上に第４〜第７層を同時塗布を行った。Coating is performed by simultaneously applying and drying the backing layer-1 and the backing layer-2 on a support provided with a double-sided undercoat layer.
Further, on the opposite side, the first to third layers were simultaneously coated, and the fourth to seventh layers were simultaneously coated thereon.
バッキング層−1,2及び第１〜第７層には塗布助剤と
して界面活性剤−３を更に含有させ、又、各層の塗布液
は、pHを6.0に調整した後、硬膜剤としてテトラキス
（ビニルスルホニルメチル）メタンとタウリンカリウム
塩との反応物（反応比1:0.75（モル比）硬膜剤−１）を
それぞれゼラチン1g中0.05gの割合で塗布直前に加え
た。The backing layers 1, 2 and the first to seventh layers further contain surfactant-3 as a coating aid, and the coating solution for each layer is adjusted to pH 6.0 and then tetrakis as a hardening agent. A reaction product of (vinylsulfonylmethyl) methane and potassium taurine (reaction ratio 1: 0.75 (molar ratio), hardener-1) was added at a ratio of 0.05 g per 1 g of gelatin and immediately before coating.
得られた熱現像感光材料を40℃で３日間保存し硬膜し
た。（熱現像感光材料−１） （７）受像材料作製 次に、下記の組成からなる色素受像層を150g/m2の写
真用バライタ紙上に塗布して色素受像材料を作成した。The obtained photothermographic material was stored at 40 ° C. for 3 days to harden. (Heat-developable photosensitive material-1) (7) Preparation of image receiving material Next, a dye image receiving layer having the following composition was applied on a 150 g / m 2 photographic baryta paper to prepare a dye image receiving material.
（受像層組成） ポリ塩化ビニル（平均重合度1100） 11g 画像安定剤−１ 0.7g 画像安定剤−２ 0.5g 画像安定剤−３ 0.3g 画像安定剤−４ 0.8g 現像促進剤−１ 0.5g 尚、塗布は上記組成物が受像材料１m2当たりの付き量
になるように塗布液を調整（溶媒：テトラヒドロフラ
ン）し、湿潤膜厚が100μｍになるようにして塗布を行
った。(Image receiving layer composition) Polyvinyl chloride (average degree of polymerization: 1100) 11 g Image stabilizer-1 0.7 g Image stabilizer-2 0.5 g Image stabilizer-3 0.3 g Image stabilizer-4 0.8 g Development accelerator-1 0.5 g The coating was performed by adjusting the coating solution (solvent: tetrahydrofuran) so that the above composition was applied per 1 m 2 of the image receiving material, so that the wet film thickness became 100 μm.
（８）熱現像感光材料の評価 得られた熱現像感光材料１〜13に赤色単色光にてウェ
ッジ露光した後、上記受像材料と重ね合わせ、特開昭63
−159852号記載のドラムベルト型熱現像装置により、14
5℃で60秒間の加熱現像を行った。 (8) Evaluation of photothermographic materials The obtained photothermographic materials 1 to 13 were subjected to wedge exposure with monochromatic red light, and then superposed on the above image receiving material.
With the drum belt type thermal developing device described in
Heat development was performed at 5 ° C. for 60 seconds.
得られた試料を室温に戻した後、受像材料を熱現像感
光材料から剥離して、色素受像材料上に色素画像を得
た。After returning the obtained sample to room temperature, the image receiving material was peeled off from the photothermographic material to obtain a dye image on the dye image receiving material.
得られた色素画像を緑反射濃度が0.5及び1.5におい
て、日立製作所株式会社製607型カラーアナライザーに
より分光反射濃度の測定を行い、これからＬ″ａ″ｂ″
表色系における色度を求め、一方上記感光材料の各々に
デジタル画像えおHe・Neレーザーで露光し、上記と同様
に熱現像を行ってプリント画像を得た。これの色調を視
感判定し、表−２に示す結果を得た。At a green reflection density of 0.5 and 1.5, a spectral reflection density of the obtained dye image was measured using a 607 type color analyzer manufactured by Hitachi, Ltd., and L "a" b "
The chromaticity in the color system was determined, and each of the above photographic materials was exposed to a digital image He / Ne laser and subjected to heat development in the same manner as described above to obtain a printed image. The color tone was visually evaluated and the results shown in Table 2 were obtained.
◎：黒白画像として充分良好 ○：僅かに着色するが、ほぼ黒白画像として使用可 △：着色しているが、黒白画像として判別可能 ×：黒白画像として適用不可 一方上記感光材料を50℃、65RH％で２日間保存した
後、上記と同様に露光、熱現像を行い、a*b*を求め更に
各色についての視感判定を行った。：: Sufficiently good as a black-and-white image ：: Slightly colored, but can be used almost as a black-and-white image △: Colored but discriminable as a black-and-white image ×: Not applicable as a black-and-white image After storage for 2 days, exposure and thermal development were carried out in the same manner as described above, a * b * was determined, and the visual perception of each color was determined.
更に上記熱現像感光材料を150℃、45秒にて熱現像を
行い、上記と同じ評価を行った。Further, the above photothermographic material was subjected to heat development at 150 ° C. for 45 seconds, and the same evaluation as above was performed.
表−２に示す結果から、本発明の熱現像感光材料１〜
10は保存前後で黒色画像が殆ど変化せず、しかも中濃度
から高濃度にかけて良好なニュートラル特性をしめして
いることが分かる。また熱現像条件を変化させても良好
なニュートラル特性が維持されていることが分かる。こ
れに対して熱現像感光材料11〜13は基準試料では良好な
黒色色調を与えるものの、保存後或は熱現像条件が変化
した時には黒色色調の変化が大きいことが分かる。特に
拡散性色素の分子量の最大値と最小値との比が0.8以上
である本発明の熱現像感光材料2,3,6〜10の黒色色調の
保存及び現像条件変化による安定性が良好であることが
分かる。From the results shown in Table 2, the photothermographic materials 1 to 5 of the invention were obtained.
10 shows that the black image hardly changed before and after storage, and that the medium exhibited good neutral characteristics from medium density to high density. It can also be seen that good neutral characteristics are maintained even when the thermal development conditions are changed. On the other hand, although the heat-developable photosensitive materials 11 to 13 give a good black tone in the reference sample, the change in the black tone is large after storage or when the heat development conditions change. Particularly, the ratio of the maximum value to the minimum value of the molecular weight of the diffusible dye is 0.8 or more, and the photothermographic materials 2, 3, and 6 to 10 of the present invention have good stability due to storage of black tones and changes in development conditions. You can see that.
表−２において色素供与物質の構造式は以下の通りで
ある。In Table 2, the structural formula of the dye-providing substance is as follows.
実施例−２ 実施例−１で作成した熱現感材−８及び−12におい
て、乳剤層及び保護層の硬膜剤の量を表−３に示したよ
うに変化させた以外は実施例−１で作成したのと同じ条
件で熱現感材の20〜23を作成した。実施例−１と同様に
熱現像処理を行って黒色色調の色度（a*，b*）を求め
た。 Example 2 Example 2 was repeated except that the amounts of the hardeners in the emulsion layer and the protective layer were changed as shown in Table 3 in the heat-sensitive materials -8 and -12 prepared in Example 1. Under the same conditions as in Example 1, heat-sensitive materials 20 to 23 were prepared. The heat development was performed in the same manner as in Example 1 to determine the chromaticity (a * , b * ) of the black color tone.
結果を表−３に示した。 The results are shown in Table-3.
表−３の結果から、本発明の熱現感材−20及び21は硬
膜度が変化しても良好な黒色安定性を示しているが、本
発明外の熱現感材においては、硬膜度が変化したときに
本発明のように安定した良好な黒色色調が得られないこ
とが分かる。From the results shown in Table 3, the heat-sensitive materials 20 and 21 of the present invention exhibited good black stability even when the degree of hardening was changed. It can be seen that when the film thickness changes, a stable and good black color tone as in the present invention cannot be obtained.
実施例−３ 実施例−１で作成した熱現感材−８において、保護層
のゼラチン量とPVPを表−４に示すように変化させた熱
現感材−24〜26を実施例−１と同様にして作成した。実
施例−１に記載の方法で黒色色調の安定性を評価し、表
−４に示す結果を得た。 Example-3 The heat-sensitive material-8 prepared in Example-1 was used, except that the amount of gelatin in the protective layer and PVP were changed as shown in Table-4. Created in the same way as The stability of black color tone was evaluated by the method described in Example 1, and the results shown in Table 4 were obtained.
表−４の結果から保護層のバインダー（ゼラチン＋PV
P）量が1g以下で黒色色調バランスが安定しており、特
に好ましくは0.8g/m2以下である本発明の熱現感材にお
いて特に黒色色調の安定性が良好であることが分かる。From the results in Table 4, the binder (gelatin + PV) of the protective layer
P) When the amount is 1 g or less, the black color tone balance is stable, and particularly preferably, the heat-sensitive material of the present invention, in which the amount is 0.8 g / m 2 or less, has particularly good black color tone stability.
実施例−４ 実施例−１で作成した熱現感材−８及び−12におい
て、使用した還元剤をＲ−１から還元剤Ｒ−１と還元剤
Ｒ−２を9:1、7:3及び5:5のモル比率で混合したものに
変えて使用した他は実施例−１と同様にして作成した。 Example-4 In the heat-sensitive materials -8 and -12 prepared in Example-1, the reducing agents used were changed from R-1 to 9: 1 and 7: 3. And prepared in the same manner as in Example 1 except that the mixture was used in a molar ratio of 5: 5.
実施例−１に記載の方法で黒色色調の安定性を評価
し、表−５に示す結果を得た。The stability of black color tone was evaluated by the method described in Example 1, and the results shown in Table 5 were obtained.
表−５の結果から２種以上の還元剤を使用した場合で
も、本発明の熱現感材では黒色色調の安定性が良好であ
ることが分かる。From the results in Table 5, it can be seen that even when two or more reducing agents are used, the heat-sensitive material of the present invention has good black color stability.
〔発明の効果〕 本発明により、低濃度域から高濃度域までの領域全般
において、黒色色調の再現性が改善され、しかも感光材
料の保存或は処理条件の変化に対して安定した黒色画像
を与えることのできる黒白画像形成用熱現像感光材料を
提供することができた。 [Effects of the Invention] According to the present invention, the reproducibility of the black color tone is improved in the entire region from the low-density region to the high-density region, and a black image that is stable with respect to changes in the storage or processing conditions of the photosensitive material. It was possible to provide a photothermographic material for forming a black-and-white image which can be provided.
Claims (3)
銀乳剤及びイエロー、マゼンタ、シアン色素供与物質を
有する黒白画像形成用熱現像感光材料において、イエロ
ー、マゼンタ、シアンの各色素供与物質から形成もしく
は放出される色素の分子量の最大のものに対する最小の
ものの分子量の比率が0.75以上であることを特徴とする
黒白画像形成用熱現像感光材料。1. A black-and-white image forming photothermographic material having a binder, a photosensitive silver halide emulsion and yellow, magenta and cyan dye-providing substances on a support, comprising a yellow, magenta and cyan dye-providing substance. Alternatively, the photothermographic material for forming a black-and-white image is characterized in that the ratio of the molecular weight of the minimum dye to the maximum of the molecular weight of the released dye is 0.75 or more.
ものの分子量の比率が0.8以上であることを特徴とする
請求項１記載の黒白画像形成用熱現像感光材料。2. The photothermographic material according to claim 1, wherein the ratio of the molecular weight of the smallest dye to the largest one of the dyes is 0.8 or more.
ものの分子量の比率が0.85以上であることを特徴とする
請求項１記載の黒白画像形成用熱現像感光材料。3. The photothermographic material according to claim 1, wherein the ratio of the minimum molecular weight to the maximum molecular weight of the dye is 0.85 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27254290A JP2906178B2 (en) | 1990-10-11 | 1990-10-11 | Photothermographic materials for black and white image formation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27254290A JP2906178B2 (en) | 1990-10-11 | 1990-10-11 | Photothermographic materials for black and white image formation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04147254A JPH04147254A (en) | 1992-05-20 |
| JP2906178B2 true JP2906178B2 (en) | 1999-06-14 |
Family
ID=17515352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27254290A Expired - Lifetime JP2906178B2 (en) | 1990-10-11 | 1990-10-11 | Photothermographic materials for black and white image formation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2906178B2 (en) |
-
1990
- 1990-10-11 JP JP27254290A patent/JP2906178B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04147254A (en) | 1992-05-20 |
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