• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A photographic silver halide material contains in at least one emulsion layer or auxiliary layer at least one dye of the formula <IMAGE> in which each of R and R<1> is CH3, C2H5 or C2H4CN; R<2> is H or CN; R<3> is <IMAGE>
    公开号:SU1027679A1
    申请号:SU797770694
    申请日:1979-07-20
    公开日:1983-07-07
    发明作者:Рейнхард Штолле；Улрих Мейзел；Гюнтер Бах；Ренате Йантос
    申请人:Феб Филмфабрик Волфенъфотохемишес Комбинат (Инопредприятие)；
    IPC主号:
    专利说明:

    The invention of a photographic material based on halogen-silver emulsions, which contains at least one photosensitive halogen-silver gelatin BbrfJ layer and at least one of the colored or washed-out filter dye. It is known to introduce organic dyes into photographic materials in order to prevent reflection and / or scattering halo. Such dyes, hereinafter referred to as filter dyes, must have a high extinction, which exactly corresponds to the given application purpose, and can be quickly, completely and irreversibly removed. Further, good water solubility and good storage stability are required, both as an aqueous solution and as an integral part of the photographic layers. Further, a photographic inactivity, i.e. filter dyes should not. affect the sensometry properties and kinetics of the appearance of photographic material. Until now, the known light absorbers only partially fulfill these requirements. Especially difficult is the lack of removal with extremely short processing time and / or the use of treatment baths that have little effect on the destruction of filter dyes. This applies particularly to the filter dyestuffs described in the invention description of the Belgian patent 43127 in the layered description of the invention to the accepted German Federal Application 144781 in the description of the invention of US Patent 3316091 and in the description of the invention of the GDR patent 109455. In some cases, with a large amount of processed material, there is an accumulation of intact filter dye in the processing baths, which subsequently leads to interfering repainting of finished photomaterials, for example, tartine (CoBool-Ombeh 19140. The same applies to those Systems that are only reversibly converted to a colorless form (for example, triphenylmethane dyes, as described in the description of the invention to French patent 1017102 and CXjEor-DKidex 1 42685.) Materials containing such dyes turn out to be colorless, but form a dye The storage of the material is such that undesirable visible staining of the material occurs. The insufficient solubility of numerous dyes also leads to difficulties in their application. In those cases when high staining is necessary, a large amount of water needed to dissolve the filter dye loads the irrigation solution heavily and during the production of the film lengthens the drying time, it also leads to sedimentation in the gelatin layer that interfere with the discoloration. Such drawbacks occur when, due to the too narrow region of absorption of filter dyes, it is necessary to use a mixture of three or more dyes in order to cover the entire photographically important region of the spectrum. In such cases, too selective absorption should be considered a disadvantage. Such substances are, for example, dyes according to the description of the invention of US patent No. 3316091, laid out description of the invention to the non-accepted application of the Federal Republic of Germany 1522427, laid out description of the invention to the non-accepted application of the Federal Republic of Germany 2262794, laid-out description of the invention to the unaccepted application of the German Federal Council No. 9462144, 94 U.S. Patent 3,560,214 and the description of the invention to the economic patent GDR 109455, which with these disadvantages, in addition, have low water solubility. Because the spectral absorption region is too narrow, they must be applied in relatively large quantities in order to ensure sufficient halo prevention. Therefore, the upper solubility limit is easily reached. The disadvantage of numerous dyes is the further time-consuming preparation of them from expensive and difficult-to-use starting materials, which leads to a high cost. The purpose of the invention is to create photographic materials with high sharpness, which, after undergoing photographic processing, especially with fast processing, are free from a bag of residual staining. The invention is based on the task of finding easily obtainable, highly soluble and rapidly bleachable filter dyes or mixtures of dyes that have high extinction absorbs light in the largest possible part of the visible spectrum in emulsion and / or gelatin layers with a high density of colored material. The problem is solved in that in a material based on halogen-silver emulsions there are at least one emulsion or auxiliary layer in at least one dye of the general formula where H, Rj-CH3, CaHj, CN H, fCJlv Rg-Or, TO X " H, Ka, K, 1Sh4, The advantage of the invention is the use of at least one emulsion or secondary layer of dyes or a mixture of dyes of the general formula with a wide absorption area and high extinction KOTOpiJie ensure effective halo prevention. A particular advantage of the invention is that at least in one emulsion or vibrating layer there is a mixture of dyes, according to the general formula, in which the substituents Rj. the various substitutes are also different. In case R CN, adhesives absorb in the whole green and red regions of the spectrum, if in H, in the blue and most green regions, a mixture of dyes with R, H is obtained and effective protection is achieved over the entire spectrum of visible Sveta. Such mixtures have particular advantages for protective layers against a reflection halo. According to the state of the art, in order to achieve comparative protection, a mixture of 3 or 4 dyes must be used, which entails a significant increase in the consumption of dyes and the corresponding difficulties in removing these dyes. This solid advantage of dyes is based on the fact that when replacing, an unexpectedly strong bathochromic color shift occurs and the absorption of these hitherto unknown dyes is supplemented in such an ideal way with the absorption of a similar dye. The visible region of the spectrum. A significant advantage of the invention is the high CO reactivity of these dyes, which manifests itself in very fast bleaching when and in irreversible conditions. in increments colorless product even with a small content of sulfate in the processing baths. In this way, they are clearly superior to other classes of oxonol and triphenylmethane dyes, which, although quickly discolored, turn back to a colored form in the acidic pH range. Compared with the known benzylidene dye class filter dyes, these dyes and their bleaching products are characterized by a high diffusion rate. Therefore, a residual washout is achieved and any kind of reverse or residual dyeing is excluded, even with highly tanning treatment baths with a minimum sulphite content. From this point of view, the dyes according to the invention are particularly superior to the dyes according to the description of U.S. Patent 3,306,091, which, due to the apparent residual dyeing, is not suitable for materials with high-speed processing. Dyes according to the invention are particularly suitable for providing such photographic materials due to the above reasons, because of the extremely QUANTY treatment time and / or baths containing little sulfite, the use of other filter dyes is impossible or possible only in low concentrations. A further advantage of the dyes according to the invention is their good water solubility, especially their siFonium salts. Since, in addition, they possess high extraction, it is possible to achieve a high density of filter dyes with an insignificant load of water from the irrigation solution, moreover, they prevent the dye crystals from settling in the layer at a high concentration of K p9 sitel1. In particular, dyes show, as compared with the known benzyl price dyes, a markedly improved solubility and favorable fringe transfer absorption. A particular advantage of the invention is a simple method for producing dyes, from commonly available low cost starting materials. Dyes, where, are obtained by condensation of the corresponding dich and -lipshkylaminobenzaldepyov with the corresponding pyrazolnes in alcohol or aqueous solutions in the presence of ammonium acetate as a condensation agent.
    Preparation of dyes as described in patent specification GDR 131178, To obtain a mixture of two dyes, agadey agrees to the formula, which differ only in the substituent or tM as the starting material is the dye with RH for dye with R CN. The absorbances of both dyes are mutually complementary in an optimal way and cover the entire photographically important region from 400 to 700 nm.
    Of course, Regardless of this, it is possible to use a mixture of at least one dye with other organic filter dyes.
    On the basis of a wide absorption area, these dyes are particularly suitable for use in special auxiliary layers to prevent halo, especially for use in gelatin layers that are on the back side of the film, in so-called NC layers.
    The properties of the dye or mixtures, as well as their containing photographic materials, are described in the following examples as compared with the known filter dyes.
    Example 1. The dyes corresponding to the state of the technique are compared (Table 1 No. 1-8, and according to the Invention (Table 1, No. 9-12, as well as a mixture of two dyes with respect to spectral absorption, diffusion behavior, and discoloration in photographic baths For this purpose, aqueous solutions of krastely 1-12 are added to a 10% solution of ordinary gelatin in such an amount that after watering onto a colorless cellulose acetate carrier and drying, filter layers are obtained which, at their respective absorption maximum, show an optimum density spine equal to 1.0. Tol1ain layers are b mm, the pH value of the gelatin solution is 5.2 + 0.2, as a dubious substance, every 1000 ml of 10% growth solution is added per kg, thief of gelatin b ml of 5% of an aqueous solution of sodium salt of 1,3-dichloro-1 5-hydroxy-is-triazine and 0.75 ml of 5% solution of chromium triacetate.
    These layers are examined as follows.
    A. Maxstrumes are measured globally (as well as optimal densities at 450,500,530,560 and 650 nm.
    The data are given in table 2.
    B. Determination of diffusion behavior by contacting for 10 minutes with a numbed gelatin layer swelled in distilled water (50 mm thick layer as receiving layer and determining the percentage diffusing diffusion under such conditions as a measure of diffusion rate (Table .2).
    B. Determination of the rate of discoloration in 1% pacTBupeWaOH, 1% Na2.5Qj solution, as well as in oak syrup ORBO 308 m ORBO 40 and A 82 (cf. ORVO - recipes, EDM.1978).
    The data compiled in table.3.
    D. Determination of residual staining of artificially aged samples at 50 ° C and 30% relative humidity, 5 days after appearance in a Pakonolit type filling machine with a follow-up time and bath composition: 60 seconds, TREV A 82,, 30 seconds dubbing fixer // Pr329 / MN / 30 s rinsing, 20C composition VanHgSr. ORVO-recipes ed. 1978
    The staining was evaluated as a percentage of the initial density after the passage of the above treatment (Table 4a) —and after additional washing with water with a value of 0 (Table 4b.
    From the above, you can do the following summary.
    With the same remaining properties, the dyes are superior to colors corresponding to the state of technology in the following points.
    Due to the high extinction, the required amount of dye to achieve comparable density is low. In the dye dye according to the invention, dyes 1 and 7 are much better. The relatively broad absorption provides good halo prevention throughout the spectrum. At this point, the dyes according to the invention clearly excelled all dyes corresponding to the state of the art (except 5J) A mixture of two dyes can create a high density throughout the spectrum. By the diffusion rate, the dyes according to the invention are superior to all other dyes (except &amp;;).
    In terms of the rate of bleaching with caustic sodium, sulphite and various photographic vanes dye 9, inventively surpasses all other dyes, dyes 2 and 1 are comparable with dyes according to the invention. After high-speed processing 6O c) only dyes according to the invention and dye 7 are almost show no residual staining and no reverse staining at acidic pH values.
    The dyes / according to the invention achieve excellent properties of the dyes corresponding to the state of the technology, only for individual items, while the dyes are in total (THE PROPERTIES clearly exceed them;
    Up im er 2G71l photo verification. Graphic activity is added by comparable optical density amounts of dyes 9 and 11 (7) ;. IAOGC6 (&amp; G / emulsions, sensitized Nm differently. For this purpose, 5 vif dye 9 or 10 mg, dye 11 is added to the emulsions given in. b. After adding a suitable wetting agent and 2 MP 5% an aqueous solution of sodium salt 1,3-dichloro-5-hydroxy-C1 & triazine as a tanning agent; the emulsion is poured onto a medium of cellulose triacetate, dried, illuminated after a step optical wedge, and 5 minutes is developed in the OPVO 40 on instructions ORVO 1100 (cf. ORVO - recipes Wolfen, 1978) /
    The relative sensitivity in different emulsions in example 2 is shown in Table 5. Dye 9 does not show any photographic
    0 activity, and dye 11 only causes a slight loss of sensitivity in one case, which is of no importance for most practical applications.
    five
    It is recognized as an invention according to the results of the examination carried out by the Office for the Invention of the German Democratic Republic.
    Table
    NASNA 2
    according to the description of the patent of France No. 103.7102
    bis-1 / - / 4-Sulfophenyl / -3-gmetylpyrazolone- / 5 / -trimethoxonol according to the invention of Belgian patent 431272, example 3
    bis-1 - / 4 geulfophenyl / -3-methylpyrazolone- / 5 / -pentamethylsiloxane according to the description of the invention of Belgium 431272, example 4
    bis- / Thiobarbituric acid x-pentamethic neson disperse silver salt in gelatin;
    according to the laid out description of the invention to the accepted application of the Federal Republic of Germany 1447813;
    Tartrazin, So € og Ziaek "19140
    1 .- ,, „.gOjH
    According to the invention according to the invention to US Patent No. 2072908-c
    CAGNG
    S1G2S312ON
    C1
    . СЖ СНз
     d
    Dye
    according to the specification of US Patent 3,306,091 Dyes according to the invention of the general formula;
    ".- /
     //
    in which
    R, N5gN, Nd
    NRiOjS
    Continued table. one
    Title

    CH C
    K, H1: CH3; H2sCN,
    R, RI - ch2-sn2-eg,
    SOjNa
    nt
    fS
    s h
    0
    "
    Hi
    X x
    s s s about and
    in -o in i)
    about MS
    about
    CM
    (N tn fO rf hf
    V
    V
    oh oh
    about
    he
    about o -1 o
    P HZ
    XXX S S S 000
    oo
    m intN cm N o M (N GM
    t-1 th v v v
    oh oh
    OVOOOOt-tOOOOrMCvtCM
    V v
    about tN
    SP
    tnmsgoche-schoch-aosg Emulsion --- ------ Ag-BK (j. without filter paint with dye 9 with dye 11 Ag-ce (Bh; without filter stitching with dye 9 with dye 11 Emulsion with filter dye 9 with dye 9 s dye 11.) without filtrokrayt with dye 9 with dye 11
    Table 5; Spectral sensitization,% Non-sensitized blue filter I red filter ----- .--- ---------- - Type 100Type 100 100Yu 100100 100100 JUS100 Spectral sensitization,% Ortopanhromatic blue filter red filter Type 100TyO SO 100100 Type UOTip 100 SO 100 100 100 Continued table. five - ,
    权利要求:
    Claims (5)
    [1]
    1. PHOTO MATERIAL. BASED ON HALOGEN-SILVER EMULSIONS / with at least one halogen-free: ribbed gelatin layer, which contains at least one benzylidene dye, distinguished by the fact that at least one emulsion or auxiliary layer contains at least one colorant of the general formula
    RJlpCHj, or < g H 5 , owC e H 4 CW ;!
    B 2 -H, OG;
    ΗΎ 01 if k 2 ~ cw t TO
    XO3S
    [2]
    2. The photographic material according to claim 1, characterized in that it contains a mixture of two dyes ^ corresponding to the general formula.
    [3]
    3. Photographic material according to claims 1 and 2, which is distinguished by the fact that a mixture of two dyes is contained, in which the dyes differ by the substituent R ir and the substituents are equal.
    [4]
    4. A photographic material according to claim 1, characterized in that a mixture of at least one dye of the general formula and other organic dyes is contained.
    [5]
    5. Photographic material according to claims 1 to 4, characterized in that the dyes are contained in a layer on the back of the photographic material.
    类似技术:
    公开号 | 公开日 | 专利标题
    DE2700651C2|1988-09-29|
    DE857738C|1952-12-01|Process for preventing staining on color images
    US2271623A|1942-02-03|Photographic emulsion
    SU1027679A1|1983-07-07|Silver halide emulsion based photographic material
    DE1915118A1|1969-10-02|A color photographic light-sensitive material containing ultraviolet absorbing compounds
    DE2026252C3|1980-01-10|Rapid processing of photographic material
    DE2453217C2|1982-05-27|Photographic recording material
    DE2108790A1|1971-09-16|Photographic silver halide emulsion
    JPS581145A|1983-01-06|Photographic sensitive silver halide material containing dye
    DE2206112C3|1981-10-01|Pyrazolin-5-one derivatives and silver halide color photographic light-sensitive material containing them
    DE2034064C3|1979-04-12|Color photographic recording material
    DE1152609B|1963-08-08|Photographic material and red-sensitive silver halide emulsion, particularly multilayer color photographic materials
    DE2030326A1|1971-01-07|Silver halide photographic emulsions
    US2150695A|1939-03-14|Antihalation layer for photographic films
    DE2626367A1|1976-12-23|ANALYTICAL MATERIAL FOR THE ANALYTICAL DETERMINATION OF A SUBSTANCE
    DE1472848A1|1969-03-06|Use of butadienyl dyes as light filter and anti-luminous dyes
    US3932188A|1976-01-13|Silver halide photographic lightsensitive material
    DE2157330A1|1972-06-22|Photographic recording material containing at least one dye which can be faded in the presence of silver
    DE2017053B2|1973-10-04|Spectra! serrsifm&#39;rsrerfes pftotographi cal recording material
    DE2344074C2|1984-04-05|Photographic lith developer
    DE1161137B|1964-01-09|Photographic photosensitive or developed and finished material
    DE1961866C2|1982-06-24|Lippmann type silver halide photographic emulsion
    DE2840634A1|1979-03-29|RECORDING MATERIAL FOR THE PRODUCTION OF IMAGES
    DE2724488C2|1985-04-18|Color photographic recording material
    DE2132393C2|1983-02-17|Photographic recording material
    同族专利:
    公开号 | 公开日
    HU182601B|1984-02-28|
    PL217768A1|1980-06-02|
    FR2433774A1|1980-03-14|
    DD138251A1|1979-10-17|
    DE2926466A1|1980-02-28|
    PL115101B2|1981-03-31|
    GB2032636A|1980-05-08|
    FR2433774B1|1985-07-12|
    BE877730A|1979-11-16|
    GB2032636B|1982-12-01|
    DD138251B1|1980-11-26|
    CS220563B1|1983-04-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB584609A|1944-12-30|1947-01-20|Harry Derek Edwards|Improvements in or relating to photographic light-sensitive materials|
    JPS5153819A|1974-11-05|1976-05-12|Fuji Photo Film Co Ltd| Harogenkaginshashinnyuzaio zokansuru hoho |
    DD131177A1|1977-05-24|1978-06-07|Reinhard Stolle|PROCESS FOR PREPARING ALPHA-SUBSTITUTED CINNAMYLIDENE DYES|
    DD131178A1|1977-05-24|1978-06-07|Reinhard Stolle|PROCESS FOR PREPARING ALPHA-CYANIDE-SUBSTITUTED STYRYLENE DYES|
    GB2002916A|1977-08-12|1979-02-28|Ciba Geigy Ag|Antihalation dye combination|GB2138961B|1983-02-21|1986-09-24|Fuji Photo Film Co Ltd|Silver halide photographic light-sensitive material containing a dye|
    JPH0433021B2|1983-02-21|1992-06-01|Fuji Photo Film Co Ltd|
    US4948717A|1986-12-23|1990-08-14|Eastman Kodak Company|Solid particle dye dispersions for photographic filter layers|
    CA1286139C|1986-12-23|1991-07-16|Donald Richard Diehl|Filter dye for photographic element|
    US4803150A|1986-12-23|1989-02-07|Eastman Kodak Company|Radiographic element exhibiting reduced crossover|
    EP0587229B1|1992-09-11|2002-05-08|Agfa-Gevaert|Photographic element containing a filter dye for rapid processing applications|
    EP0586748A1|1992-09-11|1994-03-16|Agfa-Gevaert N.V.|Filter dyes for rapid processing applications|
    EP0587230B1|1992-09-11|2003-11-26|Agfa-Gevaert|Photographic element containing a filter dye for rapid processing applications|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DD20730878A|DD138251B1|1978-08-16|1978-08-16|PHOTOGRAPHIC MATERIAL BASED ON HALOGEN SILVER EMULSIONS WITH FILTER DYES|
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