US3676139A - Color photographic printing paper - Google Patents

Color photographic printing paper Download PDF

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Publication number
US3676139A
US3676139A US790846A US3676139DA US3676139A US 3676139 A US3676139 A US 3676139A US 790846 A US790846 A US 790846A US 3676139D A US3676139D A US 3676139DA US 3676139 A US3676139 A US 3676139A
Authority
US
United States
Prior art keywords
group
layer
printing paper
fluorescent brightening
carbon atoms
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
Application number
US790846A
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English (en)
Inventor
Hiroyuki Amano
Fumihiki Nishio
Nobuo Tsuji
Kazuo Shirasu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3676139A publication Critical patent/US3676139A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/132—Anti-ultraviolet fading
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/134—Brightener containing

Definitions

  • a fluorescent brightening agent is added directly as an aqueous solution 01' an organic solvent solution thereof to an emulsion or a dispersion for a photographic silver halide emulsion layer or to a supplemental layer.
  • An indirect methd has been proposed, in which a fluorescent brightening agent is dissolved in a solvent having a high boiling point (or a mixture of a high boiling solvent and an auxiliary solvent), the solution dispersed in an aqueous gelatin solution, and this dispersion added to a photographic light-sensitive emulsion.
  • the present invention relates to a color photographic printing paper containing a fluorescent brightening agent and an ultraviolet absorbent. More particularly, the invention relates to a color photographic printing paper having a photographic layer containing a watersoluble, fluorescent brightening agent having an anti-diffusion property to fluorescent-whitening and an ultraviolet absorbent to prevent fading and stains caused by ultraviolet rays.
  • the whitening of photographic printing papers has previously been accomplished by a method comprising adding a fluorescent brightening agent to the baryta layer of a baryta paper.
  • a fluorescent brightening agent added to the baryta layer of a baryta paper.
  • the whitening effect is lost in color photographic printing paper, since such papers must also contain a compound capable of absorbing ultraviolet rays, such as, ultraviolet absorbent and a coupler.
  • R and R each represents a hydrogen atom, an alkyl group having 1-8 carbon atoms, an aryl group having 6-12 carbon atoms, a hydroxyalkyl group having 2-4 carbon atoms, or a substituted derivative thereof, a sulfoalkyl group having 1-4 carbon atoms, or an alkali metal salt or ammonium salt thereof;
  • R represents a halogen atom, OR, SR,
  • R and R each represents a hydrogen atom, an alkyl group having 1-12 carbon atoms, a hydroxyalkyl group having 1-12 carbon atoms, a sulfoalkyl group (or an alkali metal salt or an ammonium salt thereof) a carboxyalkyl group (or an alkali metal salt or an ammonium salt thereof), or an alkyl group, an aryl group having 6-18 carbon atoms, a hydroxy-, carboxyor sulfonic acidderivative thereof, or an alkali metal salt or an ammonium salt thereof, a cycloalkyl group having 2-10 carbon atoms, or a substituted cycloalkyl group; and wherein A represents an alkylene group having 4-5 carbon atoms or an alkylene group containing a heterocyclic atom or a heterocyclic atomic group; Y represents an alkylene group having 2-10 carbon atoms, a substituted alkylene group having 2-10 carbon atoms, an ally
  • the fluorescent brightening agent is less difiused out during photographic processing or washing when incorporated in a photographic emulsion layer or a supplemental layer. Further, it has been found that this is resistant to staining when exposed to ultraviolet rays. Furthermore, these fluorescent brightening agents have been found to be excellent in fluorescent intensity and wave length.
  • an ultraviolet absorbent in the photographic emulsion layer or an upper layer applied on that photographic emulsion layer for improving the fade-resistance of color images.
  • the known ultraviolet absorbents are those absorbing ultraviolet rays having wave lengths of 300-400 me. It is also known that a ultraviolet absorbent capable of absorbing ultraviolet rays having wave lengths as long as possible is more effectively employed.
  • a further object of this invention is the provision of a color photographic printing paper containing an ultraviolet absorbent and a fluorescent whitening agent which is not subject to the aforesaid disadvantages.
  • the aforesaid objects of the present invention can be achieved by incorporating a fluorescent brightening agent having at least one repeating unit represented by the general Formula I or II in at least one photographic layer of a color photographic printing paper, said layer containing an ultraviolet absorbent, and photographic layers 4 present at the side of said photographic layer containing the ultraviolet absorbent and opposite to the support side of the paper.
  • a baryta layer for example, in one embodiment of a color photographic printing paper, there are provided on a support, a baryta layer, a blue-sensitive emulsion layer containing a yellow coupler, an intermediate layer, a green-sensitive emulsion layer containing a magenta coupler, an intermediate layer, a red-sensitive emulsion layer containing a cyan coupler, and a protective layer in that order.
  • the ultraviolet absorbent is incorporated in the intermediate layer between the cyan couplercontaining emulsion layer and the magenta coupler-containing emulsion layer and the fluorescent brightening agent is incorporated in the protective layer.
  • the fluorescent brightening agent used in the present invention is a high molecular weight compound having the repeating unit of the general Formula I or II as mentioned above.
  • the ultraviolet absorbent used in this invention may be, for instance,
  • R R and R each represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an aromatic group, or a heterocyclic ring;
  • the ultraviolet absorbent may be incorporated in the coating composition for photographic layer as (1) an emulsified dispersion in an aqueous gelatin solution, (2) a solution thereof in a high boiling solvent or a mixed solvent containing a high boiling solvent and a low boiling solvent or (3) an aqueous alkaline solution thereof.
  • the high molecular Weight compounds having the repeating unit represented by aforesaid general Formula I or II are generally prepared by dissolving or dispersing in a solvent, such as water or dimethylformamide, one mol of an S-triazine-stilbene derivative having the general formula R1 in (III) wherein X represents a halogen atom or an alkoxy group having 1-4 carbon atoms and R R and M are as indicated above, and about one mol of a diamino compound represented by general Formula IV or V as follows:
  • the bis-S-triazine-stilbene derivative described by general Formula III may be prepared by conventional methods, as shown in The Journal of the Society of Organic Chemistry, Japan, vol. 20, 64 (1962).
  • the derivative may be prepared by reacting 2 mols of cyanuric chloride with one mole .of a derivative of 4,4'-diaminostilbene-2,2-disulfonate represented by the general formula l wherein R and M are as set forth above, at a temperature of about C. to C.
  • the compound thus obtained is reacted with 2 mols of a nucleophilic agent illustrated by the formula HR wherein R is as set forth above, at a temperature of from about 0 to 20 C.
  • R R, Y, and Z' in the repeating unit (I) or (H) of the high molecular weight compound of this invention are as follows: R and R may be, for example: H, -CH 2 5 3 T, 2 a)2 -CH CH OH, -CH CH CH OH, CH CH 0CH CH CH OCH --CH -SO M' (where M represents H, Na, K or NH (CH SO M, -(CH SO M', and the like.
  • R may be for example:
  • a solution of 14.7 parts by weight of cyanuric chloride in 80 parts of acetone is dispersed in a slurry of 240 parts by Weight of ice water, and the dispersion is maintained at about 0-3 C.
  • To the dispersion there is added dropwise 16.5 parts of sodium 4,4'-diaminostilbene-2,2'-disulfonate as a aqueous solution.
  • hydrochloric acid is formed in the system, and an aqueous solution of sodium carbonate is added dropwise (4.2 parts by weight sodium carbonate and 50 parts by weight water) so that the pH of the system is in the range of 4-5.
  • the system is, thereafter, stirred for about 30 minutes at about 0-5 0., and 7.5 parts of aniline is further added to the reaction mixture. Thereafter, the temperature of the system is increased to 20 C. and an aqueous solution of sodium carbonate (4.2 parts by weight sodium carbonate and 60 parts by weight water) is added gradually to the system.
  • sodium carbonate 4.2 parts by weight sodium carbonate and 60 parts by weight water
  • the compound thus obtained is soluble in a dimethylformamide-water 1:1 solvent, and the intrinsic viscosity of the compound in the same solvent is 0.32 at 30.0 C.
  • ultraviolet absorbents which may be used in the present invention are as follows:
  • CAHB (t) o dnzomon Proportions of high molecular weight fluoroscent'brightening agent which may be employed in the printing papers brightening agent of this invention range from 05-10 mg./ 100 cm. and those of the ultraviolet absorbent range from 2-20 mg./100 cm. v p
  • the fluorescent brightening agent may be added to the system by either the direct or the'indirect method as set forth above. I i
  • the fluorescent brightening agents of this invention when employed, it is possible to incorporate them in the uppermost layer without incurring such disadvantages. Hence the fluorescent brightening agents of this invention may be incorporated in the uppermost layer to be effectively utilized as an ultraviolet absorbent.
  • the high molecular weight compound of this invention may be incorporatedin any layer to effect ultraviolet preventing and fluorescent brightening action.
  • photographic emulsion in this application is defined to mean the usual gelatino silver halide light sensitive emulsions, but synthetic resins such as polyvinyl alcohol and polyvinyl acetate may be effectively employed as protective colloids for the photographic emulsion, in addition to gelatin, in this invention.
  • the order ofthe photographic layers, as well as the number of the layers, may be varied as is well known in the art.
  • the "ultraviolet absorbent of this invention may be incorporated in any layer except the protective, or uppermostlayei'.
  • the fluorescent brightening agents of this invention may be agent of this invention was incorporated in the uppermost incorporated either in the layer containing the ultraviolet layer, the use of a whitening procedure for the baryta absorbent or in a layer positioned at the side of the ultralayer was unnecessary.
  • the coupler was added as an aqueous alkaline solution brightening agent and the ultraviolet absorbent, although the reof. Thereafter a ecu-sensitive silver chlorobromrde t will be understood that the rnventlon shall not be 11memulsion containing f (3 sulfo 4 phenoxy) 3 stearoy1 5 thereby pyrazolone as a magenta coupler was applied to the blue- EXAMPLE 1 sensitive layer.
  • An ultraviolet absorbent one of the Com- Compound 1, supra, was employed as the high molecular PP -23, Supra, Was ⁇ lispersed y emulsification in weight fluorescent brightening agent, and the effect thereof flf P f and the fllspersion was added to a Was measured A color photographic paper con.
  • ThlS protective layer was formed by adding coupler, an ultraviolet absorption layer containing Com- Slowly a 4% dlmethyl fofmamlde-wfltel Solution of 0116 pound 17, supra, as the ultraviolet absorbent, a red-sensiof the compoflnds 1714, Supra, as a g molecular W g tive emulsion layer containing N-n-octadecyl-1-hydroxy-4- fluorescent brlghtenlng agent Compound 24 sulfo-Z-naphthamide as the cyan coupler, and a protective 25 mg the P f9rmlllas as Shown below, well known layer, in this order, was prepared and designated 1 fluorescent bnghtenlng agent, to an aqueous gelatm soluphotographic printing paper addition, a photo tron and applying the resulting mixture in a thickness of graphic color printing paper having the same photographic 5 lug/100 followed y y layers as above in the same order, but containing
  • R and R are each a member selected from the group consisting of a hydrogen atom, an alkyl group having 1-12 carbon atoms, a hydroxyalkyl group having 1-12 carbon atoms, a sulfoalkyl group, an alkali metal salt of said sulfoalkyl group, an ammonium salt of said sulfoal kyl group, a carboxyalkyl group, an alkali metal salt of said carboxyalkyl group, an ammonium salt of said carboxyalkyl group, an alkyl group, an aryl group having 6-18 carbon atoms, a hydroxyl derivative of said aryl group, a carboxyl derivative of said aryl group, a sulfonic acid derivative of said aryl group, an alkali metal salt of each said derivative, an ammonium salt of such said derivative, a cycloalkyl group havingZ-IO carbon 1 35 atoms, and a substituted cycloalkyl group;
  • A
  • said ultraviolet absorbent is a member selected from the group consisting of a benzotriazole, a benozophenone and a thiazolidone.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US790846A 1968-01-12 1969-01-13 Color photographic printing paper Expired - Lifetime US3676139A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP43001669A JPS4821288B1 (en)) 1968-01-12 1968-01-12

Publications (1)

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US3676139A true US3676139A (en) 1972-07-11

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US (1) US3676139A (en))
JP (1) JPS4821288B1 (en))
BE (1) BE726603A (en))
DE (1) DE1901443A1 (en))
FR (1) FR2000186A1 (en))
GB (1) GB1239732A (en))
NL (1) NL6900374A (en))

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2422087A1 (de) * 1973-05-07 1974-11-14 Eastman Kodak Co Verfahren zum schuetzen organischer verbindungen mit mindestens einer farbigen oder fluoreszierenden chromophoren gruppe vor der einwirkung sichtbarer oder ultravioletter strahlung
EP0024380A1 (en) * 1979-08-21 1981-03-04 Ciba-Geigy Ag Optical brightening agents, process for their production and photographic materials which contain these brightening agents
US4468341A (en) * 1983-10-27 1984-08-28 Ciba-Geigy Corporation Stable purified aqueous solutions of fluorescent whitening agent
US5110717A (en) * 1990-12-17 1992-05-05 Eastman Kodak Company Stability improvement of amorphous particle dispersions

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH529815A (de) * 1970-06-19 1972-10-31 Ciba Geigy Ag Verwendung von 2-(2'Hydroxyphenyl)-benztriazolverbindungen als Lichtschutzmittel
JPS49142877U (en)) * 1973-04-05 1974-12-10
DE3618373A1 (de) * 1986-05-31 1987-12-03 Basf Ag Lichtempfindliches aufzeichnungselement

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2422087A1 (de) * 1973-05-07 1974-11-14 Eastman Kodak Co Verfahren zum schuetzen organischer verbindungen mit mindestens einer farbigen oder fluoreszierenden chromophoren gruppe vor der einwirkung sichtbarer oder ultravioletter strahlung
EP0024380A1 (en) * 1979-08-21 1981-03-04 Ciba-Geigy Ag Optical brightening agents, process for their production and photographic materials which contain these brightening agents
US4336326A (en) * 1979-08-21 1982-06-22 Ciba-Geigy Ag Optical brightening agents and photographic materials which contain these brightening agents
US4468341A (en) * 1983-10-27 1984-08-28 Ciba-Geigy Corporation Stable purified aqueous solutions of fluorescent whitening agent
US5110717A (en) * 1990-12-17 1992-05-05 Eastman Kodak Company Stability improvement of amorphous particle dispersions

Also Published As

Publication number Publication date
DE1901443A1 (de) 1969-08-28
NL6900374A (en)) 1969-07-15
JPS4821288B1 (en)) 1973-06-27
BE726603A (en)) 1969-06-16
GB1239732A (en)) 1971-07-21
FR2000186A1 (en)) 1969-08-29

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