EP0785465A1 - Greffage moléculaire de durcisseurs réactifs vis à vis carboxyl sur polyesters prétraités avec une source d'énergie pour promouvoir l'adhésion de couches - Google Patents

Greffage moléculaire de durcisseurs réactifs vis à vis carboxyl sur polyesters prétraités avec une source d'énergie pour promouvoir l'adhésion de couches Download PDF

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Publication number
EP0785465A1
EP0785465A1 EP97200037A EP97200037A EP0785465A1 EP 0785465 A1 EP0785465 A1 EP 0785465A1 EP 97200037 A EP97200037 A EP 97200037A EP 97200037 A EP97200037 A EP 97200037A EP 0785465 A1 EP0785465 A1 EP 0785465A1
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EP
European Patent Office
Prior art keywords
hardener
compounds
gelatin
support
coating
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.)
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Application number
EP97200037A
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German (de)
English (en)
Inventor
Jeremy M. c/o Eastman Kodak Company Grace
Louis J. c/o EASTMAN KODAK COMPANY Gerenser
Richard A. c/o Eastman Kodak Company Castle
Janglin C/O Eastman Kodak Company Chen
Edgar E. c/o Eastman Kodak Company Riecke
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.)
Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0785465A1 publication Critical patent/EP0785465A1/fr
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    • 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
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/915—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means using mechanical or physical means therefor, e.g. corona
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners

Definitions

  • the present invention relates to the manufacture of photosensitive materials. More specifically, the present invention relates to polyester material which has been subjected to energetic treatment and a thin layer of hardener grafted thereon. In addition, the present invention relates to a gelatin grafted layer, in which a mixture of hardener and gelatin is grafted to the energetically treated polyester.
  • USSN 08/588,765 entitled, MOLECULAR GRAFTING OF HARDENER/GELATIN BLENDS TO ENERGETICALLY TREATED POLYESTERS TO PROMOTE ADHESION OF LAYERS filed concurrently herewith discloses an improvement over USSN 08/415,826 by use of hardener/gelatin blends and is also specific to amine reactive hardeners and the appropriate energetic treatment chemistry.
  • amine reactive hardeners which may present health and safety issues are needed. Furthermore, process latitude in effecting the surface treatment is desirable.
  • the present invention extends the technology previously disclosed to carboxyl reactive hardeners and energetic treatment chemistry appropriate to the carboxyl reactive chemistry. This chemistry affords safer candidates for hardener and alternatives for treatment technology.
  • the present invention comprises a method of coating a polyester support which includes passing a surface of the polyester support through an energetic treatment to produce carboxyl groups on the surface.
  • the surface of the polyester support is then coated with a carboxyl reactive hardener solution.
  • the coated support is then dried.
  • the surface of the support is then coated with a photographic emulsion.
  • the photographic emulsion can contain silver halide, or other photosensitive materials.
  • carboxyl reactive hardeners are hydrolytically unstable. Hence, it is not obvious that this approach would produce good adhesion.
  • An alternative method of coating comprises passing a surface of the polyester support through an energetic treatment which produces carboxyl groups on the surface.
  • the surface of the polyester support is then coated with a combination of carboxyl reactive hardener and gelatin in solution.
  • the coated support is then dried.
  • the surface of the support is then coated with a photographic emulsion.
  • the difficulty with blending hardener and gelatin is well demonstrated by Work, III et al (U.S. Patent 4,241,169 issued 23 December 1980). Work, III et al find that hardener/gelatin blends do not produce good adhesion unless a water soluble polyester is added to the coating solution.
  • the difficulty encountered by Work, III et al may arise from an inappropriate match of the surface chemistry of the treated support with the hardener employed.
  • the hardener is selected from the group consisting of bis(pyridylium)ethers as described in US 4,877,724, imidazolopyridinium compounds and pyrazolopyridmium compounds as described in US 5,236,822, carbamoylpyridinium compounds as described in US 4,063,952, carbamoyloxypyrdinium compounds as described in US 4,055,427, chlorotriazines as described in US 4,216,108, succinimidyloxyformamidiniums as described in US 4,612,280, chloroformamidiniums as described in US 4,673,632, alkylsulfonyloxysuccinimides as described in U.S. 4,111,926.
  • the present invention also includes a film element comprising a polyester support having a surface which has been exposed to an energetic treatment.
  • a coating of carboxyl reactive hardener which is selected from the group consisting of bis(pyridylium)ethers, imidazolopyridinium compounds, pyrazolopyridinium compounds, carbamoylpyridinium compounds, carbamoyloxypyridinium compounds, chlorotriazines, succinimidyloxyformamidiniums, chloroformamidiniums, alkylsulfonyloxysuccinimides is grafted to the surface of the polyester support. Finally, a photographic emulsion is applied to the treated and coated surface of the polyester support.
  • a further embodiment of the present invention includes a film element which comprises a polyester support having a surface which has been exposed to an energetic treatment.
  • Figure 1 shows a film element of the present invention.
  • Traditional subbing technology represents an adhesive layer approach to solving an interfacial adhesion problem.
  • some layer or pair of layers is coated onto a polyester support, typically polyethylene naphthalate (PEN) or polyethylene terephthalate (PET), in order to create a surface to which the desired functional layers,(e.g., photographic emulsions) will adhere.
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • the interaction of the subbing layers with the polyester or functional layers can be rather complex, and success hinges on the ability of the aqueous subbing layer to penetrate the polyester surface.
  • by appropriately bonding hardener molecules directly to an energetically treated surface it is possible to create a very thin layer that can interact readily with the coated photographic emulsion layer to produce excellent adhesion.
  • Typical energetic treatment include electrical discharge treatment, UV treatment, plasma treatment, electron-beam treatment, laser treatment, corona treatment and glow discharge treatment.
  • USSN 08/415,826 discloses an invention that includes exposing a polyester support to an energetic treatment that produces amine groups on the surface of the polyester support, coating the treated support with a dilute solution of hardener and appropriate solvent (e.g. water, or organic solvent), and drying the coated support. The hardener coated polyester support is then ready for photographic emulsion coating.
  • a dilute solution of hardener and appropriate solvent e.g. water, or organic solvent
  • USSN 08/588,765 filed concurrently herewith discloses an invention that includes exposing a polyester support to an energetic treatment that produces amine groups on the surface of the polyester support, coating the treated support with a dilute solution of hardener/gelatin blend and appropriate solvent (e.g. water, or organic solvent), and drying the coated support.
  • a dilute solution of hardener/gelatin blend and appropriate solvent e.g. water, or organic solvent
  • the present invention includes exposing a polyester support to an energetic treatment that produces carboxyl groups on the surface of the polyester support, coating the treated support with a dilute solution of hardener and appropriate solvent (e.g. water, or organic solvent), and drying the coated support.
  • the hardener coated polyester support is then ready for photographic emulsion coating.
  • the preferred hardeners include carboxyl reactive hardeners bis(pyridylium)ethers, imidazolopyridinium compounds, pyrazolopyridinium compounds, carbamoylpyridinium compounds, carbamoyloxypyridinium compounds, chlorotriazines, succinimidyloxyformamidiniums, chloroformamidiniums, and alkylsulfonyloxysuccinimides.
  • the present invention also includes exposing a polyester support to an energetic treatment that produces carboxyl groups on the surface of the polyester support, coating the treated support with a blend of carboxyl reactive hardener and gelatin in solvent (e.g. water, or organic solvent), and drying the coated support.
  • solvent e.g. water, or organic solvent
  • the preferred hardeners include carboxyl reactive hardeners bis(pyridylium)ethers, imidazolopyridinium compounds, pyrazolopyridinium compounds, carbamoylpyridinium compounds, carbamoyloxypyridinium compounds, chlorotriazines, succinimidyloxyformamidiniums, chloroformamidiniums, and alkylsulfonyloxysuccinimides.
  • plasma treated PEN polyethylene naphthalate coated with a dilute solution of bis(N-methyl-2-pyridylium tetrafluoroborate) ether (PD9) in water and then coated with a representative photographic emulsion. Additional examples discussed below are for plasma treated PEN coated with a dilute blend of PD9 and gelatin and then coated with a representative photographic emulsion.
  • the plasma treatments were carried out in a vacuum chamber equipped with a web drive. A controlled gas pressure was established in the electrode region of the chamber, and an AC high voltage was applied to the electrode.
  • the polyester support was conveyed through the resulting plasma and was then wound onto a take-up spindle.
  • the treated support was then removed from the chamber and was coated with a water/hardener solution or a water/hardener/gelatin solution.
  • the aqueous coated polyester support was then conveyed through a drying region and wound onto a take-up spindle.
  • a representative photographic emulsion was then coated onto the plasma treated, hardener coated polyester support.
  • FIG 1 shows the film element 10 produced by the process of the present invention.
  • the film element 10 includes a polyester support 12.
  • the polyester support is typically PEN or PET.
  • a backing layer 14 for a variety of functions such as magnetic recording, antistatic protection, lubricity, antiabrasion, antihalation and the like can be included on the backside of the support 12.
  • On the topside of the support 12 is grafted a monolayer 15 of hardener molecules subsequent to oxygen plasma treatment of the support or a gelatin grafted layer (hardener/gelatin blend) 15 subsequent to oxygen plasma treatment.
  • a photographic emulsion layer 17 adheres to the hardener-containing layer 15.
  • the present invention also includes the polyester support having either a monolayer of hardener molecules grafted to the support or a gelatin grafted layer formed from the reaction of hardener molecules with both the treated support and the gelatin.
  • pressures may be in the range of 0.02 to 2 Torr and plasma powers and web speeds may be set to deliver treatment doses from about 0.1 to 4.0 J/cm 2 .
  • the gas pressures ranged from 0.05 to 0.15 Torr; powers ranged from 150 to 600 watts, and the web speeds ranged from approximately 5.1 to 25.4 cm/s, yielding treatment doses in the range of 0.18 to 3.6 J/cm 2 .
  • hardener (PD9) concentrations ranged from 0.005 to 0.18% by weight.
  • the hardener solution was delivered at a wet coverage of approximately 0.22 cc/dm 2 , resulting in hardener levels of 0.011 to 0.39 mg/dm 2 .
  • the hardener/gelatin solution was delivered at wet coverages ranging from 0.054 cc/dm 2 to 0.43 cc/dm 2 , to obtain respective hardener and gelatin dry coverages in the range 0.032 to 0.32 mg/dm 2 and 0.538 to 5.38 mg/dm 2 .
  • Saponin was added at a level of 0.01% by weight of solution in all cases.
  • polyester support was dried at 93°C for 5 minutes as it passed through the coating apparatus.
  • the plasma treated PD9 coated polyester support was then coated with a representative photographic emulsion.
  • the emulsion was coated 4 days after the PD9 or PD9/gelatin blend was coated. Samples were taken from this roll and incubated for 24 hours at 32°C and 50% relative humidity (32/50). Am additional set of samples was kept at 21 °C and 50% relative humidity for 10 days (21/50).
  • the hardener (PD9) coverage can be adjusted to give excellent adhesion for the samples kept in 32/50 conditions.
  • the adhesion for samples kept at 21/50 conditions is not excellent, but it clearly improves with PD9 coverage.
  • the plasma condition B referred to in Table I is as follows: oxygen plasma at a pressure of 0. 1 Torr, a power of 150 W, and a web speed of 8.5 cm/s.
  • Table II provides examples of sensitivity to keeping conditions (and treatment power) for runs made by coating the emulsion directly to the glow discharge treated support.
  • the treatment gas was oxygen
  • the pressure was 0. 1 Torr
  • the web speed was 8.5 cm/s.
  • coating under some treatment conditions exhibited 0 - 1 % removal in the wet adhesion tests when tested after 10 day keeping at 21°C and 50% relative humidity, but when the samples from the same coating events were incubated for 24 hours at 32°C and 50% relative humidity prior to testing, they exhibited 99% removal in the wet adhesion test.
  • the plasma conditions listed in Table III are as follows.
  • preferred conditions are obtained from combinations of hardener to gelatin ratio, coated solids, and plasma treatment conditions within the limits disclosed herein. It is preferred to use combinations including plasma conditions from 0.18 to 3.6 J/cm 2 , hardener/gelatin ratios from 0.006 to 0.6 and coated solids from 0.57 to 5.7 mg/dm 2 .
  • plasma conditions from 0.18 to 3.6 J/cm 2
  • hardener/gelatin ratios from 0.006 to 0.6
  • coated solids 0.57 to 5.7 mg/dm 2 .
  • run C7 exhibited excellent adhesion performance, despite the high gelatin coverage.
  • the treatment conditions, hardener to gelatin ratio, and coverage are highly interactive to produce the desired adhesion.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
EP97200037A 1996-01-19 1997-01-08 Greffage moléculaire de durcisseurs réactifs vis à vis carboxyl sur polyesters prétraités avec une source d'énergie pour promouvoir l'adhésion de couches Withdrawn EP0785465A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US58904696A 1996-01-19 1996-01-19
US589046 2000-06-06

Publications (1)

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EP0785465A1 true EP0785465A1 (fr) 1997-07-23

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EP (1) EP0785465A1 (fr)
JP (1) JPH09197618A (fr)
CA (1) CA2193040A1 (fr)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE669393A (fr) * 1964-03-17 1965-12-31
US4055427A (en) 1974-02-23 1977-10-25 Agfa-Gevaert Aktiengesellschaft Process of hardening a silver halide photographic material with a 1-carbamoyloxypyridinium salt
US4063952A (en) 1974-08-17 1977-12-20 Agfa-Gevaert Aktiengesellschaft Process for hardening silver halide containing photographic layers with sulpho- or sulphoalkyl-substituted carbamoyl pyridinium compounds
US4111926A (en) 1976-02-02 1978-09-05 Fuji Photo Film Co., Ltd. Hardening agent for gelatin and method for hardening gelatin
US4216108A (en) 1977-05-10 1980-08-05 Agfa-Gevaert N.V. Hardening solution for proteinaceous materials
US4241169A (en) 1979-05-21 1980-12-23 E. I. Du Pont De Nemours & Company Gelatin-polyester-aziridine product subbing layer for polyester photographic base
US4612280A (en) 1984-10-24 1986-09-16 Fuji Photo Film Co., Ltd. Hardened gelatin and method for hardening gelatin
US4673632A (en) 1984-04-23 1987-06-16 Fuji Photo Film Co., Ltd. Hardening method for gelatin
US4689359A (en) 1985-08-22 1987-08-25 Eastman Kodak Company Composition formed from gelatin and polymer of vinyl monomer having a primary amine addition salt group
DE3730319A1 (de) * 1987-09-10 1989-03-30 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial
US4877724A (en) 1987-03-05 1989-10-31 Eastman Kodak Company Method and composition for hardening gelatin
US5236822A (en) 1991-10-03 1993-08-17 Eastman Kodak Company Method and composition for hardening gelatin
US5425980A (en) 1994-02-22 1995-06-20 Eastman Kodak Company Use of glow discharge treatment to promote adhesion of aqueous coats to substrate

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE669393A (fr) * 1964-03-17 1965-12-31
US4055427A (en) 1974-02-23 1977-10-25 Agfa-Gevaert Aktiengesellschaft Process of hardening a silver halide photographic material with a 1-carbamoyloxypyridinium salt
US4063952A (en) 1974-08-17 1977-12-20 Agfa-Gevaert Aktiengesellschaft Process for hardening silver halide containing photographic layers with sulpho- or sulphoalkyl-substituted carbamoyl pyridinium compounds
US4111926A (en) 1976-02-02 1978-09-05 Fuji Photo Film Co., Ltd. Hardening agent for gelatin and method for hardening gelatin
US4216108A (en) 1977-05-10 1980-08-05 Agfa-Gevaert N.V. Hardening solution for proteinaceous materials
US4241169A (en) 1979-05-21 1980-12-23 E. I. Du Pont De Nemours & Company Gelatin-polyester-aziridine product subbing layer for polyester photographic base
US4673632A (en) 1984-04-23 1987-06-16 Fuji Photo Film Co., Ltd. Hardening method for gelatin
US4612280A (en) 1984-10-24 1986-09-16 Fuji Photo Film Co., Ltd. Hardened gelatin and method for hardening gelatin
US4689359A (en) 1985-08-22 1987-08-25 Eastman Kodak Company Composition formed from gelatin and polymer of vinyl monomer having a primary amine addition salt group
US4695532A (en) 1985-08-22 1987-09-22 Eastman Kodak Company Photographic silver halide element containing new adhesion promoting polymeric materials and polyester support
US4877724A (en) 1987-03-05 1989-10-31 Eastman Kodak Company Method and composition for hardening gelatin
DE3730319A1 (de) * 1987-09-10 1989-03-30 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial
US5236822A (en) 1991-10-03 1993-08-17 Eastman Kodak Company Method and composition for hardening gelatin
US5425980A (en) 1994-02-22 1995-06-20 Eastman Kodak Company Use of glow discharge treatment to promote adhesion of aqueous coats to substrate

Also Published As

Publication number Publication date
CA2193040A1 (fr) 1997-07-20
JPH09197618A (ja) 1997-07-31

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