EP0849628A1 - Polyester photographic film support - Google Patents
Polyester photographic film support Download PDFInfo
- Publication number
- EP0849628A1 EP0849628A1 EP97203830A EP97203830A EP0849628A1 EP 0849628 A1 EP0849628 A1 EP 0849628A1 EP 97203830 A EP97203830 A EP 97203830A EP 97203830 A EP97203830 A EP 97203830A EP 0849628 A1 EP0849628 A1 EP 0849628A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gelatin
- film base
- polymer
- base according
- subbing 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.)
- Withdrawn
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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
- G03C1/91—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
- G03C1/76—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
- G03C1/93—Macromolecular substances therefor
Definitions
- This invention relates to a method for modifying the surface properties of polymer substrates. More particularly, the present invention relates to applying photoreactive polymers to an irradiated polyester substrate. After irradiation of the polyester substrate the photoattachable polymer is applied and subsequently coated with a gelatin subbing layer.
- a gelatin layer containing the photographic chemicals is deposited onto a polymer film which provides support and mechanical integrity to the final product.
- Cellulosic or polyester supports such as poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate)(PEN), are typically employed. Polyesters have many desirable properties including high mechanical strength, dimensional stability, durability, optical clarity, and resistance to attack by most chemicals. However, the chemical inertness of PET and PEN also results in difficulty in obtaining acceptable adhesion of polar materials, such as gelatin-based photographic emulsions, to PET and PEN substrates.
- intermediate anchoring layers are applied to the polyester film support prior to the orientation and crystallization of the support.
- Adhesion of the anchoring, or subbing, layer is promoted by a variety of methods, including the used of chlorine-containing copolymers, the application of the adhesive layer prior to the orientation and heat setting or crystallization of the polyester, and the addition of organic solvents which attack the polyester film surface.
- a subsequent gelatin-containing layer is often required prior to photographic emulsion coating.
- Disadvantages of the above described approaches include the requirement of organic solvents, such as chlorophenol and resorcinol, which pose an environmental problem, and the use of chlorinated materials which degrade at elevated temperature and therefore cannot be recycled in the polyester extrusion process, causing economic and environmental problems.
- organic solvents such as chlorophenol and resorcinol
- polymer surface treatments such as corona discharge (CDT), ultraviolet (UV), and glow discharge (GDT) treatments, are used to promote adhesion through introduction of specific functional groups which interact with subsequent coating layers as described in US Patent Nos. 4,695,532, 4,689,359, 4,933,267, 5,098,818, and 5,407,791.
- CDT provides sufficient adhesion improvements for many subbing applications, as demonstrated in US Patent Nos. 4,695,532 and 5,102,734, and is performed at atmospheric conditions so is inexpensive relative to other surface treatment methods.
- GDT provides more dramatic surface modification and rearrangement which is often necessary to obtain the desired adhesion.
- GDT is a vacuum technique so is quite expensive, requiring either very large vacuum chambers (for batch treatment) or expensive interlocks for air-to-air in-line treatment.
- UV treatment is preferred because it provides the necessary surface modification and can be conducted at atmospheric conditions so is less expensive than GDT.
- UV treatment as an approach to polyester surface treatment, is referred to in, for example, US Patent Nos. 5,407,791, 3,892,575, 4,824,699, and 5,098,818.
- a gel sub with high chlorophenol levels was used to obtain adhesion to UV treated PEN.
- a polymer/gelatin blend was grafted to polyester using UV radiation. Grafting of monomers to polymer surfaces for surface modification and adhesion improvement (not for photographic applications) is described in US Patent Nos. 4,267,202, 5,209,849, 3,977,954, 4,278,703, JP Kokoku Patent Hei[1991]-6225, and EP Patent Application 521 605 A2.
- the present invention is a photographic film base including a polyester support. Superposed on the polyester support is a polymer layer superposed having a photoreactive moiety and a gelatin reactive moiety. A gelatin subbing layer is attached to the polymer layer.
- the present invention includes a photographic element having at least one light sensitive silver halide emulsion layer on the described photograpic film base.
- the present invention also includes a process for producing a film base which includes providing a polyester support, exposing the polyester support to an energy treatment, applying a polymer coating to the polyester support, the polymer coating having a photoreactive moiety and a gelatin reactive moiety, and applying a gelatin subbing layer to the polymer coating.
- the present invention provides a silver halide photographic element which exhibits excellent adhesion between an emulsion layer and an oriented polyester support.
- the present invention contemplates a polyester photographic support having; a polymer layer containing a photoreactive moiety and gelatin reactive moiety; and a gelatin layer attached to the polymer layer. Further the present invention contemplates photographic elements having at least one light-sensitive silver halide emulsion layer on the exposed surface of the gelatin layer. In addition, the present invention contemplates a method of making a photographic support and element wherein radiation treatment is used to modify the surface of polyester support, followed by coating with a photoreactive, gelatin reactive polymer and a gelatin layer. The radiation treatment can be conducted before coating the polymer layer, after coating the polymer layer, or both before and after coating the polymer layer.
- polyester may be employed in the practice of this invention as the photographic film support, including polyethylene terephthalate, polyethylene napthalate, polyethylene isothalate, polybutalene terephthalate, polyethylene cocyclohexane dimethylterephthalate, polyethanol codimethanol cyclohexane napthalate, polycarbonates, copolymers and blends thereof and the like.
- any suitable radiation treatment for the polyester support may be employed such as, for example, corona discharge treatment, flame treatment, high energy visible light treatment, ultraviolet light, high frequency wave treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.
- Ultraviolet light is the preferred radiation source. Ultraviolet radiation in the range of 170 nm to 400 nm is most preferred. This can be obtained by utilizing a quartz UV lamp.
- a preferred intensity of UV radiation is from 100 to 5000 mJ/cm per pass under the lamp at 30 ft/min, and most preferably from 800 to 2400 mJ/cm per pass under the lamp at 30 ft/min as measured by a UVICURE high energy UV integrating radiometer produced by Electronic Instrumentation and Technology, Inc., Sterling, VA.
- the number of passes under the UV lamp is in the range if 1 to 10, most preferrably between 3 and 6.
- Photo-reactive monomers incorporated into the polymer of the subbing layer include any monomer with an abstractable hydrogen.
- Photo-reactive monomers of this invention include, but are not limited to, vinylidene chloride, vinyl chloride, styrene, butadiene, acrylonitrile, acrylates, hydroxy esters, urethanes, ureas, and vinyl ethers.
- Gelatin-reactive monomers incorporated into the polymer include all monomers containing carboxylic acid, anhydride, or primary amine groups. Such monomers include, but are not limited to, acrylic acid, itaconic acid, maleic anhydride, itaconic anhydride, acrylamide, methacrylamide, and aminoethyl esters.
- polymers which are suitable for this photo-reactive layer include a terpolymer of vinylidene chloride, acrylonitrile, and acrylic acid (VNA); a terpolymer of vinylidene chloride, methylacrylate, and itaconic acid (VMI); and a terpolymer of butylmethacrylate, 2-methyl-2-aminoethyl ester of propenoic acid, and 2-methyl-2-hydroxyethyl ester of propenoic acid (BAmH).
- VNA vinylidene chloride, acrylonitrile, and acrylic acid
- VMI vinylidene chloride, methylacrylate, and itaconic acid
- BAmH 2-methyl-2-aminoethyl ester of propenoic acid
- the polyester support is exposed to radiation, preferable UV radiation in the range of 170 nm to 400 nm.
- radiation preferable UV radiation in the range of 170 nm to 400 nm.
- a preferred intensity of UV irradiation ranges per pass under the lamp is from 50 to 5000 mJ/cm 2 , and more preferably from 800 mJ/cm 2 to 2400 mJ/cm 2 per pass, as measured by a UVICURE high energy UV integrating radiometer (UV A spectrum, 320 - 390 nm) produced by Electronic Instrumentation and Technology, Inc., Sterling, VA. 1-10 passes under the lamp at 30 ft/min are used to obtain adhesion, preferrably between 3 and 6 passes at 30 ft/min.
- the treatment may be conducted before coating the polymer, after coating the polymer layer, or both before and after coating the polymer layer.
- the polymer typically a latex polymer
- a suitable surfactant to obtain sufficient wetting of the coating.
- surfactants could include, but are not limited to, sodium lauryl sulfonate, dioctyl sodium sulfosuccinate, sodium octylphenylpolyether sulfonate, saponin and the like.
- the polymer is typically coated at solution concentrations between 0.5 and 20% by weight, to obtain a dry coverage of from 0.2 to 10 mg/dm2, preferably between 0.5 and 5 mg/dm2.
- the coating is then dried at an appropriate temperature to remove the water or solvent and coalesce the latex polymer if necessary.
- Typical conditions are in the temperature range of 50°C to 120°C, preferably between 60°C and 100°C, for times ranging between 10 s and 20 min, preferable between 1 min and 5 min.
- Polymer coatings described above may contain photosensitizers including, but not limited to, ⁇ -diketones as described in US patent 3,933,607 and free radical producers such as benzoin ethers and azobisisobutyronitrile, triplet state sensitizers such as benzophenone, photo-redox photosensitizers, and dye-reduction photosensitizers, as described in US Patent 4,267,202.
- photosensitizers including, but not limited to, ⁇ -diketones as described in US patent 3,933,607 and free radical producers such as benzoin ethers and azobisisobutyronitrile, triplet state sensitizers such as benzophenone, photo-redox photosensitizers, and dye-reduction photosensitizers, as described in US Patent 4,267,202.
- a gelatin-based subbing layer is then coated over the polymer layer.
- the gelatin-based layer is preferably a hydrophilic colloid layer in which gelatin or modified gelatin is contained as a main ingredient.
- the gelatin-based layer is typically coated from 0.5-2% solutions to obtain a dry coverage of 0.5 - 5 mg/dm 2 .
- the gelatin-based layer may contain an antistatic agent, a matting agent, a surface active agent, a crosslinking agent, and/or a dye.
- the gelatin-based is then dried at a temperature ranging from 80°C to 140°C, preferably between 100°C and 140°C for a period of 10 s to 10 min, preferably between 1 min and 5 min.
- the polymer and gelatin subbing layer can be coated by any suitable coating process well known in the art, for example, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, relief edge knife coating, gravure coating, or extrusion, utilizing a hopper as described in U.S. Patent 2,681,294.
- a suitable coating process for example, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, relief edge knife coating, gravure coating, or extrusion, utilizing a hopper as described in U.S. Patent 2,681,294.
- two or more layers can be applied sequentially or simultaneously according to the processes described in U.S. Patents 2,761,791; 3,508,947; 2,941,898 and 3,526,528.
- the polymer and gelatin subbing layer may be applied to the polyester at any suitable point in the preparation of the polyester.
- the polymer layer and gelatin subbing layer may be applied after extrusion of the polyester into a sheet before any orientation of the polymer sheet is carried out, it may be applied after orientation in a first direction such as, for example, in the machine direction or it may be applied after the biaxial orientation is completed, for example, should the polyester first be subjected to a machine direction stretching and subsequently to a transverse direction stretching, the polymer layer or gelatin subbing layer may be applied at any point in the procedure.
- the subbed support is then coated with a photographic emulsion.
- the layer is coated with a photosensitive layer or layers that contain photographic silver halide emulsion.
- the invention is applicable to both negative and reversal silver halide elements.
- the emulsion layers as taught in U.S. Patent 5,236,817, especially Examples 16 and 21 are particularly suitable. Any of the known silver halide emulsion layers, such as those described in Research Disclosure , Vol. 176, December 1978, Item 17643 and Research Disclosure Vol. 225, January 1983, Item 22534 are useful in preparing photographic elements in accordance with this invention.
- one or more layers comprising a dispersion of silver halide crystals in an aqueous solution of gelatin are applied to the substrate subsequent to the gelatin based subbing layer.
- the coating process can be carried out on a continuously operating machine wherein a single layer or a plurality of layers are applied.
- layers can be coated simultaneously on the composite support film as is described in U.S. Patent Nos. 2,761,791 and 3,508,947. Additional useful coating and drying procedures are described in Research Disclosure , Vol. 176, December 1978, Item 17643.
- Suitable photosensitive image forming layers include those which provide color or black and white images.
- the adhesion of the emulsion coated support is measured as follows:
- the emulsion surface of the green sample (before development) or dry sample (after development) was cross-hatched with a razor at 5 mm intervals to make nine squares.
- An adhesive tape (3M 610 tape) was adhered thereto and rapidly stripped off at a peel angle of 180°. The adhesion was evaluated according to the estimated percent removal of the emulsion.
- a 35 mm x 12.7 cm strip of the coating is soaked at 37.8°C. for 3 min. 15 sec. in Kodak Flexicolor Developer Replenisher.
- the strip is then scored with a pointed stylus tip across the width of the strip and placed in a small trough filled with a developer solution.
- a weighted (900 g) filled natural rubber pad, 3.49 cm diameter, is placed on top. The pad is moved back and forth across the strip 100 times. The amount of emulsion removal is then assessed in units of % removed. The lower the value the better the wet adhesion of the system.
- the sample is run through the standard C41 development process. Dry adhesion is then measured as in the Dry Adhesion Test described above.
- PEN poly(ethylene naphthalate) manufactured by Imperial Chemicals Incorporated
- ICI Imperial Chemicals Incorporated
- the uncoated PEN sample was passed under the lamp three times at a conveyor speed of 30 fpm.
- the lamp was the D bulb (emission from 200 nm to 450 nm, with major output between 350 nm and 390 nm) with an output of 120 W/cm.
- the energy density of one pass under the lamp at 30 fpm is approximately 1.5 J/cm 2 as measured by the UVICURE high energy UV integrating radiometer (UV A spectrum, 320 - 390 nm) described previously.
- UV A spectrum UV A spectrum, 320 - 390 nm
- a photo-reactive, gelatin-reactive polymer of the following formulation was then coated on a room temperature coating block to obtain a total dry coverage of 2 mg/dm 2 :
- Irradiation of 100 mm PEN was conducted using the Fusions F300 curing system described in example 1.
- the uncoated PEN sample was passed under the lamp four times at a conveyor speed of 30 fpm.
- the lamp used was the H+ bulb, which has major emissions between 215 nm and 315 nm, and at 365 nm.
- the energy density of one pass under the lamp at 30 fpm is approximately 50 mJ/cm2 as measured by the UVICURE high energy UV integrating radiometer (UV C spectrum, 240 - 270 nm) described previously.
- a photo-reactive, gelatin-reactive polymer of the following formulation was then coated on a room temperature coating block to obtain a total dry coverage of 6 mg/dm 2 :
- the coated samples was then dried for 3 min at 120°C in a standard convection oven.
- the coated PEN sample was passed under the lamp six times at a conveyor speed of 30 fpm prior to coating and drying the gelatin subbing layer and emulsion layer as described in Ex. 1 (Formulation B).
Abstract
The present invention is a photographic film
base including a polyester support. Superposed on the
polyester support is a polymer layer superposed having
a photoreactive moiety and a gelatin reactive moiety.
A gelatin subbing layer is attached to the polymer
layer. The present invention includes a photographic
element having at least one light sensitive silver
halide emulsion layer on the described photograpic film
base. The present invention also includes a process
for producing a film base which includes providing a
polyester support, exposing the polyester support to an
energy treatment, applying a polymer coating to the
polyester support, the polymer coating having a
photoreactive moiety and a gelatin reactive moiety, and
applying a gelatin subbing layer to the polymer
coating.
Description
This invention relates to a method for
modifying the surface properties of polymer substrates.
More particularly, the present invention relates to
applying photoreactive polymers to an irradiated
polyester substrate. After irradiation of the
polyester substrate the photoattachable polymer is
applied and subsequently coated with a gelatin subbing
layer.
In photographic film manufacture, a gelatin
layer containing the photographic chemicals is
deposited onto a polymer film which provides support
and mechanical integrity to the final product.
Cellulosic or polyester supports, such as poly(ethylene
terephthalate) (PET) and poly(ethylene
naphthalate)(PEN), are typically employed. Polyesters
have many desirable properties including high
mechanical strength, dimensional stability, durability,
optical clarity, and resistance to attack by most
chemicals. However, the chemical inertness of PET and
PEN also results in difficulty in obtaining acceptable
adhesion of polar materials, such as gelatin-based
photographic emulsions, to PET and PEN substrates.
To obtain acceptable adhesion of the light-sensitive
emulsion layer to the support, intermediate
anchoring layers are applied to the polyester film
support prior to the orientation and crystallization of
the support. Adhesion of the anchoring, or subbing,
layer is promoted by a variety of methods, including
the used of chlorine-containing copolymers, the
application of the adhesive layer prior to the
orientation and heat setting or crystallization of the
polyester, and the addition of organic solvents which
attack the polyester film surface. In addition, a
subsequent gelatin-containing layer is often required
prior to photographic emulsion coating.
Disadvantages of the above described
approaches include the requirement of organic solvents,
such as chlorophenol and resorcinol, which pose an
environmental problem, and the use of chlorinated
materials which degrade at elevated temperature and
therefore cannot be recycled in the polyester extrusion
process, causing economic and environmental problems.
In addition, it is often necessary to apply a subbing
layer to a polyester film which is already biaxially
oriented and heat set. It is more difficult to obtain
adhesion to biaxially oriented polyester support as
compared to unoriented polyester. Solvents used to
attack the polyester surface are less effective on the
oriented support. In this case, polymer surface
treatments, such as corona discharge (CDT), ultraviolet
(UV), and glow discharge (GDT) treatments, are used to
promote adhesion through introduction of specific
functional groups which interact with subsequent
coating layers as described in US Patent Nos.
4,695,532, 4,689,359, 4,933,267, 5,098,818, and
5,407,791. CDT provides sufficient adhesion
improvements for many subbing applications, as
demonstrated in US Patent Nos. 4,695,532 and 5,102,734,
and is performed at atmospheric conditions so is
inexpensive relative to other surface treatment
methods. GDT provides more dramatic surface
modification and rearrangement which is often necessary
to obtain the desired adhesion. However, GDT is a
vacuum technique so is quite expensive, requiring
either very large vacuum chambers (for batch treatment)
or expensive interlocks for air-to-air in-line
treatment. UV treatment is preferred because it
provides the necessary surface modification and can be
conducted at atmospheric conditions so is less
expensive than GDT.
UV treatment, as an approach to polyester
surface treatment, is referred to in, for example, US
Patent Nos. 5,407,791, 3,892,575, 4,824,699, and
5,098,818. In US Patent 5,407,791, a gel sub with high
chlorophenol levels was used to obtain adhesion to UV
treated PEN. In US Patent No. 3,892,575, a
polymer/gelatin blend was grafted to polyester using UV
radiation. Grafting of monomers to polymer surfaces
for surface modification and adhesion improvement (not
for photographic applications) is described in US
Patent Nos. 4,267,202, 5,209,849, 3,977,954, 4,278,703,
JP Kokoku Patent Hei[1991]-6225, and EP Patent
Application 521 605 A2.
US patent application No. 08/595,613, filed
on April 19,1996 provides a means for obtaining
excellent adhesion of photographic emulsion to oriented
polyester support, without the need for phenolic
solvents, chlorinated polymers, or expensive GDT
processes. However, the subbing layer contains a
reactive monomer, such as maleic anhydride, which may
be disadvantageous for health an safety reasons.
Additionally, monomeric materials may migrate through
the emulsion layers resulting in sensimetric keeping
problems.
In the present invention, the monomer of U.S.
patent application No. 08/595,613 is replaced with a
photo-attachable polymer, which would not exhibit the
problems described for monomer-containing subbing
materials described.
Thus, there is a continuing need for
polyester photographic film supports to which
subsequently applied layers will readily adhere.
Further, there exists a need to provide a means
for obtaining excellent adhesion of photographic
emulsion to oriented polyester support.
The present invention is a photographic film
base including a polyester support. Superposed on the
polyester support is a polymer layer superposed having
a photoreactive moiety and a gelatin reactive moiety.
A gelatin subbing layer is attached to the polymer
layer. The present invention includes a photographic
element having at least one light sensitive silver
halide emulsion layer on the described photograpic film
base.
The present invention also includes a process
for producing a film base which includes providing a
polyester support, exposing the polyester support to an
energy treatment, applying a polymer coating to the
polyester support, the polymer coating having a
photoreactive moiety and a gelatin reactive moiety, and
applying a gelatin subbing layer to the polymer
coating.
The present invention provides a silver
halide photographic element which exhibits excellent
adhesion between an emulsion layer and an oriented
polyester support.
The present invention contemplates a
polyester photographic support having; a polymer layer
containing a photoreactive moiety and gelatin reactive
moiety; and a gelatin layer attached to the polymer
layer. Further the present invention contemplates
photographic elements having at least one light-sensitive
silver halide emulsion layer on the exposed
surface of the gelatin layer. In addition, the present
invention contemplates a method of making a
photographic support and element wherein radiation
treatment is used to modify the surface of polyester
support, followed by coating with a photoreactive,
gelatin reactive polymer and a gelatin layer. The
radiation treatment can be conducted before coating the
polymer layer, after coating the polymer layer, or both
before and after coating the polymer layer.
Any suitable polyester may be employed in the
practice of this invention as the photographic film
support, including polyethylene terephthalate,
polyethylene napthalate, polyethylene isothalate,
polybutalene terephthalate, polyethylene cocyclohexane
dimethylterephthalate, polyethanol codimethanol
cyclohexane napthalate, polycarbonates, copolymers and
blends thereof and the like.
Any suitable radiation treatment for the
polyester support may be employed such as, for example,
corona discharge treatment, flame treatment, high
energy visible light treatment, ultraviolet light, high
frequency wave treatment, glow discharge treatment,
active plasma treatment, laser treatment and the like.
Ultraviolet light is the preferred radiation source.
Ultraviolet radiation in the range of 170 nm to 400 nm
is most preferred. This can be obtained by utilizing a
quartz UV lamp. A preferred intensity of UV radiation
is from 100 to 5000 mJ/cm per pass under the lamp at
30 ft/min, and most preferably from 800 to 2400 mJ/cm
per pass under the lamp at 30 ft/min as measured by a
UVICURE high energy UV integrating radiometer produced
by Electronic Instrumentation and Technology, Inc.,
Sterling, VA. The number of passes under the UV lamp
is in the range if 1 to 10, most preferrably between 3
and 6.
Photo-reactive monomers incorporated into the
polymer of the subbing layer include any monomer with
an abstractable hydrogen. Photo-reactive monomers of
this invention include, but are not limited to,
vinylidene chloride, vinyl chloride, styrene,
butadiene, acrylonitrile, acrylates, hydroxy esters,
urethanes, ureas, and vinyl ethers. Gelatin-reactive
monomers incorporated into the polymer include all
monomers containing carboxylic acid, anhydride, or
primary amine groups. Such monomers include, but are
not limited to, acrylic acid, itaconic acid, maleic
anhydride, itaconic anhydride, acrylamide,
methacrylamide, and aminoethyl esters. Examples of
polymers which are suitable for this photo-reactive
layer include a terpolymer of vinylidene chloride,
acrylonitrile, and acrylic acid (VNA); a terpolymer of
vinylidene chloride, methylacrylate, and itaconic acid
(VMI); and a terpolymer of butylmethacrylate, 2-methyl-2-aminoethyl
ester of propenoic acid, and 2-methyl-2-hydroxyethyl
ester of propenoic acid (BAmH).
In the invention, the polyester support is
exposed to radiation, preferable UV radiation in the
range of 170 nm to 400 nm. This is obtained using, for
example, a quartz UV lamp. A preferred intensity of UV
irradiation ranges per pass under the lamp is from 50
to 5000 mJ/cm2, and more preferably from 800 mJ/cm2 to
2400 mJ/cm2 per pass, as measured by a UVICURE high
energy UV integrating radiometer (UV A spectrum, 320 -
390 nm) produced by Electronic Instrumentation and
Technology, Inc., Sterling, VA. 1-10 passes under the
lamp at 30 ft/min are used to obtain adhesion,
preferrably between 3 and 6 passes at 30 ft/min. In
addition, the treatment may be conducted before coating
the polymer, after coating the polymer layer, or both
before and after coating the polymer layer.
The polymer, typically a latex polymer, is
then coated onto the radiated support using a suitable
surfactant to obtain sufficient wetting of the coating.
Such surfactants could include, but are not limited to,
sodium lauryl sulfonate, dioctyl sodium sulfosuccinate,
sodium octylphenylpolyether sulfonate, saponin and the
like.
The polymer is typically coated at solution
concentrations between 0.5 and 20% by weight, to obtain
a dry coverage of from 0.2 to 10 mg/dm2, preferably
between 0.5 and 5 mg/dm2. The coating is then dried at
an appropriate temperature to remove the water or
solvent and coalesce the latex polymer if necessary.
Typical conditions are in the temperature range of 50°C
to 120°C, preferably between 60°C and 100°C, for times
ranging between 10 s and 20 min, preferable between 1
min and 5 min.
Polymer coatings described above may contain
photosensitizers including, but not limited to, α-diketones
as described in US patent 3,933,607 and free
radical producers such as benzoin ethers and
azobisisobutyronitrile, triplet state sensitizers such
as benzophenone, photo-redox photosensitizers, and dye-reduction
photosensitizers, as described in US Patent
4,267,202.
A gelatin-based subbing layer is then
coated over the polymer layer. The gelatin-based layer
is preferably a hydrophilic colloid layer in which
gelatin or modified gelatin is contained as a main
ingredient. The gelatin-based layer is typically
coated from 0.5-2% solutions to obtain a dry coverage
of 0.5 - 5 mg/dm2. Additionally, the gelatin-based
layer may contain an antistatic agent, a matting agent,
a surface active agent, a crosslinking agent, and/or a
dye. The gelatin-based is then dried at a temperature
ranging from 80°C to 140°C, preferably between 100°C
and 140°C for a period of 10 s to 10 min, preferably
between 1 min and 5 min.
The polymer and gelatin subbing layer can be
coated by any suitable coating process well known in
the art, for example, dip coating, air knife coating,
curtain coating, roller coating, wire bar coating,
relief edge knife coating, gravure coating, or
extrusion, utilizing a hopper as described in U.S.
Patent 2,681,294. When two or more layers are coated
they can be applied sequentially or simultaneously
according to the processes described in U.S. Patents
2,761,791; 3,508,947; 2,941,898 and 3,526,528.
The polymer and gelatin subbing layer may be
applied to the polyester at any suitable point in the
preparation of the polyester. For example, the polymer
layer and gelatin subbing layer may be applied after
extrusion of the polyester into a sheet before any
orientation of the polymer sheet is carried out, it may
be applied after orientation in a first direction such
as, for example, in the machine direction or it may be
applied after the biaxial orientation is completed, for
example, should the polyester first be subjected to a
machine direction stretching and subsequently to a
transverse direction stretching, the polymer layer or
gelatin subbing layer may be applied at any point in
the procedure.
The subbed support is then coated with a
photographic emulsion. Subsequent to the application
of the gelatin based subbing layer to the polyester
support, the layer is coated with a photosensitive
layer or layers that contain photographic silver halide
emulsion. The invention is applicable to both negative
and reversal silver halide elements. For reversal
films, the emulsion layers as taught in U.S. Patent
5,236,817, especially Examples 16 and 21 are
particularly suitable. Any of the known silver halide
emulsion layers, such as those described in Research
Disclosure, Vol. 176, December 1978, Item 17643 and
Research Disclosure Vol. 225, January 1983, Item 22534
are useful in preparing photographic elements in
accordance with this invention. Generally, one or more
layers comprising a dispersion of silver halide
crystals in an aqueous solution of gelatin are applied
to the substrate subsequent to the gelatin based
subbing layer. The coating process can be carried out
on a continuously operating machine wherein a single
layer or a plurality of layers are applied. For
multicolor elements, layers can be coated
simultaneously on the composite support film as is
described in U.S. Patent Nos. 2,761,791 and 3,508,947.
Additional useful coating and drying procedures are
described in Research Disclosure, Vol. 176, December
1978, Item 17643. Suitable photosensitive image
forming layers include those which provide color or
black and white images.
The invention will be further illustrated by
the following examples. Each of the elements are then
coated with a photographic emulsion containing silver
halide and an image coupler.
The adhesion of the emulsion coated support
is measured as follows:
The emulsion surface of the green sample
(before development) or dry sample (after development)
was cross-hatched with a razor at 5 mm intervals to
make nine squares. An adhesive tape (3M 610 tape) was
adhered thereto and rapidly stripped off at a peel
angle of 180°. The adhesion was evaluated according to
the estimated percent removal of the emulsion.
A 35 mm x 12.7 cm strip of the coating is
soaked at 37.8°C. for 3 min. 15 sec. in Kodak
Flexicolor Developer Replenisher. The strip is then
scored with a pointed stylus tip across the width of
the strip and placed in a small trough filled with a
developer solution. A weighted (900 g) filled natural
rubber pad, 3.49 cm diameter, is placed on top. The
pad is moved back and forth across the strip 100 times.
The amount of emulsion removal is then assessed in
units of % removed. The lower the value the better the
wet adhesion of the system.
The sample is run through the standard C41 development
process. Dry adhesion is then measured as in the Dry
Adhesion Test described above.
Adhesion test results for the following
examples are in Table 1.
Irradiation of 100 mm poly(ethylene
naphthalate) (PEN) manufactured by Imperial Chemicals
Incorporated (ICI) was conducted using the Fusions F300
curing system with model LC-6 benchtop conveyor
(Fusions UV Curing Systems, 7600 Standish Place,
Rockville, MD 20855-2798). The uncoated PEN sample
was passed under the lamp three times at a conveyor
speed of 30 fpm. The lamp was the D bulb (emission
from 200 nm to 450 nm, with major output between 350 nm
and 390 nm) with an output of 120 W/cm. The energy
density of one pass under the lamp at 30 fpm is
approximately 1.5 J/cm2 as measured by the UVICURE high
energy UV integrating radiometer (UV A spectrum, 320 -
390 nm) described previously. A photo-reactive,
gelatin-reactive polymer of the following formulation
was then coated on a room temperature coating block to
obtain a total dry coverage of 2 mg/dm2:
- Component 1:
- 1.0 weight percent BAmH polymer
- Component 2:
- 0.1 weight percent saponin surfactant
- balance:
- deionized water
- Component 1:
- 1.0 weight percent gelatin
- Component 2:
- 0.01 weight percent saponin
- Component 3:
- 0.01 weight percent potassium chromium sulfate
- balance:
- deionized water
Irradiation of 100 mm PEN was conducted using the
Fusions F300 curing system described in example 1. The
uncoated PEN sample was passed under the lamp four
times at a conveyor speed of 30 fpm. The lamp used was
the H+ bulb, which has major emissions between 215 nm
and 315 nm, and at 365 nm. The energy density of one
pass under the lamp at 30 fpm is approximately 50
mJ/cm2 as measured by the UVICURE high energy UV
integrating radiometer (UV C spectrum, 240 - 270 nm)
described previously. A photo-reactive, gelatin-reactive
polymer of the following formulation was then
coated on a room temperature coating block to obtain a
total dry coverage of 6 mg/dm2:
- Component 1:
- 3.0 weight percent VNA polymer
- Component 2:
- 0.1 weight percent saponin surfactant
- balance:
- deionized water
The coated samples was then dried for 3 min
at 120°C in a standard convection oven. The coated PEN
sample was passed under the lamp six times at a
conveyor speed of 30 fpm prior to coating and drying
the gelatin subbing layer and emulsion layer as
described in Ex. 1 (Formulation B).
The procedure in example 2 was repeated, but
the UV irradiation steps were eliminated.
The procedure of Invention Example 2 was
repeated with the following exceptions. The following
polymer formulation was used:
- Component 1:
- 5.0 weight percent VNA polymer
- Component 2:
- 0.1 weight percent saponin surfactant
- Component 3:
- 0.05 weight percent resorcinol
- balance:
- deionized water
The uncoated PEN sample was passed under the
D bulb two times at a conveyor speed of 30 fpm prior to
coating Formulation D and 3 times at 30 fpm after
coating Formulation D. The coating was dried 5 min at
140°C. Subsequently Formulation B and emulsion were
coated as in Example 2.
The procedure of Invention Example 3 was
repeated using VMI for the polymer (component 1) in
Formulation D.
The procedure of Invention Example 4 was
repeated using the H+ bulb rather than the D bulb.
The procedure of Invention Example 3 was repeated,
except that the uncoated PEN sample was passed under
the D bulb one times at a conveyor speed of 30 fpm
prior to coating Formulation D and six times at 30 fpm
after coating Formulation D. The coating was dried 5
min at 90°C.
Wet and Dry Adhesion Results for Invention and Comparison Examples | |||
Sample | Cross hatch dry tape adhesion | Post-process dry tape adhesion | Wet Adhesion |
Invention Ex. 1 | A | A | A |
Invention Ex. 2 | A | A | A |
Comparison Ex. 2 | D | D | D |
Invention Ex.3 | A | A | A |
Invention Ex. 4 | A | A | A |
Invention Ex.5 | A | A | A |
Invention Ex. 6 | A | A | A |
Definition of codes: Cross hatch dry tape adhesion and wet adhesion - A: 0-5% removed, B: 5-20% removed, C: 20-50% removed, D: 50-100% removed. |
Claims (10)
- A photographic film base comprising;a polyester support;a polymer layer superposed on said support, said polymer having a photoreactive moiety and a gelatin reactive moiety; anda gelatin subbing layer attached to the polymer layer.
- The film base according to claim 1 wherein said polymer having a photoreactive moiety and a gelatin reactive moiety is selected from the group consisting of terpolymers of vinylidene chloride, acrylonitrile, and acrylic acid; terpolymers of vinylidene chloride, methylacrylate, and itaconic acid; terpolymers of butylmethacrylate, 2-methyl-2-aminoethyl ester of propenoic acid; and 2-methyl-2-hydroxyethyl ester of propenoic acid.
- The film base according to claim 1 wherein said polymer layer further comprises a phenol type material.
- The film base according to claim 1 wherein the polyester support is selected from the group consisting of polyethylene terephthalate, polyethylene napthalate, polyethylene isothalate, polybutalene terephthalate, polyethylene cocyclohexane dimethylterephthalate, polyethanol codimethanol cyclohexane napthalate, polycarbonates, and copolymers thereof.
- The film base according to claim 1 wherein said gelatin subbing layer further comprises an antistatic agent.
- The film base according to claim 1 wherein said gelatin subbing layer further comprises a matting agent.
- The film base according to claim 1 wherein said gelatin subbing layer further comprises a surface active agent.
- The film base according to claim 1 wherein said gelatin subbing layer further comprises a surfactant.
- The film base according to claim 1 wherein said gelatin subbing layer further comprises a cross-linking agent.
- The film base according to claim 1 wherein said gelatin subbing layer further comprises a dye.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US76775396A | 1996-12-17 | 1996-12-17 | |
US767753 | 1996-12-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0849628A1 true EP0849628A1 (en) | 1998-06-24 |
Family
ID=25080471
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97203830A Withdrawn EP0849628A1 (en) | 1996-12-17 | 1997-12-05 | Polyester photographic film support |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0849628A1 (en) |
JP (1) | JPH10186579A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1220030A1 (en) * | 2000-12-29 | 2002-07-03 | Eastman Kodak Company | Amine modified gelatin layer for improved adhesion of photographic elements after annealing |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2698235A (en) * | 1950-03-16 | 1954-12-28 | Du Pont | Photographic elements |
US3488195A (en) * | 1966-06-29 | 1970-01-06 | Eastman Kodak Co | Light-sensitive photographic element |
US3502475A (en) * | 1967-07-13 | 1970-03-24 | Du Pont | Highly adherent coated films and method of producing same |
US3892575A (en) * | 1971-12-13 | 1975-07-01 | Minnesota Mining & Mfg | Method of modifying the surface properties of a substrate |
US3988157A (en) * | 1972-07-17 | 1976-10-26 | Agfa-Gevaert N.V. | Process for adhering hydrophilic layers to dimensionally stable polyester films |
US4135932A (en) * | 1975-09-26 | 1979-01-23 | Bexford Limited | Process for preparation of photographic film involving corona treatment of polystyrene containing subbing layers and product |
GB1549317A (en) * | 1975-03-04 | 1979-08-01 | Konishiroku Photo Ind | Method of adhesive properties of plastics films |
EP0477670A1 (en) * | 1990-09-14 | 1992-04-01 | Konica Corporation | Silver halide photographic light-sensitive material |
-
1997
- 1997-12-05 EP EP97203830A patent/EP0849628A1/en not_active Withdrawn
- 1997-12-16 JP JP34607397A patent/JPH10186579A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2698235A (en) * | 1950-03-16 | 1954-12-28 | Du Pont | Photographic elements |
US3488195A (en) * | 1966-06-29 | 1970-01-06 | Eastman Kodak Co | Light-sensitive photographic element |
US3502475A (en) * | 1967-07-13 | 1970-03-24 | Du Pont | Highly adherent coated films and method of producing same |
US3892575A (en) * | 1971-12-13 | 1975-07-01 | Minnesota Mining & Mfg | Method of modifying the surface properties of a substrate |
US3988157A (en) * | 1972-07-17 | 1976-10-26 | Agfa-Gevaert N.V. | Process for adhering hydrophilic layers to dimensionally stable polyester films |
GB1549317A (en) * | 1975-03-04 | 1979-08-01 | Konishiroku Photo Ind | Method of adhesive properties of plastics films |
US4135932A (en) * | 1975-09-26 | 1979-01-23 | Bexford Limited | Process for preparation of photographic film involving corona treatment of polystyrene containing subbing layers and product |
EP0477670A1 (en) * | 1990-09-14 | 1992-04-01 | Konica Corporation | Silver halide photographic light-sensitive material |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1220030A1 (en) * | 2000-12-29 | 2002-07-03 | Eastman Kodak Company | Amine modified gelatin layer for improved adhesion of photographic elements after annealing |
US6517947B2 (en) | 2000-12-29 | 2003-02-11 | Eastman Kodak Company | Amine modified gelatin layer for improved adhesion of photographic elements after annealing |
Also Published As
Publication number | Publication date |
---|---|
JPH10186579A (en) | 1998-07-14 |
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