BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] This invention relates to imaging elements and more particularly to photographic
imaging elements.
[0002] Support materials for imaging elements often employ layers comprising glassy, hydrophobic
polymers such as polyacrylates, polymethacrylates, polystyrenes, or cellulose esters,
for example. One typical application is as a backing layer to provide resistance to
scratches, abrasion, blocking, and ferrotyping. The latter two properties relate to
the propensity of layers applied onto the support material or imaging element to stick
together as a result of the adverse humidity, temperature, and pressure conditions
that may occur during the manufacture and use of the imaging element.
[0003] These glassy polymers are typically coated from organic solvent-based solutions to
yield a continuous film upon evaporation of the solvent. However, because of environmental
considerations, it is desirable to replace organic solvent-based coating formulations
with water-based coating formulations. The challenge has been to provide imaging elements
containing layers having similar physical and chemical properties in the dried film
to that obtained with organic solvent-based coatings, but which are the result of
water-based coating compositions substantially free of organic solvents.
[0004] Water insoluble polymer particles contained in aqueous latexes and dispersions reported
to be useful for coatings on photographic films typically have low glass transition
temperatures (Tg) to insure coalescence of the polymer particles into a strong, continuous
film. Generally the Tg of such polymers is less than 50°C., frequently the Tg is no
more than 30°C. Typically these polymers are used in priming or "subbing" layers which
are applied onto the film support to act as adhesion promoting layers for photographic
emulsion layers. Such low Tg polymers, although useful when they underly an emulsion
layer, are not suitable as, for example, backing layers since their blocking and ferrotyping
resistance are poor. To fully coalesce a polymer latex with a higher Tg requires significant
concentrations of coalescing aids. This is undesirable for several reasons.
Volatilization of the coalescing aid as the coating dries is not desirable from an
environmental standpoint. In addition, subsequent recondensation of the coalescing
aid in the cooler areas of the coating machine may cause coating imperfections and
conveyance problems. Coalescing aid which remains permanently in the dried coating
will plasticize the polymer and adversely affect its resistance to blocking, ferrotyping,
and abrasion. Thus, there is a need for imaging elements containing layers that perform
various functions not having the disadvantages associated with layers applied from
organic solutions.
[0005] US Patent No. 4,822,727 describes a silver halide photographic light-sensitive material
having on a support at least one light-sensitive silver halide emulsion layer and
at least one light-insensitive upper layer on the emulsion layer, in which at least
one light-insensitive upper layer contains a polymer latex having a glass transition
point of at least 20°C and said light-insensitive layer and/or at least one other
light-insensitive layer contains a polymer latex having a glass transition point of
lower than 20°C.
SUMMARY OF THE INVENTION
[0006] The invention provides an imaging element comprising a support, at least one light-sensitive
layer e.g. a silver halide emulsion layer, and at least one coalesced layer coated
from a continuous aqueous phase having dispersed therein a mixture of film-forming
colloidal polymeric particles having an average particle size of from 10 to 500 nm
and non-film-forming colloidal polymeric particles having an average particle size
of from 10 to 500nm.
[0007] The coalesced layers are especially suitable for imaging elements due to their high
transparency and toughness.
DETAILED DESCRIPTION OF THE INVENTION
[0008] While the invention is applicable to all types of imaging elements such as, thermal
imaging elements, electrophotographic elements, vesicular elements and the like, the
invention is particularly applicable for use in photographic elements which, for the
purpose of simplicity of explanation, will be referred to hereinafter. The coalesced
layers can be employed as subbing layers, overcoat layers, backing layers, receiving
layers, barrier layers, timing layers, antihalation layers, antistatic layers, stripping
layers, mordanting layers, scavenger layers, antikinking layers, transparent magnetic
layers. The coalesced layers in accordance with this invention are particularly advantageous
due to superior physical properties including transparency, toughness necessary for
providing resistance to scratches, abrasion, blocking and ferrotyping, in addition
to environmental considerations such as, the preparation of layers substantially free
of solvents and general procedural advantages including ease of preparation together
with short drying times.
[0009] The invention further provides an imaging element comprising a support having disposed
thereon an antistat layer and an overlying protective layer of a coalesced layer of
film-forming colloidal polymeric particles and non-film-forming colloidal polymeric
particles.
[0010] The protective layer is coated from an aqueous composition comprising a mixture of
film-forming, water dispersible polymeric particles and non-film-forming, water dispersible
polymeric particles. The mixture of polymers with different film-forming characteristics
yields an overcoat composition that readily forms a high quality, continuous transparent
film that prevents the loss of antistatic properties during film processing and provides
scratch and abrasion resistance.
[0011] The antistatic layer described in U.S. Patent 4,203,769 is prepared by coating an
aqueous colloidal solution of vanadium pentoxide. Preferably, the vanadium pentoxide
is doped with silver. A polymer binder, such as vinylidene chloride-containing terpolymer
latex or a polyesterionomer dispersion, is preferably employed in the antistatic layer
to improve the integrity of the layer and to improve adhesion to the undercoat layer.
The weight ratio of polymer binder to vanadium pentoxide can range from about 1:5
to 200:1, but, preferably 1:1 to 10:1. The antistatic coating formulation may also
contain a wetting aid to improve coatability. Typically, the antistat layer is coated
at a dry coverage of from about 1 to 200 mg/m
2.
[0012] Antistatic layers described in U.S. Patent No. 4,070,189 comprise a crosslinked vinylbenzene
quaternary ammonium polymer in combination with a hydrophobic binder wherein the weight
ratio of binder to antistatic crosslinked polymer is about 10:1 to 1:1.
[0013] The antistatic compositions described in U.S. Patents 4,237,194; 4,308,332; and 4,526,706
comprise a coalesced, cationically stabilized latex and a polyaniline acid addition
salt semiconductor wherein the latex and semiconductor are chosen so that the semiconductor
is associated with the latex before coalescing. Particularly preferred latex binders
include cationically stabilized, coalesced, substantially linear, polyurethanes. The
weight ratio of polymer latex particles to polyaniline in the antistatic coating composition
can vary over a wide range. A useful range of this weight ratio is about 1:1 to 20:1.
Typically, the dried coating weight of this antistatic layer is about 40 mg/m
2 or less.
[0014] Whether colloidal polymeric particles are film-forming or non-film-forming is determined
by the following test:
[0015] An aqueous coating formulation of 3% by weight of colloidal polymeric particles free
of organic solvent or coalescing aid, is applied to a sheet of polyethylene terephthalate
in a wet coverage of 10 ml/m
2 and dried for 2 minutes at 75°C. Polymers that form clear, transparent continuous
films under these conditions are film-forming, while those that do not form clear,
transparent continuous films are non-film-forming, for the purpose of this invention.
[0016] The coalesced layers in accordance with this invention are formed from colloidal
polymeric particles that are a discontinuous phase of solid, water-insoluble particles
suspended in a continuous aqueous medium. The solid, water insoluble particles of
both the film-forming and non-film-forming polymers have an average particle size
of from 10 to 500 nm, preferably from 10 to 200 nm. The film forming polymer is present
in the coalesced layer in an amount of from 20 to 70 percent by weight and preferably
from 30 to 50 percent by weight based on the total weight of the layer.
[0017] The imaging elements in accordance with this invention comprise a support material
having thereon at least one coalesced layer coated from an aqueous composition comprising
a mixture of a film-forming, water dispersible polymer and a non-film-forming, water
dispersible polymer. The support material may comprise various polymeric films including
cellulose esters, such as cellulose acetate, cellulose diacetate, cellulose triacetate,
cellulose acetate butyrate, cellulose propionate; polycarbonate, polystyrene, polyolefins,
such as, polyethylene, polypropylene; polyesters, such as polyethylene terephthalate,
polyethylene naphthalate; and paper or glass. Polyester film support is preferred.
The thickness of the support is not critical. Support thickness of 50 µm to 254 µm
(2 to 10 mil) can be employed, for example, with very satisfactory results. The polyester
support typically employs an undercoat or primer layer well known in the art that
comprise, for example, a vinylidene chloride/methyl acrylate/itaconic acid terpolymer
or vinylidene chloride/acrylonitrile/acrylic acid terpolymer as described in U.S.
Patent Nos. 2,627,088; 2,698,235; 2,698,240; 2,943,937; 3,143,421; 3,201,249; 3,271,178;
and 3,501,301.
[0018] Coating compositions for preparing coalesced layers in accordance with the invention
comprise a continuous aqueous phase having dispersed therein a mixture of film-forming
polymeric particles (component A) and non-film-forming polymeric particles (component
B). As in the coalesced layers, as indicated above, Component A comprises 20 to 70%
of the total weight of components A and B of the coating composition. Other additional
compounds may be added to the coating composition, depending on the function of the
particular layer, including surfactants, emulsifiers, coating aids, matte particles,
rheology modifiers, crosslinking agents, inorganic fillers such as metal oxide particles,
pigments, magnetic particles e.g. cobalt doped gamma iron oxide and biocides. The
coating composition may also include small amounts of organic solvents, preferably
the concentration of organic solvent is less than 1 weight % of the total coating
composition.
[0019] The non-film-forming polymer (B) comprises glassy polymers that provide resistance
to blocking, ferrotyping, abrasion and scratches. Non-film-forming polymer B is present
in the coating composition and in the photographic layer in an amount of from 30 to
80 and preferably from 50 to 70 percent based on the total weight of film-forming
polymer (A) and non-film-forming polymer (B). These polymers include addition-type
polymers and interpolymers prepared from ethylenically unsaturated monomers such as
acrylates including acrylic acid, methacrylates including methacrylic acid, acrylamides
and methacrylamides, itaconic acid and its half esters and diesters, styrenes including
substituted styrenes, acrylonitrile and methacrylonitrile, vinyl acetates, vinyl ethers,
vinyl and vinylidene halides, and olefins. In addition, crosslinking and graft-linking
monomers such as 1,4-butyleneglycol methacrylate, trimethylolpropane triacrylate,
allyl methacrylate, diallyl phthalate, divinyl benzene may be used. Other polymers
that may comprise component B include water-dispersible condensation polymers such
as polyesters, polyurethanes, polyamides, and epoxies. Polymers suitable for component
B do not give transparent, continuous films upon drying when the above-described test
is applied.
[0020] The film-forming polymer (A) comprises polymers that form a continuous film under
the extremely fast drying conditions typical of the photographic film manufacturing
process. Polymers that are suitable for component A are those that give transparent,
continuous films when the above-described test is applied and include addition-type
polymers and interpolymers prepared from ethylenically unsaturated monomers such as
acrylates including acrylic acid, methacrylates including methacrylic acid, acrylamides
and methacrylamides, itaconic acid and its half esters and diesters, styrenes including
substituted styrenes, acrylonitrile and methacrylonitrile, vinyl acetates, vinyl ethers,
vinyl and vinylidene halides, and olefins. In addition, crosslinking and graft-linking
monomers such as 1,4-butyleneglycol methacrylate, trimethylolpropane triacrylate,
allyl methacrylate, diallyl phthalate, divinyl benzene may be used. Other suitable
polymers useful as component A are film-forming dispersions of polyurethanes or polyesterionomers.
[0021] The colloidal polymeric particles can be prepared either by emulsion polymerization
or by emulsifying pre-formed polymers in water with a proper dispersing agent. In
both cases, chain transfer agents including mercaptans, polymercaptans, and halogen
compounds can be used in the polymerization mixture to moderate the polymer molecular
weight. The weight average molecular weight of prepared polymers may vary from 5,000
to 30,000,000 and preferably from 50,000 to 10,000,000.
[0022] Preparation of polyurethane dispersions is well-known in the art and involves chain
extending an aqueous dispersion of a prepolymer containing terminal isocyanate groups
by reaction with a diamine or diol. The prepolymer is prepared by reacting a polyester,
polyether, polycarbonate, or polyacrylate having terminal hydroxyl groups with excess
polyfunctional isocyanate. This product is then treated with a compound that has functional
groups that are reactive with an isocyanate, for example, hydroxyl groups, and a group
that is capable of forming an anion, typically this is a carboxylic acid group. The
anionic groups are then neutralized with a tertiary amine to form the aqueous prepolymer
dispersion.
[0023] The term polyesterionomer refers to polyesters that contain at least one ionic moiety.
Such ionic moieties function to make the polymer water dispersible. These polyesters
are prepared by reacting one or more dicarboxylic acids or their functional equivalents
such as anhydrides, diesters, or diacid halides with one or more diols in melt phase
polycondensation techniques as described in U.S. Patents 3,018,272; 3,929,489; 4,307,174;
4,419,437. Examples of this class of polymers include, for example, Eastman AQ polyesterionomers,
manufactured by Eastman Chemical Co.
[0024] Typically the ionic moiety is provided by some of the dicarboxylic acid repeat units,
the remainder of the dicarboxylic acid repeat units are nonionic in nature. Such ionic
moieties can be anionic or cationic, but, anionic moieties are preferred for the present
invention. Preferably, the ionic dicarboxylic acid contains a sulfonic acid group
or its metal salt. Examples include the sodium, lithium, or potassium salt of sulfoterephthalic
acid, sulfonaphthalene dicarboxylic acid, sulfophthalic acid, and sulfoisophthalic
acid or their functional equivalent anhydride, diester, or diacid halide. Most preferably
the ionic dicarboxylic acid repeat unit is provided by 5-sodiosulfoisophthalic acid
or dimethyl 5-sodiosulfoisophthalate.
[0025] The nonionic dicarboxylic acid repeat units are provided by dicarboxylic acids or
their functional equivalents represented by the formula:

where R is an aromatic or aliphatic hydrocarbon or contains both aromatic and aliphatic
hydrocarbons. Exemplary compounds include isophthalic acid, terephthalic acid, succinic
acid and adipic acid.
[0026] Suitable diols are represented by the formula: HO-R-OH, where R is aromatic or aliphatic
or contains both aromatic and aliphatic hydrocarbons. Preferably the diol includes
one or more of the following: ethylene glycol, diethylene glycol, or 1,4-cyclohexanedimethanol.
[0027] The polyesterionomer dispersions comprise from about 1 to about 25 mol %, based on
the total moles of dicarboxylic acid repeat units, of the ionic dicarboxylic acid
repeat units. The polyesterionomers have a glass transition temperature (Tg) of about
60°C. or less to allow the formation of a continuous film.
[0028] The film-forming polymeric particles, the non-film-forming polymeric particles or
both type particles may include reactive functional groups capable of forming covalent
bonds by intermolecular crosslinking or by reaction with a crosslinking agent (i.e.,
a hardener). Suitable reactive functional groups include: hydroxyl, carboxyl, carbodiimide,
epoxide, aziridine, vinyl sulfone, sulfinic acid, active methylene, amino, amide,
allyl.
[0029] The coating compositions in accordance with the invention may also contain suitable
crosslinking agents that may effectively be used in the coating compositions of the
invention including aldehydes, epoxy compounds, polyfunctional aziridines,. vinyl
sulfones, methoxyalkyl melamines, triazines, polyisocyanates, dioxane drivatives such
as dihydroxydioxane, carbodiimides, chrome alum, and zirconium sulfate. The crosslinking
agents may react with functional groups present on either the film-forming polymers,
the non-film-forming polymers or on both.
[0030] Matte particles well known in the art may be used in the coating composition of the
invention, such matting agents have been described in Research Disclosure No. 308,
published Dec 1989, pages 1008 to 1009. When polymeric matte particles are employed,
the polymers may contain reactive functional groups capable of forming covalent bonds
by intermolecular crosslinking or by reaction with a crosslinking agent (i.e., a hardener)
in order to promote improved adherence to the film-forming and non-film-forming polymers
of the invention. Suitable reactive functional groups include: hydroxyl, carboxyl,
carbodiimide, epoxide, aziridine, vinyl sulfone, sulfinic acid, active methylene,
amino, amide, allyl.
[0031] The coating compositions of the present invention may also include lubricants or
combinations of lubricants to reduce sliding friction of the photographic elements
in accordance with the invention. Virtually any type of water soluble or dispersible
lubricants can be used. For example, (1) water soluble or dispersible paraffin or
wax-like materials, including vegetable waxes, insect waxes, mineral waxes, petroleum
waxes, synthetic waxes, carnauba wax, as well as wax-like components that occur individually
in these waxes, (2) perfluoro- or fluoro- or fluorochloro-containing materials, which
include poly(tetrafluoroethylene), poly(trifluorochloroethylene), poly(vinylidene
fluoride), poly(trifluorochloroethylene-co-vinyl chloride), poly(meth)acrylates containing
fluoro or perfluoroalkyl side groups, (3) poly(meth)acrylates or poly(meth)acrylamides
containing long alkyl side groups, (4) silicone lubricants including siloxane containing
various (cyclo)alkyl, aryl, epoxypropylalkyl, polyoxyethylene, and polyoxypropylene
side groups.
[0032] The above lubricants also may contain reactive functional groups such as hydroxyl,
carboxyl, carbodiimide, epoxide, aziridine, vinyl sulfone, sulfinic acid, active methylene,
amino, and amide. The lubricants can be incorporated in the coating composition in
an amount from 0.1 to 150 mg/m
2, preferably from 0.1 to 90 mg/m
2.
[0033] Any of the reactive functional groups of the polymers and any of the crosslinking
agents described in U.S. Patent 5,057,407 and the patents cited therein may be used
in accordance with this invention.
[0034] The compositions of the present invention may be applied as aqueous coating formulations
containing up to about 50% total solids by coating methods well known in the art.
For example, hopper coating, gravure coating, skim pan/air knife coating, spray coating,
and other methods may be used with very satisfactory results. The coatings are dried
at temperatures up to 150°C. to give dry coating weights of 20 mg/m
2 to 10 g/m
2.
[0035] The invention is applicable to thermal imaging elements wherein the coalesced layer
may be employed as supports, dye-donor elements, dye-image receiving layers, barrier
layers, overcoats, binders as described in U.S. Patents 5,288,689; 5,283,225; 4,772,582;
5,166,128.
[0036] The invention is further illustrated by the following examples in which parts and
percentages are by weight unless otherwise stated. Polymeric particles used in the
example coatings together with the film-forming character of each are listed in Table
1. The film forming characteristic of each polymer is defined by the test set forth
above.
TABLE 1
| Polymer |
Polymer Composition |
Tg,°C. |
Description |
| P-1 |
Methyl methacrylate homopolymer |
125 |
Non-film-forming |
| P-2 |
Methyl methacrylate/methacrylic acid 97/3 |
130 |
Non-film-forming |
| P-3 |
Methacrylonitrile homopolymer |
115 |
Non-film-forming |
| P-4 |
Methacrylonitrile/methacrylic acid 97/3 |
115 |
Non-film-forming |
| P-5 |
Styrene/methacrylic acid 97/3 |
100 |
Non-film-forming |
| P-6 |
Butyl acrylate/acrylic acid 97/3 |
-40 |
Film-forming |
| P-7 |
Butyl acrylate/methyl methacrylate/acrylic acid 48.5/48.5/3 |
20 |
Film-forming |
| P-8 |
butyl acrylate/2-sulfo-1,1-dimethylethyl acrylamide/methyl 2-acrylamido-2-methoxyacetate
90/5/5 |
-20 |
Film-forming |
| P-9 |
Dow 620 latex (styrene-butadiene) |
15 |
Film-forming |
| P-10 |
Dow 615 latex (styrene-butadiene) |
10 |
Film-forming |
| P-11 |
ICI Neorez 960 polyurethane dispersion |
10 |
Film-forming |
| P-12 |
Eastman Chemical Co. AQ29D polyesterionomer dispersion |
29 |
Film-forming |
| P-13 |
Eastman Chemical Co. AQ55D polyesterionomer dispersion |
55 |
Film-forming |
Comparative Samples A-G and Examples 1-16
[0037] Aqueous coating solutions comprising 3 weight % total solids were coated with a doctor
blade onto polyethylene terephthalate film support that had been subbed with a terpolymer
latex of acrylonitrile vinylidene chloride, and acrylic acid. The coating was dried
at 90°C. for one minute and the coating appearance recorded, the results are listed
in Table 2. Transparent, high-quality films that are comparable in appearance to organic
solvent applied coatings were obtained for the coating compositions of the invention.
TABLE 2
| Coating |
Polymer A Film Forming |
Polymer B Non-film-forming |
B/A |
Appearance |
| Sample A |
none |
P-1 |
100/0 |
Powdery/non-continuous |
| Sample B |
none |
P-2 |
100/0 |
Powdery/non-continuous |
| Sample C |
none |
P-3 |
100/0 |
Powdery/non-continuous |
| Sample D |
none |
P-4 |
100/0 |
Powdery/non-continuous |
| Sample E |
none |
P-5 |
100/0 |
Powdery/non-continuous |
| Sample F |
P-11 |
P-1 |
90/10 |
Very hazy/non-continuous |
| Sample G |
P-11 |
P-1 |
80/20 |
Hazy |
| Example 1 |
P-11 |
P-1 |
72.5/27.5 |
Excellent |
| Example 2 |
P-11 |
P-1 |
70/30 |
Excellent |
| Example 3 |
P-11 |
P-2 |
70/30 |
Excellent |
| Example 4 |
P-11 |
P-3 |
70/30 |
Excellent |
| Example 5 |
P-11 |
P-4 |
70/30 |
Excellent |
| Example 6 |
P-11 |
P-5 |
70/30 |
Excellent |
| Example 7 |
P-6 |
P-2 |
70/30 |
Excellent |
| Example 8 |
P-6 |
P-2 |
70/30 |
Excellent |
| Example 9 |
P-7 |
P-2 |
70/30 |
Excellent |
| Example 10 |
P-8 |
P-2 |
70/30 |
Excellent |
| Example 11 |
P-9 |
P-1 |
70/30 |
Continuous film/slight haze |
| Example 12 |
P-10 |
P-1 |
70/30 |
Continuous film/slight haze |
| Example 13 |
P-12 |
P-2 |
70/30 |
Excellent |
| Example 14 |
P-13 |
P-2 |
70/30 |
Excellent |
| Example 15 |
P-11 |
P-2 |
50/50 |
Excellent |
| Example 16* |
P-11 |
P-2 |
60/40 |
Excellent |
| *- PFAZ® 322 polyfunctional aziridine, Sybron Chemicals Inc., added at 10 wt % of
solids. |
Comparative Samples H, I and Examples 17-25
[0038] The following examples demonstrate the excellent physical properties that are obtained
with coating compositions of the invention. Aqueous formulations comprising 3 weight
% total solids were applied onto subbed film support as in the previous examples and
dried at 90°C. for one minute to give transparent films with a dry coating weight
of 750 mg/m
2. Taber abrasion for the coatings were measured and compared with a 750 mg/m
2 coating of Elvacite 2041 (methyl methacrylate polymer sold by E.I. DuPont de Nemours
and Co.) that had been coated from methylene chloride solution. The Taber abrasion
tests were performed in accordance with the procedures set forth in ASTM D1044. The
results are given in Table 3.
TABLE 3
| Coating |
Description |
Taber Abr. (% haze) |
| Sample H |
Solvent coated Elvacite 2041 |
7.0 |
| Sample I |
P-11 |
13.5 |
| Example 17 |
P-2/P-11 70/30 ratio |
7.0 |
| Example 18 |
P-2/P-11 70/30 ratio, with aziridine * |
7.0 |
| Example 19 |
P-2/P-11 72.5/27.5 ratio, with aziridine* |
7.0 |
| Example 20 |
P-2/P-12 70/30 ratio |
9.8 |
| Example 21 |
P-2/P-13 70/30 ratio |
11.0 |
| Example 22 |
P-2/P-13 70/30 ratio, with aziridine* |
8.4 |
| Example 23 |
P-2/P-11 50/50 ratio with aziridine* |
7.0 |
| Example 24 |
P-2/P-11 40/60 ratio with aziridine* |
11.0 |
| Example 25 |
P-2/P-11/Ludox AM 35/32.5/32.5 |
7.5 |
| *- PFAZ® 322 polyfunctional aziridine, Sybron Chemicals Inc., added at 10 wt % of
solids. |
Comparative Samples J-L and Examples 26-39
[0039] The following examples show that the coating compositions of the invention provide
void-free, impermeable films that are comparable with organic solvent applied layers.
A subbed polyester film support as previously described was coated with an aqueous
antistatic formulation comprising 0.025 weight % of silver-doped vanadium pentoxide,
0.075 weight % of a terpolymer latex of methylacrylate, vinylidene chloride, and itaconic
acid (15/83/2) and dried at 100°C. to yield an antistatic layer having a dry weight
of about 8 mg/m
2. Aqueous coating compositions of the invention containing 1 to 3 weight % solids
were applied over the antistatic layer and dried for 90 seconds at 100°C. to yield
transparent coatings having a dry weight of 250 to 750 mg/m
2. It is known (described in U.S. Patents 5,006,451 and 5,221,598) that the antistatic
properties of the vanadium pentoxide layer are destroyed after film processing if
not protected by an impermeable barrier. Thus, the permeability of the example coatings
could be evaluated by measuring the antistatic properties of the samples after processing
in conventional film developing and fixing solutions.
[0040] The samples were soaked in high pH (11.3) developing and fixing solutions as described
in U.S. Patent 4,269,929, at 38°C. for 60 seconds each and then rinsed in distilled
water. The internal resistivity (using the salt bridge method) of the processed samples
at 20% relative humidity was measured and compared with the internal resistivity before
processing. The coating compositions and results are reported in Table 4. The results
show that coating compositions of the invention give void-free coatings that are as
impermeable as a solvent cast film (sample J) and are far superior to an aqueous coating
composition comprising only the high Tg methyl methacrylate copolymer dispersion alone
(sample K).
TABLE 4
| Coating |
Description |
Coating Weight (mg/m2) |
Resistivity Before Process log Ω/sq. |
Resistivity After Process log Ω/sq. |
| Sample J |
Solvent Coated Elvacite 2041 |
750 |
7.5 |
7.7 |
| Sample K |
P-2 without film-forming polymer |
750 |
7.5 |
>14.0 |
| Sample L |
P-11 without non-film-forming polymer |
750 |
9.3 |
10.3 |
| Example 26 |
P-2/P-12 70/30 ratio |
750 |
7.9 |
8.3 |
| Example 27 |
P-2/P-13 70/30 ratio |
750 |
8.0 |
8.1 |
| Example 28 |
P-2/P-11 70/30 ratio |
750 |
8.0 |
8.9 |
| Example 29 |
P-2/P-11 70/30 ratio, with aziridine* |
750 |
7.6 |
7.6 |
| Example 30 |
P-2/P-7 70/30 ratio, with aziridine* |
750 |
7.6 |
7.6 |
| Example 31 |
P-5/P-11 70/30 ratio |
750 |
7.6 |
7.7 |
| Example 32 |
P-5/P-13 70/30 ratio |
750 |
7.6 |
7.8 |
| Example 33 |
P-3/P-11 70/30 ratio |
750 |
8.0 |
8.0 |
| Example 34 |
P-4/P-11 70/30 ratio, with aziridine* |
750 |
7.8 |
7.9 |
| Example 35 |
P-2/P-11 70/30 ratio, with aziridine* |
250 |
8.5 |
8.7 |
| Example 36 |
P-2/P-11 50/50 ratio |
1000 |
7.3 |
7.2 |
| Example 37 |
P-2/P-11 40/60 ratio |
1000 |
7.3 |
7.9 |
| Example 38 |
P-2/P-11 70/30 ratio with aziridine* and polymethylmethacrylate 2 µm matte |
750 |
7.2 |
7.3 |
| Example 39 |
P-2/P-11 70/30 ratio with aziridine* and polymethylmethacrylate-co-methacrylic acid
2 µm matte |
750 |
7.4 |
7.5 |
| *- PFAZ® 322 polyfunctional aziridine, Sybron Chemicals Inc., added at 10 wt % of
solids. |
Examples 40-42
[0041] In addition to testing procedures already described, Paper Clip Friction (PCF) and
Single Arm Scratch were measured for the following examples using the procedure set
forth in ANSI IT 9.4-1992 and ANSI PH 1.37-1977, respectively. These examples serve
to illustrate the excellent lubricity and scratch resistance that can be obained with
coating compositions of the invention upon incorporation of various lubricant materials.
The coatings of the invention were applied over a conductive layer comprising vanadium
pentoxide as described in previous examples.
TABLE 5
| Coating |
Description |
Coating Weight (mg/m2) |
Resistivity Before Process log Ω/sq. |
Resistivity After Process log Ω/sq. |
PCF |
Single Arm Scratch (gms) |
| Example 40 |
P-2/P-11 70/30 ratio, with aziridine.* Michemlube** 160 at 7.5mg/m2 |
1000 |
8.2 |
7.6 |
0.20 |
-- |
| Example 41 |
P-2/P-11/Teflon 30+ 62/35/3 ratio with aziridine* |
750 |
7.6 |
7.6 |
0.15 |
70 |
| Example 42 |
P-2/P-11/Teflon 3170+ 62/35/3 ratio with aziridine* |
750 |
7.8 |
7.9 |
0.125 |
110 |
| + - Teflon 30 and Teflon 3170 aqueous dispersions available from DuPont de Nemours
and Co. |
| ** Aqueous carnauba wax dispersion sold by Michelman Inc. |
| *- PFAZ® 322 polyfunctional aziridine, Sybron Chemicals Inc., added at 10 wt % of
solids. |
Example 43
[0042] This example illustrates the incorporation of a conductive metal oxide particle in
the coatings used in the invention. A coating comprising a 15/35/50 weight ratio of
polymer P-2/polymer P-11/conductive tin oxide particles was applied onto a subbed
polyester support to give a transparent coating with a total dried weight of 1000
mg/m
2. The conductive tin oxide was Keeling & Walker CPM375 antimony-doped tin oxide that
had been milled to an average particle size of about 50nm. The surface resistivity
of the coating measured at 20% RH before and after film processing using a two-point
probe was 9.9 and 10.3 log Ω/square, respectively.
1. An imaging element comprising a support, at least one light-sensitive layer and at
least one coalesced layer obtainable from a continuous aqueous phase having dispersed
therein a mixture of film-forming water insoluble colloidal polymeric particles having
an average particle size of from 10 to 500 nm and non-film-forming water insoluble
colloidal polymeric particles having an average particle size of from 10 to 500nm,
said film-forming colloidal polymeric particles forming clear, transparent continuous
films and said non-film-forming colloidal polymeric particles not forming clear, transparent
continuous films when an aqueous coating formulation of 3% by weight of colloidal
polymeric particles free of organic solvent or coalescing aid, is applied to a sheet
of polyethylene terephthalate in a wet coverage of 10 ml/m2 and dried for 2 minutes at 75°C.
2. An imaging element comprising a support, a light-sensitive layer and an antistat layer,
the antistat layer being overcoated with a protective layer of a coalesced layer as
defined in claim 1.
3. The imaging element of Claims 1 or 2 wherein the film-forming colloidal polymeric
particles are present in the coalesced layer in an amount of from 20 to 70 percent
by weight based on the total weight of the layer.
4. The imaging element of Claims 1 or 2 wherein the light-sensitive layer is a silver
halide emulsion layer.
5. The imaging element of Claims 1 or 2 wherein the light-sensitive layer is a thermal
imaging layer.
6. The imaging element of Claims 1 or 2 wherein the polymer of the film-forming colloidal
particles is an addition polymer.
7. The imaging element of Claims 1 or 2 wherein the polymer of the film-forming colloidal
particles is a condensation polymer.
8. The imaging element of Claim 1 wherein the coalesced layer contains metal oxide particles.
9. The imaging element of Claim 8 wherein the metal oxide particles are conductive metal
oxides.
10. The imaging element of Claim 9 wherein the conductive metal oxide is tin oxide.
11. The imaging element of Claim 10 wherein the tin oxide is antimony doped.
12. The imaging element of Claim 1 wherein the coalesced layer contains magnetic particles.
13. The imaging element of Claim 12 wherein the magnetic particles are cobalt doped gamma
iron oxide.
14. The imaging element of Claims 1 or 2 wherein the film-forming colloidal polymeric
particles or the non-film-forming colloidal polymeric particles are crosslinked.
15. The imaging element of Claims 1 or 2 wherein the film-forming colloidal polymeric
particles include addition-type polymers and interpolymers prepared from ethylenically
unsaturated monomers.
16. The imaging element of Claims 1 or 2 wherein the film-forming colloidal polymeric
particles include film-forming dispersions of polyurethane or polyesterionomers.
1. Abbildungselement mit einem Träger, mindestens einer lichtempfindlichen Schicht und
mindestens einer zusammengeflossenen Schicht, die aus einer stetigen wässrigen Phase
erzeugbar ist, in der eine Mischung aus filmbildenden, nicht wasserlöslichen kolloidalen
Polymerpartikeln mit einer mittleren Partikelgröße von 10 bis 500 nm und nicht filmbildenden,
nicht wasserlöslichen, kolloidalen Polymerpartikeln mit einer mittleren Partikelgröße
von 10 bis 500 nm dispergiert ist, wobei die filmbildenden, kolloidalen Polymerpartikel
klare, transparente, durchgehende Filme bilden, und wobei die nicht filmbildenden,
kolloidalen Polymerpartikel keine klaren, transparenten, durchgehenden Filme bilden,
wenn eine wässrige Beschichtungsformulierung von 3 Gew.-% kolloidaler Polymerpartikel
und ohne ein organisches Lösemittel oder eine Koaleszenzhilfe auf einen Bogen aus
Polyethylenterephthalat in einem Nassauftrag von 10 ml/m2 aufgetragen und für 2 Minuten bei 75°C getrocknet wird.
2. Abbildungselement mit einem Träger, einer lichtempfindlichen Schicht und einer Antistatikschicht,
wobei auf die Antistatikschicht eine Schutzschicht einer zusammengeflossenen Schicht
aufgetragen ist, wie in Anspruch 1 dargelegt.
3. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die filmbildenden, kolloidalen Polymerpartikel in der zusammengeflossenen Schicht
in einer Menge von 20 bis 70 Gew.-%, bezogen auf das Gesamtgewicht der Schicht, vorliegen.
4. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die lichtempfindliche Schicht eine Silberhalogenid-Emulsionsschicht ist.
5. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die lichtempfindliche Schicht eine thermische Abbildungsschicht ist.
6. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Polymer der filmbildenden, kolloidalen Partikel ein Additionspolymer ist.
7. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Polymer der filmbildenden, kolloidalen Partikel ein Kondensationspolymer ist.
8. Abbildungselement nach Anspruch 1, dadurch gekennzeichnet, dass die zusammengeflossene Schicht Metalloxidpartikel enthält.
9. Abbildungselement nach Anspruch 8, dadurch gekennzeichnet, dass die Metalloxidpartikel leitfähige Metalloxide sind.
10. Abbildungselement nach Anspruch 9, dadurch gekennzeichnet, dass das leitfähige Metalloxid Zinnoxid ist.
11. Abbildungselement nach Anspruch 10, dadurch gekennzeichnet, dass das Zinnoxid antimondotiert ist.
12. Abbildungselement nach Anspruch 1, dadurch gekennzeichnet, dass die zusammengeflossene Schicht Magnetpartikel enthält.
13. Abbildungselement nach Anspruch 12, dadurch gekennzeichnet, dass die Magnetpartikel kobaltdotiertes Gammaeisenoxid sind.
14. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die filmbildenden, kolloidalen Polymerpartikel oder die nicht filmbildenden, kolloidalen
Polymerpartikel vernetzt sind.
15. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die filmbildenden, kolloidalen Polymerpartikel Additionspolymere und Interpolymere
enthalten, die aus ethylenisch ungesättigten Monomeren hergestellt sind.
16. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die filmbildenden, kolloidalen Polymerpartikel filmbildende Dispersionen von Polyurethan
oder Polyesterionomeren enthalten.
1. Elément formateur d'image comprenant un support, au moins une couche photosensible
et au moins une couche coalescée pouvant être obtenue à partir d'une phase aqueuse
continue dans laquelle est dispersé un mélange de particules colloïdales polymères
filmogènes insolubles dans l'eau ayant une taille moyenne comprise entre 10 et 500
nm et de particules colloïdales polymères non filmogènes insolubles dans l'eau ayant
une taille moyenne comprise entre 10 et 500 nm, lesdites particules colloïdales polymères
filmogènes formant des films continus limpides et transparents et lesdites particules
colloïdales polymères non filmogènes ne formant pas de films continus limpides et
transparents, lorsqu'une formulation aqueuse de revêtement contenant 3 % en poids
de particules colloïdales polymères, sans solvant organique, ni agent de coalescence,
est appliquée sur une feuille de poly(éthylène téréphtalate) à une teneur à l'état
humide de 10 ml/m2, puis séchée pendant 2 minutes à 75 °C.
2. Elément formateur d'image comprenant un support, une couche photosensible et une couche
antistatique, la couche antistatique étant revêtue d'une couche de protection coalescée
telle que définie dans la revendication 1.
3. Elément formateur d'image selon la revendication 1 ou 2, dans lequel les particules
colloïdales polymères filmogènes sont présentes dans la couche coalescée en une quantité
comprise entre 20 et 70 pourcent en poids par rapport au poids total de la couche.
4. Elément formateur d'image selon la revendication 1 ou 2, dans lequel la couche photosensible
est une couche d'émulsion aux halogénures d'argent.
5. Elément formateur d'image selon la revendication 1 ou 2, dans lequel la couche photosensible
est une couche de formation d'image thermique.
6. Elément formateur d'image selon la revendication 1 ou 2, dans lequel le polymère des
particules colloïdales filmogènes est un polymère d'addition.
7. Elément formateur d'image selon la revendication 1 ou 2, dans lequel le polymère des
particules colloïdales filmogènes est un polymère de condensation.
8. Elément formateur d'image selon la revendication 1, dans lequel la couche coalescée
contient des particules d'oxyde métallique.
9. Elément formateur d'image selon la revendication 8, dans lequel les particules d'oxyde
métallique sont des oxydes métalliques conducteurs.
10. Elément formateur d'image selon la revendication 9, dans lequel l'oxyde métallique
conducteur est l'oxyde d'étain.
11. Elément formateur d'image selon la revendication 10, dans lequel l'oxyde d'étain est
dopé à l'antimoine.
12. Elément formateur d'image selon la revendication 1, dans lequel la couche coalescée
contient des particules magnétiques.
13. Elément formateur d'image selon la revendication 12, dans lequel les particules magnétiques
sont des particules d'oxyde de fer gamma dopé au cobalt.
14. Elément formateur d'image selon la revendication 1 ou 2, dans lequel les particules
colloïdales polymères filmogènes ou les particules colloïdales polymères non filmogènes
sont réticulées.
15. Elément formateur d'image selon la revendication 1 ou 2, dans lequel les particules
colloïdales polymères filmogènes comprennent des polymères d'addition et des interpolymères
préparés à partir de monomères ayant une insaturation de type éthylénique.
16. Elément formateur d'image selon la revendication 1 ou 2, dans lequel les particules
colloïdales polymères filmogènes comprennent des dispersions filmogènes de polyuréthane
ou de polyesterionomères.