Photographic imaging element containing matting agents

A photographic imaging element comprising a support, at least one light-sensitive silver halide layer, and a light-insensitive layer comprising a polymer particle of the formula: EQU (A).sub.x (B).sub.y (C).sub.z (I) where A is a polyfunctional ethylenically unsaturated crosslinking monomer, B is an ethylenically unsaturated monomer containing carboxylic acid groups, C is a monofunctional ethylenically unsaturated monomer other than B, x is about 0.1 to 2 mole percent, y is about 35 to 70 mole percent and z equals 100-(x+y) mole percent.

CROSS REFERENCE TO RELATED APPLICATION 
Reference is made to and priority claimed from U.S. Provisional Application 
Ser. No. 60/004,231, filed 25 Sep. 1995, entitled PHOTOGRAPHIC IMAGING 
ELEMENT CONTAINING MATTING AGENTS. 
FIELD OF THE INVENTION 
This invention relates to photographic imaging elements and particularly to 
silver halide photographic elements containing matting agents. 
BACKGROUND OF THE INVENTION 
It is conventional to incorporate finely powdered grains or matting agents 
into the protective layer of a photographic element to increase the 
surface roughness to achieve the following: (1) reduce self-adhering of 
the material, (2) reduce sticking of the material to manufacturing and 
processing devices, (3) improve the antistatic properties of the material, 
and (4) improve the vacuum adhesiveness of the material in contact 
exposure to prevent Newton's rings. The matting agents are commonly very 
small particles of organic or inorganic materials, such as silicone 
dioxide, magnesium oxide, titanium dioxide, calcium carbonate, poly(methyl 
methacrylate), poly(vinyltoluene), poly(methyl methacrylate-co-methacrylic 
acid), and so on. 
Matting of the protective layer suffers, however, from various 
disadvantages. For example, it reduces the transparency of the 
photographic elements after processing and increases the graininess of the 
picture. It has been heretofore known to include processing removable 
polymer particles, sometimes referred to as soluble matte, in protective 
layers. High concentrations of processing removable matte are needed 
especially when the unprocessed photographic elements are used or stored 
at high relative humidities and at elevated temperatures of from 
30.degree. to 40.degree. C. High concentrations are also needed to prevent 
contact specks which cause adverse sensitometric defects when the 
unprocessed materials are rolled up. 
The use of a high level of processing removable matte provides a 
satisfactory solution to conventional films for amateur use, for which the 
processed, or developed, film strips are returned to the consumer in 
synthetic resin pouches, or sleeves, where the frontside and backside of 
the film do not come in contact with each other. 
Recent patents have disclosed photographic systems where the processed 
element may be re-introduced into a cassette. This system allows for 
compact and clean storage of the processed element until such time when it 
may be removed for additional prints or to interface with display 
equipment. Storage in the cassette is preferred to facilitate location of 
the desired exposed frame and to minimize contact with the negative during 
subsequent usage. U.S. Pat. No. 5,173,739 discloses a cassette designed to 
thrust the photographic element from the cassette, eliminating the need to 
contact the film with mechanical or manual means. Published European 
Patent Application 0 476 535 A1 describes how the developed film may be 
stored in such a cassette. The dimensions of such a so-called thrust 
cassette requires that the processed photographic element is wound tightly 
and under pressure, causing direct close contact between the front and 
back sides which results in ferrotyping, especially at high temperature 
and high relative humidity. Processing removable matte does not prevent 
this problem. 
In recent years, rapid processing and high temperature drying after 
processing have become common practice for photographic materials. The 
high temperature dried films, for example 60.degree. C. (harsh drying), 
tend to aggravate ferrotyping which results from close contact, especially 
under elevated humidity and temperature. When ferrotyping is sufficiently 
severe, the resulting prints are unacceptable. Films dried at lower 
temperatures, for example 40.degree. C. (mild drying), tend to show much 
less ferrotyping. The reason for this difference is not understood. 
DESCRIPTION OF RELATED ART 
It has been heretofore known to employ matting agents in photographic 
materials that include a degree of crosslinking and acid functional groups 
to prevent settling of the matting agent in the coating solution and which 
does not generate a stain in the processing solution. 
SUMMARY OF THE INVENTION 
Therefore, an objective of the present invention is to provide a silver 
halide photographic element capable of being rehoused in a cartridge after 
processing which has excellent image quality and low printing granularity, 
and superior resistance to sticking and ferrotyping between its front and 
backsides at high temperatures and in moist environments. 
In accordance with this invention, a photographic imaging element comprises 
a support, at least one light-sensitive silver halide layer, and a 
light-insensitive layer comprising a polymer particle of the formula: 
EQU (A).sub.x (B).sub.y (C).sub.z (I) 
where A is a polyfunctional ethylenically unsaturated crosslinking monomer, 
B is an ethylenically unsaturated monomer containing carboxylic acid 
groups, C is a monofunctional ethylenically unsaturated monomer other than 
B, x is about 0.1 to 2 mole percent, y is about 35 to 70 mole percent and 
z equals 100-(x+y) mole percent. 
The polymer particles in accordance with this invention can be included in 
any layer of the imaging element, but preferably are included in the 
protective layer of the imaging element, in a separate light-insensitive 
layer over the protective layer of the imaging element, or in a layer in 
close proximity to the top-most protective layer so that the polymer matte 
particles protrude above the surface of the top-most layer of the imaging 
element. The polymer matte particles have a mean size of from 0.5 to 
10.mu., preferably from 0.5 to 6.mu., and most preferably from 0.8 to 
3.mu.. 
The utilization of elements in accordance with the above unexpectedly 
provides excellent image quality and low printing granularity with 
superior resistance to sticking and ferrotyping.

DESCRIPTION OF PREFERRED EMBODIMENTS 
Photographic elements in a cassette are shown generally in U.S. Pat. No. 
5,173,730 and in the attached FIG. 1. In FIG. 1, the film material 
includes a photographic element 12 encased in a suitable cassette 14. The 
cassette includes an inlet/outlet 16 for entrance and exit of the 
photographic element 12 into and out of the cassette 14. The photographic 
element 12 may be wound upon a suitable spool 18 or on itself (not shown). 
Photographic elements according to this invention can differ widely in 
structure and composition. For example, they can vary greatly in regard to 
the type of the support, the number and composition of the imaging forming 
layers, and the kinds of auxiliary layers that are included in the 
elements. Typical supports include cellulose nitrate film, cellulose 
acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene 
terephthalate) film, poly(ethylene naphthalate film, polycarbonate film, 
and the like. 
In accordance with the present invention, the matte particles have a 
composition given by formula I, in which A is a polyfunctional 
ethylenically unsaturated crosslinking monomer, B is an ethylenically 
unsaturated monomer containing carboxylic acid groups, C is a 
monofunctional ethylenically unsaturated monomer other than B, x is about 
0.1 to 2 mole percent, preferably from 0.5 to 2 mole percent, y is about 
35 to 70 mole percent, preferably from 35 to 60 mole percent, and z equals 
100-(x+y) mole percent. While the matting agent may be incorporated into 
any layer of the element, it is preferably incorporated into the surface 
protective layer of the element. By surface protective layer is meant 
either the emulsion side surface protective layer, or the backing side 
surface protective layer, or both. However, it is particularly preferable 
to incorporate the matting agent in the outermost emulsion side surface 
protective layer. For the purpose of simplicity in explanation, the terms 
"protective layer" and "surface protective layer" will be used throughout 
this specification. However, it is to be understood that the matting 
agents may be employed in any light-insensitive layer. The matting agent 
of the present invention is employed at a coating weight coverage of 0.001 
to 0.3 g/m.sup.2, preferably from 0.002 to 0.2 g/m.sup.2, and most 
preferably from 0.005 to 0.15 g/m.sup.2. 
The protective layer of the present invention can be coated directly on the 
top of a light-sensitive layer or can be used together with an ultraviolet 
ray protective layer or an interlayer. In general, the outermost 
protective layer of the present invention has a thickness of from 0.2 to 3 
.mu.m, and preferably from 0.5 to 2 .mu.m, and most preferably from 0.6 to 
1.5 .mu.m. A very thick protective layer will diminish the matting effect 
and a very thin layer will adversely affect the matte particle adhesion. 
The matte particles for use in accordance with this invention can be made 
by various well-known techniques in the art, such as, for example, 
crushing, grinding or pulverizing of polymer down to the desired size, 
emulsion polymerization, dispersion polymerization, suspension 
polymerization, solvent evaporation from polymer solution dispersed as 
droplets, and the like (see, for example, Arshady, R. in "Colloid & 
Polymer Science", 1992, No 270, pages 717-732; G. Odian in "Principles of 
Polymerization", 2nd Ed. Wiley(1981); and W. P. Sorenson and T. W. 
Campbell in "Preparation Method of Polymer Chemistry", 2nd Ed, Wiley 
(1968)). A suitable method of preparing matte particles in accordance with 
this invention is by a limited coalescence technique where polyaddition 
polymerizable monomer or monomers are added to an aqueous medium 
containing a particulate suspending agent to form a discontinuous (oil 
droplet) phase in a continuous (water) phase. The mixture is subjected to 
shearing forces, by agitation, homogenization and the like to reduce the 
size of the droplets. After shearing is stopped an equilibrium is reached 
with respect to the size of the droplets as a result of the stabilizing 
action of the particulate suspending agent in coating the surface of the 
droplets and then polymerization is completed to form an aqueous 
suspension of polymer particles. This process is described in U.S. Pat. 
Nos. 2,932,629; 5,279,934; and 5,378,577 incorporated herein by reference. 
Another method of preparing matte particles in accordance with this 
invention is by a process including forming a suspension or dispersion of 
ethylenically unsaturated monomer droplets in an aqueous media, and 
polymerizing the monomer to form solid polymer particles. Optionally, 
subsequent to the formation of the droplets and before the commencement of 
the polymerization reaction, an effective amount of a hydrophilic colloid 
such as gelatin can be added to the aqueous media. 
Suitable polyfunctional ethylenically unsaturated crosslinking monomers 
which can be used as Component A of the present invention are monomers 
which are polyfunctional with respect to the polymerization reaction, and 
include esters of unsaturated monohydric alcohols with unsaturated 
monocarboxylic acids, such as allyl methacrylate, allyl acrylate, butenyl 
acrylate, undecenyl acrylate, undecenyl methacrylate, vinyl acrylate, 
vinyl methacrylate; dienes such as butadiene and isoprene; esters of 
saturated glycols or diols with unsaturated monocarboxylic acids, such as 
ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene 
glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol 
dimethacrylate; and polyfunctional aromatic compounds such as divinyl 
benzene; higher functional crosslinking monomers such as trimethyol 
propane trimethacrylate, pentaerythritol tetramethacrylate mixtures 
thereof and the like. Preferably, monomer A is ethylene glycol 
dimethacrylate, ethylene glycol diacrylate, or divinylbenzene. Most 
preferably, monomer A is ethylene glycol dimethacrylate. 
Suitable ethylenically unsaturated monomers containing carboxylic acid 
groups which can be used as component B include acrylic monomers such as 
acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic 
acid, fumaric acid; monoalkyl itaconate including monomethyl itaconate; 
monoethyl itaconate, and monobutyl itaconate, monoalkyl maleate including 
monomethyl maleate, monoethyl maleate, monobutyl maleate; citraconic acid; 
styrenecarboxylic acid; mixtures thereof and the like. Preferably, monomer 
B is acrylic acid, methacrylic acid, ethacrylic acid or itaconic acid. 
Most preferably, monomer B is methacrylic acid. 
Suitable ethylenically unsaturated monomers other than B which can be used 
as component C include alkyl esters of acrylic acid or methacrylic acid, 
such as, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 
ethyl acrylate, butyl acrylate, hexyl acrylate, n-octyl acrylate, lauryl 
methacrylate, 2-ethylhexyl methacrylate, nonyl acrylate, benzyl 
methacrylate; the hydroxyalkyl esters of the same acids, such as, 
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl 
methacrylate; the nitrile and amides of the same acids such as 
acrylonitrile, methacrylonitrile, acrylamide and methacrylamide; vinyl 
esters, such as, vinyl acetate, vinyl propionate, vinylidene chloride; 
vinyl chloride; and vinyl aromatic compounds, such as, styrene, t-butyl 
styrene, ethyl vinyl benzene, vinyl toluene; dialkyl maleates; dialkyl 
itaconates; dialkyl methylene-malonates; mixtures thereof and the like. 
Preferably, monomer C is styrene, vinyl toluene, methyl methacrylate, or 
ethyl methacrylate. Most preferably, monomer C is methyl methacrylate. 
The matte particle surface may include reactive functional groups which 
form covalent bonds with binders 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, and the like. There is no particular restriction on the amount of 
reactive groups present, but their concentrations are preferably in the 
range of from 0.5 to 10 weight percent. The particle surface may be 
surrounded with a layer of colloidal inorganic particles as described in 
U.S. Pat. No. 5,288,598, or a layer of colloidal polymer latex particles 
which have affinity with suitable binder as described in U.S. Pat. No. 
5,279,934, or a layer of gelatin as described in U.S. Pat. No. 4,855,219. 
Processing removable mattes can be used together with other processing 
surviving matte particle in the practice of the invention to further 
enhance the resistance of the photographic element to ferrotyping and 
blocking. Such processing removable mattes include particles of, for 
example, copolymers of alkyl (meth)acrylates and methacrylic acid, or 
acrylic acid, or itaconic acid, copolymers of alkyl (meth)acrylates and 
maleic monoesters or monoamides, copolymers of styrene or vinyl toluene 
and .alpha.,.beta.-unsaturated mono- or di-carboxylic acids, or 
dicarboxylic monoesters or monoamides, graft copolymers containing maleic 
anhydride or methacrylic acid, and dicarboxylic acid mono-ester of a 
cellulose derivative, such as phthalate and hexahydro phthalate of methyl 
cellulose, hydroxyethyl cellulose, or hydroxypropyl methyl cellulose. Such 
processing soluble mattes are described in further detail in U.S. Pat. No. 
2,992,101; 3,767,448; 4,094,848; 4,447,525; and 4,524,131. 
The light-insensitive layer also includes a suitable hydrophilic binder 
such as naturally occurring substances such as proteins, protein 
derivatives, cellulose derivatives (e.g., cellulose esters), 
polysaccharides, casein, and the like, and synthetic water permeable 
colloids such as poly(vinyl lactams), acrylamide polymers, poly(vinyl 
alcohol) and its derivatives, hydrolyzed polyvinyl acetates, polymers of 
alkyl and sulfoalkyl acrylates and methacrylates, polyamides, polyvinyl 
pyridine, acrylic acid polymers, maleic anhydride copolymers, polyalkylene 
oxide, methacrylamide copolymers, polyvinyl oxazolidinones, maleic acid 
copolymers, vinyl amine copolymers, methacrylic acid copolymers, 
acryloyloxyalkyl sulfonic acid copolymers, vinyl imidazole copolymers, 
vinyl sulfide copolymers, homopolymer or copolymers containing styrene 
sulfonic acid, and the like. Gelatin is the most preferred hydrophilic 
binder. 
Gelatin can be used together with other water dispersible polymers as 
binders in the practice of the present invention. The water dispersible 
polymers can be incorporated into either light-sensitive or 
light-insensitive layers. Suitable water dispersible polymers include both 
synthetic and natural water dispersible polymers. Synthetic water 
dispersible polymers may contain a nonionic group, an anionic group, or a 
nonionic group and an anionic group in the molecular structure. The 
nonionic group may be, for example, an ether group, an ethylene oxide 
group, an amide group, or a hydroxyl group. The anionic group may be, for 
example, a sulfonic acid group or the salt thereof, a carboxylic acid 
group or the salt thereof, or a phosphoric acid group or the salt thereof. 
The natural water soluble polymer may include a nonionic group, an anionic 
group, or a nonionic group and an anionic group in the molecular 
structure. The water dispersible polymers may be incorporated into the 
photographic materials of the present invention in an amount of preferably 
at least 0.5 percent, preferably from 1 to 50 percent, and most preferably 
from 2 to 30 percent based on the amount of the whole coated amount of 
gelatin on the side having a layer containing the matte particle of the 
present invention. 
Water dispersible polymers useful for the present invention include vinyl 
polymer latex particles prepared by such as emulsion polymerization 
process, water-borne polyurethane dispersions, water-borne epoxy 
dispersions, water-borne polyester dispersions, and the like. The mean 
size of the dispersed particles is within the range of from 0.01 to 0.2 
.mu.m, preferably from 0.02 to 0.1 .mu.m. 
The binder should be chosen so that it effectively adheres the matte 
particles to the surface of the element. For a crosslinkable binder such 
as gelatin, the binder is preferably crosslinked so as to provide a high 
degree of cohesion and adhesion. Crosslinking agents or hardeners which 
may effectively be used in the coating compositions of the present 
invention include aldehydes, epoxy compounds, polyfunctional aziridines, 
vinyl sulfones, melamines, triazines, polyisocyanates, dioxane derivatives 
such as dihydroxydioxane, carbodiimides, chrome alum, zirconium sulfate, 
and the like. 
Any lubricant can be used in the outermost layer of the present invention. 
Typical lubricants include (1) silicone based materials disclosed, for 
example, in U.S. Pat. Nos. 3,489,567; 3,080,317; 3,042,522; 4,004,927; and 
4,047,958, and in British Pat. Nos. 955,061 and 1,143,118; (2) higher 
fatty acids and derivatives, higher alcohols and derivatives, metal salts 
of higher fatty acids, higher fatty acid esters, higher fatty acid amides, 
polyhydric alcohol esters of higher fatty acids, etc., disclosed in U.S. 
Pat. Nos. 2,454,043; 2,732,305; 2,976,148; 3,206,311; 3,933,516; 
2,588,765; 3,121,060; 3,502,473; 3,042,222; and 4,427,964; in British 
Patent Nos. 1,263,722; 1,198,387; 1,430,997; 1,466,304; 1,320,757; 
1,320,565; and 1,320,756; and in German Patent Nos. 1,284,295 and 
1,284,294; (3) liquid paraffin and paraffin or wax like materials such as 
carnauba wax, natural and synthetic waxes, petroleum waxes, mineral waxes 
and the like; (4) perfluoro- or fluoro- or fluorochloro-containing 
materials, which include poly(tetrafluoroethlyene), 
poly(trifluorochloroethylene), poly(vinylidene fluoride), 
poly(trifluorochloroethylene-co-vinyl chloride), poly(meth)acrylates or 
poly(meth)acrylamides containing perfluoroalkyl side groups, and the like. 
Lubricants useful in the present invention are described in further detail 
in Research Disclosure No. 308, published December 1989, page 1006. 
The protective layer useful in the practice of the invention may optionally 
contain surface active agents, antistatic agents, charge control agents, 
thickeners, ultraviolet ray absorbers, processing removable dyes, high 
boiling point solvents, silver halide particles, colloidal inorganic 
particles, magnetic recording particles, and various other additives. 
The matte-containing layer useful in the practice of the invention can be 
applied by any of a number of well-know techniques, such as dip coating, 
rod coating, blade coating, air knife coating, gravure coating and reverse 
roll coating, extrusion coating, slide coating, curtain coating, and the 
like. After coating, the protective layer is generally dried by simple 
evaporation, which may be accelerated by known techniques such as 
convection heating. Known coating and drying methods are described in 
further detail in Research Disclosure No. 308, Published December 1989, 
pages 1007 to 1008. 
The photographic element of the present invention can contain an 
electrically conductive layer, which can be either a surface protective 
layer or a sub layer. The surface resistivity of at least one side of the 
support is preferably less than 1.times.10.sup.12 .OMEGA./square, more 
preferably less than 1.times.10.sup.11 .OMEGA./square at 25.degree. C. and 
20 percent relative humidity. To lower the surface resistivity, a 
preferred method is to incorporate at least one type of electrically 
conductive material in the electrically conductive layer. Such materials 
include both conductive metal oxides and conductive polymers or oligomeric 
compounds. Such materials have been described in detail in, for example, 
U.S. Pat. Nos. 4,203,769; 4,237,194; 4,272,616; 4,542,095; 4,582,781; 
4,610,955; 4,916,011; and 5,340,676. 
The present invention is also directed to a single use camera having 
incorporated therein a photographic element as described above. Single use 
cameras are known in the art under various names: film with lens, 
photosensitive material package unit, box camera and photographic film 
package. Other names are also used, but regardless of the name, each 
shares a number of common characteristics. Each is essentially a 
photographic product (camera) provided with an exposure function and 
preloaded with a photographic material. The photographic product comprises 
an inner camera shell loaded with the photographic material, a lens 
opening and lens, and an outer wrapping(s) of some sort. The photographic 
materials are exposed in camera, and then the product is sent to the 
developer who removes the photographic material and develop it. Return of 
the product to the consumer does not normally occur. 
Single-use cameras and their methods of manufacture and use are described 
in U.S. Pat. Nos. 4,801,957; 4,901,097; 4,866,459; 4,849,325; 4,751,536; 
4,827,298; European Patent Applications 460,400; 533,785; 537,225; all of 
which are incorporated herein by reference. 
The protective overcoat layer in accordance with this invention may be 
positioned over a transparent magnetic recording layer as described in 
U.S. Pat. Nos. 5,395,743; 5,397,826; 5,413,903; 5,432,050; 5,434,037; and 
5,436,120. 
The photographic processing steps to which the raw film may be subject may 
include, but are not limited to the following: 
(1) color developing.fwdarw.bleach-fixing.fwdarw.washing/stabilizing; 
(2) color 
developing.fwdarw.bleaching.fwdarw.fixing.fwdarw.washing/stabilizing; 
(3) color 
developing.fwdarw.bleaching.fwdarw.bleach-fixing.fwdarw.washing/stabilizin 
g; 
(4) color 
developing.fwdarw.stopping.fwdarw.washing.fwdarw.bleaching.fwdarw.washing. 
fwdarw.fixing.fwdarw.washing/stabilizing; 
(5) color 
developing.fwdarw.bleach-fixing.fwdarw.fixing.fwdarw.washing/stabilizing; 
(6) color 
developing.fwdarw.bleaching.fwdarw.bleach-fixing.fwdarw.fixing.fwdarw.wash 
ing/stabilizing; 
Among the processing steps indicated above, the steps (1), (2), (3), and 
(4) are preferably applied. Additionally, each of the steps indicated can 
be used with multistage applications as described in Hahm, U.S. Pat. No. 
4,719,173, with co-current, counter-current, and contraco arrangements for 
replenishment and operation of the multistage processor. 
Any photographic processor known to the art can be used to process the 
photosensitive materials described herein. For instance, large volume 
processors, and so-called minilab and microlab processors may be used. 
Particularly advantageous would be the use of Low Volume Thin Tank 
processors as described in the following references: WO 92/10790; WO 
92/17819; WO 93/04404; WO 92/17370; WO 91/19226; WO 91/125677; WO 
92/07302; WO 93/00612; WO 92/07301; WO 02/09932; U.S. Pat. No. 5,294,956; 
EP 559,027; U.S. Pat. No. 5,179,404; EP 559,025; U.S. Pat. No. 5,270,762; 
EP 559,026; U.S. Pat. No. 5,313,243; U.S. Pat. No. 5,339,131. 
The present invention will now be described in detail with references to 
examples; however, the present invention should not be limited to these 
examples. 
EXAMPLES 
Matte Particles Used in the Example Coatings are listed in Table 1. 
TABLE 1 
______________________________________ 
MATTE TICLES 
Particle 
ID Composition Size (.mu.m) 
______________________________________ 
M-1.sup.a 
Poly(methyl methacrylate) 0.8 
M-2.sup.a 
Poly(methyl methacrylate) 1.2 
M-3.sup.a 
Poly(methyl methacrylate) 1.5 
M-4.sup.a 
Poly(methyl methacrylate) 1.7 
M-5.sup.a 
Poly(methyl methacrylate) 2.2 
M-6.sup.a 
Poly(methyl methacrylate) 2.4 
M-7.sup.b 
Poly(vinyl toluene) 1.8 
M-8.sup.a 
Poly(vinyl toluene-co-divinyl benzene) 80/20 
1.5 
M-9.sup.a 
Poly(vinyl toluene-co-divinyl benzene) 80/20 
0.9 
M-10.sup.a 
Poly(vinyl toluene-co-divinyl benzene) 80/20 
1.2 
M-11.sup.a 
Poly(vinyl toluene-co-divinyl benzene) 80/20 
2.0 
M-12 Poly(methyl methcarylate) 2.5 
M-13 Poly(methyl methacrylate-co-methacrylic acid) 
3.0 
45/55 
M-14 Poly(methyl methacrylate-co-methacrylic acid-co- 
1.0 
ethylene glycol dimethacrylate) 60.2/37.3/2.5 
M-15 Poly(methyl methacrylate-co-methacrylic acid-co- 
1.0 
ethylene glycol dimethacrylate) 59.3/39.5/1.2 
M-16 Poly(methyl methacrylate-co-methacrylic acid-co- 
1.4 
ethylene glycol dimethacrylate) 46/53.9/0.1 
M-17 Poly(methyl methacrylate-co-methacrylic acid-co- 
1.4 
ethylene glycol dimethacrylate) 45.8/53.9/0.3 
M-18 Poly(methyl methacrylate-co-methacrylic acid-co- 
1.4 
ethylene glycol dimethacrylate) 45.4/54/0.6 
M-19 Poly(methyl methacrylate-co-methacrylic acid-co- 
1.4 
ethylene glycol dimethacrylate) 44.6/54.3/1.1 
______________________________________ 
.sup.a The matte is made in accordance with U.S. Pat. No. 4,855,219. 
.sup.b The matte is colloidal silica covered according to U.S. Pat. No. 
5,378,577. 
Examples 1 to 6 
A series of photographic elements are prepared as follows: A poly(ethylene 
naphthalate) support having an antihalation layer on one side and an 
antistatic layer overcoated with a transparent magnetic recording layer on 
the other side is coated on the antihalation layer with the following 
imaging forming layers in sequence. 
Interlayer: This layer comprises 2,5-di-t-octyl-1,4-dihydroxy benzene 
(0.075 g/m.sup.2), tri(2-ethylhexyl)phosphate (0.113 g/m.sup.2), and 
gelatin (0.86 g/m.sup.2). 
Slow Cyan Dye-forming Layer: This layer comprises a red sensitive silver 
bromoiodide emulsion (3.3 mole percent iodide) (0.324 .mu.m grain size) 
(0.387 g/m.sup.2 silver), compound CC-1 (0.355 g/m.sup.2), IR-4 (0.011 
g/m.sup.2), B-1 (0.075 g/m.sup.2), S-2 (0.377 g/m.sup.2), S-3 (0.098 
g/m.sup.2), and gelatin (1.64 g/m.sup.2). 
Mid Cyan Dye-forming Layer: This layer comprises a blend of a red sensitive 
silver bromoiodide emulsion (3.3 mole percent iodide) (0.488 .mu.m grain 
size) (0.816 g/m.sup.2 silver) and a red sensitive, tabular grain, silver 
bromoiodide emulsion (4.5 mole percent iodide) (0.98 .mu.m diameter by 
0.11 .mu.m thick) (0.215 g/m.sup.2 silver), compound CC-1 (0.183 
g/m.sup.2), IR-3 (0.054 g/m.sup.2), B-1 (0.027 g/m.sup.2), CM-1 (0.011 
g/m.sup.2), S-2 (0.183 g/m.sup.2), S-3 (0.035 g/m.sup.2), S-5 (0.054 
g/m.sup.2), and gelatin (1.35 g/m.sup.2). 
Fast Cyan Dye-forming Layer: This layer comprises a red sensitive, tabular 
grain, silver bromoiodide emulsion (4.5 mole percent iodide) (1.10 .mu.m 
diameter by 0.11 .mu.m thick) (1.08 g/m.sup.2 silver), compound CC-1 
(0.161 g/m.sup.2), IR-3 (0.038 g/m.sup.2), IR-4 (0.038 g/m.sup.2), CM-1 
(0.032 g/m.sup.2), S-2 (0.237 g/m.sup.2), S-5 (0.038 g/m.sup.2), and 
gelatin (1.35 g/m.sup.2). 
Interlayer: This layer comprises 2,5-di-t-octyl-1,4-dihydroxy benzene 
(0.075 g/m.sup.2), tri(2-ethylhexyl)phosphate (0.113 g/m.sup.2), and 
gelatin (0.86 g/m.sup.2). 
Slow Magenta Dye-forming Layer: This layer comprises a blend of a green 
sensitive, tabular grain, silver bromoiodide emulsion (1.5 mole percent 
iodide) (0.7 .mu.m diameter by 0.112 .mu.m thick) (0.258 g/m.sup.2 Ag), 
and a green sensitive, tabular grain, silver bromoiodide emulsion (1.3 
mole percent iodide) (0.54 .mu.m diameter by 0.086 .mu.m thick) (0.409 
g/m.sup.2 Ag), compound M-1 (0.204 g/m.sup.2), MM-1 (0.038 g/m.sup.2), 
ST-1 (0.020 g/m.sup.2), S-1 (0.26 g/m.sup.2), and gelatin (1.18 
g/m.sup.2). 
Mid Magenta Dye-forming Layer: This layer comprises a green sensitive, 
tabular grain, silver bromoiodide emulsion (4.5 mole percent iodide) (0.61 
.mu.m diameter by 0.12 .mu.m thick) (0.646 g/m.sup.2 Ag), compound M-1 
(0.099 g/m.sup.2), MM-1 (0.027 g/m.sup.2), IR-2 (0.022 g/m.sup.2), ST-1 
(0.010 g/m.sup.2), S-1 (0.143 g/m.sup.2), S-2 (0.044 g/m.sup.2), and 
gelatin (1.41 g/m.sup.2). 
Fast Magenta Dye-forming Layer: This layer comprises a green sensitive; 
tabular grain, silver bromoiodide emulsion (4.5 mole percent iodide) (0.98 
.mu.m diameter by 0.113 .mu.m thick) (0.699 g/m.sup.2 Ag), compound M-1 
(0.052 g/m.sup.2), MM-1 (0.032 g/m.sup.2), IR-2 (0.022 g/m.sup.2), ST-1 
(0.005 g/m.sup.2), S-1 (0.111 g/m.sup.2), S-2 (0.044 g/m.sup.2), and 
gelatin (1.123 g/m.sup.2). 
Yellow Filter Layer: This layer comprises 2,5-di-t-octyl-1,4-dihydroxy 
benzene (0.075 g/m.sup.2), YD-2 (0.108 g/m.sup.2), Irganox 1076 sold by 
Ciby Geigy (0.01 g/m.sup.2), S-2 (0.121 g/m.sup.2) and gelatin (0.861 
g/m.sup.2). 
Slow Yellow Dye-forming Layer: This layer comprises a blend of a blue 
sensitive, tabular grain, silver bromoiodide emulsion (4.5 mole percent 
iodide) (1.4 .mu.m diameter by 0.131 .mu.m thick) (0.161 g/m.sup.2 Ag), a 
blue sensitive, tabular grain, silver bromoiodide emulsion (1.5 mole 
percent iodide) (0.85 .mu.m diameter by 0.131 .mu.m thick) (0.0.108 
g/m.sup.2 Ag), and a blue sensitive, tabular grain, silver bromoiodide 
emulsion (1.3 mole percent iodide) (0.54 .mu.m diameter by 0.086 .mu.m 
thick) (0.161 g/m.sup.2 Ag), compound Y-1 (0.915 g/m.sup.2), IR-1 (0.032 
g/m.sup.2), B-1 (0.0065 g/m.sup.2), S-1 (0.489 g/m.sup.2), S-3 (0.0084 
g/m.sup.2), and gelatin (1.668 g/m.sup.2). 
Fast Yellow Dye-forming Layer: This layer comprises a blue sensitive, 
tabular grain, silver bromoiodide emulsion (4.5 mole percent iodide) (2.3 
.mu.m diameter by 0.128 .mu.m thick) (0.43 g/m.sup.2 Ag), compound Y-1 
(0.15 g/m.sup.2), IR-1 (0.032 g/m.sup.2), B-1 (0.0054 g/m.sup.2), S-1 
(0.091 g/m.sup.2), S-3 (0.0070 g/m.sup.2), and gelatin (0.753 g/m.sup.2). 
UV Protective Layer: This layer comprises compound UV-1 (0.111 g/m.sup.2), 
UV-2 (0.111 g/m.sup.2)S-4 (0.222 g/m.sup.2), silver bromide Lippmann 
emulsion (0.215 g/m.sup.2 Ag), and gelatin (0.7 g/m.sup.2). 
##STR1## 
Preparation of Light-Insensitive Layer 
A light-insensitive layer containing gelatin binder and matting agents 
listed in Table 1 is coated on the top of the UV layer and has the 
following composition: 
TABLE 2 
______________________________________ 
COMPOSITION OF THE LIGHT-INSENSITIVE LAYER 
(DRY WEIGHT) 
______________________________________ 
Gelatin, lime processed 
888 mg/m.sup.2 
Silicone lube, DC-200 (Dow Corning) 
40.1 mg/m.sup.2 
Fluorad FC-134 (3M Co.) 
3.9 mg/m.sup.2 
Aerosol OT (American Cyanamide) 
21.5 mg/m.sup.2 
Surfactant Olin 10G (Olin Corp.) 
27.2 mg/m.sup.2 
Matte 1 (Table 3) 
Matte 2 (Table 3) 
______________________________________ 
Table 3 shows the compositions of the light-insensitive layer of each 
photographic element prepared. 
TABLE 3 
______________________________________ 
Coverage Coverage 
Matte 1 
(mg/m.sup.2) 
Matte 2 (mg/m.sup.2) 
______________________________________ 
Example 1 M-8 53.8 M-13 107.6 
(Comparison) 
Example 2 M-16 53.8 M-13 107.6 
(Invention) 
Example 3 M-17 53.8 M-13 107.6 
(Invention) 
Example 4 M-18 53.8 M-13 107.6 
(Invention) 
Example 5 M-19 53.8 M-13 107.6 
(Invention) 
Example 6 M-3 53.8 M-13 107.6 
(Comparison) 
______________________________________ 
Evaluation of the Surface Roughness 
The surface roughness is evaluated by using a Gould Microtopographer 200, 
which measures the surface roughness in terms of the number of peaks per 
centimeter as a function of distance above the mean line. The peak is 
defined as the point of maximum height on that portion of a profile which 
lies above the mean line and between two intersections of the profile and 
the meanline (ANSI B46.1-1978). The result is reported in Table 4 as peaks 
per centimeter (PPCM) at a distance of 0.13 .mu.m above the mean line. 
Evaluation of the Abrasion Resistance 
To evaluate the abrasion resistance of the protective overcoat, discs of 
coatings after processing are placed on a Taber Abrader and abraded in 
accordance with ASTM method D1044. Since the outermost layer contains 
matting agents, the measurement based on percentage light transmission or 
difference in percentage haze (Delta Haze) before and after Taber abrasion 
cannot be used to measure the abrasion resistance of the coatings. 
Instead, a Gould Microtopographer 200 is used to measured the surface 
roughness within the track area of the samples after Taber abrasion. The 
surface roughness is then analyzed in terms of two parameters: PPCM which 
counts the number of scratches produced by Taber wheels per centimeter and 
Ra which accounts for the average surface roughness. The product of the 
two (Ra.times.PPCM) is used here to quantify the extent of surface 
scratches. The larger the Ra.times.PPCM value, the poorer the scratch 
resistance of the sample. The results are summarized in Table 4. 
Evaluation of Ferrotyping Resistance 
A group of six 35 mm strips having a length of 305 mm (12 inches) of the 
feature film (raw or processed) are placed in a 70 percent or 80 percent 
relative humidity (RH) chamber for a minimum of 16 hours. The strips are 
stacked, sensitized side to unsensitized side and wrapped in foil, placed 
inside a moisture proof wrap, and sealed. The sealed package is then 
placed above a flat glass plate and under a brass bar of the same size 
with weight of 6.89 Kgs (15 lbs). The package, with the glass plate and 
brass bar is then placed in a 37.8.degree. C. (100.degree. F.) room for 17 
hours. After storage, the bag is opened, the top and bottom strips are 
discarded, and the remaining strips are visually inspected for ferrotyping 
against the following scale: 
______________________________________ 
% of area showing 
Value ferrotyping 
______________________________________ 
A 0 to &lt;5 
B 5 to &lt;20 
C 20 to &lt;50 
D 50 to 100 
______________________________________ 
The testing results are reported in Table 4. 
TABLE 4 
______________________________________ 
PPCM 
PPCM PPCM Change Ra x Ferrotyping.sup.c 
(Mild).sup.a 
(Harsh).sup.b 
(%) PPCM 80% RH 
______________________________________ 
Example 1 
401 309 23 9.3 B 
(Comparison) 
Example 2 
538 477 11.3 7.8 A 
(Invention) 
Example 3 
563 503 10.7 6.7 A 
(Invention) 
Example 4 
530 507 4.3 7.5 A 
(Invention) 
Example 5 
510 476 6.7 7.1 A 
(Invention) 
Example 6 
419 328 22 6.1 B 
(Comparison) 
______________________________________ 
The comparison Examples 1 and 6 contain a 1.5 .mu.m poly(vinyl 
toluene-co-divinyl benzene) matte and a 1.5 .mu.m poly(methyl 
methacrylate) matte, respectively. They show a significant loss in the 
element protective surface roughness upon harsh drying (60.degree. C. and 
2 minutes). On the other hand, Invention Examples 2 to 5 contain matte 
particles of the present invention, and the change in their surface 
roughness upon harsh drying is much smaller. In other words, the 
photographic elements in accordance with the present invention have 
unexpectedly robust performance in photofinishing laboratories. 
Examples 7 to 19 
Examples 7 to 19 are prepared as in Examples 1 to 6 except the 
light-insensitive protective layer which has the composition shown in 
Table 5. 
TABLE 5 
______________________________________ 
COMPOSITION OF THE LIGHT-INSENSITIVE LAYER 
(DRY WEIGHT) 
______________________________________ 
Gelatin, lime processed 
888 mg/m.sup.2 
Silicone lube, DC-200 (Dow Corning) 
40.1 mg/m.sup.2 
Fluorad FC-134 (3M Co.) 
3.9 mg/m.sup.2 
Aerosol OT (American Cyanamide) 
21.5 mg/m.sup.2 
Surfactant Olin 10G (Olin Corp.) 
27.2 mg/m.sup.2 
Matte 1 (Table 6) 
______________________________________ 
Both ferrotyping protection and surface roughness for these elements are 
evaluated in a similar way to those for Examples 1 to 6. The results are 
reported in Table 6. 
Evaluation of the RMS Granularity 
The graininess of a photographic picture is caused primarily by the 
developed dye clouds, image silver and light scatter from matting agents 
in the protective overcoat layers. The Root Mean Square (RMS) Granularity 
is evaluated by the method described in ANSI Ph 2.40 (1985) entitled "Root 
Mean Square (RMS) Granularity of Film (images on One Side Only)-Method for 
Measurement". By comparing RMS Granularity of the listed samples with a 
film that contains no matte, the granularity due to the matte is 
determined. The test results are reported in Table 6. 
TABLE 6 
__________________________________________________________________________ 
Increase 
Ferrotyping.sup.a 
Coverage 
PPCM 
PPCM 
in RMS 
80% RH/ 
Matte 
(mg/m.sup.2) 
(Mild) 
(Harsh) 
Granularity 
37.8.degree. C. 
__________________________________________________________________________ 
Example 7 
M-1 107.6 
309 151 1 D 
(Comparison) 
Example 8 
M-2 107.6 
736 504 1 B 
(Comparison) 
Example 9 
M-3 107.6 
663 578 2 B 
(Comparison) 
Example 10 
M-5 107.6 
638 526 4 A 
(Comparison) 
Example 11 
M-7 107.6 
479 307 8 B 
(Comparison) 
Example 12 
M-8 107.6 
653 347 6 B 
(Comparison) 
Example 13 
M-9 107.6 
389 205 1 C 
(Comparison) 
Example 14 
M-10 
107.6 
633 433 2 B 
(Comparison) 
Example 15 
M-11 
107.6 
482 433 8 B 
(Comparison) 
Example 16 
M-12 
107.6 
336 296 6 B 
(Comparison) 
Example 17 
M-14 
107.6 
771 746 1 B 
(Comparison) 
Example 18 
M-15 
107.6 
811 815 1 A 
(Invention) 
Example 19 
M-17 
107.6 
-- -- 1 A 
(Invention) 
__________________________________________________________________________ 
.sup.a Ferrotyping test is done on the harsh dried processed films. 
Above examples contain matte particles of different sizes and compositions. 
Clearly, only those examples which contain matte particles in accordance 
with the present invention show both good RMS printing granularity and 
superior ferrotyping performance. 
Examples 20 to 24 
Examples 20 to 24 (Table 7) are prepared as in Examples 1 to 6. These 
examples show benefits of use of a combination of matte particles of the 
present invention with other processing surviving matting agents. 
TABLE 7 
______________________________________ 
Increase in 
Ferrotyping.sup.a 
Matte 1 Matte 2 RMS 80% RH/ 
Coverage 
Coverage Granularity 
37.8.degree. C. 
______________________________________ 
Example 20 
M-2 M-13 0.5 C 
(Comparison) 
53.8 mg/m.sup.2 
107.6 mg/m.sup.2 
Example 21 
M-4 M-13 1.5 C 
(Comparison) 
53.8 mg/m.sup.2 
107.6 mg/m.sup.2 
Example 22 
M-4 M-13 3.0 A 
(Comparison) 
107.6 mg/m.sup.2 
107.6 mg/m.sup.2 
Example 23 
M-2 M-18 0.5 A 
(Invention) 
53.8 mg/m.sup.2 
107.6 mg/m.sup.2 
Example 24 
M-4 M-18 1.5 A 
(Invention) 
53.8 mg/m.sup.2 
107.6 mg/m.sup.2 
______________________________________ 
.sup.a Ferrotyping test is done on the harsh dried processed films. 
Comparison Examples 20 and 21 contain 53.8 mg/m.sup.2 of a 1.2 .mu.m 
poly(methyl methacrylate) matte and a 1.7 .mu.m poly(methyl methacrylate) 
matte, respectively, in combination with a processing removable matte 
(M-13). They show good RMS printing granularity. However, their 
ferrotyping performance is poor. Comparison Example 22 contains 107.6 
mg/m.sup.2 of the 1.7 .mu.m poly(methyl methacrylate) matte in combination 
with the processing removable matte. It has good ferrotyping performance 
but unacceptable RMS printing granularity invention Examples 23 and 24 
contain 53.8 mg/m.sup.2 of a 1.2 .mu.m poly(methyl methacrylate) matte and 
a 1.7 .mu.m poly(methyl methacrylate) matte, respectively, in combination 
with the matte particle in accordance with the present invention. Clearly, 
the use of an additional 107.6 mg/m.sup.2 of matte particle of the present 
invention does not lead to an increase in RMS printing granularity. In 
this regard, the matte particles of present invention are comparable to a 
processing removable matte. However, the matte particles of the present 
invention are processing survival matte as evidenced by the unexpectedly 
excellent post process ferrotyping performance of invention Examples 23 
and 24.