FIELD OF THE INVENTION
[0001] The present invention relates to UV sensitive negative acting silver halide photographic
elements, and more particularly to UV sensitive negative acting silver halide photographic
elements which can be handled under room lighting conditions without significant loss
in image density, and which upon development of a half-tone image thereon can be dry
etched with improved performance characteristics.
BACKGROUND OF THE ART
[0002] Light sensitive recording materials may suffer from a phenomenon known as halation
which causes degradation in the quality of the recorded image. Such degradation may
occur when a fraction of the imaging light which strikes the photosensitive layer
is not absorbed but passes through to the film base on which the photosensitive layer
is coated. A portion of the light reaching the base may be reflected back to strike
the photosensitive layer from the underside. Light thus reflected may, in some cases,
contribute significantly to the total exposure of the photosensitive layer. Any particulate
matter in the photosensitive element may cause light passing through the element to
be scattered. Scattered light which is reflected from the film base will, on its second
passage through the photosensitive layer, cause exposure over an area adjacent to
the point of intended exposure. It is this effect which leads to image degradation.
Silver halide based photograhic materials (including photothermographic materials)
are prone to this form of image degradation since the photosensitive layers contain
light scattering particles. The effect of light scatter on image quality is well documented
and is described, for example, in T. H. James "The Theory of the Photographic Process",
4th Edition, Chapter 20, Macmillan 1977.
[0003] It is common practice to minimise the effects of light scatter by including a light
absorbing layer within the photographic element. To be effective the absorption of
this layer must be at the same wavelengths as the sensitivity of the photosensitive
layer. In the case of imaging materials coated on transparent base, a light absorbing
layer is frequently coated on the reverse side of the base from the photosensitive
layer. Such a coating, known as an "antihalation layer", effectively prevents reflection
of any light which has passed through the photosensitive layer.
[0004] A similar effect may be achieved by a light absorbing layer interposed between the
photosensitive layer and the base. This construction, described as an "antihalation
underlayer" is applicable to photosensitive coatings on transparent or non-transparent
bases. A light absorbing substance may be incorporated into the photosensitive layer
itself, in order to absorb scattered light. Substances used for this purpose are known
as "acutance dyes". It is also possible to improve image quality by coating a light
absorbing layer above the photosensitive layer of a wet processed photographic element.
Coatings of this kind, described in U.S. Patent Specification No. 4,312,941 prevent
multiple reflections of scattered light between the internal surfaces of a photographic
element.
[0005] When the wavelength of sensitivity of the imaging medium is within the visible regions
of the electromagnetic spectrum it is often necessary to have the antihalation dye
rendered colorless prior to viewing of the final image. If the dye is not rendered
colorless, the visible antihalation dye will provide a background density or stain
to the final image. Antihalation dyes can be rendered colorless by way of heat bleaching,
development solution bleaching, a specific bleaching solution, or removal from the
medium in a dissolving bath.
[0006] When the wavelength of sensitivity of the medium, and hence the wavelength of absorption
of the antihalation dye, is outside the visible region, it is not necessary to decolorize
the antihalation dye since it has no color (i.e., it is not visible). Some antihalation
dyes may have absorption tails that extend into the visible region and would therefore
have to be decolorized (e.g., U.S. Patent 4,581,325).
[0007] It is very desirable to produce silver halide photographic elements for duplicating
and contacting processes which may be handled safely in bright white light. The benefits
of this include ease of working and inspection of the element during exposure and
processing, and generally more pleasant working conditions for the operators. Negative
acting silver halide elements can generally be made resistant to fogging in room light
by making use of an accentuated low intensity reciprocity failure effect.
[0008] In the use of negative acting ultraviolet radiation sensitive photographic silver
halide emulsions and elements, it is desirable to have the elements room light or
white light handlable. Providing these emulsions and elements with ultraviolet radiation
sensitivity below 400nm can provide an element with good room light handlability.
These elements, primarily useful as black and white image forming elements, can still
benefit from and often need backside antihalation layers in order to provide sharp
images. Using UV absorbing antihalation dyes without any significant tail in the visible
region of the electromagnetic spectrum has eliminated the need for decolorizing of
the antihalation dye.
[0009] It has been discovered by applicants, however, that when half-tone images produced
from such UV sensitive photographic media are used in dry etch processes, there is
an adverse affect on the process from the residual antihalation dye. In the dry etch
process, the photosensitive medium of this invention is repeatedly exposed through
the black-and-white half-tone color separation image. These multiple exposures increase
the dot sizes, minimizing on-press dot gain or correcting color balance or tone. If
the UV dye is not present in the antihalation layer of the unexposed UV sensitive
film, what is ordinarily observed is that the higher percentage dots expand to fill
in the highlights (veiling) before there is sufficient dot gain in the low percentage
and intermediate dots. Conversely if the UV dye is still present in the imaged medium
after processing then subsequent exposures to duplicating, proofing or plate materials
necessitates higher exposure to burn through the high UV Dmin areas which causes a
shift in dot size, leading to inaccurate dot reproduction.
[0010] Thus two key requirements are 1) that the UV dye be present during the image step
of the unimaged material for optimal dry etching, and 2) that the UV dye be removed
during the chemical process for optimal subsequent contact exposures.
[0011] U.S. Reissue Patent No. 30,303 describes UV absorbing dyes useful as filter dyes
in photographic elements. The claims are for molecules of the type

wherein n is 1 or 2, when n is 1, R₁ and R₂ are independently chosen to represent
hydrogen, an alkyl group of 1 to 10 carbon atoms, or a cyclic alkyl group of 5 or
6 carbon atoms provided that R₁ and R₂ cannot both be hydrogen, or R₁ and R₂ taken
together represent the atoms necessary to complete a cyclic amino group and when n
is 2 at least one of R₁ and R₂ is alkylene and G represents an electron withdrawing
group.
[0012] They are incorporated in a photographic element of a suport, silver halide layer(s)
and in UV filter layer containing above dye. Alternatively, they can be in the film
support. The examples given refer to color negative coatings, though black and white
constructions are not excluded. No mention is made of water solubilization or bleachability.
There use is to protect the film of unwanted UV exposure to give a more balanced color
rendition.
[0013] Similar abilities are described in U.S. Patents 4,307,184 and 4,756,908. The first
patent refers to polymeric versions of the dye class and is fairly far removed from
our proposed use. The second patent refers to particular versions of Formula I (R₁-R²-allyl
for 3, and R short chain alkyl, C₁-C³ R₁=opt. subs long chain alkyl >C₁₀). Advantages
are claimed for improved absorption profiles, easier and more consistent dispersions
obtainable and show a reduced speed loss compared to the derivatives claimed in Reissue
Patent 30,303. Again the main application is for the UV filter dye in the color negative
constructions. The dyes are hydrophobic in U.S. Patents 4,307,184 and 4,576,908 and
presumably would not be bleached in processing. In fact it is usually preferred to
be nonbleachable and nondiffusing to give UV protection after processing. In U.S.
Patent 4,307,183 the supersensitizing combination of a polymeric version of Formula
I with a methine spectral sensitizer in silver halide constructions is claimed.
[0014] Of more relevance is U.S. Patent Application Serial No. [F/381] where water solubilized
versions of I are claimed in direct positive (black and white) silver halide constructions.
A general formula of water solubilization is used which may make it novel compared
to the glass and uses disclosed in Reissue Patent 30,303. The dye has to be reactively
associated with the silver halide emulsion and is not disclosed specifically as a
backside coating. Advantages are claimed for improved white light safety with minimal
residual UV stain after processing.
SUMMARY OF THE INVENTION
[0015] According to the present invention, there is provided a UV sensitive negative acting
silver halide photographic element for contacting processes which can be safely handled
under white light, said element comprising a support, a hydrophilic colloidal silver
halide emulsion layer comprising negative acting silver halide grains, and a backside
coated antihalation layer, wherein said backside coated antihalation layer comprises
a water removable UV absorbing compound having at least 80% absorption in the range
of 350 to 400 nm.
DETAILED DESCRlPTION OF THE INVENTION
[0016] The present invention relates to a UV sensitive negative acting silver halide photographic
element comprising a support, a hydrophilic colloidal silver halide emulsion layer
comprising negative acting UV sensitive photographic silver halide grains, and at
least a backside coated UV absorbing antihalation layer, wherein said antihalation
layer comprises a water removable UV absorbing compound having at least 80% of absorption
in the range of 350 to 400 nm.
[0017] Preferably, the UV absorbing compounds for use in the silver halide photographic
element according to the present invention correspond to the general formula:

in which:
R₁ and R₂, the same or different, each represents an alkyl group, an aryl group or
a cyclic alkyl group, or R₁ and R₂ taken together represent the atoms necessary to
complete a cyclic amino group,
G represents an electron withdrawing group, and at least one of R₁, R₂ and G is substituted
with a water solubilizing group.
[0018] In the above general formula (I):
R₁ and R₂ can be the same or different and represent alkyl groups, preferably alkyl
groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 4 carbon
atoms, including substituted alkyl groups such as cyanoalkyl or alkoxyalkyl groups,
aryl groups, preferably aryl groups having 6 to 20 carbon atoms, more preferably aryl
groups having 6 to 10 carbon atoms or cyclic alkyl groups, preferably cyclic alkyl
groups having 5 or 6 carbon atoms or R₁ and R₂ taken together represent the elements
necessary to complete a cyclic amino group such as, for example, a piperidino, a morpholino,
a pyrrolidino, a hexahydroazepino and a piperazino group,
G represents an electron withdrawing group of any electron withdrawing groups known
in the art such as, for example, CN, NO₂, COOR or SO₂R wherein R represents an alkyl
group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl
group having 1 to 4 carbon atoms, or an aryl group (such as phenyl or naphthyl), preferably
an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6
to 10 carbon atoms, and
at least one of R₁, R₂ and G is substituted with a water solubilizing group of any
water solubilizing groups known in the art such as, for example, a COOH group or an
alkaline metal or ammonium salt thereof, a SO₃H group or an alkaline metal or ammonium
salt thereof, a hydroxy group, a quaternary ammonium salt containing group, a phosphate
group or a polyoxyalkylene group.
[0019] More preferably, the UV absorbing compounds for use in the silver halide photographic
elements according to the present invention correspond to the general formula:

in which:
R₁ represents an alkyl group having 1 to 10 carbon atoms, preferably a lower alkyl
group having 1 to 4 carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl,
butyl, isobutyl or tert-butyl group, and
R₃ represents an alkylene group having 1 to 10 carbon atoms whose carbon atom chain
may comprise divalent groups such as, for example, -O-, -S-, -COO- or -SO₂-.
[0020] The UV absorbing compounds of the photographic elements according to the present
invention have a strong absorption in the region of the electromagnetic spectrum at
the boundary between the UV and the visible region. The UV absorbing compounds according
to this invention have a peak or plateau in its absorbing spectrum around 380 nm.
At least 80% of their absorption is in the range of from 350 to 400 nm, their absorption
below 350 nm being such as not to affect significantly the response of the silver
halide emulsion to the UV radiation of the exposure light, preferably such as not
to absorb more than 30% of the radiation emitted by exposure lamps having a maximum
emulsion wavelength of 317nm. Additionally, the UV absorbing compounds of the photographic
elements according to the present invention are highly soluble in water, so that they
can be washed out of the element during processing, without a significant retention
of UV absorption. Preferably, the absorption of the element in D
min areas after processing is, in the range from 300 nm to 400 nm, less than 0.10.
[0021] The following are examples of water soluble UV absorbing compounds which are applicable
to the present invention:

[0022] The UV absorbing compounds of this invention can be prepared according to methods
well known in the art. The UV absorbing compounds of general formulas (I) and (II)
can be prepared by treating an appropriate amine compound containing the water solubilizing
group with an appropriate intermediate in an organic solvent at boiling temperature
followed by usual techniques for isolating the compounds. Useful intermediates are
for example described in U.S. Patent 4,045,229.
[0023] The following is a preparative example of a UV absorbing compound for use in the
present invention.
PREPARATIVE EXAMPLE
Compound (1):
N-(3-allylidenemalononitrile)-sarcosine
[0024] Sarcosine (89.1 grams, 1 mole) was dissolved in 170 ml of water containing NaOH (40
grams, 1 mole) and 450 ml of methanol. Acetanilidoallylidenemalononitrile (216 grams,
0.91 moles) was then added with stirring. The mixture was refluxed for 30 minutes
and then cooled in ice. The addition of 100 ml of 37% HCl separated a yellow colored
solid that was filtered and crystallized from a 2:1 ethanol-water mixture. The obtained
product (112 grams, yield 65%) had a M.P. = 170-2°C and a percent analysis for C₉H₉N₃O
as follows:
|
N% |
C% |
H% |
Calculated |
21.98 |
56.54 |
4.74 |
Found |
21.66 |
56.22 |
4.72 |
Spectrophometric analysis :
λmax (in water) = 374nm
ε (in water) = 52,000
The product is soluble in water upon addition of a stoichiometric quantity of NaOH.
[0025] In the photographic elements of this invention, the UV absorbing compounds are used
in an aqueous penetrable binder layer hydrophilic colloidal layer on the backside
of the base or support layer. Said backside layer is further from the exposure light
source than the silver halide emulsion layer and on the opposite side of the base
from the silver halide emulsion layer. In order to incorporate the UV absorbing compounds
into an hydrophilic colloidal layer of the silver halide photographic elements according
to this invention, they may be added in the form of a water solution to the hydrophilic
colloidal coating composition. The amount of the UV absorbing compounds used, although
different according to the type of the compound or of silver halide emulsion to be
used, is generally about 0.02g/m² or greater (preferably no more than 0.3g/m²). The
antihalation dye should provide an absorbance between 350 and 400 nm (e.g., 375 nm)
of at least 0.3, preferably at least 0.5, and more preferably at least 0.8.
[0026] It is well known in the art that silver halides have a high natural sensitivity to
UV radiations and that silver bromide also has a relatively high sensitivity to blue
and shorter wavelength visible light, while silver chloride has a relatively low sensitivity
to blue and to shorter wavelength visible light. Therefore, silver halide emulsions
for use in the photographic elements according to this invention are preferably higher
chloride silver halide emulsions. They preferably contain at least 50% mole and more
preferably at least 75% mole of silver chloride. The higher the silver chloride content,
the lower is the natural blue and visible light sensitivity, even if the UV radiation
sensitivity remains high. More preferably, the silver halide emulsions to be used
in type photographic elements according to the present invention are emulsions wherein
at least 75% by weight of all silver halide grains are silver halide grains wherein
at least at 80% mole is silver chloride. The remaining silver halide, if any, will
be silver bromide and/or silver iodide but the latter should normally be present in
an amount not exceeding 10% mole. In case of silver halides comprising chloride in
the range of from 50 to 75% mole, the remaining halide being essentially bromide,
the spectral sensitivity is even more extended to visible region and it may be useful
to combine the UV absorbing compounds according to this invention with dyes capable
of absorbing visible radiations so that the photographic element can be safely handled
in bright light conditions. The dyes include, for example, oxonol dyes, benzylidene
dyes, and the like, which can be bleachable or washable during processing. Examples
of useful dyes are described, for example, in U.S. patent 4,140,531. In conventional
emulsions sensitizing dyes are used to extend the sensitivity of the emulsion to longer
wavelengths of visible light. This is not required with the emulsions used in the
present invention. It also appears to be desirable for the high chloride silver halide
emulsions to have a relatively small grain size, e.g. a mean grain size of from 0.05
to 0.6 micron, the preferred grain size being in the range of from 0.05 to 0.3 microns
and the most preferred being from 0.05 to 0.1 micron. The high chloride silver halide
grains preferably have a cubic shape, but may have other shapes, such as octahedra,
spheres, tabular shapes, etc.
[0027] In the present invention, silver halides are preferably prepared in the presence
of at least a doping metallic element of the 8th Group of the Periodic Table of Elements,
such as rhodium, iridium and ruthenium, which acts as electron acceptor. Said doping
element is preferably chosen among water-soluble iridium salts, water-soluble ruthenium
salts, or water-soluble rhodium salts. Iridium salts include iridium and alkaline
metal halides, such as potassium iridium (III) hexachloride and sodium iridium (III)
hexabromide. Rhodium salts include rhodium halides, such as rhodium (III) trichloride
and rhodium (IV) tetrachloride and rhodium and alkaline metal halides such as potassium
rhodium (III) hexabromide and sodium rhodium (III) hexachloride. These salts may be
added in a quantity of from 0.5x10⁻⁴ to 10x10⁻⁴ moles, and preferably from 2x10⁻⁴
to 7x10⁻⁴ moles per mole of silver halide.
[0028] Gold compounds, used for chemical sensitization, include alkali metal chloroaurates,
chloroauric acid, gold sulfide, gold selenide, and the like. Said gold compounds are
generally used in a quantity of from 1x10⁻⁶ to 10⁻⁴ moles per mole of silver halide.
[0029] The UV sensitive silver halide emulsions of the photographic elements according to
this invention may contain various other photographic additives wich include sensitizers,
desensitizers, solarization accelerators, stabilizers, hardeners, coating aids, preservatives,
matting agents, antistatic agents, and the like, as described, for example, in U.S.
Patent 4,495,274.
[0030] Gelatin is generally used as hydrophilic colloid for the silver halide photographic
elements of the present invention. As hydrophilic colloids, gelatin derivatives, natural
substances such as albumin, casein, agar-agar, alginic acid and the like, and hydrophilic
polymers such as polyvinyl alcohol, polyvinylpyrolidone, cellulose ethers, partially
hydrolized polyvinyl acetate, and the like can be used in addition to or instead of
gelatin. Further, gelatin can be partially substituted with polymer latexes obtained
by emulsion polymerization of vinyl monomers, such as polyethylacrylate latexes, to
improve the physical characteristics of the photographic layers.
[0031] Support bases used in the negative-acting silver halide photographic elements according
to this invention can be any of the conventionally used support bases, such as glass,
cloth, metal, film including for example cellulose acetate, cellulose acetate-butyrate,
cellulose nitrate, polyester, polyamine, polystyrene, and the like, paper including
baryta-coated paper, resin-coated paper, and the like.
[0032] The silver halide photographic elements according to this invention may be used in
the field of Graphic Arts for various purposes, such as, for example, for contacting,
for reproduction, for making offset printing masters, as well as in radiography for
special purposes, in electron photography, and the like, where high UV sensitivity
is required together with low blue light sensitivity.
[0033] The silver halide photographic elements according to this invention are highly UV
sensitive and give high contrast and low minimum density (fog) when they are exposed
with light rich in UV rays, and they can be handled in bright white room light.
[0034] These and other advantages according to the present invention will be illustrated
with reference to the following examples.
EXAMPLE 1
[0035] A silver halide emulsion containing 84 mole % chloride and 16 mole % bromide was
prepared by adding simultaneously and under stirring, over a period of 25 minutes,
with a double-jet technique, water solution B and water solution C to water gelatin
solution A, said water solutions having the composition reported herein below.
Solution A
Water - g 833.3
Gelatin - g 25
Polyvinylpyrrolidone (K-30) - 6.33
KBr - ml 0.167 (1N)
Solution B
Water - g 368
AgNO₃ - g 170
Solution C
Water - g 361.3
KCl - g 62.65 (0.84 moles)
KBr - g 19.04 (0.16 moles)
Na₃RhCl₆.12H₂O - g 0.200
[0036] The gelatin solution was kept at constant temperature of 30°C. The addition rate
of solution B was constant, while the addition rate of solution C varied such as to
maintain the millivolt of the emulsion thus formed at a value of 120 ± 2 mv measured
with a specific electrode for Br ion and a reference electrode of the saturated Ag/AgCl
type. The emulsion, wherein the soluble salts had been removed with the conventional
coagulation method, had a mean grain diameter of 0.09µm. The emulsion was then chemically
sensitized with sodium thiosulfate and sodium gold chloride. At the end of the chemical
sensitization a triazole stabilizer was added and the emulsion was prepared for coating
with the addition of additional gelatin, coating surface active agents and formaldehyde
hardener.
[0037] The emulsion was then coated at a silver coating weight of 2.7g Ag/m² onto a polyethylene
terephthalate support base which was backed with green antihalation layers that had
varying amounts of yellow, blue and UV dye as shown as explained in Table 1 and Figures
1 and 2.
[0038] The resulting films were exposed through a 0-2, 20 cm continuus wedge. The exposing
lamp was a violux 1500S UV lamp at a distance of 52 inches from the film plane.
[0039] The exposed films were developed in 3M RDC developer for 20 sec at 40°C and fixed
in 3M fix roll fixer.
[0040] Dmin, Dmax, Speed at .2, Toe Contrast, and Average Contrast of the resulting coatings
show that the E-E sensitivity are essentially the same.
[0041] Next the dry etching characteristics were examined which demonstrates the resulting
improvement by incorporating the UV dye into the antihalation formulation.
[0042] In order to evaluate the dry etching characteristics it is first necessary to determine
the optimum dot-for-dot exposure in the E-E mode.
[0043] For these tests a hard dot original was used. The optimum contact exposure which
we will define as producing a Dmax >4.0 with a dot reproduction within 1% at the midtone
turned out to be 18 units.
[0044] The dry etch test then consists of making contact exposures to the original of 1x,
2x, 4x, 6x, 8x, 10x, 12x, 14x and 16x the dot-for-dot exposure. The resulting dot
enlargement is measured. Both the highlight, shadow and midtone are of importance
with the objective being to obtain a very cbntrolled movement of all dot sizes and
as large a movement as possible in the midtone and shadow before the highlights veil
in.
TABLE 1
Antihalation Characteristics of the Various Coatings |
Coating No. |
Absorbance |
|
*B |
*Y |
*UV |
1 |
.83 |
.34 |
.18 |
2 |
.80 |
.34 |
.38 |
3 |
.80 |
.33 |
.50 |
4 |
.80 |
.48 |
0.24 |
5 |
.82 |
.49 |
.69 |
*B is oxonol blue 628 which has an absorbance peak at 650nm |
*Y is oxonol yellow K which has an absorbance peak at 430nm |
*UV is the water soluble UV dye number 1 of this invention which has an absorbance
peak of 370nm |
TABLE 2
Sensitometry of the Various Coatings |
Ctg. No. |
Dmin |
Dmax |
S.2 |
Toe Contrast |
Average Contrast |
1 |
.04 |
4.5 |
-2.86 |
2.09 |
9.8 |
2 |
.04 |
4.5 |
-2.87 |
2.14 |
9.8 |
3 |
.04 |
4.5 |
-2.87 |
2.20 |
9.6 |
4 |
.04 |
4.5 |
-2.86 |
2.17 |
9.4 |
5 |
.04 |
4.5 |
-2.88 |
2.17 |
9.2 |
TABLE 3
Dry Etch Results
[0045] Table 3 shows how dramatically the addition of the UV dye to the antihalation backing
affects the resulting dry etching characteristics. It holds back veiling in the highlights
allowing greater movement in the midtone and shadow ends.
TABLE 3
Dry Etch Results |
|
|
Coating 1 |
Coating 2 |
Coating 3 |
Coating 4 |
Coating 5 |
|
|
10% |
50% |
91% |
10% |
50% |
91% |
10% |
50% |
91% |
10% |
50% |
91% |
10% |
50% |
91% |
Exposure |
Original Target |
|
|
|
Invention |
Invention |
|
|
|
Invention |
|
Resulting contact dot |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
18 Units |
|
91 |
51 |
9 |
91 |
51 |
9 |
91 |
51 |
9 |
91 |
51 |
9 |
91 |
51 |
9 |
2X |
|
93 |
54 |
10 |
92 |
53 |
10 |
92 |
53 |
9 |
92 |
53 |
10 |
92 |
53 |
10 |
4X |
|
96 |
58 |
11 |
94 |
57 |
11 |
94 |
57 |
10 |
94 |
57 |
11 |
93 |
56 |
11 |
6X |
veiling |
99 |
63 |
12 |
95 |
60 |
12 |
95 |
59 |
11 |
97 |
60 |
12 |
94 |
59 |
11 |
8X |
|
|
|
|
97 |
62 |
12 |
96 |
61 |
12 |
99 |
63 |
13 |
95 |
60 |
12 |
10X |
|
|
veiling |
99 |
64 |
13 |
97 |
63 |
12 |
|
|
|
96 |
61 |
12 |
12X |
|
|
|
|
|
|
|
98 |
64 |
13 |
|
|
|
97 |
63 |
13 |
14X |
|
|
|
|
|
|
|
98 |
65 |
13 |
|
|
|
97 |
64 |
13 |
16X |
|
|
|
|
|
veiling |
99 |
66 |
14 |
|
|
|
98 |
65 |
14 |