AU619309B2 – Combination of photosensitive elements for use in radiography
– Google Patents
AU619309B2 – Combination of photosensitive elements for use in radiography
– Google Patents
Combination of photosensitive elements for use in radiography
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Info
Publication number
AU619309B2
AU619309B2
AU37121/89A
AU3712189A
AU619309B2
AU 619309 B2
AU619309 B2
AU 619309B2
AU 37121/89 A
AU37121/89 A
AU 37121/89A
AU 3712189 A
AU3712189 A
AU 3712189A
AU 619309 B2
AU619309 B2
AU 619309B2
Authority
AU
Australia
Prior art keywords
silver halide
screen
layer
radiation
group
Prior art date
1988-07-14
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU37121/89A
Other versions
AU3712189A
(en
Inventor
Sergio Pesce
John M. Winslow
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1988-07-14
Filing date
1989-06-28
Publication date
1992-01-23
1989-06-28
Application filed by Minnesota Mining and Manufacturing Co
filed
Critical
Minnesota Mining and Manufacturing Co
1990-01-18
Publication of AU3712189A
publication
Critical
patent/AU3712189A/en
1992-01-23
Application granted
granted
Critical
1992-01-23
Publication of AU619309B2
publication
Critical
patent/AU619309B2/en
2009-06-28
Anticipated expiration
legal-status
Critical
Status
Ceased
legal-status
Critical
Current
Links
Espacenet
Global Dossier
Discuss
238000002601
radiography
Methods
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title
claims
description
18
-1
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Caenorhabditis elegans gars-1 gene
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Chemical compound
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Chemical compound
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2
XSCHRSMBECNVNS-UHFFFAOYSA-N
benzopyrazine
Natural products
N1=CC=NC2=CC=CC=C21
XSCHRSMBECNVNS-UHFFFAOYSA-N
0.000
description
2
125000000484
butyl group
Chemical group
[H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H]
0.000
description
2
229910052799
carbon
Inorganic materials
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description
2
150000001732
carboxylic acid derivatives
Chemical class
0.000
description
2
125000002057
carboxymethyl group
Chemical group
[H]OC(=O)C([H])([H])[*]
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description
2
239000000084
colloidal system
Substances
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description
2
239000003086
colorant
Substances
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description
2
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crystal
Substances
0.000
description
2
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dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane
Chemical compound
[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O
GXGAKHNRMVGRPK-UHFFFAOYSA-N
0.000
description
2
230000000694
effects
Effects
0.000
description
2
235000019325
ethyl cellulose
Nutrition
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2
229920001249
ethyl cellulose
Polymers
0.000
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2
125000001153
fluoro group
Chemical group
F*
0.000
description
2
150000002344
gold compounds
Chemical class
0.000
description
2
229910052736
halogen
Inorganic materials
0.000
description
2
150000002367
halogens
Chemical class
0.000
description
2
MTNDZQHUAFNZQY-UHFFFAOYSA-N
imidazoline
Chemical compound
C1CN=CN1
MTNDZQHUAFNZQY-UHFFFAOYSA-N
0.000
description
2
239000012770
industrial material
Substances
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description
2
239000004615
ingredient
Substances
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2
239000007788
liquid
Substances
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2
229910052744
lithium
Inorganic materials
0.000
description
2
229920001220
nitrocellulos
Polymers
0.000
description
2
238000003199
nucleic acid amplification method
Methods
0.000
description
2
235000005985
organic acids
Nutrition
0.000
description
2
239000011368
organic material
Substances
0.000
description
2
LFSXCDWNBUNEEM-UHFFFAOYSA-N
phthalazine
Chemical compound
C1=NN=CC2=CC=CC=C21
LFSXCDWNBUNEEM-UHFFFAOYSA-N
0.000
description
2
XNGIFLGASWRNHJ-UHFFFAOYSA-N
phthalic acid
Chemical compound
OC(=O)C1=CC=CC=C1C(O)=O
XNGIFLGASWRNHJ-UHFFFAOYSA-N
0.000
description
2
239000004014
plasticizer
Substances
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description
2
239000004848
polyfunctional curative
Substances
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2
229920000642
polymer
Polymers
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description
2
229920002451
polyvinyl alcohol
Polymers
0.000
description
2
235000019422
polyvinyl alcohol
Nutrition
0.000
description
2
239000004800
polyvinyl chloride
Substances
0.000
description
2
229920000915
polyvinyl chloride
Polymers
0.000
description
2
125000001436
propyl group
Chemical group
[H]C([*])([H])C([H])([H])C([H])([H])[H]
0.000
description
2
230000008313
sensitization
Effects
0.000
description
2
ADZWSOLPGZMUMY-UHFFFAOYSA-M
silver bromide
Chemical compound
[Ag]Br
ADZWSOLPGZMUMY-UHFFFAOYSA-M
0.000
description
2
HKZLPVFGJNLROG-UHFFFAOYSA-M
silver monochloride
Chemical compound
[Cl-].[Ag+]
HKZLPVFGJNLROG-UHFFFAOYSA-M
0.000
description
2
238000003756
stirring
Methods
0.000
description
2
238000003860
storage
Methods
0.000
description
2
239000000126
substance
Substances
0.000
description
2
239000004094
surface-active agent
Substances
0.000
description
2
DLQKNXAWCPRERG-UHFFFAOYSA-N
terbium thulium
Chemical compound
[Tb][Tm]
DLQKNXAWCPRERG-UHFFFAOYSA-N
0.000
description
2
CBDKQYKMCICBOF-UHFFFAOYSA-N
thiazoline
Chemical compound
C1CN=CS1
CBDKQYKMCICBOF-UHFFFAOYSA-N
0.000
description
2
230000008719
thickening
Effects
0.000
description
2
WFKWXMTUELFFGS-UHFFFAOYSA-N
tungsten
Chemical compound
[W]
WFKWXMTUELFFGS-UHFFFAOYSA-N
0.000
description
2
229910052721
tungsten
Inorganic materials
0.000
description
2
239000010937
tungsten
Substances
0.000
description
2
238000005406
washing
Methods
0.000
description
2
150000005208
1,4-dihydroxybenzenes
Chemical class
0.000
description
1
125000001637
1-naphthyl group
Chemical group
[H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H]
0.000
description
1
HIYWOHBEPVGIQN-UHFFFAOYSA-N
1h-benzo[g]indole
Chemical class
C1=CC=CC2=C(NC=C3)C3=CC=C21
HIYWOHBEPVGIQN-UHFFFAOYSA-N
0.000
description
1
125000000143
2-carboxyethyl group
Chemical group
[H]OC(=O)C([H])([H])C([H])([H])*
0.000
description
1
125000001731
2-cyanoethyl group
Chemical group
[H]C([H])(*)C([H])([H])C#N
0.000
description
1
125000001622
2-naphthyl group
Chemical group
[H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H]
0.000
description
1
CBHTTYDJRXOHHL-UHFFFAOYSA-N
2h-triazolo[4,5-c]pyridazine
Chemical class
N1=NC=CC2=C1N=NN2
CBHTTYDJRXOHHL-UHFFFAOYSA-N
0.000
description
1
QOXOZONBQWIKDA-UHFFFAOYSA-N
3-hydroxypropyl
Chemical group
[CH2]CCO
QOXOZONBQWIKDA-UHFFFAOYSA-N
0.000
description
1
SXIFAEWFOJETOA-UHFFFAOYSA-N
4-hydroxy-butyl
Chemical group
[CH2]CCCO
SXIFAEWFOJETOA-UHFFFAOYSA-N
0.000
description
1
244000215068
Acacia senegal
Species
0.000
description
1
101710134784
Agnoprotein
Proteins
0.000
description
1
102000009027
Albumins
Human genes
0.000
description
1
108010088751
Albumins
Proteins
0.000
description
1
241000272814
Anser sp.
Species
0.000
description
1
244000255890
Biophytum sensitivum
Species
0.000
description
1
BTBUEUYNUDRHOZ-UHFFFAOYSA-N
Borate
Chemical compound
[O-]B([O-])[O-]
BTBUEUYNUDRHOZ-UHFFFAOYSA-N
0.000
description
1
CPELXLSAUQHCOX-UHFFFAOYSA-M
Bromide
Chemical compound
[Br-]
CPELXLSAUQHCOX-UHFFFAOYSA-M
0.000
description
1
229920000742
Cotton
Polymers
0.000
description
1
SNRUBQQJIBEYMU-UHFFFAOYSA-N
Dodecane
Natural products
CCCCCCCCCCCC
SNRUBQQJIBEYMU-UHFFFAOYSA-N
0.000
description
1
KIWBPDUYBMNFTB-UHFFFAOYSA-N
Ethyl hydrogen sulfate
Chemical compound
CCOS(O)(=O)=O
KIWBPDUYBMNFTB-UHFFFAOYSA-N
0.000
description
1
101150111247
GRS1 gene
Proteins
0.000
description
1
229920000084
Gum arabic
Polymers
0.000
description
1
101100479551
Methanopyrus kandleri (strain AV19 / DSM 6324 / JCM 9639 / NBRC 100938) glyS gene
Proteins
0.000
description
1
239000006057
Non-nutritive feed additive
Substances
0.000
description
1
229910019142
PO4
Inorganic materials
0.000
description
1
SJEYSFABYSGQBG-UHFFFAOYSA-M
Patent blue
Chemical compound
[Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1
SJEYSFABYSGQBG-UHFFFAOYSA-M
0.000
description
1
ISWSIDIOOBJBQZ-UHFFFAOYSA-N
Phenol
Chemical compound
OC1=CC=CC=C1
ISWSIDIOOBJBQZ-UHFFFAOYSA-N
0.000
description
1
206010034960
Photophobia
Diseases
0.000
description
1
239000004952
Polyamide
Substances
0.000
description
1
239000004793
Polystyrene
Substances
0.000
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1
239000004372
Polyvinyl alcohol
Substances
0.000
description
1
229910006069
SO3H
Inorganic materials
0.000
description
1
235000021355
Stearic acid
Nutrition
0.000
description
1
FZWLAAWBMGSTSO-UHFFFAOYSA-N
Thiazole
Chemical compound
C1=CSC=N1
FZWLAAWBMGSTSO-UHFFFAOYSA-N
0.000
description
1
ZMZDMBWJUHKJPS-UHFFFAOYSA-M
Thiocyanate anion
Chemical compound
[S-]C#N
ZMZDMBWJUHKJPS-UHFFFAOYSA-M
0.000
description
1
229910052775
Thulium
Inorganic materials
0.000
description
1
229920002433
Vinyl chloride-vinyl acetate copolymer
Polymers
0.000
description
1
229920001986
Vinylidene chloride-vinyl chloride copolymer
Polymers
0.000
description
1
FJWGYAHXMCUOOM-QHOUIDNNSA-N
[(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate
Chemical compound
O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O
FJWGYAHXMCUOOM-QHOUIDNNSA-N
0.000
description
1
238000002835
absorbance
Methods
0.000
description
1
239000000205
acacia gum
Substances
0.000
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1
235000010489
acacia gum
Nutrition
0.000
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1
239000000980
acid dye
Substances
0.000
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1
229920006322
acrylamide copolymer
Polymers
0.000
description
1
230000009471
action
Effects
0.000
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1
238000007792
addition
Methods
0.000
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1
239000000654
additive
Substances
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1
239000000853
adhesive
Substances
0.000
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1
230000001070
adhesive effect
Effects
0.000
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1
230000002776
aggregation
Effects
0.000
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1
238000004220
aggregation
Methods
0.000
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1
229920000615
alginic acid
Polymers
0.000
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1
235000010443
alginic acid
Nutrition
0.000
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1
125000003342
alkenyl group
Chemical group
0.000
description
1
125000005250
alkyl acrylate group
Chemical group
0.000
description
1
125000002947
alkylene group
Chemical group
0.000
description
1
239000004411
aluminium
Substances
0.000
description
1
229910052782
aluminium
Inorganic materials
0.000
description
1
XAGFODPZIPBFFR-UHFFFAOYSA-N
aluminium
Chemical compound
[Al]
XAGFODPZIPBFFR-UHFFFAOYSA-N
0.000
description
1
125000000129
anionic group
Chemical group
0.000
description
1
230000002742
anti-folding effect
Effects
0.000
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1
239000002216
antistatic agent
Substances
0.000
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1
239000007864
aqueous solution
Substances
0.000
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1
238000000149
argon plasma sintering
Methods
0.000
description
1
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barium oxide
Chemical compound
[Ba]=O
QVQLCTNNEUAWMS-UHFFFAOYSA-N
0.000
description
1
229910001864
baryta
Inorganic materials
0.000
description
1
230000008901
benefit
Effects
0.000
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1
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benzo[g][1,3]benzothiazole
Chemical compound
C1=CC=CC2=C(SC=N3)C3=CC=C21
IIUUNAJWKSTFPF-UHFFFAOYSA-N
0.000
description
1
125000003236
benzoyl group
Chemical group
[H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O
0.000
description
1
125000000319
biphenyl-4-yl group
Chemical group
[H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H]
0.000
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1
238000004061
bleaching
Methods
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1
125000001246
bromo group
Chemical group
Br*
0.000
description
1
125000004799
bromophenyl group
Chemical group
0.000
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1
125000004744
butyloxycarbonyl group
Chemical group
0.000
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1
239000000298
carbocyanine
Substances
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1
150000001735
carboxylic acids
Chemical class
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1
239000003054
catalyst
Substances
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catalytic reduction reaction
Methods
0.000
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1
125000002091
cationic group
Chemical group
0.000
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1
229920002678
cellulose
Polymers
0.000
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1
229920006217
cellulose acetate butyrate
Polymers
0.000
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1
239000002738
chelating agent
Substances
0.000
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1
125000001309
chloro group
Chemical group
Cl*
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1
238000000975
co-precipitation
Methods
0.000
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1
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contaminant
Substances
0.000
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1
229920001577
copolymer
Polymers
0.000
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1
125000004122
cyclic group
Chemical group
0.000
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1
238000010586
diagram
Methods
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1
125000002147
dimethylamino group
Chemical group
[H]C([H])([H])N(*)C([H])([H])[H]
0.000
description
1
238000009826
distribution
Methods
0.000
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1
125000003438
dodecyl group
Chemical group
[H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])*
0.000
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1
238000001035
drying
Methods
0.000
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1
238000005516
engineering process
Methods
0.000
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1
150000002148
esters
Chemical class
0.000
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1
125000001301
ethoxy group
Chemical group
[H]C([H])([H])C([H])([H])O*
0.000
description
1
125000003754
ethoxycarbonyl group
Chemical group
C(=O)(OCC)*
0.000
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1
238000011156
evaluation
Methods
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1
230000001747
exhibiting effect
Effects
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1
239000007850
fluorescent dye
Substances
0.000
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1
NBVXSUQYWXRMNV-UHFFFAOYSA-N
fluoromethane
Chemical compound
FC
NBVXSUQYWXRMNV-UHFFFAOYSA-N
0.000
description
1
239000011521
glass
Substances
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150000004676
glycans
Chemical class
0.000
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1
230000012010
growth
Effects
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1
101150003862
grsA gene
Proteins
0.000
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1
ZMZDMBWJUHKJPS-UHFFFAOYSA-N
hydrogen thiocyanate
Natural products
SC#N
ZMZDMBWJUHKJPS-UHFFFAOYSA-N
0.000
description
1
SMWDFEZZVXVKRB-UHFFFAOYSA-O
hydron;quinoline
Chemical compound
[NH+]1=CC=CC2=CC=CC=C21
SMWDFEZZVXVKRB-UHFFFAOYSA-O
0.000
description
1
150000002460
imidazoles
Chemical class
0.000
description
1
230000006872
improvement
Effects
0.000
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1
238000011065
in-situ storage
Methods
0.000
description
1
238000011835
investigation
Methods
0.000
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1
125000002346
iodo group
Chemical group
I*
0.000
description
1
125000003253
isopropoxy group
Chemical group
[H]C([H])([H])C([H])(O*)C([H])([H])[H]
0.000
description
1
125000001449
isopropyl group
Chemical group
[H]C([H])([H])C([H])(*)C([H])([H])[H]
0.000
description
1
230000031700
light absorption
Effects
0.000
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1
208000013469
light sensitivity
Diseases
0.000
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1
239000000314
lubricant
Substances
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1
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maintenance of location
Effects
0.000
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1
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matting agent
Substances
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1
238000005649
metathesis reaction
Methods
0.000
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1
125000001434
methanylylidene group
Chemical group
[H]C#[*]
0.000
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1
125000002496
methyl group
Chemical group
[H]C([H])([H])*
0.000
description
1
JZMJDSHXVKJFKW-UHFFFAOYSA-M
methyl sulfate(1-)
Chemical compound
COS([O-])(=O)=O
JZMJDSHXVKJFKW-UHFFFAOYSA-M
0.000
description
1
125000002816
methylsulfanyl group
Chemical group
[H]C([H])([H])S[*]
0.000
description
1
238000013508
migration
Methods
0.000
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1
230000005012
migration
Effects
0.000
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1
125000004573
morpholin-4-yl group
Chemical group
N1(CCOCC1)*
0.000
description
1
WAHWCUPSBZVYPH-UHFFFAOYSA-N
n,n-diethylethanamine;sodium
Chemical compound
[Na].CCN(CC)CC
WAHWCUPSBZVYPH-UHFFFAOYSA-N
0.000
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1
239000000025
natural resin
Substances
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1
229910017464
nitrogen compound
Inorganic materials
0.000
description
1
QIQXTHQIDYTFRH-UHFFFAOYSA-N
octadecanoic acid
Chemical compound
CCCCCCCCCCCCCCCCCC(O)=O
QIQXTHQIDYTFRH-UHFFFAOYSA-N
0.000
description
1
OQCDKBAXFALNLD-UHFFFAOYSA-N
octadecanoic acid
Natural products
CCCCCCCC(C)CCCCCCCCC(O)=O
OQCDKBAXFALNLD-UHFFFAOYSA-N
0.000
description
1
125000002347
octyl group
Chemical group
[H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H]
0.000
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229920000620
organic polymer
Polymers
0.000
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1
VLTRZXGMWDSKGL-UHFFFAOYSA-M
perchlorate
Inorganic materials
[O-]Cl(=O)(=O)=O
VLTRZXGMWDSKGL-UHFFFAOYSA-M
0.000
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1
VLTRZXGMWDSKGL-UHFFFAOYSA-N
perchloric acid
Chemical compound
OCl(=O)(=O)=O
VLTRZXGMWDSKGL-UHFFFAOYSA-N
0.000
description
1
CMCWWLVWPDLCRM-UHFFFAOYSA-N
phenidone
Chemical compound
N1C(=O)CCN1C1=CC=CC=C1
CMCWWLVWPDLCRM-UHFFFAOYSA-N
0.000
description
1
NBIIXXVUZAFLBC-UHFFFAOYSA-K
phosphate
Chemical compound
[O-]P([O-])([O-])=O
NBIIXXVUZAFLBC-UHFFFAOYSA-K
0.000
description
1
239000010452
phosphate
Substances
0.000
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1
229910052698
phosphorus
Inorganic materials
0.000
description
1
IJAPPYDYQCXOEF-UHFFFAOYSA-N
phthalazin-1(2H)-one
Chemical compound
C1=CC=C2C(=O)NN=CC2=C1
IJAPPYDYQCXOEF-UHFFFAOYSA-N
0.000
description
1
QWYZFXLSWMXLDM-UHFFFAOYSA-M
pinacyanol iodide
Chemical compound
[I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC
QWYZFXLSWMXLDM-UHFFFAOYSA-M
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1
239000002985
plastic film
Substances
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229920006255
plastic film
Polymers
0.000
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1
229920001490
poly(butyl methacrylate) polymer
Polymers
0.000
description
1
229920003229
poly(methyl methacrylate)
Polymers
0.000
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1
229920002401
polyacrylamide
Polymers
0.000
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1
229920002239
polyacrylonitrile
Polymers
0.000
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Classifications
G—PHYSICS
G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
G03C5/16—X-ray, infrared, or ultraviolet ray processes
G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
Description
L::
619309 S F Ref: 100090 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class ,pt Complete Specification Lodged: Accepted: Published: Priority: Related Art: S. ft.
59 fl4 ft Name and Address of Applicant: Address for Service: Minnesota Mining and Manufacturing Company 3M Center Saint Paul Minnesota 55101 UNITED STATES OF AMERICA Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Combination of Photosensitive Elements for use in Radiography The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/4 SABSTRACT OF DISCLOSURE Combination of photosensitive elements for use in radiography consisting of a pair of radiographic fluorescent screens and a double-side coated silver halide radiographic element. Each screen is arranged adjacent to each silver halide layer and each screen is capable of I imagewise emitting radiation to which the adjacent silver halide layer is sensitive when imagewise exposed to X radiation. The combination is characterized in that one fluorescent screen emits a first radiation in a first ooo wavelength region of the electromagnetic spectrum and the other fluorescent screen emits a second radiation in a second wavelength region of the electromagnetic spectrum, oV;. and each silver halide layer is substantially insensitive 1 0O0 *to the radiation emitted by the opposite screen.
1″ 00SO*
*A
-I IA- IP1007F393AU Combination of Photosensitive Elements for Use in Radiography FIELD OF THE INVENTION The present invention relates to a combination of photosensitive elements for use in radiography and, more in particular, to a combination of a fluorescent phosphor screen pair and a double-side coated silver halide radiographic element for use in industrial or medical radiography.
@6 BACKGROUND OF THE INVENTION ooIn radiography, and particularly in medical radiog- 0 raphy, light-sensitive elements having silver halide emulsion layers coated on both faces of a transparent support (called double-side coated silver halide elements) are used. Said double coated silver halide ele- ‘o ments are generally used in combination with fluorescent phosphor screens in order to reduce the X radiation exposure necessary to obtain the required image. Generally, one fluorescent phosphor screen is used in association with each silver halide emulsion layer of the double coated element. The silver halide emulsions used in the double coated element are sensitized to a region of the electromagnetic spectrum corresponding to the wave length of the light emitted by the phosphor materials used in the fluorescent phosphor screens, thus obtaining a significant amplification factor.
The quality of the image obtained upon X radiation exposure of said screen pair and double coated silver halide element combination and development of said double coated silver halide element is negatively affected by crossover exposure. Crossover exposure, which causes a 2 reduction in image sharpness, occurs in double coated silver halide elements when light emitted by one fluorescent phosphor screen passes through the adjacent silver halide emulsion layer and, the light having been spread by the support, imagewise exposes the silver halide emulsion layer on the opposite face of the support.
The crossover exposure causes poor definition even if light-sensitive elements are used which employ reduced silver halide coverages to lower the costs or increase the processing speed of the element. In fact, the decrease of the emulsion turbidity increases the amount of light available for crossover and therefore worsens the image.
To reduce the crossover exposure, dyes or pigments can be used within the radiographic element. The absorption of said dyes or pigments is in a region of the electromagnetic spectrum corresponding to the wavelength of j the light emitced by the fluorescent phosphor screens.
The dyes or pigments absorb some of the light emitted by Ij the fluorescent phosphor screen so that imaging of a sil- S ver halide emulsion layer by the opposite screen is rei duced by absorbance of the light from the opposite screen by the anticrossover dyes or pigments. These dyes or pigments are eliminated during the photographic developing, fixing and washing process of the exposed material; they can be for instance washed away or, more preferably, bleached while processing the radiographic element.
The dyes can be incorporated In any layer of the light-sensitive element: in the emulsion layer, in an intermediate layer between the emulsion and the base, or in the subbing layer of the support base. It is preferred to incorporate the dyes in a layer different from that containing the emulsion to avoid possible desensitization phenomena. Since 1978, Minnesota Mining and Manufacturing Company has sold a radiographic element under the name of -3 3M Trimax TM Type XUD X-Ray Film to be used in combination with 3M Trimax TM Intensifying Screens. Such radiographic element comprises a transparent polyester base, each surface of which has a silver halide emulsion layer sensitized to the light emitted by the screens. Between the emulsion and the base is a gelatin layer containing water-soluble acid dyes, which dyes can be decolorized during processing and have an absorption in a region of the electromagnetic spectrum corresponding to the wavelength of the light emitted by the screens and of the spectral sensitivity of the emulsion. The dyes are anchored in the layer by means of a basic mordant consisting of polyvinylpyridine.
000006 In the practical solution of reducing the crossover exposure by using a mordanted dye layer (as described for 00 SO instance in the European Patent Application 101,295), some problems are created which up to now have not yet been solved properly. In fact, the improvement of image definition involves not only a natural decrease of the light-sensitive element sensitivity caused by the absorption of the transmitted light which otherwise would take •r part in the formation of a part of the image, but also the possibility of desensitization phenomena due to the migration of dye not firmly mordanted in the silver halide emulsion layer. There is also a problem with residual stain even after processing, the retention of significant quantities of thiosulfate from the fixing bath which causes image yellowing upon long-time storage on shelf, and lengthening of the drying times after processing because of element thickening.
Other approaches have been suggested to reduce crossover, as reported hereinafter.
US Patent 3,923,515 discloses a relatively lower speed silver halide emulsion between the support and a higher speed silver halide emulsion layer to reduce 4 4 crossover.
US Patent 4,639,411 discloses a photographic element, to be used with blue emitting intensifying screens,having reduced crossover, said element comprising coated on both sides of a transparent support a blue sensitive silver halide emulsion layer and, interposed between the support and the emulsion layer, a blue absorbing layer comprising bright yellow silver iodide grains of a specific crystal structure.
Japanese Patent Application 62-52546 discloses a f:ee: radiographic element of improved image quality comprising coated on both sides of a transparent support a light sensitive silver halide emulsion layer and, interposed e.g between the support and the emulsion layer, a layer containing water insoluble metal salt particles having ade sorbed on their surface a dye. Said dye has a maximum absorption within the range of 20 nm of the maximum absorption of said silver halide and corresponds to the light emitted by intensifying screens. Silver halides are disclosed as preferred metal salt particles.
Japanese Patent Application 62-99748 discloses a radiographic element of improved image quality comprising coated on both sides of a transparent support a light- S. sensitive silver halide emulsion layer and, interposed between the support and the emulsion layer, a silver S* e halide emulsion layer having substantially no light-sensitivity.
The approaches of using light-insensitive silver halide layers as anticrossover layers interposed between the support and the light-sensitive silver halide emulsion layers, although preferred to using dyes or pigments, encounter some problems such as the increase of silver coverage and bad bleaching characteristics in photographic processing (residual stain).
The following are additional documents illustrating the state of the art.
BE 757,815 discloses a combination of a silver halide element and an intensifying screen comprising a fluorescent compound emitting light of wavelength less than 410 nm.
US 4,130,428 discloses a combination of two fluorescent screens and a double coated silver halide element wherein the maximum emission of the screens is in the wavelength range of 450-570 nm and silver halide layers are sensitive to light in the same wavelength range.
US 3,795,814, 4,070,583 and GB 2,119,396 disclose rare earth oxyhalide phosphors activated with terbium S and/or thulium employed in fluorescent screens having UV goose: emission.
FR 2,264,306 discloses a combination of a silver halide element and fluorescent screen comprising a rare earth activated rare earth oxyhalide phosphor having it c: ~maximum emission in the wavelength range of 400-500 nm.
EP 88,820 discloses a radiographic fluorescent screen comprising a first blue emitting phosphor layer and a second green emitting phosphor layer to be combined with a silver halide element having spectral sensitivity in the blue-green region («ortho-type» elements).
JP 60175-000 discloses a combination of a double coated silver halide element and a screen pair wherein the fluorescent layers of the two screens have different wavelength region emissions and each screen comprises an organic dye to absorb the light emitted by the opposite screen.
EP 232,888 discloses a combination of a double coated silver halide element and a pair of front and back intensifying screens wherein said front and back screens, emitting light in the same wavelength region, have different modulation transfer factors to be used in low energy radiography.
S. 6S
A
6 US 4,480,024 discloses the combination of a silver halide photothermographic element and a rare-earth intensifying screen which are uniquely adapted to one another for the purpose of industrial radiographic imaging. The photothermographic element is dye-sensitized to the spectral emission of the screen and the cbmbination of screen and element has an amplification factor greater or equal to at least 50. According to this invention preferably a single screen is used in combination with a single-side coated photothermographic element or double screens with either single-side or a double-side coated photothermographic elements, the latter without any significant benefit and at increased cost of film.
SUMMARY OF THE INVENTION The present invention provides a combination of a pair of radiographic fluorescent screens and a double coated silver halide radiographic element. Each screen is arranged adjacent to each silver halide layer and each screen is capable of imagewise emitting radiation to which the adjacent silver halide layer is sensitive when imagewise exposed to X radiation. The combination is characterized in that one fluorescent screen emits a first radiation in a first wavelength region of the electromagnetic spectrum and the other fluorescent screen emits a second radiation in a second wavelength region of the electromagnetic spectrum, and each silver halide layer is substantially insensitive to the radiation emitted by the opposite screen.
In particular, the present invention provides for a combination of a pair of front and back radiographic fluorescent screens and a double coated silver halide radiographic element, wherein the first radiation emitted by said front screen has a wavelength which differs from S S 0@ S 0@
S
S.
S.
S
0*0S *c S be S
S
OS S 00 r I i i rrr I -i in– i-
‘N
i 7 the second radiation emitted by said back screen by at least 50 nm, and each silver halide layer is substantially insensitive to the radiation emitted by the opposite screen.
More in particular, the present invention provides for a combination of a pair of front and back radiographic fluorescent screens and a double coated silver halide radiographic element, wherein said front screen comprises a non-actinic radiation, preferably green radiation, emitting phosphor and is arranged adjacent to a front silver halide layer comprising a silver halide emulsion spectrally sensitized to the light emitted by said front a screen, and said back screen comprises an actinic radiation, preferably UV radiation, emitting phosphor and is arranged adjacent to a back silver halide layer comprising a silver halide emulsion insensitized to the visually observable regions of the electromagnetic spectrum.
The combination of screen pair and double coated silver halide element for use in radiography according to the present invention provides images having superior image quality, particularly less crossover, as compared to conventional radiographic screen pair and double silver halide element combinations without causing negative .I effects, such as significant loss of sensitivity, residual stain, image instability upon storage, excessive element thickening and increased silver coverage. The combination may be used in industrial or medical radiography.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of a radiographic element and screen pair combination of the present invention.
Figures 2 and 4 are graphs illustrating emission spectra of radiographic fluorescent screens of the -8 present invention.
Figures 3 and 5 are graphs illustrating spectral sensitivity of a double-side coated silver halide radiographic element of the present invention.
Figures 6 and 7 are graphs illustrating sharpness and granularity versus sensitivity of radiographic double coated silver halide element and screen pair combinations.
DETAILED DESCRIPTION OF THE INVENTION S e The present invention will be now described in detail.
O Figure 1 shows in greater detail a combination of tail •e .the screen pair and the double silver halide element of S this invention. The combination comprises three separate photosensitive elements: a double coated silver halide a radiographic element 10, a front screen 21 and a back screen S* •e As shown, the double coated silver halide radiographic element 10 comprises a support 11 and coated on r its opposite faces are the subbing layers 12 and 13. A front silver halide emulsion layer 15 is coated over the subbing layer 13 and a back silver halide emulsion layer 14 is coated over the subbing layer 12 on the opposite 0 face of the support. Protective layers 16 and 17 are coated over the silver halide emulsion layers 14 and respectively.
As shown, the front radiographic fluorescent screen 21 comprises a support 29, a reflective layer 27, a fluorescent phosphor layer 25 and a protective layer 23. Similarly, the back radiographic fluorescent screen 20 comprises a support 28, a reflective layer 26, a fluorescent phosphor layer 24 and a protective layer 22.
In practical use, the screen pair and the silver -9 halide element are compressed in a radiographic cassette with the front screen arranged adjacent and in close contact with the front silver halide emulsion layer and the back screen is arranged adjacent and in close contact with the back silver emulsion halide layer. Imagewise X radiation enters the screen pair and silver halide element combination through the front screen support 29 and reflective layer 27 and passes the front screen fluorescent phosphor layer 25. A portion of the X radiation is absorbed in the phosphor layer 25. The remaining X radiation passes through the protective layers 23 and 17. A small portion of the X radiation is absorbed in the front silver halide emulsion layer 15, thereby contributing directly to the formation of a latent image in said front silver halide emulsion layer 15. The major portion of the X radiation passes through the subbing layer 13, the sup- T oport 11 and the subbing layer 12. Again, a small portion S of the X radiation is absorbed in the back silver halide emulsion layer 14, thereby contributing directly to the formation of a latent image in said back silver halide emulsion layer 14. Again, the major portion of the X radiation passes through the protective layers 16 and 22 and is absorbed in the back fluorescent phosphor layer 24. The imagewise X radiation is principally absorbed in 24. The imagewise X radiation is principally absorbed in the fluorescent phosphor layers 24 and 25, thereby profo* ducing the emission of longer wavelength radiation. Ac- S. cording to the present invention, the first radiation S»emitted by the front fluorescent phosphor layer 25 exposes the adjacent front silver halide emulsion layer and the second radiation emitted by the back fluorescent phosphor layer 24 exposes the adjacent back silver halide emulsion layer 14. The silver halide emulsions are substantially insensitive to the radiation emitted by the opposite fluorescent phosphor layer. Said radiation emitted by a fluorescent phosphor layer passing to at least 10 some extent beyond the adjacent silver halide emulsion layer penetrates the subbing layers and the support tn expose the opposite silver halide emulsion layer. This fact, while increasing to some extent the speed of the screen pair and silver halide element combination, would have the effect of impairing the image sharpness by crossover exposure. The terms «actinic» and «non-actinic» radiation according to the presen invention are used to indicate, respectively, radiation of wavelenght shorter than 500 nm (Ultraviolet and blue radiation), preferably from 300 to less than 500 nm, and radiation of wavelength S from 500 nm upwards (green, red and Infrared radiation), S preferably from 500 to 1200 nm. The term «insensitive» as used herein, describes either primary or intrinsic insensitivity of the silver halide grain emulsion (or layer j including it) to a certain range of wavelengths, as defined, or secondary or induced insensitivity (or unreachability) of the silver halide emulsion (or layer including it) in the double silver halide element because
SOS.
of filter action excercised by a further emulsion layer or layers interposed between the considered «insensitive» layer and the radiation emitting screen or by filter dyes or agents included in the considered layer or in such interposed layers. Accordingly, the latent image formed by radiation (preferably comprised between 300 and 1200 «0 nm) exposure in each silver halide emulsion layer is primarily formed by exposure to the radiation emitted by the adjacent fluorescent phosphor layer, with no significant contribution by opposite screen. Preferably, the radiation exposure necessary to produce a Dmax of 1.0 on said front silver halide layer will produce a Dmax of less than 0.2 on the back silver halide emulsion layer under the same development conditions. Conversely, an exposure at the Xmax of the back layer that produces a Dmax of will produce a Dmax of less than 0.2 on the front layer.
I S -11- The terms «front» and «back» in the present invention are used to distinguish the different elements of the unsymmetrical screen pair and double coated silver halide element combination not their position relating to exposing X radiation source. Accordingly, X radiation may enter the unsymmetrical screen pair and double-side coated silver halide element through either the front fluorescent phosphor screen or the back fluorescent phosphor screen.
The term «silver halide element» in the present invention includes both silver halide «photographic» elements which use liquid development to produce the final image and silver halide «photothermographic» elements, often referred to as «diy silver» elements, which do not S» use liquid development to produce the final image, as described thereinafter. In both photographic and photo- *thermographic silver halide elements, exposure of the silver halide to radiation produces small clusters of silver ions. The imagewise distribution of these clusters is known in the art as the latent image. This latent im-
SOS.
age generally is not visible by ordinary means and the L• light-sensitive element must be further processed in order to produce a visual image. This visual image is pro- S duced by the catalytic reduction of silver which is in catalytic proximity to the specks of the latent image.
The photographic silver halide element is preferably used in medical radiography and the photothermographic silver S: halide element is preferably used in industrial radiography.
Accordingly, the present invention relates to a combination of photosensitive elements for use in radiography comprising two separate front and back X-ray fluorescent screens and a silver halide radiographic element comprising a support base and front and back silver halide emulsion layers each coated on one surface of said 12 support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein 1) said front screen comprises a first radiation emitting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and 2) said back screen comprises a second radiation emitting phosphor and said back silver halide layer comprises silver halide grains sensitive to said second radiation emitted by said back screen, characterized in that a) said first radiation emitted by said front screen S has a wavelength which differs from said second radiation ooooo S emitted by said back screen by at least 50 nm, b) said front silver halide emulsion layer is substantially insensitive to said second radiation emitted by said back screen, and c) said back silver halide emulsion layer is sub- @00e stantially insensitive to said first radiation emitted by said front screen, the difference in wavelength region of said first and second radiations and the insensitivity of each silver halide layer to radiation emitted by opposite screen being such to reduce crossover exposure of at least 10 percent when compared with a symmetrical combination of a pair of green ight emitting fluorescent screens and a double coated green sensitized silver halide emulsion radiographic element.
According to a preferred embodiment of this invention, in the combination of a pair of front and back radiographic fluorescent screens and a double coated silver halide radiographic element, said front screen comprises a non-actinic radiation, preferably green light, emitting i 13 phosphor and is arranged adjacent to a front silver halide layer comprising a silver halide emulsion spectrally sensitized to the radiation emitted by said front screen, and said back screen comprises an actinic radiation, preferably UV light, emitting phosphor and is arranged adjacent to a back silver halide layer comprising a silver halide emulsion insensitized to the visually observable regions of the electromagnetic spectrum (that is 410 to 750 nm).
Preferably, the phosphors used in the front fluorescent screens applied in the present invention emit radiation in the green or red region of the visible spectrum.
More preferably, said phosphors emit radiation in the green region of the visible spectrum. Most preferably, said phosphors emit radiation having more than about of its spectral emission above 480 nm and its maximum of emission in the wavelength range of 530-570 nm. Green emitting phosphors which may be used in the front fluorescent screens of the present invention include rare earth activated rare earth oxysulfide phosphors of at least one rare earth element selected from yttrium, lanthanum, gadolinium and lutetium, rare earth activated rare earth oxyhalide phosphors of the same rare earth elements, a phosphor composed of a borate of the above rare earth elements, a phosphor composed of a phosphate of the above rare earth elements and a phosphor composed of tantalate of the above rare earth elements. These rare earth green emitting phosphors have been extensively described in the patent literature, for example in US Patents 4,225,653, 3,418,246, 3,418,247, 3,725,704, 3,617,743, 3,974,389, 3,591,516, 3,607,770, 3,666,676, 3,795,814, 4,405,691, 4,311,487 and 4,387,141. These rare earth phosphors have a high X-ray stopping power and high efficiency of light emission when excited with X radiation and enable radiologists to use substantially lower X
I.
14 radiation dosage levels. Particularly suitable phosphors for use in the front fluorescent screens of the present invention are terbium or terbium-thulium activated rare earth oxysulfide phosphors represented by the general formula (I) (Lnl-a-b, Tba Tb)20 2 S
(I)
wherein Ln is at least one rare earth element selected from lanthanum, gadolinium and lutetium, and a and b are numbers such as to meet the conditions 0.0005 a 0.09 and 0 b S 0.01, respectively, and terbium or terbiumthulium activated rare earth oxysulfide phosphors represented by the general formula (II) S(Y-c-a-b’ Lnc Tb, Tb)22S (II) i S wherein Ln is at least one rare earth element selected from lanthanum, gadolinium and lutetium, and a, b and c are numbers such as to meet the conditions 0.0005 a 0.09, 0 5 b 5 0.01 and 0.65 5 c 5 0.95, respectively.
Figure 2 shows an emission spectrum of a front fluorescent screen comprising a fluorescent layer of (Gd 1 -0.
05 Tb0.
05 2 0 2 S phosphor as green emitting phosphor, expressed as fluorescence versus wavelengths (nm).
The front silver halide emulsion layer, to be arranged according to this invention adjacent to the front fluorescent screen, comprises silver halide grains which are optically sensitized to the spectral region of the IL, radiation emitted by the screens, preferably to a spectral region of an interval comprised within 25 nm from the wavelength of the maximum emission of the screen, more preferably within 15 nm, and most preferably within nm. The silver halide grains of the front silver sr r I ;r -i halide layer have adsorbed on their surface spectral sensitizing dyes that exhibit absorption maxima in the regions of the visible spectrum where the front fluorescent screen emits. Preferably,spectral sensitizing dyes according to this invention are those which exhibit J aggregates if adsorbed on the surface of the silver halide grains and a sharp absorption band (J-band) with a bathocromic shifting with respect to the absorption maximum of the free dye in aqueous solution. Spectral sensitizing dyes producing J aggregates are well known in the art, as illustrated by F. M. Hamer, Cyanine Dyes and Related Compounds, John Wiley and Sons, 1964, Chapter XVII and by T. H. James, The Theory of the Photographic Process, 4th edition, Macmillan, 1977, Chapter 8.
SIn a preferred form, J-band exhibiting dyes are S* cyanine dyes. Such dyes comprise two basic heterocyclic nuclei joined by a linkage of methine groups. The heterocyclic nuclei preferably include fused benzene rings to enhance J aggregation.
The heterocyclic nuclei are preferably quinolinium, benzoxazolium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium and naphthoselenazolium quaternary salts.
J-band type dyes preferably used in the present invention have the following general formula (III): R R R I 1 II3 i 4 I 2 0 R -N(-CH=CH) mC==CH-CH=)=N -R (III) (A )k (B wherein
Z
1 and Z 2 may be the same or different and each represents the elements necessary to complete a cyclic nucleus derived from basic heterocyclic nitrogen compounds such as oxazoline, oxazole, benzoxazole, the L A I -16naphthoxazoles naphth{2,1-djoxazole, naphth(2,3-d)oxazole, and naphth{1,2-d)oxazole), thiazoline, thiazole, benzothiazole, the naphthothiazoles naphtho{2,1-d)thiazole), the thiazoloquinolines thiazolo(4,5-b~quinoline), selenazoline, selenazole, benzoselenazole, the naphthoselenazoles naphtho{1,2-d~selenazole, 3H-indole 3,3-dimethyl3H-indole), the benzindoles 1,1-dimethylbenz-indole), imidazoline, imidazole, benzimidazole, the naphthimidazoles naphtht2,3-d}imidazole), pyridine, and quinoline, which nuclei may be substituetd on the ring by one or more of a wide variety of substituents such as hydroxy, the halogens 0 fluoro, bromo, chloro, and iodo), alkyl groups or substituted alkyl groups methyl, ethyl, propyl, isopropsees* yl, butyl, octyl, dodecyl, 2-hydroxyethyl, 3-sulfopropyl, carboxymethyl, 2-cyanoethyl, and trif luoromethyl) aryl too 0@ *ogroups or substituted aryl groups phenyl, 1naphthyl, 2-naphthyl, 4-sulfophenyl, 3-carboxyphenyl, and 4-biphenyl), aralkyl groups benzyl and phenethyl), alkoxy gtoups methoxy, ethoxy, and isopropoxy), 0* aryloxy groups phenoxy and l-naphthoxy), alkylthio groups ethylthio and methylthio), arylthio groups phenylthio, p-tolythio, and 2-naphthylthio), methylenedioxy, cyano, 2-thienyl, styryl, amino or substituted amino groups anilino, dime thylani li no, diethylanilino, and morpholino), acyl groups acetyl and benzoyl), and sulfo groups, Rand Rcan be the same or different and represent alkyl groups, aryl groups, alkenyl groups, or aralkyl groups, with or without substituents, carboxymethyl, 2-hydroxyethyl, 3-sulfopropyl, 3-sulfobutyl, 4sulfobutyl, 2–nethoxyethyl, 2-sulfatoethyl, 3-thiosulfatoethyl, 2-phosphonoethyl, chiorophenyl, and bromophenyl), I. U 17
R
3 represents a hydrogen atom,
R
4 and R 5 can be the same or different and represent a hydrogen atom or a lower alkyl group of from 1 to 4 carbon atoms, p and q are 0 or 1, except that both p and q preferably are not 1, m is 0 or 1 except that when m is 1 both p and q are 0 and at least one of Z and Z represents imidazoline, oxazoline, thiazoline, or selenazoline, A is an anionic group, B is a cationic group, and k and 1 may be 0 or 1, depending on whether ionic S substituents are present. Variants are, of course, possi- 0. ble in which R1 and R 3
R
2 and R 5 or R1 and R 2 together represent the atoms necessary to complete an alkylene bridge.
In the most preferred form of this invention, whereoin the phosphors of the front fluorescent screen are rare earth phosphors emitting in the green region of the visible spectrum, said optical sensitizing dyes adsorbed on said silver halide grains of the front silver halide layer are represented by the following general formula (IV): *see. R O R R eo 6 o10 /0 8 -CH=C-CH= (IV) I N+ (X )nl R N N R SI
R
11 R12 wherein
R
10 represents a hydrogen atom or a lower alkyl group of from 1 to 4 carbon atoms methyl, and ethyl),
R
6
R
7
R
8 and R 9 each represents a hydrogen atom, a halogen atom chloro, bromo, iodo, and fluoro), a ip; hydroxy group, an alkoxy group methoxy and ethoxy), an amino group amino, methylamino, and dimethylamino), an acylamino group acetamido and propionamido), an acyloxy group acetoxy group), an alkoxycarbonyl group methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl), an alkyl group methyl, ethyl, and isopropyl), an alkoxycarbonylamino group ethoxycarbonylamino) or an aryl group phenyl and tolyl), or, together, R 6 and R 7 and, respectively, R8 and R9 can be the atoms necessary to complete a benzene ring (so that the heterocyclic nucleus results to be, for example, an a-naphthoxazole nucleus, a P-naphthoxazole or a P,P’- S naphthoxazole),
R
1 1 and R12 each represents an alkyl group (e.g.
methyl, propyl, and butyl), a hydroxyalkyl group 2hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl), an acetoxyalkyl group 2-acetoxyethyl and 4-acetoxybutyl), an alkoxyalkyl group 2-methoxyethyl and 3methoxypropyl), a carboxyl group containing alkyl group carboxymethyl, 2-carboxyethyl, 4-carboxybutyl, and e** 2-(2-carboxyethoxy)-ethyl), a sulfo group containing alkyl group 2-sulfoethyl, 3-sulfopropyl, 4- sulfobutyl, 2-hydroxy3- sulfopropyl, 2-(3-sulfopropoxy)-propyl, p-sulfobenzyl, and p-sulfophenethyl), a benzyl group, a phenetyl group, a vinylmethyl group, and the like, X represents an acid anion a chloride, bromide, iodide, thiocyanate, methylsulfate, ethylsulfate, perchlorate, and p-toluensulfonate ion), and n represents 1 or 2.
The alkyl groups included in said substituents R 6 61
R
7
R
8
R
9
R
10 and R 11 and, more particularly, the alkyl portions of said alkoxy, alkoxycarbonyl, alkoxycarbonylamino, hydroxyalkyl, acetoxyalkyl groups and of the alkyl groups associated with a carboxy or sulfo group each preferably contain from 1 to 12, more preferably s e 0 0 S 0 S S. S
S.
S S *0
S
S
OS
S. 1 19 from 1 to 4 carbon atoms, the total number of carbon atoms included in said groups preferably being no more than The aryl groups included in said substituents R6′
R
7 Rg and R 9 each preferably contain from 6 to 18, more preferably from 6 to 10 carbon atoms, the total number of carbon atoms included in said groups arriving up to carbon atoms.
The following are specific examples of J-band sensitizing dyes belonging to those represented by the general formula (IV) above: Dye R10 R6 R7 R8 R9 R11 R12 X n A C2H 5 H 5-C1 H 5′-C1 (CH 2 3
S
3
(CH
2 3 SO3H 1
CII
B C 2
H
5 H 5-C1 H 5′-C 6 H5 (CH 2 3 SO3 (CH2) 2HSO3H 1 C CH 3 H 5-0CH 3 H 5′-0CH 3
C
2 H5 (CH 2 3
S
3 1 D C2H 5 6-CH 3 5-C1 H 5′-C1 (CH 2 4 0 3
(CH
2 3 0 3 H 1 E C2H 5 H 5-C1 H 5′-C1 C2H 5 C2HG I 2 Triethylamine salt Sodium salt Figure 3 shows the sensitivity spectrum of a front silver halide layer comprising silver bromoiodide grains comprising 2.3 mole percent iodide and having adsorbed on their surface the optical sensitizing dye A above, expressed as sensitivity versus wavelengths (nm).
Preferably, the phosphors used in the back fluorescent screens applied in the present invention emit radiation in the ultraviolet region of the electromagnetic spectrum. More preferably, said phosphors emit radiation having more than about 80% of their spectral emission below 410 nm and their maximum of emission in the I 20 wavelength range of 300-360 nm. Ultraviolet emitting phosphors which may be used in the back fluorescent screens of the present invention include ultraviolet emitting phosphors known in the art such as lead or lanthanum activated barium sulfate phosphors, barium fluorohalide phosphors, lead activated barium silicate phosphors, gadolinium activated yttrium oxide phosphors, barium fluoride phosphors, alkali metal activated rare earth niobate or tantalate phosphors etc. Ultraviolet emitting phosphors are described for example in BE 703,998 and 757,815, in EP 202,875 and by Buchanan et al., J. Applied Physics, vol. 9, 4342-4347, 1968,and by Clapp and Ginther, J. of the Optical Soc. of America, vol. 37, 355-362, 1947. Particularly suitable ultraviolet emitting phosphors for use in the back fluorescent Sscreens of the present invention are those represented by the general formula (V) o (Y1-2/3x-1/3y’ Srx’ Liy) TaO 4 wherein x and y are numbers such as to meet the condi- -5 -4 tions 10 <5 x 1 and 10 4 y 0.1as described in EP 202,875.
Figure 4 shows an emission spectrum of a back fluorescent screen comprising a fluorescent layer of Sr, Li)TaO 4 phosphor as ultraviolet emitting phosphor, expressed as fluorescence versus wavelengths (nm).
'.The back silver halide emulsion layer, arranged according to this invention adjacent to the back actinic light emitting phosphor screen, comprises silver halide grains which are not optically sensitized but possess the inherent spectral sensitivity of the known types of photosensitive silver halides. Said inherent spectral sensitivity of the conventional silver halide emulsions used in photographic films as known ranges in the ia 21 ultraviolet and blue region of the electromagnetic spectrum.
Figure 5 shows the sensitivity spectrum of a back silver halide emulsion layer comprising silver bromoiodide grains comprising 2.3 percent mole iodide and having no optical sensitizing dye adsorbed on their surface, expressed as sensitivity versus wavelenghts (nm).
According to the present invention, the non-actinic radiation (preferably green light) emitted by the front screen imagewise exposes the adjacent front silver halide layer comprising silver halide grains optically sensitized to the radiation emitted by said screens. Part of said non-actinic radiation reaches the opposite back silver halide layer but does not crossover expose the silver e halide grains of the back silver halide layer as those grains are not optically sensitized to the radiation emitted by said front screen. The ultraviolet or blue I" emission of the back fluorescent screen undergoes absorption by the adjacent back silver halide layer and imagewise exposes the silver halide grains which are not optically sensitized, rather than crossover passing to the opposite front silver halide layer. This is due to the fact that silver halide grains possess a good inherfees ent absorption of light with a wavelength below 500 nm and a strong light scattering of ultraviolet and blue light through the dispersed silver halide particles of go* the emulsion layer. The above implies not having a large amount of ultraviolet or blue light of the back fluorescent screen to expose the opposite front silver halide layer. The crossover exposure reduction attained with the screen pair and double silver halide element combination of this invention is preferably at least 10 percent, more preferably at least 20 percent in comparison with a conventional combination of green emitting fluorescent screens and double coated green sensitized silver halide 22 radiographic element. Accordingly, the image sharpness is improved by reducing crossover exposure using a unique combination of conventional silver halide emulsion layers and fluorescent screens.
The light-sensitive double-side coated silver halide radiographic element comprises a transparent polymeric base of the type commonly used in radiography, for instance a polyester base, and in particular a polyethylene terephthalate base.
In the silver halide photographic elements of this invention, the silver halide emulsions coated on the two surfaces of the support, the front optically sensitized silver halide emulsion and the back optically unsensitized silver halide emulsion, may be similar or different S* and comprise emulsions commonly used in photographic elements, such as silver chloride, silver iodide, silver chloro-bromide, silver chloro-bromo-iodide, silver bromide and silver bromo-iodide, the silver bromoiodide being particularly useful for radiographic elements. The silver halide grains may have different shapes, for instance cubic, cctahedrical, tabular shapes, and may have epitaxial growths; they generally have mean sizes ranging from 0.1 to 3 Vm, more preferably from 0.4 to 1.5 im. The emulsion are coated on the support at a total silver coverage comprised in the range from about 3 to 6 grams per square meter. The silver halide binding material used is 00 a water-permeable hydrophilic colloid, which preferably S. is gelatin, but other hydrophilic colloids, such as gelatin derivatives, albumin, polyvinyl alcohols, alginates, Shydrolized cellulose esters, hydrophilic polyvinyl polymers, dextrans, polyacrylamides, hydrophilic acrylamide copolymers and alkylacrylates can also be used alone or in combination with gelatin.
As regards the processes for silver halide emulsion preparation and use of particular ingredients in the I a 23 emulsion and in the light-sensitive element, reference is made to Research Disclosure 18,431 published in August 1979, wherein the following chapters are dealt with in deeper details: IA. Preparation, purification and concentration methods for silver halide emulsions.
IB. Emulsion types.
IC. Crystal chemical sensitization and doping.
II. Stabilizers, antifogging and antifolding agents.
IIA. Stabilizers and/or antifogging.
IIB. Stabilization of emulsions chemically sensitized with gold compounds.
IIC. Stabilization of emulsions containing polyalkylene Soxides or plasticizers.
IID. Fog caused by metal contaminants.
IIE. Stabilization of materials comprising agents to increase the covering power.
IIF. Antifoggants for dichroic fog.
IIG. Antifoggants for hardeners and developers comprising hardeners.
IIH. Additions to minimize desensitization due to folding.
III. Antifoggants for emulsions coated on polyester bases.
IIJ. Methods to stabilize emulsions at safety lights.
IIK. Methods to stabilize X-ray materials used for high temperature, Rapid Access, roller processor transport processing.
III. Compounds and antistatic layers.
IV. Protective layers.
V. Direct positive materials.
VI. Materials for processing at room light.
IX. Spectral sensitization.
X. UV sensitive materials.
XII. Bases.
I,
24 The silver halide photothermographic elements of this invention basically comprise a light insensitive, reducible silver source, a light sensitive material which generates silver when irradiated, and a reducing agent for the silver source. The light sensitive material is generally photographic silver halide which must be in catalytic proxymity to the light insensitive silver source. Catalytic proximity is an intimate physical association of these two materials so that when silver specks or nuclei are generated by the irradiation or light exposure of the photographic silver halide, those nuclei are able to catalyze the reduction of the silver source by the reducing agent. It has been long understood that silver is a catalyst for the reduction of silver ions and the silver-generating light sensitive silver halide cataeeoep lyst progenitor may be placed into catalytic proximity .6 with the silver source in a number of different fashions, r.
such as partial metathesis of the silver source with a halogen-containing source US Pat. No. 3,457,075), coprecipitation of the silver halide and silver source *e C C S material US Pat. No. 3,839,049), and any other
S..
method which intimately associates the silver halide and the silver source.
The silver source used in this area of technology is a material which contains a reducible source of silver ions. The earliest and still preferred source comprises a e" silver salts of long chain fatty carboxylic acids, usually of from 10 to 30 carbon atoms. The silver salt of behenic acid or mixtures of acids of like molecular weight have been primarily used. Salts of other organic acids or other organic materials such as silver imidazolates have been proposed, and British Pat. No. 1,110,046 discloses the use of complexes of inorganic or organic silver salts as image source materials. Silver salts of long chain to 30, preferably 15 to 28 carbon atoms) fatty carboxylic 25 acids are preferred in the practice of the present invention.
Photothermographic emulsions are usually constructed as one or two layers per side of the support. Single layer construction must contain the silver source material, the silver halide, the developer and binder as well as optional additional materials such as toners, coating aids and other adjuvants. Two-layer constructions must contain the silver source and the silver halide in an emulsion layer (usually the layer adjacent the support) and the other ingredients in the second layer or both layers. The silver source material should constitute from about 20 to 70 percent by weight of the imaging layer.
Preferably it is present as 30 to 55 percent by weight.
S The second layer in a two-layer construction would not affect the percentage of the silver source material de- 0* sired in the single imaging layer.
The silver halide may be any photosensitive silver halide as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, etc., and may be added to the emulsion layer in any fashion which places it in catalytic proximity to the silver source. The silver halide is generally present as 0.75 to 15 percent by weight of the ~iaging layer, although larger amounts are useful. It is preferred to use from 1 to 10 percent by weight silver halide in the imaging layer and most preferred to use from 1.5 to 7.0 percent. The vast list of photographic adjuvants and processing aids may be used in silver halide emulsion preparation. These materials include chemical sensitizers (including sulfur and gold compounds), development accelerators onium and polyonium compounds), alkylene oxide polymer accelerators, antifoggant compounds, stabilizers azaindenes, especially the tetra- and pentaazaindenes), surface active 1 26 agents (particularly fluorinated surfactants), antistatic agents (particularly fluorinated compounds), plasticizers, matting agents, and the like.
The reducing agent for the silver ion may be any material, preferably organic material, which will reduce silver ion to metallic silver. Conventional photographic developers such as phenidone, hydroquinones, and cathecol are useful, but hindered phenol reducing agents are preferred. The reducing agents should be present as 1 to percent by weight of the imaging layer. In a two-layer construction, if the reducing agent is in the second layer, slighty higher proportions, of from about 2 to percent tend to be more desirable.
Toners such as phthalazinone, phthalazine and go phthalic acid are not essential to the construction, but I highly desirable. These materials may be present, for example, in amounts of from 0.2 to 5 percent by weight.
o S* The binder may be selected from any of the well known natural and synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, S cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, and the like. Copolymers and terpolymers are, of course, included in these Soe definitions. The polyvinyl acetals, such as polyvinyl butyral and polyvinyl formal, and vinyl copolymers, such S as polyvinyl acetate/chloride are particularly desirable.
The binders are generally used in a range of 20 to percent by weight of each layer, and preferably about to 55 percent by weight.
As previously noted, various other adjuvants may be added to the photothermographic emulsions of the present invention. For example, toners, accelerators, acutance dyes, sensitizers, stabilizers, surfactants, lubricants, coating aids, antifoggants, leuco dyes, chelating agents, and various other well known additives may be usefully 27 incorporated. The use of acutance dyes matched to the spectral emission of the intensifying screen is particularly desirable.
The balance in properties of the photothermographic emulsion must be precisely restricted by the proportions of materials in the emulsion. The proportions of the silver salt and organic acid are particularly critical in obtaining necessary sensitometric properties in the phototheriographic element for radiographic use. In conventional photothermographic emulsions, it is common to use approximately pure salts of organic acids behenic acid, stearic acid and mixtures of long chain acids) as the substantive component of the emulsion. Sometimes minor amounts or larger amounts of the acid component are S •S S included in the emulsion. In the practice of the present ooooo.
invention the molar ratio of organic silver salt to organic acid must be in the range of 1.5/1 to 6.2/1 65 S (salt/acid). Below that range, the contrast has been found to be too low, and above that range the speed and background stability of the emulsion drop off unacceptably. It is preferred that the ratio be in the range of 2.0/1 to 3.50/1.
The silver halide may be provided by in situ halidization or by use of pre-formed silver halide.
The process of industrial radiography would be per- Sa. formed by using a conventional X-ray projection source or other high energy particle radiation sources including gamma and neutron sources. As well known in the art, the particular phosphors used have a high absorption coefficient for the radiation emitted from the source. Usuall.y this radiation is high energy particle radiation which is defined as any of X-rays, neutrons and gamma radiation.
The industrial material would be placed between the controllable source of X-rays and the industrial radiographic system of the present invention. A controlled exposure
'I:I
-;i.li 28 of X-rays would be directed from the source and through the industrial material so as to enter and impact the radiographic system at an angle approximately perpendicular to the plane or surface of the intensifying screens and the photothermographic film contiguous to the inside surface of the, screens. The radiation absorbed by the phosphors of the screens would cause light to be emitted by the screens which in turn would generate a latent image in the silver halide grains of the two emulsion layers. Conventional thermal development would then be used on the exposed film.
The X radiation image converting screens of this invention have a fluorescent layer comprising a binder and a phosphor dispersed therein. The fluorescent layer is formed by dispersing the phosphor in the binder to prepare a coating dispersion, and then applying the coating dispersion by a conventional coating method to form a uniform layer. Although the fluorescent layer itself can be a radiation image converting screen when the fluorescent layer is self-supporting, the fluorescent layer is generally provided on a substrate to form a radiation .*image converting screen. Further, a protective layer for physically and chemically protecting the fluorescent layer is usually provided on the surface of the fluorescent layer. Furthermore, a primer layer is sometimes provided between the fluorescent layer and the substrate to closely bond the fluorescent layer to the substrate, and a reflective layer is sometimes provided between the substrate (or the primer) and the fluorescent layer.
The binder employed in the fluorescent layer of the X radiation image converting screens of the present invention, can be, for example, one of the binders commonly used in forming layers: gum arabic, protein such as gelatin, polysaccharides such as dextran, organic polymer binders such as polyvinylbutyral, polyvinylacetate, A I 29 nitrocellulose, ethylcellulose, vinylidene-chloride-vinylchloride copolymer, polymethylmethacrylate, polybutylmethacrylate, vinylchloride-vinylacetate copolymer, polyurethane, cellulose acetate butyrate, polyvinyl alcohol, and the like.
Generally, the binder is used in an amount of 0.01 to 1 part by weight per one part by weight of the phosphor. However, from the viewpoint of the sensitivity and the sharpness of the screen obtained, the amount of the binder should preferably be small. Accordingly, in consideration of both the sensitivity and the sharpness of the screen and the easiness of application of the coating dispersion, the binder is preferably used in an amount of 0.03 to 0.2 parts by weight per one part by weight of the phosphor. The thickness of the fluorescent layer is generally within the range of 10 um to 1 mm.
In the radiation image converting screens of the S present invention, the fluorescent layer is generally coated on a substrate. As the substrate, various materials such as polymer material, glass, wool, cotton, paper, metal, or the like can be used. From the viewpoint of handling the screen, the substrate should preferably be processed into a sheet or a roll having flexibility. In this connection, as the substrate is preferably either a plastic film (such as a cellulose triacetate film, polyester film, polyethylene terephthalate film, polyamide film, polycarbonate film, or the like), or ordinary paper or processed paper (such as a photographic paper, baryta paper, resin-coated paper, pigment-containing paper which contains a pigment such as titanium dioxide, or the like). The substrate may have a primer layer on one surface thereof (the surface on which the fluorescent layer is provided) for the purpose of holding the fluorescent layer tightly. As the material of the primer layer, an _~11_1 I: r- _i 30 ordinary adhesive can be used. In providing a fluorescent layer on the substrate (or on the primer layer or on the reflective layer), a coating dispersion comprising the phosphor dispersed in a binder may be directly applied to the substrate (or to the primer layer or to the reflective layer).
Further, in the X radiation image converting screens of the present invention, a protective layer for physically and chemically protecting the fluorescent layer is generally provided on the surface of the fluorescent layer intended for exposure (on the side opposite the substrate). When, as mentioned above, the fluorescent layer is self-supporting, the protective layer may be provided on both surfaces of the fluorescent layer. The protective layer may be provided on the fluorescent layer by directly applying thereto a coating dispersion to form the protective layer thereon, or may be provided thereon by e• ee bonding thereto the protective layer formed beforehand.
As the material of the protective layer, a conventional material for a protective layer such a nitrocellulose, ethylcellulose, cellulose acetate, polyester, polyethyl- Ss ene terephthalate, and the like can be used.
The X radiation image converting screens of the sepresent invention may be colored with a colorant. Further, the fluorescent layer of the radiation image converting screen of the present invention may contain a white powder dispersed therein. By using a colorant or a 0 white powder, a radiation image converting screen which provides an image of high sharpness can be obtained.
EXAMPLES
The invention can be better illustrated by reference to the following specific examples and comparative investigations.
31 Green Emitting Phosphor Screen GRS 1 A high resolution green emitting phosphor screen, screen GRS 1 was prepared consisting of a (Gd1-0.
0 Tb0.05 202S phosphor with average particle grain size of 3 um coated in a hydrophobic polymer binder at a phosphor coverage of 270 g/m 2 and a thickness of 70 um on a polyester support. Between the phosphor layer and the support a reflective layer of TiO 2 particles in a poly(urethane) binder was coated. The screen was overcoated with a cellulose triacetate layer.
Green Emitting Phosphor Screen GRS 2 A medium resolution green emitting phosphor screen, (I screen GRS 2 was prepared consisting of a (Gd 1 0.
0 5 I 'Tb 0 05 2 S phosphor with average particle grain size of S4 Im coated in a hydrophobic polymer binder at a phosphor coverage of 480 g/m 2 and a thickness of 120 un on a polyester support. Between the phosphor layer and the support a reflective layer of TiO 2 particles in a poly(urethane) binder was coated. The screen was overcoated with a cel- Slulose triacetate layer.
UV Emitting Phosphor Screen UVS 3 An UV emitting phosphor screen, screen UVS 3 was prepared consisting of the type NP-3040 Sr, Li)TaO 4 phosphor of Nichia Kagaku Kogyo K.K. with average particle grain size of 5.1 ui coated in a hydrophobic polymer binder at a phosphor coverage of 450 g/m 2 and a thickness of 110 um on a polyester support. Between the phosphor layer and the support a reflective layer of TiO 2 particles in a poly(urethane) binder was coated. The screen was overcoated with a cellulose triacetate layer.
ii-:_L r :Ftl (lii;~ii-i.l I 1 32 Light-sensitive Photographic Film GRUVF 1 A light-sensitive film having a green sensitized silver halide emulsion layer (hereinafter designated front layer) coated on one side of the support and a spectrally unsensitized silver halide emulsion layer (hereinafter designated back layer) coated on the other side of the support, film GRUVF 1 was prepared in the following manner. On one side of a polyester support was coated a green sensitized silver halide gelatin emulsion layer containing cubic silver bromoiodide grains (having 2.3 mole percent iodide and an average grain size of *0 0.65 pm) at 2.57 g/m 2 Ag and 1.9 g/m 2 gelatin. The emulsion was sulfur and gold chemically sensitized and speco trally sensitized with 1,070 mg/ mole Ag of the green sensitizing Dye A, anhydro-5,5'-dichloro-9-ethyl- 3 ,3'-bis(3-sulfopropyl)-oxacarbocyanine hydroxyde triethylamine salt. A protective overcoat containing 0.9 g/m 2 gelatin was applied to said silver bromoiodide front e. layer. On the other side of the polyester support was coated a spectrally unsensitized silver halide silver halide gelatin emulsion layer containing cubic silver bromoiodide grains (comprising a 1:1 by weight blend of silver bromoiodide grains having 2 mole percent iodide and an average grain size of 1.3 LUm and silver bromoiodide grains having 2.3 mole percent iodide and an average grain size of 0.65 um) at 2.51 g/m 2 Ag and 1.8 g/m 2 gelatin. The emulsion was sulfur and gold chemically senj sitized. A protective overcoat containing 0.9 g/m 2 gelatin was applied to said silver bromoiodide back layer.
Light-sensitive Photographic Film GRUVF 2 A light-sensitive film having a green sensitized silver halide emulsion layer (hereinafter designated i m m n -I -Ir- -u~Y rwar i, 33 front layer) coated on one side of the support and a spectrally unsensitized silver halide emulsion layer (hereinafter designated back layer) coated on the other side of the support, film GRUVF 2 was prepared in the following manner. On one side of a polyester support was coated the green sensitized silver halide gelatin emulsion layer containing cubic silver bromoiodide grains of the front layer of film GRUVF 1 (having 2.3 mole percent iodide and an average grain size of 0.65 un) at 2.60 g/m 2 Ag and 1.9 g/m 2 gelatin. The emulsion was sulfur and gold chemically sensitized and spectrally sensitized with 1,070 mg/Ag mole of the green sensitizing Dye A, anhydro-5,5'-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)- oxa- *carbocyanine hydroxyde triethylamine salt. A protective overcoat containing 0.9 g/m 2 gelatin was applied to said silver bromoiodide front layer. On the other side of the o..
polyester support was coated a spectrally unsensitized silver halide silver halide gelatin emulsion layer containing cubic silver bromoiodide grains of the front layer of film GRUVF 1 (having 2.3 mole percent iodide and an **average grain size of 0.65 jun) at 2.49 g/m 2 Ag and 1.9 g/m 2 gelatin. The emulsion was sulfur and gold chemically sensitized. A protective overcoat containing 0.9 g/m 2 gelatin was applied to said silver bromoiodide back layer.
Light-sensitive Photographic Film UVUVF 3 A light-sensitive film having a spectrally unsensitized silver halide emulsion layer coated on each side of a support, film UVUVF 3 was prepared in the following manner. On each side of a polyester support was coated a spectrally unsensitized silver halide silver halide gelatin emulsion layer containing cubic silver bromoiodide grains of the front layer of film GRUVF 1 (having 2.3 mole x. I 34 percent iodide and an average grain size of 0.65 um) at 2.60 and 2.49 g/m 2 Ag, respectively, and 1.9 g/m 2 gelatin. The emulsion was sulfur and gold chemically sensitized. A protective overcoat containing 0.9 g/m 2 gelatin was applied to each silver bromoiodide layer.
Light-sensitive Photographic Film GRGRF 4 A light-sensitive film having a green sensitized silver halide emulsion layer coated on each side of a support, film GRGRF 4 was prepared in the following manner. On each side of a polyester support was coated the green sensitized silver halide gelatin emulsion layer containing cubic silver bromoiodide grains of the front layer of film GRUVF 1 (having 2.3 mole percent iodide and an average grain size of 0.65 jun) at 2.18 g/m 2 Ag and 1.9 g/m 2 gelatin. The emulsion was sulfur and gold chemi- S* cally sensitized and spectrally sensitized with 1,070 mg/ mole Ag of the green sensitizing Dye A, chloro-9-ethyl-3,3'-bis(3-sulfopropyl)- oxacarbocyanine hydroxyde triethylamine salt. A protective overcoat containing 0.9 g/m 2 gelatin was applied to each silver bromoiodide layer.
Comparison of Screen Pairs and Light-sensitive Photographic Films Pairs of screens in combination with double coated light-sensitive photographic films described above were exposed as follows. Referring to Figure 1, film-screens combinations were made in which the front screen was in contact with the front emulsion layer and the back screen was in contact with the back emulsion layer. Each screen pair-film combination was exposed to X-rays from a tungsten target tube operated at 80 kVp and 25 mA from a 1 35 distance of 120 cm. The X-rays passed through an aluminium step wedge before reaching the screen-film combination. Following exposure the films were processed in
TM
a 3M Trimatic M XP507 processor using 3M XAD/2 developer replenisher and 3M XAF/2 fixer replenisher.
The speed and the image quality are reported in the following table. Percent crossover was calculated by using the following equation: 1 Percent Crossover x 100 antilog (6 logE) S wherein 6 logE is the difference in speed between the two emulsion layers of the same film when exposed with a *0S@ o single screen (the lower the percent crossover, the better the image quality).
TABLE
Comb. Screen Pair Film Rel. Speed Crossover Front/Back log E 05 1 GRS 1
/GRS
1
GRGRF
4 0.00 37 2 UVS 3
/UVS
3
UVUVF
3 -0.39 9 3 GRS 1
/UVS
3
GRUVF
2 -0.22 4 9 4 GRS1/UVS 3 GRUVF 1 0.00 9 5 GRS /UVS GRUVF +0.18 4 2 3 1 crossover measured in the front emulsion layer crossover measured in the back emulsion layer Sharpness and granularity of the screen pair-film combinations were determined as follows. Each screen pair-film combination was exposed to X-rays from a tungsten tube operated at 80 kVp and 25 mA from a distance of 36 150 cm. The X-rays passed through a 100 u thick lead Funk target sold by Huttner Company before reaching the screen-film combination. Following exposure the films were processed in the 3M TrimaticTM XP507 processor using 3M XAD/2 developer replenisher and 3M XAF/2 fixer replenisher. Sharpness and granularity of the processed films were determined by visual examination of ten observers skilled in making image comparisons. Figures 6 and 7 are graphs illustrating the sharpness (SH) and granularity (GR) versus the difference of sensitivity 6S of the double coated silver halide element and fluorescent screen pair combinations and that of green sensitive double coated element combined with green emitting fluorescent screen pair taken as reference. In the graphs, the higher the numbers of sharpness and granularity, the better is the sharpness and granularity. Sharpness and granularity 0.
of the UV and blue light sensitive double coated silver I halide element combined with UV emitting fluorescent screen pair are the best but at the lower level of sensitivity, while sharpness and granularity of the double 1 coated element and screen pair combinations of this invention are better or comparable to that of green sensi- 00. tive double coated element combined with green emitting fluorescent screen pair at comparable or higher level of sensitivity.
o 0o o0
I
i i 9 I o I -37 Light-sensitive Photothermographic Film GRBLF a) Preparation of the silver soap.
To 20 1 of water at 80 0 C were added 634.5 g of Humbo acid 9022 (a long chain fatty carboxylic acid comprising
C
20
C
22 5% C 18 and 5% other acid), 131 g Humbo acid 9718 (a long chain fatty carboxylic acid comprising
C
18 and 5% C 16 and 0.44 moles of a 0.08 uLm cubic silver bromoiodide mole iodide) emulsion. While stirring, were added 89.18 g NaOH dissolved in 1.25 1 water, then 19 ml of cone. HNO 3 diluted with 50 ml water. At 55 0
C
were added 364.8 g AgNO 3 dissolved in 2.5 1 water at 55 0 C. The mixture was heated at 55 0 C for one hour while stirring slowly, centrifugated while spray washing until 20,000 ohms resistance of water was obtained and dried.
Preparation of the silver salt homogenate.
S. Silver soap powder above (12% by weight), toluene (20% by weight) and methylethyl ketone (68% by weight) were mixed, soaked over-night, added with 12 g polyvinylbutyral (Butwar T B-76) and homogenized at 4,000, then 8,000 PSI.
1 '4 c) Preparation of the first trip.
200 g of the silver soap homogenate above were added with g methylethyl ketone and 30 g polyvinylbutyral
TM
(Butwar B-76) and mixed for one-half hour. The mixture was added with 2.2 ml of a 10% HgBr 2 in methanol, stirred for 5 minutes, then added with 4 g of Nonox T W50 Developer of formula H C OH HO C 4
H
4 4 9 o CH o (CH 2 4
CH
I j i 38 One 50 g part of the dispersion above was added with 0.6 ml of a solution of 0.04 g per 10 ml of the following blue sensitizer S
C
C =S N C--N-CH 2
COOH'(C
2
H
5 3
N
O
A second 50 g part of the dispersion above was added with 0.6 ml of a solution of 0.05 g per 10 ml of the fol- S lowing green sensitizer CH COONa O 0
C=S
C =CH-CH=C S N
-N-C
6
H
C2H 5
O
d) Coating of the first trip.
The blue sensitized dispersion above was coated on a -4 clear 4 mil (2 x 10 m) polyethyleneterephthalate support at 5 mils over the support and dried for 3 minutes at 87 0 C. On the opposite side of the support the green sensitized dispersion above was coated at 5 mils over the support and dried for 3 minutes at 87 0
C.
e) Preparation of the second trip.
I
i- 1 39 Component Parts by Weight A. Methylethyl ketone 78.58 B. Acetone 12.02 I
C.
D.
E.
F.
G.
H.
I.
Methanol FC-431 (3M Fluorocarbon) Phthalazine 4-Met.yl-phthalic acid Tetrachlorophthalic anhydride Tetrachlorophthalic acid Cellulose acetate ester 4.91 0.04 0.59 0.41 0.27 0.12 3.06 0 Oe .me .e Is
C*
0*9g
C
S. 0
C
S. S a S.r
*S
A through H were added to a container and mixed until solids were dissolved. I was then added and mixed for one hour until was dissolved.
f) Coating of the second trip.
On the blue sensitizing coating previously applied, the second trip was coated over the first at 2.25 mils and dried for 3 minutes at 87 0 C. The film was turned over and, on the green sensitized coating previously applied, the second trip was coated at 2.25 mils and dried for 3 minutes at 87 0
C.
g) Evaluation of the film.
A sample of the finished double-side coated photothermographic film was exposed with a xenon flash sensitometer through a 460 nanometer narrow band filter at a setting of 10 3 seconds through a 0-4 continous density wedge. The exposed sample was processed for four seconds at 131 0 C in a roller driven thermal processor. The sensitometry was recorded as Dmin=0.21 and Dmax= 4 22 Another sample was exposed and processed as above but using a 560 nanometer narrow band filter. The sensitometr- was recorded as D min=0.21 and Dm =2.19.
Clearly there is no cross-over from the green sensitized Clearly there is no cross-over from the green sensitized layer to the blue sensitizing layer. The blue sensitized layer when coated singly on one side of a polyester substrate recorded an image as follows D 0n.1 3 and D =2.56.
max
Claims (21)
1. A combination of photosensitive elements for use in radiography comprising two separate front and back X-ray fluorescent screens and a silver halide radiograph- ic element comprising a support base and front and back silver halide emulsion layers each coated on one surface of said support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein 1) said front screen comprises a first radiation emit- ting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and 2) said back screen comprises a second radiation emit- ting phosphor and said back silver halide layer com- prises silver halide grains sensitive to said second radiation emitted by said back screen, characterized in that a) said first radiation emitted by said front screen is in a wavelength region of non-actinic radiation and said second radiation emitted by said back screen is in a wavelength region of actinic radiation, b) said first radiation emitted by said front screen has a wavelength which differs from said second radiation emitted by said back screen by at least nm, c) said front silver halide emulsion layer is substan- tially insensitive to said second radiation emitted by said back screen, and d) said back silver halide emulsion layer is sub- 42 stantially insensitive to said first radiation emit- ted by said front screen, the difference in wavelength region of said first and second radiations and the insensitivity of each silver halide layer to radiation emitted by opposite screen be- ing such to reduce crossover exposure of at least 10 per- cent when compared with a symmetrical combination of a pair of green light emitting fluorescent screens and a double coated green sensitized silver halide radiograph- Iic element.
2. The combination of claim i, wherein a) said front screen comprises a non-actinic light emitting phosphor and said front silver halide layer comprises silver halide grains spectrally sensitized B! to the radiation emitted by said front screen, and b) said back screen comprises a UV emitting phosphor and said back silver halide layer comprises spec- trally insensitized silver halide grains. o•
3. The combination of claim 1, wherein said front screen comprises a substantially green emitting phosphor.
4. The combination of claim 1, wherein said front screen comprises a green emitting phosphor having more than 80% of its spectral emission above 480 nm and its o o maximum of emission in the wavelength range of 530 570 nm. The combination of claim i, wherein said front screen comprises a green emitting phosphor represented by the general formula I (Lnl-a-b' Tba Tmb) 2 0 2 S 43 wherein Ln is at least one rare earth selected from lanthanium, gadolinium and lutetium, and a and b are num- bers such as to meet the conditions of 0.0005 a s 0.09 and 0 5 b 0.01, respectively, or the general formula (Y1-c-a-bLncTba,'Tmb202 wherein Ln is at least one rare earth selected from lan- thanium, gadolinium and lutetium, and a, b and c are num- bers such as to meet the conditions of 0.0005 5 a 0.09, 0 b 0.01 and 0.65 c 0.95, respectively.
6. The combination of claim 1, wherein said front screen comprises a terbium-activated gadolinium or lan- thanium oxysulphide phosphor having substantially emis- sion peaks at 487 and 545 nm.
7. The combination of claim 1, wherein said front silver halide layer comprises silver halide grains spec- trally sensitized with spectral sensitizing dyes of the cyanine or merocyanine dyes. 00 8. The combination of claim 4, wherein said front silver halide layer comprises silver halide grains spec- trally sensitized with sensitizing dyes in such a way that it is sensitive for light in wavelength range of 530 570 nm.
9. The combination of claim 4, wherein said front silver halide emulsion layer comprises silver halide grains spectrally sensitized with sensitizing dyes repre- sented by the general formula i .A 44 R\ R R. 6 N 10 8 R CH=C-CH= (X) R7 N N R9 7 I I 9 R R 11 12 wherein R 1 0 represents a hydrogen atom or an alkyl group, R 6 R, R 8 and R each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkyl group, an alkoxycarbonyl- amino group or an aryl group, or, together, R 6 and R7, and respectively R 8 and R can be the atoms necessary to S8 9 complete a benzene ring, R 11 and R12 each represent an 1 alkyl group, a hydroxyalkyl group, an cetoxyalkyl group, an alkoxyalkyl group, a carboxyl group containing alkyl group, a sulfo group containing alkyl group, a benzyl group, a phenethyl group or a vinylmethyl group, X rep- resents an acid anion and n represents 1 or 2.
10. The combination of claim 2, wherein said back screen comprises a UV emitting phosphor having more than 80% of its spectral emission below 410 nm and its maximum of emission in the wavelength range of 300 360 nm.
11. The combination of claim 2, wherein said back screen comprises a UV emitting phosphor selected in the class consisting of lead or lanthanum activated barium sulfate phosphors, barium fluorohalide phosphors, lead activated barium silicate phosphors, gadolinium activated yttrium oxide phosphors, barium fluoride phosphors, and alkali metal activated rare earth niobate or tantalate phosphors.
12. The combination of claim 2, wherein said back 45 screen comprises a UV emitting phosphor corresponding to the general formula (Y1-2/3x-1/3y' Srx' Liy) TaO 4 wherein x and y are numbers such as to meet the condi- tions 10 x 1 and 10 4 y 0.1.
13. The combination of claim 2, wherein said back silver halide layer comprises chemically sensitized spec- trally insensitized silver bromoiodide grains. I S*
14. A method for recording a radiation image com- prising the steps of imagewise exposing to X radia- S* tions a combination of photosensitive elements comprising two separate front and back X-ray fluorescent screens and *a silver halide radiographic element comprising a support base and front and back silver halide emulsion layers each coated on one surface of said support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein 1) said front screen comprises a first radiation emit- ting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and 2) said back screen comprises a second radiation emit- ting phosphor and said back silver halide layer com- prises silver halide grains sensitive to said second radiation emitted by said back screen, and (ii) developing said silver halide radiographic ele- ment halide, characterized in that a) said first radiation emitted by said front screen has a wavelength which differs from said second ra- diation emitted by said back screen by at least 46 nm, b) said front silver halide emulsion layer is substan- tially insensitive to said second radiation emitted by said back screen, and c) said back silver halide emulsion layer is substan- tially insensitive to said first radiation emitted by said front screen, the difference in wavelength region of said first and second radiations and the insensitivity of each silver halide layer to radiation emitted by opposite screen be- ing such to reduce crossover exposure of at least 10 per- cent when compared with a symmetrical combination of a pair of green light emitting fluorescent screens and a double coated green sensitized silver halide radiograph- Sic element.
15. The method for recording a radiation image ac- cording to claim 14, wherein i i said front screen comprises a non-actinic radiation emitting phosphor and said front silver halide layer *comprises silver halide grains spectrally sensitized to the radiation emitted by said front screen, and b) said back screen comprises a UV emitting phosphor and said back silver halide layer comprises spec- trally insensitized silver halide grains.
16. The method for recording a radiation image ac- cording to claim 14, wherein said front screen comprises a green emitting phosphor having more than 80% of its spectral emission above 480 nm and its maximum of emis- sion in the wavelength range of 530 570 nm.
17. The method for recording a radiation image according to claim 14, wherein said front screen compris- es a green emitting phosphor represented by the general -I 47 47 formula (Lnla-b, Tb a Tmb) 2 0 2 S wherein Ln is at least one rare earth selected from lan- thanium, gadolinium and lutetium, and a and b are numbers such as to meet the conditions of 0.0005 a 0.09 and 0 b 0.01, respectively, or the general formula (Yl-c-a-bLnc,TbaTmb)202Tb wherein Ln is at least one rare earth selected from lan- thanium, gadolinium and lutetium, and a, b and c are num- fi bers such as to meet the conditions of 0.0005 5 a 5 0.09, 0 b 0.01 and 0.65 c 5 0.95, respectively. S* 18. The method for recording a radiation image i according to claim 14, wherein said front screen compris- es a terbium-activated gadolinium or lanthanium oxysul- phide phosphor having substantially emission peaks at 487 and 545 nm.
19. The method for recording a radiation image according to claim 14, wherein said front silver halide layer comprises silver halide grains spectrally sensi- I tized with spectral sensitizing dyes of the cyanine or S" merocyanine dyes. The method for recording a radiation image according to claim 14, wherein said front silver halide layer comprises silver halide grains spectrally sensi- tized with sensitizing dyes in such a way that it is sen- sitive for light in wavelength range of 530 570 nm.
21. The method for recording a radiation image -48 according to claim 14, wherein said front silver halide emulsion layer comprises silver halide grains spectrally sensitized with sensitizing dyes represented by the gen- eral formula R 6 0 R 0o R 1 8 -CH=C-CH= (X n R7 N N R I7 11 12 wherein R10 represents a hydrogen atom or an alkyl S group, R6, R7, R 8 and R 9 each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an a amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkyl group, an alkoxycarbonyl- *o amino group or an aryl group, or, together, R 6 and R7, and respectively R 8 and R 9 can be the atoms necessary to complete a benzene ring, R 1 1 and R12 each represent an alkyl group, a hydroxyalkyl group, an acetoxyalkyl group, an alkoxyalkyl group, a carboxyl group containing alkyl group, a sulfo group containing alkyl group, a benzyl group, a phenethyl group or a vinylmethyl group, X rep- resents an acid anion and n represents 1 or 2.
22. The method for recording a radiation image according to claim 14, wherein said back screen comprises a UV emitting phosphor having more than 80% of its spec- tral emission below 410 nm and its maximum of emission in the wavelength range of 300 360 nm.
23. The method for recording a radiation image according to claim 14, wherein said back screen comprises a UV emitting phosphor selected in the class consisting of lead or lanthanum activated barium sulfate phosphors, -CI-ilil-l. .ILliU-~m* *W 49 barium fluorohalide phosphors, lead activated barium silicate phosphors, gadolinium activated yttrium oxide phosphors, barium fluoride phosphors, and alkali metal activated rare earth niobate or tantalate phosphors.
24. The method for recording a radiation image according to claim 14, wherein said back screen comprises a UV emitting phosphor corresponding to the general formula (Y1-2/3x-1/3y' Sry, Li z TaO 4 wherein x and y are numbers such as to meet the conditions 10 5 x 1 and 10- 4 y 0.1. The method for recording a radiation image according to claim 14, wherein said back silver halide layer comprises chemically sensitized spectrally insensitized silver bromoiodide grains.
26. A combination of photosensitive elements for use in radiography comprising two separate front and back X-ray fluorescent screens and a silver halide radiographic element comprising a support base and front and back silver halide emulsion layers each coated on one S" surface of said support, wherein said front screen is arranged _i 50 adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein i) said front screen comprises a first radiation emit- ting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and 2) said back screen comprises a second radiation emit- ting phosphor and said back silver halide layer com- prises silver halide grains sensitive to said second radiation emitted by said back screen, characterized in that e a) said first radiation emitted by said front screen S e has a wavelength which differs from said second radiation emitted by said back screen by at least nm, S b) said front silver halide emulsion layer is substan- tially insensitive c: said second radiation emitted by said back screen, and c) said back silver halide emulsion layer is substan- tially insensitive to said first radiation emitted by said front screen, the difference in wavelength region of said first and second radiations and the insensitivity of each silver halide layer to radiation emitted by opposite screen be- 4 0 ing such to reduce crossover exposure of at least 10 per- cent when compared with a symmetrical combination of a pair of green light emitting fluorescent screens and a double coated green sensitized silver halide radiograph- ic element. 'M A combination of photosensitive elements for use in radiography comprising two separate front and back X-ray fluorescent screens and a silver halide radiograph- ic element comprising a support base and front and back C Be C 4 CS S b S S, S. S* 4 S S* 'S 51 silver halide emulsion layers each coated on one surface of said support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein 1) said front screen comprises a first radiation emit- ting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and 2) said back screen comprises a second radiation emit- ting phosphor and said back silver halide 'ayer com- prises silver halide grains sensitive to said second radiation emitted by said back screen, characterized in that a) said first radiation emitted by said front screen is in a first wavelength region of the electromagnetic spectrum and said second radiation emitted by said back screen is in a second wavelength region of the electromagnetic spectrum, b) said front silver halide emulsion layer is substan- tially insensitive to said second radiation emitted by said back screen, and c) said back silver halide emulsion layer is substan- tially insensitive to said first radiation emitted by said front screen. I 4i 52 T. A combination of photosensitive elements, substantially as herein described with re/erence to any one of Figures 1 to 7 or the Examples excluding the Comparative Examples. i. '3 A method for recording a radiation image, sustantially as herein defined with reference to any one of the Examples excluding the comparative Examples. 3I,. A silver halide radiographic element substantially as herein described with reference to any one of Figures 1 to 7 or any one of the Examples excluding the Comparative Examples DATED this TWENTY-SIXTH day of JUNE 1989 S* Minnesota Mining and Manufacturing Company Patent Attorneys for the Applicant 1 SPRUSON FERGUSON 0C KI .e S cS r« JED/287P
AU37121/89A
1988-07-14
1989-06-28
Combination of photosensitive elements for use in radiography
Ceased
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(en)
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IT2136188A
IT1226917B
(en)
1988-07-14
1988-07-14
COMBINATION OF PHOTOSENSITIVE ELEMENTS FOR USE IN RADIOGRAPHY.
IT21361/88
1988-07-14
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Combination of photosensitive elements for use in radiography
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Radiographic elements with selected speed relationships
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1989-07-12
1991-10-18
Minnesota Mining & Mfg
BOX WITH REINFORCEMENT SCREENS FOR USE WITH A RADIOGRAPHIC FILM.
JP2847574B2
(en)
*
1990-01-23
1999-01-20
コニカ株式会社
Silver halide photographic light-sensitive material having improved sharpness and rapid processing property and method for photographing the same
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1992-07-28
1995-11-27
COMBINATION OF PHOTOSENSITIVE ELEMENTS FOR USE IN RADIOGRAPHY
IT1256597B
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1992-10-05
1995-12-12
ASSEMBLY OF FILMS AND MULTIPLE CONTRAST RADIOGRAPHIC SCREENS
EP0633497B1
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1993-07-08
1998-10-14
Agfa-Gevaert N.V.
Medical x-ray recording system
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FR787017A
(en)
*
1934-05-02
1935-09-16
Ig Farbenindustrie Ag
A method of producing radiographic prints, using radiographic reinforcement sheets
US4639411A
(en)
*
1986-03-11
1987-01-27
Eastman Kodak Company
Radiographic elements exhibing reduced crossover
US4803150A
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1986-12-23
1989-02-07
Eastman Kodak Company
Radiographic element exhibiting reduced crossover
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Agfa Gevaert
Combination of photosensitive element suited for use in radiography
CA1196733A
(en)
*
1981-05-26
1985-11-12
Thomas D. Lyons
Radiographic emulsions
JPS6141144A
(en)
*
1984-07-31
1986-02-27
Fuji Photo Film Co Ltd
Radiation sensitized screen and formation of radiation image
1988
1988-07-14
IT
IT2136188A
patent/IT1226917B/en
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1989-06-28
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FR787017A
(en)
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1934-05-02
1935-09-16
Ig Farbenindustrie Ag
A method of producing radiographic prints, using radiographic reinforcement sheets
US4639411A
(en)
*
1986-03-11
1987-01-27
Eastman Kodak Company
Radiographic elements exhibing reduced crossover
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1989-02-07
Eastman Kodak Company
Radiographic element exhibiting reduced crossover
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