CA1116391A

CA1116391A - Phosphor-containing compositions and their use in x-ray photography

Info

Publication number: CA1116391A
Application number: CA000306703A
Authority: CA
Inventors: Andre R. Suys; Willy K. Van Landeghem
Original assignee: Agfa Gevaert NV
Current assignee: Agfa Gevaert NV
Priority date: 1977-08-31
Filing date: 1978-07-04
Publication date: 1982-01-19
Also published as: EP0000961B1; FR2401976B1; JPS5438281A; BE858256A; DE2862054D1; EP0000961A1; FR2401976A1

Abstract

Abstract of the Disclosure Phosphor-containing compositions and their use in X-ray photography.
A composition of matter is described suitable for use as fluorescent screen in X-ray photography. The com-position of matter comprises halide-containing phosphor particles and in order to improve the stability against moisture of these particles, a non-metal organic com-pound of the formula R-X or X-R'-X
wherein R and R1 are organic groups preferably comprising at least 6 C-atoms, and not containing a reactive hydro-gen as does X, and X is a group containing a reactive hydrogen atom. The compound has a solubility of not more than 5 g in 100 ml of water at 15°C.

GV.996

Description

~L639~

Phosphor-containi~g compositions and their use in X-ray ~hoto~ra~hv ~ he present invention relates to phosphor-containing compositions of matter and more particularly to improved radiation conversion screens comprising halide contain-ing phosphors and a process for produclng such composi-tions and screens.
A first class of radiation conversion screens are X-ray intensifying screens containing fluorescent sub-stances which are employed for absorbing X-rays and con-verting sald rays into Iight to which silver halide of a photographic material is more sensitive than to direct X-ray exposure. ~hese screens also called radiographic intensifying screens are customarily arranged inside a cassette, so that each side of a silver halide film~
emulsion-coated on bo-th sides, after~the cassette has been closed is in ~ntimate contact with an adjacent screen.
In exposing the film the X-rays pass through one side of the cassette, through one entire intensifying (front) screen, through the light-sensitive silver halide film emulsion-coated on both sides and strike the fluorescent substances (phosphor particles) of the second (rear) in-tensifying screen. This causes both screens -to ~luoresce and to emit fluorescent light into at least the adjacent silver halide emulsion la~er, which is inherently sensi-GV.9g6 ...~

' -, :

, tive or spectrally sensiti~ed to the light emitted by the screens~
A second class of radiation conversion screens are the so-called "fluoroscopic screens". Such screens have the function of producing a direc-tly viewable image in correspondence with a pattern of penetrating radiation~
A third class of radiation conversion screens are fluorescent screens used in conjunction with a photo-cathode that emits photoelectrons under the influence of the fluorescent light of the screen. Such screens find application e.g. in image intensifier or image conversion tubes. In said tubes normally also a fluorescent screen is present which transforms the impact of fast moving electrons in light.
~he commonly used ~-ray intensifying screens co~prise a support and a layer of fluorescent particles dispersed in a coherent film-forming macromolecular binder medium~
Normally a protective coating is applied on top of the fluorescent layer to shield said layer from ambient in-fluences e.g. moisture, air and mechanical abrasion.
Usually these protective coatings are composed of cellulose derivatives or synthe-tic polymers as described, e.g., in the United States Patent Specification 3,164,719 of Herbert Bauer, issued January 5, 1965.
Generally, layers comprising cellulosic derivatives are somewhat permeable to moisture and therefore more hydrophobic but also more costly synthetic polymers e.g.
polymers containing fluorine atoms are applied to shield the phosphor layer from moisture.
~he protection from moisture is required not only to prevent the fluorescent layer from staining but also to prevent water from adsorbing to the phosphor particles.
Unlike calcium tungstate a broad class of halide co~tain-ing phosphors is more or less hygroscopic and even small G~.9g6 -amounts of water reduce the fluorescent light-emitting power of the phospor after a certain time so that the intensifying screen becomes useless in the long run.
So far one has only tried to remedy these defects as described in the United States Patent Specifications 3,164,719, already mentioned hereinbefore and 3,836,784 of Clayton W. Bates and Reichard A. Wallace, issued September 17, 1974, e.g. by mixing the phosphor particles with a hydrophobic polymeric binder or by coating the phosphor layer with a special protective h-ighly water-impermeable layer. The hydrophobic polymers have to be used in rather large amounts, which reduces the light-emitting power of the screen.
The protective layers do not always have the desired mech-anical strength and adherence to the phosphor layer and often require a high temperature coating procedure because of poor solubility of the polymers.
It is an object of the present invention to provide a composition of matter, which incorporates halide-containing phosphor particles, and wherein the phosphor particles are better protected against the influence of moisture and loss of fluore-scence power.
It is more particularly an object of the present invention to provide better moisture-resistant radiation conversion screens incorporating particles of a halide-containing phosphor.
It is another object of the present invention to provide ~a process for preparing such screens having an improved stability with respect to their fluorescent light-emitting power.
In accordance with the present invention a composition of ~' of matter is provided, which composition includes halide-con-taining phosphor particles, and ~hich are halide-con-taining rare-earth metal compounds in whihc one rare-earth metal is present as a host metal and at least one rare-earth metal is present as an activator metal, and which are admixed or combined in contact with or have reacted with at least one organic compound in such a way that the Eluorescing power oE the phosphor particles is less susceptible to the deleterious influence of humidity and wherein said organic compound is a non-metal organic compound corresponding to one of the following general formulae:
R-X and X-R -X
wherein:
R represents a monovalent organic group, preferably of at least 6 carbon atoms e.g. a hydrocarbon group, R represents a bivalent oryanic group, preferably of at least 6 carbon a~oms, e.g. a bivalent hydrocarbon group, with the proviso that these R and Rl groups contain no reactive hydrogen such as contained in X, and X represents a group containing reactive hydrogen, said compound upon reacting with acétyl chloride being capable of splitting off chlorine in the form of hydrogen chloride in the circumstances of the test A wherein stoichiometric amounts of acetyl chloride and of the organic compound to be examined are dissolved in anhydrous benzene and refluxed therein for 24 hours in the presence of a stoichiometric amount of pyridinei the pyridinium chloride formed being separated from the cooled reactive mixture at 20C. by filtering or centrifuging; if pyridinium chloride crystals are contained in the cooled reaction mixture, the compound is usable as a ~tabilizing agent herein, said compound having a solubility at 15C. of no more than 5 g in 100 ml of water, said compound being present in an amount suffi-cient to protect the fluoresence power of said phosphor particles from moisture.
In the formula X-Rl-X the groups X may be the same or different chemical groups.
Test A
Stoichiometric amounts of acetyl chloride and of the or-ganic compound to be examined are dissolved in anhydrous benzene and refluxed herein for 24 h in the presence of a stoichiometric amount of pyridine. The pyridinium chloride formed is separated from the cooled reactive mixture (20C) by filtering or centri-fuging. If pyridinium chloride crystals happen to be contained in the cooled reaction mixture, the compound meets the demand, viz. to be usable as a stabilising agent in the present invention.
. . ~
.

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~ 3 If the organic compolmd to be examined is a primary or secondary amine, pyridine may be omit-ted from the reac-tion mixture and the chlorides corresponding with these amines form in -the reaction.
Pyridine is normally used as hydrogen chloride sca-venger in alcoholysis (see John H.Bil]man and Elisabeth S.Cleland in Methods of Synthesis in Organic ~hemistry -Edward Brothers, Inc. Ann ~rbor, Mich., U.S.A. (1951) 78.
The use of pyridine as condensing agent in the prepara-tion of acid anhydrides star-ting from a carboxylic acid chloride and a carboxylic acid has been described by Wagner and Zook, Synthetic Organic Chemistry - John Wiley and Sons (1953) 558~ -Suitable non-metal organic compounds are non-rnetal organic compounds according to the above general formulae wherein X is a mercapto group9 a primary or secondary amino group, a carboxyl group or a hydroxyl group, which is linked to an aliphatic group or aromatic nucleus.
l'he invention includes compositions of matter as hereinbefore defined wherein (an) organic compound(s) having said effect of stabilising the phosphor against the influence of moisture (is) are present at the surfaces of the phosphor particles. Such compound(s) is (are) applied to or deposited on the phosphor particles, or result from a reaction with such phosphor particles e.g after it (-they) has (have) been dissolved in a liquid medium and then brought in dissolved state into contact with the phosphor particles.
lhe invention includes compositions of matter as hereinbefore defined wherein the phosphor particles bearing one or more organic compounds affording protection against moisture are dispersed in a binder.
~ he invention also includes any intensifying screen consisting of or incorporating a layer formed wholly or in GV.996 part of a composition of matter according to the inven-tion as above defined, with or without any one or more of the optional features above or hereinafter referred to.
A preferred optional feature resides in the employ-ment as agent for the purposes of reducing the adverseeffects of moisture on the phosphor, of an organic com-pound or a combination of such compounds whose potential protective power satisfies a certain test. ~his test (hereafter called -the "Standard ~est") has been devised for the purpose of assessing the level of effectiveness of any selected organic compounds for phosphor protection in accordance with the invention and is as follows :
Standard test _ _ _ _ _ _ (1) An X-ray image in-tensifying screen (~creen A) is pre-pared from the following composition :
terbium-activated lanthanum oxybromide phosphor 100 g organic substance (compound or combination of organic compounds) -to be tested 0.5 g poly~vinyl-n-butyral) containing 12%
by weight of non-acetalized vinyl alcohol units and having an average molecular weight of 50,000 12~5 g ethylene glycol monomethyl ether 4~ g by ball-milling to reduce the particle size to 7 Hegman ~ineness measured with a ~egman gage as specified in AS~ 1210, fil-tering the resulti~g dispersion, de-aerating it and applying the com-position to a baryta-coated paper of 290 g per m2 at a coverage of 500 g/m2.

(2) A second X-ray image i~tensifying screen (screen B) is prepared in the same way as screen A except that the organic substance to be tested is omitted.

(3) Screen A is treated with moisture by applying onto the phosphor layer of the screen a wet circular piece of filter paper having a dry weight of 1.355 g, a dia-GV.996 meter of 15 c~ and a water content of 3100 g, air-tightly enclosing the screen A together with the applied filter paper in a polyethylene bag, keeping the bag for 64 h at 60C in a ventilated cabinet and then removing the screen from the bag, removing the filter paper and drying the screen in air for 30 min at 80C.

(4) ~he screens A and B (the former having been moisture-treated as above described) are subjected to an X-ray exposure while the phosphor layers are in contact with distinct areas of the same silver halide emulsion layer of a photographic material having a transparent emulsion layer support and the e~posed photographic material is developed~ the X-ray exposure and develop-ment being such that in the area of the emulsion layer which was in contact with screen B a spectral density of at least 1.00 above inherent fog is obtained; and the composition of the silver halide material and the development being such that gradually increasing exposures of the silver halide emulsion area in contact with screen ~ would give a silver image density versus log exposure curve having a gamma value (maximum gra-dient of the characteri~stic curve) of 3;

(5) the densities DA and DB obtained in the areas of the emulsion layer, which were exposed in contact with screens A and B are measured;

(6) the actual loss of fluorescent light-emitting power of the moisture-treated screen A is computed on the basis of the spectral densities 3A and DB measured in step 5 above and the gamma value 3.
An organic compound or combination of organic com-pounds is regarded as satisfying the above Standard ~est if the result of the determination~in step 6 is that the fluorescent light-emitting power of screen A incorporat-ing that c~mpound or combination of compounds is at least GV.9~6 3L~i3~

25% of tha-t of the non-moisture treated screen B. In the most preferred embodiment of the invention the organic compound(s) affording the moisture pro-tection is (are) such that when such compound(s) is (are) used in screen A in the Standard q`est -the fluorescent light-emitting power of screen A is at least 65% and most preferably a-t least 75% of that of the non-moisture treated screen B.
If screen B in -the S-tandard Test were to be moisture-treated like screen A before being subjected to the ex-posure and development mois-ture trea-ted screen B would show a fluorescen-t power of less than 1~/o relative to that of the non-moisture treated screen ~.
As already indica-ted a mixture or combination of organic stabilizing compounds can be employed in aLy one screen composition.
Preferably use is made of at least one organic com-pound, which is colourless and upon reaction with the phosphor yields a colourless hydrophobic reaction product at the surface of the phosphor particles.
A first class of suitable organic compounds for use according to this invention comprises organic compounds wherein reactive hydrogen is directly bound to sulphur, e.g. in thiols. Preferably thiols are used that contain a hydrocarbon group of at least 6 carbon atoms. Such thiols including aliphatic as well as aromatic represen-tatives have been described by Arthur I.Vogel, ~extbook of Practical Organic Ghemistry, ~ongmans 3rd ed. (1959~
p. 502. Yery good results are obtained with 1-n-dodecane-thiol (laurylmercaptan).
A second class of organic compounds for use according to this invention are organic compounds that contain the reactive hydrogen in an amino group, i.e. primary or se-condary amines. Preferably aliphatic primary or secondary amines are used that contain a hydrocarbon group of àt G~.9~

least ~ carbon atoms. Especially good results are ob-tained with 1-n-dodecylamine (laurylamine).
A third class of organic compounds for use according to this invention are organic compounds that contain the reactive hydrogen in a carboxyl group. Preferably aliphatic carboxylic acids are used that contain a hydrocarbon group of at least 6 carbon atoms. Very good resul-ts are obtained with dodecanoic acid (lauric acid), but aliphatic carboxylic acids containing more than one carboxyl group are considered too, e.g. hexadecylenesucci-nic acid and octadecylsuccinic acid r A fourth class of organic compounds for use according to this invention are organic compounds that contain the reactive hydrogen in a hydroxyl group, which is preferably linked to a hydrocarbon group of at least 6 carbon atoms, such as e.g. in lauryl alcohol, p-t-amylphenol and iso-hexadecyl alcohol.
~ he hydrocarbon groups as referred to hereinbefore may comprise substituents that do not enhance the wa-ter-solubility of the organic compounds beyond the already given value. Suitable substituents rendering the compounds more hydrophobic are halogen atoms, e.g. fluorine9 chlo-rine and bromine, such as e.g. in p-bromophenol and per-fluorocaprylic acid.
~he above mentioned organic compounds can be used in combination with metal-organic compounds that are des-cribed as stabilisers for halide-containing phosphor par-ticles in the D~-0~ 2~710,497.
~o be mentioned in that respect are, e.g., organotin compounds and organobismuth compounds. Many of them are known as hydrogen chloride or hydrogen bromide scavenger or are known for the slowdown of thermal degradation of poly(vinyl chloride). ~xamples of such compounds are ~ r1'p he~ylb~,s m~h triphenylantimony, ~Y~#~r~ and tetraphenyltin.

GV.9gb - 10 _ ~ preferred class of stabilizing organometal com-pounds for use in combination with the organic compounds according to -the present invention corresponds to the following formula :
RmSnXL~ m wherein :
R is a hydrocarbon group, e.g. an alkyl group, X is one to three electronegative substituents e.g. oxygen in substituted form as in an alkoxy or in a carboxylate group, or is an electronegative sulphur substituent or a water-repelling sulphur-con-taining substituent linked through sulphur to -the tin atom e.g. a thioether, a mercaptide or xanthate group, and m is 1, 2, or 3, excluding X being three, two or one halo-gen atom(s) when m is 1, 2 or 3 respectively.
Examples of such compounds are dibutyltin bis(oxo-octylthioglycolate), also ca]led dibutyltin S,S'-bis(n-octylmercapto acetate) and (C4Hg)2Sn--~O-~-R)2 R being -CH ~ C4H9 described as stabilizing agent for polyvinyl chloride by D.HOSolomon, ~he Chemistry of Organic ~ilm ~ormers, John Wiley & Sons, IncO New York, p.175 to 177 (1967), and di-butyltin maleat'e, dibutyltin lauryl mercaptide, and di(n-octyl)-tin S,S'-bis(iso-octylmercapto acetate) described by Kirk-Othmer, ~ncyclopaedia of Chemical ~echnology, 2nd compl. revised edition, VolO 21, p.390 (1965) and in J.Polymer Sci. Part A, Vol. 2 (1964) 1801-1813.
A composition of matter of -the present invention com prises halide-containing phosphor particles, preferably inorganic halide-containing phosphor particles, by admix-ture combined with (a) said organic stabilizing substanca(s) optionally in a binder medium.
In one process for preparing a composition of matter GV.9g~

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according to the present invention the halide-containing phosphor particles are allowed to come in intimate con-tact with the organic stabilizing substance(s3 in an orga-nic liquid medium wherein said substance(s) dissolve and thus treated particles are separated out and dried.
In one process for preparing a radiation conversion screen according to the presen-t inven-tion the halide-containing phosphor particles are dispersed in an organie liquid medium in the presence of (a) dissolved binding agent(s) and at least one dissolved organic stabilizing substa~ce. According to one embodiment the dispersing proceeds in a ball mill.
Preferably the organic stabilizing substance(s) is (are) combined by admixture with the halide-containing phosphor particles in a selected phosphor binder layer combination in an amount suf:Eicient to maintain the fluorescent light-emitting power of the layer in a moisture treatment as defined above :Eor screen (~) at a level of at least 25% and preferably at a level of at least 75% of the level before said treatment.
~ he amount of organic stabili2ing substance or mixture of stabilizing substances sui-table for a practically use-ful increase in stability against moisture of the applied halide-containing phosphor particles can be determined by simple tests.
Effective amounts of organic stabilizers, e.g. with regard to lanthanum oxybromide phosphors, are in the range of 0.05 to 10 g per 100 g of phosphor. More hygros-copic phosphors such as cesium iodide phosphors may be used in conjunction with higher amounts of stabilizer(s).
In the production of a radia-tion conversion sereQn according to the present invention the dispersion may be coated and dried on a permanent support, e.g. a cardboard or resin sheet, or coated on a temporary support to form GV.9g~

39~

a self-supporting sheet later on. ~he solvent(s) used in the preparation of the coating composition is (are) nor-mally evaporated under reduced pressure. An ultrasonic treatrnent can be applied -to improve the packing density and to perform the de-aeration of the phosphor-~inder combination. Before the optional applica-tion of a pro-tective coating the phosphor-binder layer may be calen-dered to improve the packing density (i.e. the number of grams of phosphor per cm3 of dry coating).
Self-supporting screens of this invention can also be prepared by means of "hot-pressing", excluding the use of solvent(s) in the manufacture of the screens.
To provide high X-ray efficiency it is preferably that a minimum amount of binder be employed in the fluorescent layer. However, the less binding agent the more brittle the layer, so that a compromise has to be made. ~he thicker the fluorescent layer of a screen, the higher its intensification, but the image sharpness is decreased accordingly so that a balance between speed and definition has to be sought. ~uitable binders for use in the preparation of the fluorescent layers are, e.g., a cellulose acetate butyrate, polyalkyl (meth)acry-lates, e.g. polymethyl me-thacrylate, a polyvinyl-n-butyral, a copoly(vinyl acetate/vinyl chloride) and a copoly(acry-lonitrile/butadiene/styrene) or a copoly(vinyl chloride/vinyl acetate/vinyl alcohol) or mixtures thereof. lhe preferred binders are halogen-free polymers or copolymers.
Optionally, a light-reflecting layer is provided be-tween the fluorescent layer and its support to enhance the exposure of the silver halide emulsion material.
~ o the phosphor-containing layer a protective coating may be applied preferably having a thickness in the range of 5 to 25 ~m and be~ng composed of any film-forming poly-meric material that is phd~graphically inert towards a GV.~6 silver halide e~lsion layer.
Polymeric materials sui,-table for that purpose in-clude~ e.g., cellulose derivatives e.g. cellulose nitrate, cellulose triacetate, cellulose acetate propionate, cellulose ace-tate butyra-te, polyamides, polystyrene, poly-~inyl acetate, polyvinyl chloride, silicone resins, poly (acrylic ester) and poly(me-thacrylic es-ter) resins, fluori-nated hydrocarbon resins, and mixtures of the foregoing materials. Representative examples of various individual members of these binder materials include the following resinous materials : poly(methyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), copoly-mers of n-butyl methacrylate and isobutyl methacryla-te, copolymers of vinylidene fluoride and hexafluoropropylene, copolymers of vinylidene fluoride and triflùorochloro-ethylene, copol~mers of vinylidene fluoride and tetra-fluoroe-thylene, terpolymers of vinylidene fluoride, hexa-fluoropropylene and tetrafluoroethylene, and poly(vinyli-dene fluoride).
According to a special embodiment -the outer face of the screen intended for contact with the photographic silver halide emulsion material contains a solid parti-culate material that has a static friction coefficie~t (~) at room temperature (20C) of less than 0.50 on steel.
Antistatic substances may be applied to the screen to reduce the risk of electrical potential differences resulting in sparking. ~or example, the screens are treated with the "A~lI-S~A~" 6 spray, which leaves on odourless transparent antistatic deposit. AN~I-STA~ is ~rl~
~0 a trade ~ e of Braun ~aboratories Div. Barrett Chemical Co. Inc., Philadelphia, Pa., U.S.A.
At least a part of the halide-containing phosphor particles in the present composition of matter are prefera-bly halide-containing rare-earth metal compounds, in which GV.9~6 the host metal of the phosphor is a rare-earth metal and the activa-tor consists of one or more other rare-earth metals. ~or example, these phosphors contain yttrium, gadolinium, lanthanum, or cerium as a host metal and at least one of the metals of the group of terbium, europium, dysprosium, -thulium, samarium and ytterbium as activator metal.
Preferred phosphors of this class correspond to one of the following general formulae :
~a(1 n)Tbn OX
wherein X is halogen such as e.g. chlorine, bromine, or fluorine, and n is from 0.006 to 0.0001, the halogen being present preferably in the range of between about the stoichiometric amount and about 2.5 percen-t differing therefrom; or (1-w-y) w y wherein X is chlorine or bromine w is 0.0005 to 0.006 mole of the oxyhalide, and y is 0.00005 to 0.005 per mole of the oxyhalide.
Cerium may replace lanthanum in an amount described in the U.K.Patent Specification 1,247,602 filed October 9, 1969 by General Electric and Co.
~ he preparation of terbium-activated lanthanum oxy-chloride and lanthanum oxybromide phosphors emitting visible light is described~ e.gO, in U.K.Patent Specifi-cation 1,247,602 mentioned hereinbefore, the ~rench Patent Specifications 2,021,398 and 2,021,399 both filed October 23, 1969 by General Electric and Co, and the published German Patent Applications (DE-OS) 1,952,812 filed October 21, 1969 and 2,161,958 filed December 14, 1971 both by General Electric and Co. Suitable lanthanum oxychloride-fluoride phosphors are described in the published German Patent Application (DE-OS) 2,329,396 filed June 8, 1973 by Siemens A.G.
G~.9g6 I'he preparation of lanthanum oxyhalides activated with terbium and ytterbium is described, e.g., in the published German Patent Application (DOS) 2,161,958 mentioned hereinbefore.
Oxyhalides of lan-thanum and gadolinium activated with thulium are described, e.g., for use in radiographic intensifier screens in the United States Patent Specifi-cation 3,795,814 of Jacob G.Rabatin, issued March 5, 1974.
An ultraviolet-emi-tting phosphor is barium fluoride chloride activated with europium(II) as described, e.g., in the French Patent Specification 2,185,667 filed May 23, 1973 by Philips Gloeilampenfabrieken ~.V. According to an embodime~t the present composi-tion of matter is a com-position wherein at least a part of said phosphor parti-cles consists of said barium fluoride chloride.
An X-ray image intensifier screen employing rather hygroscopic sodium-activated cesium iodide is described in the United States Patent Specifica-tion 3,836,784, already mentioned hereinbefore. ~ccording to an embodi-ment the present composition of matter is a compositionwherein at least a part of the phosphor particles is sodium-activa-ted cesium iodi-de.
I'he thickness of the supported fluorescent layer may vary within a broad range but is preferably in the range of 0.05 to 0.5 mm~
~ 'he coverage of the phosphors is, e.g., in the range of approximately 200 to 800 g/sq.m and preferably approxi-mately 300 to 600 g/sq.m.
I'he image sharpness obtainable with a fluorescent screen-silver halide material system can be improved con-siderably by incorporating a fluorescent light-absorbing dye, called "screening dye" herein, into the fluorescent screen material, e.g. into the fluorescent layer or into a layer adjacent thereto e.g. into a subjacent anti-G~.9~6 reflectiorl layer. As the oblique radiation covers a large path in the screen material, it is attenuated by the screening dye or dyes -to a greater extent than the radiation impinging normally. ~he term "screening dye"
used herein includes dyestuffs (i.e. coloured substances in molecularly divided :Eorm) as well as pigments.
Diffuse radiation reflecting from the support of the fluorescent screen material can be mainly attenuated in an anti-reflection layer containing the screening dyes subjacent to the fluorescent layer.
~ he screening dye need not to be removed from the fluorescent screen material and may therefore be any dye or pigment absorbing in the emission spectrum of the fluorescent substance(s). ~hus black substances such as carbon black particles of an average size of 0.15 to 0.60 ~m incorporated in said anti-reflection layer or the phosphor layer yield quite satisfactory results.
~ he screening dye(s) is (are) preferably used in the fluorescent layer e.g. in an amount o~ at least 0.5 mg per sq.m. When used in the a~ti-reflection layer, however, the amount of said dye(s) is not limited.
A suitable screening dye for use in the fluorescent screens emitting in the green range (500 to 600 nm) of the visible spectrum is, e.g., Neozapor~ ~ire Red (C.I. Solvent Red 119), an azochromium rhodamine complex. Other suitable screening dyes are C.I. ~olvent Red 8, 25, 30, 31, 32, 35, 71, 98, 99, 100, 102, 109, 110, 118, 124 and 130.
~ he non-self-supporting phosphor-binder composition may be coated on a wide variety of supports, e.g. cardboard and plastic ~ilm, e.g. polyethylene terephthalate film.
A support used in a fluorescent screen of the prese~t in-vention may be coated with (a) subbing layer(s) to improve the adherence of the fluorescent coating thereto.
Screens according to the present invention may be GV.9~ ~ PF ~R~

used in conjunction with light-sensitive silver halide materials emulsion-coated on one or both sides of the support.
~ he following examples illus-trate the present inven-5 tion.
_xam~le 1 Preparation of screen A
A mixture consisting of 100 g of terbium-activated lanthanum oxybromide phosphor, 0. 5 g of lauric acid as stabilizing compound~ 12.5 g of poly(vinyl-n-butyral) still containing ~2% by weight of non-acetalized vinyl alcohol units and having an average molecular weight of 50,000, and 48 g of ethylene glycol monomethyl ether were ball-milled to a fineness of grind corresponding with

7 NS Hegman fineness of grind measured with the Hegman gauge as specified in AS~M D1210. ~he dispersion obtained was filtered and after de-aeration coated onto a baryta-coated paper of 290 g per sq.m at a coverage of 500 g per sq.m to form said screen A.
20 Preparat-ion of screen B
~ he X-ray image intensifying screen (B) was manufac-tured as described for screen (A) with the difference that the stabili~ing compound was omitted from the composition of the screen.
25 Moisture treatment _~.
~ he moisture treatment of screens (A) and (~) pro-ceeded by covering congruently the phosphor coating of each of the screens (A) and (B) with a wet circular plece of filter paper having a weight of 1.355 g in dry state, a diameter of 15 cm, and a water content of 3.100 g.
Subsequently, -the covered screens (A) and (B) were sepa-rately packed air-tight in a polyethylene bag and kept at 60C for 64 h in a ventilated cabinet. ~he screens (A) and (B) were removed then from the bag and after removal of the fil-ter paper dried in the air for 30 min at 80C.
GV.996 X-ray exposure and developmen-t The thus moisture-treated screens (A) and (B) and a screen (B1) which was like screen B but was untrea-ted with moisture, ~?ere exposed to X-rays in contact with a CUP.IX
RP1 film (Curix is a trade mark of the Applicant for a medical X-ray film). The exposure was e:Efec-ted to such a degree that after development for 23 s at 35C in Agfa-Gevaert's hardening developer G 138 containing hydroquinone and 1-phenyl-3-pyrazolidinone as developing agents and glutaraldehyde as a hardener the area of the silver halide material exposed in contact with the untrea-ted screen (B1) showed a transmission spec-tral clensity of 1082 above fog~
After ~radually increasing exposures with screen (B ) of the above film material and said development of the film as described a silver image with a gamma (~ ) of 3 is obtained~
'~he transmission spectral denslties obtained with the moisture-treated screens (A) and (B) were 1.76 and zero above fog respectively~
~he actual loss in fluorescence power of screen (A) was computed as follows :
density (~ D) = 1.82 - 1.76 = 0.06 ~ log exposure (~ log E) = ~D = 0306 = 0.02 antilog 0.02 = 1.05 ; 1/1.05 = 0.95 100% - 95% = 5%.
A usable result was also obtained by replacing lauric acid by a same amount of 1-n~dodecylamine.

Pre aration of screen I
- 5 g of a 40% by weight solution in toluene of E~ACI~E
B 2044 (ELVACI~ 2044 is a trade r~ of E.I~ du Pont de Nemours & Co. (Inc.), Wilmington, Del., U.S.A., for a poly-n-butyl methacrylate) - 100 g of LaOBr: 0.02 ~b: 0.0005 Yb phosphor particles GV.9~6 prepared according to published German Patent Specifi-cation 2,161,958, - 0.5 g of the stabilizing compound : laurylmercaptane, and - 251.2 g of toluene were ball-milled for 4 h, whereupon a further amount of 10.5 g of EI~ACIrlE 2044 (trade ~ff~e) was added and ball-milling was continued up to a Hegman fineness of grind of 7 NS (average phosphor particle size 7 ~m) measured with the Hegman gauge as specified in ASr~M D1210.
r~he dispersion ob-tained was coated at a coverage of 500 g per sq.m of phosphor on a subbed polyethylene tereph-thalate support and dried.
~e ~ g~
Screen II was prepared in the same way as described for screen I with the differencej however, that the sta-bilizing compound was omi-tted from the composition.
Moisture treatment ~ . . ~
Circular pieces of screen I and screen II each of them having a diameter of 15 cm were separately covered congruently with a wet circular piece of filter paper having a weight of 1.355 g in dry state, a diameter of 15 cm, and a water content of 3.100 g. Each of the thus co~ered screens was packed air-tight separately in a poly-ethylene bag and kept at 60C in a ventilated cabinet for64 h. Subseguently, the covered screens were removed from the polye-thylene bag and the pieces of screens I and II
after separation from the filter paper were dried in the air for 30 min at 80C.
~
rIhe moisture-treated screens I and II and an untreated screen II were exposed to X-rays in contact with a CURIX
(trade mark) RP1 film. r~he e~posure was effected to such a degree that after development for 23 s at 35C in Agfa-GV.996 - 20 _ Gevaert's haldening developer G 138 containing hydroqui-none and 1-phenyl-3-pyrazolidinone as developing agents and glu-taraldehyde as a hardener the area of the silver halide material exposed in contact with the untreated screen II'showed a transmission spectral density of 1.25 above fog.
Computed from the difference in density obtained with the moisture-treated screen I and non-moisture-trea-ted screan II' the ac-tual loss in fluorescence power of screen I was 7.9 %.
Example 3 Preparation_of_scre__ P
A mixtu~e consisting of 100 g of terbium-activated lanthanum oxybromide phosphor, 0.5 g of lauryl alcohol as stabilizing compound, 12.5 g of poly(vinyl-n-butyral) s-ti]l containing 12% by weigh-t of non-acetalized vinyl alcohol units and having an average molecular weight of 50,000 and 48 g of ethylene glycol monomethyl ether were ball-milled to 7 NS Hegman fineness of grind measured with the Hegman gauge as specified in AS~M D1210. ~he disper-sion obtained was filtered and after de-aeration coated onto a baryta-coated paper of 290 g per sq.m at a coverage of 150 g of phosphor per sq.m to form screen P.
~he phosphor layer was overcoated with a protective coating from a 7.5% solution in ethylene glycol monomethyl ether of cellulose acetate butyrate having a degree of substitution (DS) of ace-tyl 1.31 and a DS of butyryl of 1.51. ~he dried protective coa-ting had a coating weight of 10 g per sq.m.
Preparation of screen Q
The X-ray image intensifying screen Q was manufactured as described for screen P with the difference that the stabilizing compound was omitted from the composition of the screen.

GV.9~

Preparation of screen R
~ he X-ray image in-tensifying screen R was manufac-tured as described for screen P with the difference that before coating the oxybromide phosphor dispersion was mixed with a calcium tungstate phosphor dispersion pre-pared as described for the lanthanum oxybromide phosphor dispersion of screen P wi-th the only difference that the oxybromide phosphor was replaced by a same amount of cal-cium tungsta-te. ~he calcium tungstate phosphor dispersion was added in an amoun-t such -that -thefinal dispersion con-tained the oxybromide phosphor and calcium tungstate phos-phor in a ratio of 1:2.
~ he phosphor mixture dispersion was coated on the same support as described for screen P at a phosphor mixture coverage of 150 g of terbium-activated lanthanum oxybromide phosphor and 300 g of calcium tungstate per sq.m.
Moisture treatment _ ~ he moisture treatment of screens P, Q and R proceeded by incuba-tion in a cabinet having inside an atmosphere of 85% relative humidity at 20C. Said incubation treat-ment was effected for a period of 2 weeks. ~fter that period the fluorescence power of screen Q was completely lost and screen P showed randomly distributed spots and small craters. ~creen R did not show any trace of dete-rioration. When screens P and R were X-ray exposed in contact with separate strips of the same silver halide emulsion film the developed film s-trip exposed in combi-nation with screen P showed more than 100 white spots per s~.dm whereas the developed film strip which wa~ exposed in contact with screen R did not show any spots a-t all and wa-s evenly blackened.
~ he ratio of -the intensification factors of screens P
and R was 1:1.

GV.9g6

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition of matter including halide-containing phosphor particles, which are halide-containing rare-earth metal compounds in which one rare-earth metal is present as a host metal and at least one rare-earth metal is present as an activator metal, in contact with or reacted with at least one non-metal organic compound corresponding to one of the following general formulae:
R-X and X-R -X
wherein:
R represents a monovalent organic group,.
R1 represents a bivalent organic group, with the proviso that these R and R1 groups contain no reactive hydrogen such as contained in X, and X represents a group containing reactive hydrogen, said compound upon reacting with acetyl chloride being capable of splitting off chlorine in the form of hydrogen chloride in the circumstances of the test A wherein stoichiometric amounts of acetyl chloride and of the organic compound to be examined are dissolved in anhydrous benzene and re-fluxed therein for 24 hours in the presence of a stoichio-metric amount of pyridine; the pyridinium chloride formed being separated from the cooled reactive mixture at 20°C.
by filtering or centrifuging; if pyridinium chloride crystals are contained in the cooled reaction mixture, the compound is usable as a stabilizing agent herein, said com-pound having a solubility at 15°C. of no more than 5 g in 100 ml of water, said compound being present in an amount sufficient to protect the fluorescence power of said phos-phor particles from moisture.

2. A composition according to claim 1, wherein the phos-phor particles bearing one or more of said organic substances affording protection against moisture are dispersed in a binder.

3. A composition of matter according to claim 1, which composition includes halide-containing phosphor particles by admixture combined with at least one said organic substance, wherein said substance when used in the circumstances of the following test is capable of maintaining the fluorescent light-emitting power of the test-phosphor to a level of at least 25%
of its original fluorescent light-emitting power, said test comprising the following steps:
(1) the production of X-ray image intensifying screens (A) and (B), (2) a moisture treatment of screen (A), (3) an X-ray exposure of said screens (A) and (B) in contact with distinct areas of a photographic silver halide emulsion material and the development of said material, (4) the measurement of the spectral densities obtained in the areas of said material that have been exposed in contact with said screens (A) and (B), and (5) the computation of the actual loss of fluorescent light-emitting power of the moisture-treated screen (A) in comparison with screen (B) from the spectral density results obtained in step (4), - the production of the X-ray image intensifying screen (A) proceeding as follows:
100 g of terbium-activated lanthanum oxybromide phosphor, 0.5 g of the substance to be tested, 12.5 g of poly(vinyl-n-butyral) containing still 12% by weight of non-acetalized vinyl alcohol units and having an average molecular weight of 50,000 and 48 g of ethylene glycol mono-methyl ether are ball-milled to a fineness of grind corresponding with 7 NS Hegman measured with the Hegman gauge as specified in ASTM D1210, whereupon the dispersion obtained is filtered and after deaeration coated onto a baryta-coated paper of 290 g per sq.m at a coverage of 500 g per sq.m to form said X-ray image intensifying screen A, - the production of the X-ray image intensifying screen (B) proceeding as described for screen (A) with the difference that the substance to be tested is left out of the composition of the screen, - the moisture treatment of screen (A) proceeding by covering congruently the phosphor coating of screen (A) with a wet cir-cular piece of filter paper having a weight of 1.355 g in dry state, a diameter of 15 cm and a water-content of 3.100 g, thereupon air-tight packing the thus covered screen (A) in a polyethylene bag and keeping the thus packed covered screen (A) at 60°C for 64 h in a ventilated cabinet followed by the re-moving of said screen (A) from the bag and after removal of the filter paper drying at the air at 80°C for 30 min, - X-ray exposure of the thus treated screen (A) and untreated screen (B) proceeding while having said screens with the phosphor coating in contact with the silver halide emulsion layer side of a same photographic silver halide emulsion material with transparent base, the X-ray exposure and the subsequent devel-opment of the silver halide material being such that with screen (B) a spectral density of at least 1.00 above inherent fog is obtained in the silver halide material area contacting screen (B); the silver halide material and development are such that after gradually increasing exposures with screen (B) a silver image is obtained whose density versus log exposure curve has a gamma value of 3;
- the measurement of the transmission spectral densities DA and DB proceeding in the areas of the developed silver halide emul-sion material that during the exposure have been in contact with screens (A) and (B) respectively;
- the computing of the actual loss of fluorescent light-emitting power of the moisture treated screen (A) in comparison with screen (B) proceeding on the basis of the spectral density re-sults DA and DB and the gamma 3.

4. A composition of matter in the form of an X-ray image fluorescent screen, which comprises said composition of claim 1 in a layer containing a binding agent.

5. A composition of matter according to any of claims 1, 2 and 3, wherein said organic compound is an organic compound wherein the reactive hydrogen atom is linked directly to a sul-phur atom, or which compound contains the reactive hydrogen atom in an amino group, a carboxyl group or a hydroxyl group.

6. A composition according to claim 4, wherein the host metal is yttrium, gadolinium, lanthanum or cerium and the activator metal is at least one of the metals of the group of terbium, europium, dysprosium, thulium, samarium and ytterbium.

7. A composition according to claim 4, wherein the rare-earth metal compound corresponds to one of the following formulae :

wherein X is halogen and n is from 0.006 to 0.0001, or wherein X is chlorine or bromine w is 0.0005 to 0.006 mole of the oxyhalide, and y is 0.00005 to 0.005 per mole of the oxyhalide.

8. A composition according to claim 4, wherein said rare-earth metal compound is a terbium-activated lanthanum oxybromide phosphor.

9. A composition according to any of claims 1, 2 and 3, wherein the phosphor particles and the organic compound are present in a binding agent consisting of a halogen-free polymer or copolymer.