DE2444520A1 - PROCESS FOR THE PRODUCTION AND STABILIZATION OF IMAGES IN FREE-RADICAL PHOTO-SENSITIVE MATERIALS - Google Patents

Description

PATENT DEPARTMENT

LEVERKUSEN

Process for the production and stabilization of images in free radical forming photosensitive materials

The present invention relates to a recording method for making a permanent or stabilized Image resulting from the informational exposure of a photosensitive material that forms free radicals, as hereinafter defined, this process including inactivation of photosensitivity. of the compound, which generates the free radical.

With the expression "free radical forming photosensitive Material "used in the present specification * means a photosensitive material in which at least one of the photosensitive ingredients, one to UV radiation and / or visible light-sensitive, organic polyhalogen compound which generates photoradicals when exposed to it.

Photographic dye-forming systems based on the use of such a polyhalogen compound and a dye precursor compound have been described, for example, in the following publications: RA Fotland in J.Phot.Sei., 18 (1970), 33-37, in US - Patents 3 102 810 and 3 377 167, in British patents 1 151 578 and 1 073 345 and in Belgian patents 771 848, 786 973, 787 339 and 790 340, which correspond to British patent applications 41 749/70, 40 349/71, 42 802/71 or 48 804/71 .
In all of these dye-forming systems, carbon tetrabromide and / or iodoform are those commonly used. AG 1293

GV 781

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Compounds that generate photo radicals, as these compounds are characterized by their photosensitivity when they be compared with other representatives of the class of photosensitive, organic polyhalogen compounds.

One of the currently known stabilization techniques make use of the volatility of carbon tetrabromide, which can easily be removed from the unexposed parts of the recording material by evaporation. A suitable stabilization temperature is, for example, in the range of 100 to 15O ⁰ O.

The evaporation of carbon tetrabromide in the environment however, the operator poses a problem because the compound is not physiologically inert and is considered to be toxic classified (see I. Sax, Dangerous Properties of Industrial Materials, 1968).

The poison problem remains even when another commonly used stabilization technique is used, the is based on the extraction of the photosensitive polyhalogen compound.

In the known extraction stabilization technique, a solvent for the photosensitive polyhalogen compound is used used, wherein the solvent does not attack the binder of the recording layer or only weakly. Some Solvents such as diethyl ether, although they are excellent extractants, cannot because of the risk of explosion be used. Other suitable extraction solvents belonging to the class of liquid, halogenated, aliphatic Hydrocarbons belong, are immiscible with water and must not be discharged into the sewage.

■ A recording process with image stabilization has now been implemented found, which includes the following steps:

(1) Image-wise exposure to active electromagnetic radiation of a recording material in a recording layer a dye precursor compound and

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at least one photosensitive, organic polyhalogen compound which is capable of photoradicals and a dye with this dye precursor compound when exposed to UV radiation and / or visible light.

(2) Transformation by heating the non-decomposed polyhalogen compound into a non-photosensitive substance by reaction with at least one of the following stabilizing substances: triphenylamine, a "soft base" which is an element of the group consisting of phosphorus, arsenic, antimony, bismuth, selenium and Contains tellurium, and a <X, / 3 -ethylenically unsaturated compound in which at least the d -carbon atom of at least one ethylene group is bonded to cyano, a gyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group or an aryl group wherein the stabilizing substances are present in a layer adjacent to the recording layer to allow reaction with the non-photodecomposed polyhalogen compound when heated.

In the present invention, the expression “soft base” is understood to mean a substance whose logarithm of the reaction rate constant of the reaction of the base with the trans-Pt (CcHcN) ₂ Cl ₂ complex is greater than 3. Soft bases which have this property are described in Science, 151, 172-177 (1966) and in J. Chem. Educ, 4 £, 581-587 (1968), in particular in Table 3 of the article "Acids and Bases, HSAB "by Ralph G. Pearson.

The present invention also relates to an integrated copying material in which the photosensitive polyhalogen compound and the stabilizing agent have no direct chemical contact at room temperature (20-3O ⁰ C), but are in a state in which active contact is effected when the material is used to a temperature above

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60 ° C heated.

In the case of the integrated copying material system, various techniques can be used in order to keep the polyhalogen compound and the stabilizing agent below 60 ^° C. outside of active chemical contact. For example, by enclosing at least one of the reagents in capsules or droplets which have a shell or shell made of one material, usually a polymeric material or wax, which prevents direct contact with the other reagent. The capsule shells or droplet shells are torn or softened by heating, as a result of which the reagents can come into active contact.

Preferred integrated copying materials according to the present invention contain the photosensitive, organic polyhalogen compound and the stabilizer below 60 ^° C. outside of chemical contact in separate binder layers in which the layer containing the stabilizer is adjacent to the layer containing the polyhalogen compound. It is applied from a solution in a volatile liquid that is a non-solvent for the polyhalogen compound and the binder present in the image layer containing the polyhalogen compound and the dye precursor compound. A premature reaction is effectively prevented by adding a vinyl carbazole homopolymer or copolymers binder, which contains the dye precursor compound, e.g. a spiropyran compound, and the polyhalogen compound and which is in ethanol or in a first layer on the support, e.g. a resin base, of the recording material Methanol is not or only slightly soluble, is applied and the stabilizer is attached in a polymeric binder which is very soluble in Xthanol. Preferred binders for the basin layer are cellulose nitrate, polyvinyl acetate, ethyl cellulose and polyvinyl butyral.

^GV * ⁷⁸¹ 509813/1104

When applied to a removable backing, the vinyl carbazole polymer or copolymer! itself, the dye precursor compound and the polyhalogen compound contains, serve as a base; however, this is preferably placed on a non-removable, hita * estaniLe3n EHm applied, e.g., a polyester film, preferably a polyethylene terephthalate film. The ratio of vinyl carbazole homopolymer or copolymer to form the dye precursor compound in the integrated sheet material there can be between about 20 to 2 parts by weight of polymer to 1 part by weight of dye precursor compound.

The triphenylamine and the "soft base" stabilizer are preferred at least in an equimolar amount with respect to the photosensitive .Polyhalogen compound in the recording material available.

The molar amount of the, ρ- ethylenically unsaturated compound is preferably twice greater than the molar amount of the photosensitive polyhalogen compound in the recording material.

If plasticizers are used in the layer which contains the triphenylamine, the "soft base ¹¹ and / or <*, (5-ethylenically unsaturated compound"), preference is given to those who do not make the recording material opaque, i.e. to those who include The plasticizer should therefore be soluble in the same solvent as the binder. It should be essentially non-volatile under normal storage conditions. Suitable plasticizers for cellulose nitrate are polyalkylene glycol and camphor.

Particularly suitable stabilizers of the "soft base" type of The elements phosphorus, arsenic, antimony or bismuth correspond to the following structural formula:

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ir

X-Ar

in the

X is phosphorus, arsenic, antimony or bismuth, and Ar is an aryl group such as a phenyl group.

The use of such triaryl compounds in a photosensitive Mixture containing a leuco dye compound and a photosensitive organic halogen compound ent holds is already in British patent specification 1,161,058 has been described.

Preferred stabilizing agents will be of the "soft base" type in the following table 1 with their structural formers, the melting point and with references to their manufacture "

Table 1

Structural formula Enamel Manufacturing No. Point reference or Boil Point Cc) 1 ^ i Y $ 74-76 P. Pfeiffer, Ber. (HO- ^ V) JP-H η 22. ^ 620 (1904) 'Ί ^ β Cr '$ d. 200 O. Neunhoeffer, Ber., 2 ± _t 2515 (CH-CH ₂ -CH ₂ -CH ₂ ), P. (1961) 3 (<f>) e.g. bp
150
(50 mm
Hg) W. Davies, J.
Chem. Soc, 1929
33 4th 50 G. Hiers, Org. Synt.Coll.Vol.1 535

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5 (CH - ^) Sb - 127 T. Talalaevce 3 ^ ~ y 3 J.Gen.Chem. U.S.S.R. 16 777 (1946T 6th ₍ _ j _Se b.p. H. Leicester, 165 Org.Synth.Coll. (12 mm Vol. II, 238 Hg)

Cf ₁ ß> -ethylenically unsaturated compounds suitable for use in accordance with the invention correspond to the following general formula:

X- (CH = CH-) _n Y

in which:

X is an aryl group, e.g. phenyl, CN, -CH ₂ CN, an acyl group, e.g. benzoyl, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group,

Y is hydrogen or one of the groups mentioned under X, and η the numbers 1 or 2.

Preferred unsaturated compounds are in the following table 2 with their structural formulas, the melting point and with references to their manufacture.

Table 2

No. Structural formula Boil Manufacturing point (bp) reference or Enamel point (mp) in ⁰ C 1 CH ₀ = CH-CN (bp) 78 C. Honreu, Bull. Soc. C. Chim.France (4) 22, 903 2 CH - CO-CH = XCH ₀ (bp) 72 A.Sladkov, J.Gen.Chem. O fl «-
0 U.S.S.R., 24,459 (1954)

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-CH = CH - ^^> -CH = CH-CH-CH-

(bp) 118

(mp) 125

(mp) 147

(mp) 59

P.Bruylants, Bull Soc.Chim. Beige 31 176

Beilstein, E II
Vol. 5 (1W), 537

Beilstein, E II
Vol. 5 (1943), 589

Beilstein, E II
Vol. 7 (1948), 423

The stabilizers mentioned above, which are particularly advantageously used in connection with carbon tetrabromide, are also useful in stabilizing photosensitive Materials effective, the photosensitive, organic polyhalogen compounds that are not carbon tetrabromide.

Photosensitive, organic polyhalogen compounds, which reduced one through reaction with the stabilizers mentioned Photosensitivity, fall under the following general formula which includes carbon tetrabromide:

where mean:

A, B, X and Y each represent a halogen atom such as chlorine, bromine or iodine, or

one of the radicals A, B, X or Y including an alkyl group a substituted alkyl group, e.g., a halogen-substituted alkyl radical, a hydroxyalkyl radical, or a Aralkyl radical such as benzyl, a quinoxaline group, an aryl group, a substituted aryl group, an aroyl group or an arylsulfonyl group, and the other radicals chlorine, Bromine or iodine or two of the radicals A, B, X or Y represent an aromatic acyl group, e.g. benzoyl, and the others Free radicals chlorine, bromine or iodine.

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Particularly suitable representatives that correspond to this general formula are organic halides, such as carbon tetra bromide, bromoform, iodoform, hexachloroethane, hexabromoethane, pentabromathane, 1,1,2,2-tetrabromoethane, * , ^Ä , * - tribromoacetopherion, Λ, «, «-Tribromomethylsulfonylbenzene and their chlorine- or nitro-substituted derivatives, tribromosthanol and the 2-tribromomethylquinoxaline compounds, which are described in the Belgian patent V ^[ j> 7,145.

The following examples illustrate the present invention, but without restricting them to this. The figures for parts, percentages and ratios are if nothing otherwise indicated, weight information.

example 1

24 parts carbon tetrabromide, 24 parts iodoform, 24 parts 3-methyl-di-y9-naphtho spiropyran, 100 parts of poly-N-vinylcarbazole, 2 parts of silicone oil, dissolved in 1446 parts of trichlorethylene and 1336 parts of methylene chloride, are used for the application the image layer A on a polyethylene terephthalate support used in the ratio of 95 ml per m.

The stabilization layer B is on the layer A in

a ratio of 38 ml per m and the following composition applied: 50 ml of a 5% solution of cellulose nitrate in ethanol and 50 ml of a 10% solution of triphenylstibine in ethylene glycol monomethyl ether.

After drying, this material is exposed for 20 s with ultraviolet radiation in a Actina SH (trade name) -Diazokopiergerät with a UV lamp of 1000 Watt and 8 s at 130 ⁰ C hitzt-er.. A light-stable image is obtained.

Example 2

On the same image layer as in Example 1, a sta-

2 bilization layer in a ratio of 76 ml per square meter and

the following composition applied: 50 ml of a «r U X> ^GV * ^{? Ö1} 509813/1104

Ethyl cellulose solution in dioxane and 50 ml of a 10% triphenylstibine solution in ethylene glycol monomethyl ether.

After drying, this material is exposed to UV radiation as in Example 1 and 30 s at IJO ⁰ C (or 90 s at 120 ⁰ C.). A light-stable image is obtained.

Example ^

On the same picture layer of Example 1 is in a ratio A stabilizing layer of the following composition was applied at a rate of 76 ml per m: 50 ml of a 10% strength Polyvinyl butyrall solution in ethanol and 50 ml of a 7 # solution Triphenylstibine solution in ethylene glycol monomethyl ether.

After drying, this material is exposed to light as in Example 1 and ^{heated at 130 °} C. for 6 s. A light-stable image is obtained.

Example 4

A stabilizing layer is applied to the same image layer as in Example 1 in a ratio of 152 ml per m the following composition applied: 50 ml of a 20% Polyvinyl acetate solution in methanol and 50 ml of a 12 # Tritolylstibine solution in benzene.

After drying, this material is subjected to imagewise exposure as in Example 1 and heated for 40 s at 130 ⁰ C. A stable picture is obtained.

Example 5

On the same image layer as in Example 1 is in one

ρ
A stabilizing layer of the following composition was applied at a ratio of 152 ml per m: 50 ml of a 20 % cellulose nitrate solution in methanol and 50 ml of a 10 % diphenylselenide solution in methanol.

After drying, this material is exposed image-like bulky in Example 1 and heated for 40 s at 130 ⁰ C. A light-stable image is obtained.

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Example 6

On the same image layer as in Example 1 is in one

Ratio of 152 ml per m of a stabilizing layer the following composition applied: 50 ml of a 30% Ethyl cellulose solution in ethanol and 50 ml of a 12% strength Propene-3-nitrile solution in ethanol.

After drying, this material is exposed as bildraässig in Example 1 and heated for 40 s at 130 ⁰ C. A light-stable image is obtained.

Example 7

On the same image layer as in Example 1 is in one

ο
A ratio of 152 ml per m of a stabilizing layer of the following composition is applied: 50 ml of a 20 % polyvinyl acetate solution in ethanol and 50 ml of a 10% triphenylphosphine solution in methanol.

After drying, this material with UV radiation is imagewise exposed and heated for 40 s at 130 ⁰ C. A light-stable image is obtained.

Example 8

A polyethylene terephthalate carrier 0.10 mm thick

p is in a ratio of 76 ml per m with the following Composition coated: 50 ml of a 10% phenolic Resin solution in methanol and 50 ml of an 8 # triphenylstibine solution in ethylene glycol monomethyl ether. A photosensitive layer of the composition is placed on top of this stabilization layer applied from layer A of Example 1, but in

a ratio of 152 ml per m.

After drying, this material is exposed to UV radiation and heated at 130 ° C. for 2 minutes. A stable picture is obtained.

Example 9

A polyethylene terephthalate carrier 0.10 mm thick

is used in a ratio of 152 ml per m with the following GV.781 509813/1104

Coated composition: 12 parts ο , «, cx-tribromoquinoxaline-2, 12 parts 3-methyl-di-yi-naphthospiropyran, 50 parts poly-N-vinylcarbazole, 1 part silicone oil, dissolved in 1446 parts trichlorethylene and 1336 parts methylene chloride.

A stabilizing layer in one is applied to this image layer

ο
Ratio of 76 ml per m and the following composition applied: 50 ml of a 10% triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10% ethyl cellulose solution in methanol.

After drying, this material is exposed to UV radiation and heated for 4 s at 140 ° C. A light-stable image is obtained.

Example 10

A polyethylene terephthalate carrier with a thickness of 0.10 mm is applied at a ratio of 152 ml per m with the following Coated composition: 15 parts carbon tetrabromide, 15 parts iodoform, 15 parts 3-methyl-di- ^ e-naphthospiropyran as dye precursor, 1.5 parts Michler's ketone, 50 parts Polystyrene dissolved in 1446 parts of trichlorethylene and 1336 Parts of methylene chloride.

A stabilization layer in

a ratio of 76 ml per m and the following composition applied: 50 ml of a 10% triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10% Ethyl cellulose solution in methanol.

After drying, this material is exposed to UV radiation and ^{heated at 130 °} C. for 30 s. A light-stable image is obtained.

Example 11

A polyethylene terephthalate carrier with a thickness of 0.10 mm

is used in a ratio of 152 ml per m with the following Coated composition: 20 parts carbon tetrabromide,

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25 parts of 4-p-dimethylaminostyrylquinoline as dye precursor, 50 parts of polystyrene dissolved in 1446 parts of trichlorethylene and 1336 parts of methylene chloride.

A stabilizing layer in one is applied to this image layer

2
A ratio of 76 ml per m and the following composition is applied: 50 ml of a 10 # strength triphenylstibine solution in ethylene glycol monomethyl ether and 50 ml of a 10 # strength ethyl cellulose solution in methanol.

After drying, this material is exposed to UV radiation and ^{heated at 130 °} C. for 1 min. A light-stable image is obtained. · "

Example 12

On the same image layer as in Example 1 is in one

A ratio of 50 ml per m of a stabilizing layer of the following composition was applied: 35 ml of a 10 % polyvinylbutyral solution in methanol, 10 ml of ethylene glycol monomethyl ether and 35 ml of a 5% solution of compound 4 of Table 2 in toluene.

After drying, this material is exposed as in Example 1 with UV radiation and heated for 60 s at 130 G ^0. A light-stable image is obtained.

Example 13

A stabilizing layer of the following composition is applied to the same image layer as in Example 1 in a ratio of 76 ml per m: 40 ml of a 10 % polyvinyl butyral solution in methanol and 40 ml of a 5 % solution of triphenylamine in toluene.

After drying, this material is exposed to UV radiation as in Example 1 and ^{heated at 130 °} C. for 60 s. A light-stable image is obtained.

50981 3/1 1 (H.

Example 14

On the same image layer as in Example 1 is in one

ο
A ratio of 50 ml per m of a stabilization layer of the following composition is applied: 40 ml of a 10% strength polyvinylbutyral solution in methanol and 40 ml of a 5% strength solution of compound 6 of Table 2 in ethylene glycol monomethyl ether.

After drying, this material is exposed to UV radiation as in Example 1 and ^{heated at 130 °} C. for 45 s. A light-stable image is obtained.

^GV * ⁷⁸¹ 509Ö13 / 1

Claims (20)

Claims 1. Recording method with image stabilization, characterized in that that it includes the following steps: (1) imagewise exposure to active electromagnetic radiation of a recording material that is in a Recording layer a dye precursor compound and at least one photosensitive, organic poly- ^ Contains halogen compound that is capable of photoradicals and a dye comprising the dye precursor compound to be generated when exposed to UV radiation and / or visible light, (2) heating the photo-exposed recording material, whereby the non-decomposed polyhalogen compound is converted into a non-photosensitive substance, by reaction with at least one of the following stabilizing agents: triphenylamine, a soft one Base, which contains an element of the group phosphorus, arsenic, antimony, bismuth, selenium and tellurium, and a <*, £ -ethylenic unsaturated compound in which at least the carbon atom of at least one ethylene group is bound to cyan, a cyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group,. a carbamoyl group or an aryl group, the stabilizing substance is present in a layer which is adjacent to the recording layer in order to Heat the reaction with the non-photodecomposed polyhalogen compound to enable. 2. Recording method according to claim 1, characterized in that that the stabilizing agent corresponds to the following general formula: X- (CH-CH-) _n Y in which: X is an aryl group, -CN ₁ -CH ₂ CN, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group, Gv.781 -509813/1 10A • I is hydrogen or a group represented by X, and η the numbers 4 or 2 « 3 · Recording method according to claim 1 or 2, characterized characterized in that the stabilizing agent is present in an integral copy film in which it is in a binder layer is included, which the record? voltage layer is adjacent. 4. characterized jet recording method according to any of claims 1 to 3>, that the implementation of non-decomposed Polyhalοgenverbindung »is effected by heating the photo-exposed recording material about 60 ⁰ C. 5 recording method according to any one of claims 1 to 4- ^, characterized by the use of a recording material which, on a carrier, contains a first layer which which is a vinyl carbazole homopolymer or copolymer, the photosensitive polyhalogen compound and a dye precursor compound, wherein the stabilizing agent or the mixture of stabilizing agents is contained in a polymeric binder in a top layer, which is on top of the first layer of a solvent is attached, which is non-dissolving for the binder of the first layer. 6. Recording method according to claim 5, characterized in that that the binder of the top layer is cellulose nitrate. 7 recording method according to any one of claims 1 to 6, characterized in that the dye precursor compound is a spiropyran compound. 8. Recording method according to any one of claims 1 to 7, characterized in that the recording layer is carbon tetrabromide or a mixture of carbon tetrabromide and contains iodoform. 50981 3/11 OA 9 recording method according to any one of claims 1 to 8, characterized in that the soft base corresponds to the following structural formula: ir X-Ar
Sr
in the : X represents phosphorus, arsenic, antimony or bismuth and Ar represents an aryl group. 10. Recording method according to any one of claims 1 to 8, characterized in that the triphenylamine or the soft base in the recording material in at least one equimolar amount with respect to the photosensitive polyhalogen compound is available. 11. Recording method according to either of claims 1 and 3 to 9, characterized in that the «, / 3 -ethylenically unsaturated Compound is present in the recording material in a molar amount which is at least twice greater than the molar amount of the photosensitive polyhalogen compound. 12.Integral copier material that contains a dye precursor compound, at least one photosensitive, organic polyhalogen compound and contains a stabilizing agent or a mixture of stabilizing agents, characterized in that that the polyhalogen compound and the stabilizing agent are carried out at room temperature by a direct chemical Καα-cycle be kept, but in such a condition that by heating the material to a temperature of over 60 ° C active contact is effected with the stabilizing agent triphenylamine, a soft base that contains phosphorus, arsenic, antimony, Contains bismuth, selenium or tellurium, or an «, A-ethylenic is unsaturated compound in which at least the oil carbon atom is attached to at least one ethylene group Cyano, a cyanomethyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group or an aryl group is bonded. ^GV * 781. 509813/1 104 13. Integral copying material according to claim 12, characterized in that the polyhalogen compound and the stabilizing ^{agent are kept outside chemical contact at less than 6O 0} C in separate binder layers in which the layer containing the stabilizing agent is adjacent to the layer containing the photosensitive polyhalogen compound wherein the former is applied from a solution in a volatile liquid and this liquid is a non-solvent for the polyhalogen compound and for the binder of the layer containing the polyhalogen compound and the dye precursor compound. 14. Integral copy material according to any one of claims 12 and 13, characterized in that the recording material on a carrier in a first layer is a vinyl carbazole homopolymer or copolymer binder containing the dye precursor compound and the photosensitive Contains polyhalogen compound, and in a top layer which is applied to the first layer, the stabilizing agent in a binder applied from a solvent containing ethanol. 15 integral copying material according to claim 14, characterized in that that the top layer acts as a binder using cellulose nitrate, polyvinyl acetate, ethyl cellulose or polyvinyl butyral contains. 16. Integral copy material according to any one of claims 12 to 15, characterized in that the dye precursor compound is a spiropyran compound. 17-Integral copy material according to any of claims 12 to 16, characterized in that the dais soft base of the following structural formula: • X-Ar GV.781 509813/1104 which mean: .. - X phosphorus, arsenic, antimony or vismuth and Ar is an aryl group. 18. Integral copying material according to any one of claims 12 to 16, characterized in that the 4φ -ethylenically unsaturated compound corresponds to the following structural formula: X- (CH = CH-) _n Y in which:. X is an aryl group, -CW ₁ -CH ₂ CN, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group, Y is hydrogen or a group represented by X, and η the numbers 1 or 2. 19 · Integral copy material according to any one of claims 12 to 18, characterized in that the triphenylamine or the soft base in this material is based on the photosensitive Polyhalogen compound in at least equimolar Amount is included. 20. Integral copying material according to any one of claims 12 to 18, characterized in that the <A , ^ S -ethylenically unsaturated compound is contained in the material in a molar amount which is at least twice greater than the molar amount of the photosensitive polyhalogen compound. 50 9813/1104