DE2241563A1 - PROCEDURE FOR Awareness-raising OF MATERIALS - Google Patents

Description

AGFA-GEVAEET AKTIENGESELLSCHAFT

Process for sensitizing print-out materials. Priority: Great Britain, August 2, 1971, note number 40 349/71

This invention relates to photographic recording and reproduction of information and on suitable materials.

The use of special spiropyrans in the production of photographic recording materials is e.g. from the US Pat. No. 2,953,454, "those described therein Spiropyrans are characterized by the fact that they are characterized by activating, electromagnetic energy can be reversibly converted into a colored form.

In many applications, such a reversible conversion is undesirable and efforts have therefore been made to use a colored To get a copy, the color of which does not fade if you keep it in the dark or with further exposure to radiation to electromagnetic radiation which is different in wavelength from the radiation originally applied.

In the German patent specification 1 274 655 there is a recording material has been described, by which one can obtain stable, colored print-out images by mixing spiropyrans used with a compound, which activates with electromagnetic radiation, releases photolytically formed free radicals can.

The starting substances for these radicals are preferred halogenated organic compounds. ■ ·

A-G ^ 1015 309®1 @ / 10 @@

The recording materials described in the latter patent require quite long exposure times when using the usual UV radiation sources.

It is the object of the present invention to provide a method for increasing the photosensitivity of recording materials to increase, which contain a photosensitive compound, which upon information-wise exposure to active, electromagnetic radiation produces a color image by reacting with a spiropyran compound.

Another object of the present invention is to provide a method to remove a latent or barely visible Visualize or amplify image produced with the spiropyran and a photosensitive compound. This process is called "optical development" hereafter, because it works with a uniform exposure in the wavelength range electromagnetic radiation caused by the tiildmässjgen Dye traces formed by exposure are absorbed.

It is another object of the present invention for these methods to provide useful photographic materials.

One has now. found that photosensitivity in terms of on the formation of a directly visible image or the optical development sensitivity of a recording material which is used in intimate mixture:

(1) at least one spiropyran compound, and

(2) at least one UV sensitive compound capable of contacting the spiropyran compound upon exposure to UV radiation to produce a dye salt contains,

is increased by using in effective relation with this mixture an organic compound which contains an amide or urea grouping, and that of the corresponds to the following general formula:

R "- C - NH - Ro

¹ ti c.

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in the "mean:

E ^ an organic group, for example of the type which is present in a carboxylic acid chloride, for example an alkyl group, an aryl group or a heterocyclic group including these groups in substituted form, or a -NHR, - or -N ^ fcJ group, in which R _x and R ,. each represent an alkyl group or an aryl group, e.g. a phenyl group including these groups in substituted form,

R _{2 is} hydrogen or an organic group, for example an alkyl group, an aryl group, for example a phenyl group or a heterocyclic group including these groups in substituted form.

Preferred sensitizers according to the above general formula are acetanilide and acetanilide derivatives.

Examples of usable sensitizers according to the general formula are listed in Table 1 below:

Table 1

Number of
link Structural formula Enamel
Point
⁰ C Source
to the manuf
lung 1 4 -S-NH-COCH ₂
^T * J 150 Ber. 60, 219
(I927T 2 H ₁ -C _O 0- <f ~%, -NH-CO-CH,
J C-. ^ - - _χ A 135 Arch.der
pharmacy
(1926) 324 3 H ₃ C-CO- ^ y -NH-CO-CH ₃ 166 Rec.Trav.
Chim. 41,659
(1922) 4th H ^ C-> - ^. -NH-CO-CH, 147 Monthly 48,
128 OCH ₃ 5 A-NH-CO-CH ₃ 130 Ber. 42.3103
(19O9T

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10

11

12th

NH-CO-CH-

OH

H ^ C-CO-NH- <£ 3 -

CH ι

HC-

CH

-NH-C0-CH

168

170

102

H ₂ C-CO-NH 3

-CO-CH ₀ -CH ₀ -CH

H ₃ C-CO-HN

-CHO

-NH-CO-CH ₂ -SH

O = C

142

156

111

242

J.pr.Cliein. [2] 84,530 (1911)

Annals 234 (1890p

Ber.21,1159 (1888T "

Ber. ^, 2643 (1900)

Ber.16.2003 (188 "3T

HeIv.Chim. Acta H,

J.pr.Chem. [21 84,649

A. Vogel, Practical Organic Chemistry, Longmans, Green and Co * Ltd. London, 3rd Ed / p. 64t

GV.5

309810/100 (1

14th ^ Y ^ 5n-KH-COCH, 132 J.Chem.Soc.
1926, 8 15th 82 • 16 CH, NHCO- <£ ^ 80-81 Am.Soc.24,
763

Spiropyran compounds used in photographic image production according to the present invention are suitable Spiropyrans, which contain at least one pyran ring, which is a condensed in the ortho- and meta-position to the oxygen atom Benzo-, naphtho- or other substituted or not substituted, higher, aromatic, polycyclic, condensed Has a ring system, e.g. an anthracene or a phenanthrene ring system, as e.g. in a spirodibenzopyran, a spirodinaphthopyran, a spirobenzonaphthopyran, a 1,3,3-trimethylindolinobenzospiropyran, a 1,3 j 3-trimethylindolinonaphthospiropyran or such spiropyrans is present, the fused, aromatic nuclei of the anthracene or Contain phenanthrac type. In these spiropyrans the Pyran rings, the fused-on benzo rings, the fused-on higher, aromatic rings and the 1,3} 3-trimethylindoline ring be substituted.

Suitable substituents for this are, for example, hydrocarbon groups such as alkyl groups, for example lower alkyl groups such as methyl, substituted alkyl groups, for example halogen- or phenyl-substituted alkyl groups, alkylene ester groups, for example a -CH2-C00C ₂ H, group, alkylenecarboxy groups, for example a -CHg- COOH group, carbonamide groups or substituted carbonamide groups, for example a -COM- ^ J ^ · group, a halogen atom, nitro, hydroxy, an alkoxy or aryloxy group or a substituent which bonds the carbon atoms together in the 3,3 'position in the spiropyran system , for example a (CHg ^ chain, where η is 2 or 3.

GV.561

309810/1000

General formulas that include particularly suitable spiropyrans, are the following:

s Λ »ΧΙ ' ⁵

^f 2 * *

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in which mean:

R, R _-1 , R ¹ ^ i, E ₂ , R ¹ 2 »Rz and R ¹ , each hydrogen, an aliphatic group, a substituted, aliphatic group, for example a C ^ -C ₂₀ -alkyl group, a substituted C ^ -CgQ-alkyl group, in particular methyl, ethyl, propyl, amyl, hexadecyl or halo-alkyl group, a halogen atom, nitro, hydroxy, an alkoxy or aryloxy group, a phenyl group or a substituted phenyl group, piperidyl, an alkylene -Ester group, e.g. a -CH ₂ -COOC ₂ Hc group, an alkylenecarboxyl group, e.g. a -CH ₂ -COOH group, a carbonamide group or a substituted carbonamide group, e.g. a -CONH- <^ Z ^ group, or Ryj and R ¹ ^ together represent a - (CH ₂ ) chain, where η is 2 or 3, to bond the carbon atoms together in the 3 and 3 'positions.

Suitable spiropyran compounds and their preparation are described in German Offenlegungsschrift 1,269,665, 1,274,655, 286,110, 1,286,111 and 1,286,112, in J.Prakt.Chem. (2) 114 , (1926), in J.Am.Chem.Soc. 216288 (1952) and in J. Chem. Soc. (1934), 1571.

Preferred spiropyran compounds are spirodinaphthopyrans and Spirobenzonaphthopyrans, their naphtho and / or benzo rings or Rings can be substituted.

An illustrative list of particularly useful spiropyran compounds is given in Table 2 below.

Table 2

Spiropyran compound Melting point
( ⁰ C) 257 '

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204

208

CH ₂ -COOH

185 164

CH ₂ -COOC ₂ H

166

CH ₂ -CO-NH-,

210.

238-

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10.

11.

COCH

12. OH

ί. OCH

140

180

260

> 260

> 260

> 260

168

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16.

CH,

CH.

18th

OCH,

OCH,

19th

20th

H_C _y CH_

³ V

^H 3 ^C \ / ^CH 3 CH,

- = v

CH,

CH,

21.

CH,

110

110

185 206

1H0

GV.561

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22nd

CH 3

CH,

23-

25-

26th

193 158

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H, C- (CH _p ) -H

Br-

144

180 160

112

309810/100 π

32

33 35.

36.

.0

H ₂₁ CO jy

^ o

approx

200

152

160

approx 250

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37.

38.

39.

OCH.

CO '

Ο ⁰ '

173

133

146

To the production of the diarylspiropyrans and the indolinarylnpiropyrans To illustrate in more detail, the following Herstollungabeirpiolc are given.

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Manufacturing 1
Her

In a three-necked 2 liter flask fitted with a reflux condenser and a tube reaching almost to the bottom of the piston for the gas supply are introduced:

Ethanol 1 liter

Butanone. 22 ml (0.25 WoI)

2-hydroxy-1-naphthaldehyde 86 g (0.5 mol)

The flask is shaken until the ingredients are partially dissolved. Dry hydrogen chloride gas is used in such Speed introduced so that it is fully absorbed and allows ethanol reflux to begin. The already strongly blue colored mixture cooled in a mixture of ice and sodium chloride and the introduction of hydrogen chloride gas continued until saturation. Green pyrylium salt crystals are formed in the reaction mixture; crystallization is allowed to proceed overnight in a refrigerator.

The pyrylium salt formed is filtered off with suction and washed with ethanol and then suspended in 300 ml of ethanol.

A 10 wt .-% aqueous ammonium hydroxide solution is under Stir added until the mixture is finally alkaline. During this process the mixture becomes colorless.

The crystalline product obtained is filtered off with suction with water [; na / aGchenind dried.

'/ Aim oohlusG the spiropyran compound in 600 ml of benzene is lmikriatallisiert, separated off again and dried under reduced Pnick at 50-60 ⁰ C. Yield: 45 g. Melting point:

, 2

In '-MtK ¹ Ii 100 inT-K' -) Ibon, d <;. r; i: .it; a reflux condenser.

-; y ■ < . ■

? 0 '1

• is, the following ingredients are introduced;

Salicylaldehyde 3.7 S (0.03 mol)

1i3,3-trimethyl-2-methylene indolenine 5.1 g (0.03 mol) Ethanol 90 ml ■

The solution is boiled under reflux for 2 hours, then cooled and filtered. ;

To separate a solid product, water ί is added to the filtrate added. The solid product is filtered off with suction, washed with water and dried under vacuum conditions.

The spirane compound obtained is recrystallized from 15 ml of hexane.
Yield: 5g · Melting point: 93

The compound that is capable of forming a dye salt ζ with a spiropyran when it is activated by electromagnetic radiation to produce is preferred according to the present invention wisely used as an organic polyhalogen compound of the a halogen-containing radical can be separated photolytically. Compounds that have this property correspond of the following general formula:

in which A, B, X and Y each represents a halogen atom such as chlorine, bromine or iodine, or one of the radicals A, B, X or Y is one Alkyl (group or a substituted alkyl group, e.g. a halogenated alkyl group, a hydroxyalkyl group or a Aralkyl group, e.g. benzyl, an aryl group, a substituted one Means aryl group or an aroyl group, while the other radicals are chlorine, bromine and iodine, or wherein at least two of the radicals A, B, X or Y are used represent aromatic acyl groups such as benzoyl and the other radical chlorine, bromine or iodine.

Suitable representative examples of compounds using this alic according to my formula are organic halides, such as carbon tetrabromide, bromoform, iodoform, hexachloroethane,

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Hexabromoethane, pentabromoethane, 1,1,2,2-tetrabromoethane, α, α, α-tribromoacetophenone and tribromoethanol.

The amount of the sensitizer according to the above, general formula can vary widely as it depends on the intensity of the desired effect.

Preferred amounts of the sensitizer vary between a weight ratio range of 1: 1 "to 0.1: 1 with regard to the spiropyran compound (s).

The spiropyran compound (or compounds) are preferred in a mixture with a 5- to 20-fold amount by weight a photosensitive organic compound such as Carbon tetrabromide is used. This ratio is not binding, since useful results e.g. with the spiropyran and of the photosensitive polyhalogen compound can be obtained at a weight ratio of 1: 1 to 1:50.

A sensitizer of the above general formula can be used alone or together with one or more sensitizers one of the following classes can be used: A) organic compounds that contain two radicals (the term Radical includes both group and atom) contain different electron affinity, which is determined by a conjugated System are tied to each other.

Suitable sensitizing agents of class (A) are those Cemäfja of the following general formulas (I), (II), (in) (V) or (VI): · '

DZO = X
R.

I) -Z-Y-Z-D

(III)

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H ™ C = L ₁ -L ₂ - L ₃ - R. H
. \ I.
_c A N I. Il C-R

(V) (VI)

in which mean:

D is an electron donating group, e.g. an alkyl, (preferably C 1-4 alkyl), cycloalkyl or aralkyl-substituted Amino or hydroxy group, preferably a monoalkylamino group, a dialkylamino group or an alkoxy group,

Z is a conjugate system, e.g., a polymethine chain, a Azamethine chain including chain that is substituted or is part of a ring structure, e.g. Phenylene or naphthyl rings,

R is hydrogen, a hydrocarbon group, e.g. an alkyl, an aryl or a heterocyclic group, preferably a methyl group or a phenyl group, or the aim Schlieren of a homocyclic or heterocyclic ring atoms necessary with an atom of group Z,

CL to complete a ring or ring system notwondicon non-metal atoms in which the group C = X over a conjugated system is attached to an electron donating group as described for D,

X is an electronegative atom or such a group, e.g. oxygen, = II-R, where R is hydrogen or an aromatic group

CN

is, sulfur, selenium, = CC _CN or another bivalent electron-withdrawing group known in organic chemistry, but X preferably represents oxygen or sulfur,

GV. '- 61

309810Μ0Π0

Q ₂ the non-metal atoms necessary to complete a ring or ring system, in which the group DZG _{n is} bonded via a conjugated system to an electron-withdrawing group, e.g. a carbonyl, thiocarbonyl, sulfonyl or dicyanomethylene group, or the necessary atoms that are connected to the carbon atom of the group DZC _{x form} a heterocyclic ring which has an electronegative character with respect to the group D, e.g. a benzoxazole ring,

Y is an electron withdrawing group, e.g. -C-C-, -S-, -S-, or

0 0 0 0Ό

the group -C-, in which X has the same meaning as described above X has "

Q, a heterocyclic nucleus that has an electron donating Group, e.g. a Di alkyDsmino group, which is represented by a

• P conjugated system is connected to the group = C _X g, in which P and Q each represent an electron-withdrawing substituent, for example a cyano group, or in which P and Q together represent the atoms necessary for closing a heterocyclic ring with an electronegative character, for example such as it is present in merocyanine dyes, like a ketomethylene ring, of which a Rhodaninkera is a particular example, L ^ and L, each a methine group or substituted methine group, Lg a simple chemical bond, a. · <*, (3-ethylenically unsaturated, bivalent Group, for example a -CH = CH- group or a large number of such groups bonded to one another, or L 1, L2 and L _3. Together represent a double bond which bonds the group Q _7. "C to the group C ~.

Preferred compounds which correspond to the formula (I) are:

GH

Preferred compounds within the scheme of formula (II)

are : .--..

3098 T-OAt-000

^C M

CH

oo

Preferred compounds which correspond to the formula (III) are described, for example, in the Belgian patent 7 ^ 7 849 ". Representative examples of these are:

v /

CH

= 0

-ο

ϊ "3

_ C

-ο

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Preferred compounds corresponding to formula (IV) are Styryl dye bases and styryl vinyl dye bases and compounds how :

12th

13th

■ N

(U.S. Patent 2,793,792) (J.Prakt.Chem. (2), 157,
Page 219 ())

(Ber. 82, page 1748 (19%)) ..

c = o

16.

H..C

0.

N - N

(Ber. 82, page 1748 (1956))

(U.S. Patent 3,189,447)

Preferred compounds which correspond to formula (VI) are described in British! 'at-jiitnclirift 853 880, e.g.

-nc / ^X N

IN THE

HC-G-

3 0 9 8 10/1000

Preferred compounds corresponding to formula (V) are merocyanines, for example those described in the British patent 131 238 are described. Representative examples of these

are : .

CH

¹⁹ '0 X Γ 1 Γ " ⁼ i Γ

^H 3 C-C ^
! ♦ S. Y O = C- - C CH ₃ CH, -N C = S N- - Ν O = C-— A ^J I. i
- N 20th I. S. c =, c CH_-CH = CH Ύ ^ Ji N O = C f = ^s . N CH, I. f C ₂ H ₅ 2 ^pp 21. A. - Ν II C-NIIO I.

SS _x

22. ILC '' ^N C = c '^ C = S

² II Il

H ₂ CN O = CN- ₂ CH

CII. ^J I 5

23. / _N / _x

H Π C = C C = S

² II »I

ILC-NO = C - NC ₂ H,

2, 2 5

nc '^ c = cn - cn = c c = s

² I »I ·

! IC CH O = C-N-C

309810/100 f)

= CH - CH =

(CH_), - O-SO H 2 j5 5

O = C

c = s

^C 2 ^H _r 2 5 ^C 2 ^H 5

(B) organic compounds that have an aromatic ring or contain a ring system in which two adjacent carbon atoms your ring or ring system and an adjacent one Ring are common, which has no conjugate character and are bonded at one end to the aromatic ring or the ring system by a carbon / carbon bond and at the other end to the ring or to the ring system attached through an electron donating group such as a secondary or tertiary amino group; the organic. Compounds include those having a ring or ring system in substituted form.

Preferred compounds of class (B ¹ ) are described in Belgian patent 727,433, for example. Representative examples of these are:

2G-.

CH-

ir ^vCII 3

CII

3 H.

-Cr

309P1 0/1000

. in which mean:

η is a positive integer greater than 2, and

R is hydrogen, an alkyl group, or a substituted alkyl group .

(C) polymeric compounds containing recurring units of the following, general structure include:

in which:

Z sulfur or a simple bond,

A is a single bond or a divalent hydrocarbon group, e.g. a -CHp group,

R _x . Hydrogen or a lower alkyl group, e.g. methyl,

Rp is hydrogen or a lower alkyl group, e.g. methyl or ethyl,

Q ₁ and Q ₂ on the one hand and Q ^ and Q ^ on the other hand in each case is hydrogen or in pairs together represent the atoms necessary to close an adjacent carbocyclic ring or an adjacent carbocyclic ring system, said ring _or; ^ .as ring system can be substituted, preferably θϊϊϊφη. »aromatic ring (e.g. a benzene ring), or a substituted, aromatic ring, e.g. a halogenated (chlorine, bromine or iodine substituted) benzene ring,

η the number 1 or 2,

GV.561

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The K-vinyl polymers and N-vinyl copolymers can be prepared by using one of the various known polymerization processes, for example by bead or emulsion polymerization or by polymerization in solution, the polymerization being carried out by free radicals, by ion formation or by radiation, e.g. with actinic light , can be initiated. It must be noted that the degree of polymerization is not critical and can vary within wide limits. With regard to the copolymers it must also be noted that the content of groups that correspond to the general formula given above is not critical and, as shown below in the table of copolymers with N-vinylcarbazole units, can vary within wide limits, eg · between 20 and 95% j if one takes into account the properties of the compounds used in the production of the copolymers, as well as the required sensitizing and / or mechanical properties. In general, the best results are achieved with copolymers whose vinyl carbazole unit content is between 40 and 90 % .

The preparation of suitable poly-N-vinylcarbazoles ¹ is described, for example, in German patents 931.731, 936 421,

1,097,680, and 1,158,367, and U.S. Patent 2,072 described. The production of poly-N-vinylpyrroIs is analogous.

The; The preparation of suitable N-vinylcarbazole copolymers is described in British patent specification 964 875, which patent specification also describes a preparation process for poly (N-allyl ~ carbazole) (E ^ * CH, and R ₂ »H) and also for poly (N-propenylcarbassol) ( R ₁ -H, R ₂ = H ₅ A = -CH ₂ -).

The poly-N-vinylindoles are in the German Offenlegungsschrift • 1 906 831 and 1 917 747. The poly-N-vinyldiphenylamine is in the German Offenlegungsschrift

2 007 692. Halogenated poly-N-vinyl carbazoles has been published in Japanese Patent Applications

OV. '/, 1

3Q9810 / 100O

21 875/67, 25 230/67, 7 592/68, 19 751/67 and 7 591/68. ' ^: ''■■■■

To illustrate, suitable vinyl copolymers, which contain N-vinylcarbazole units in the following table 2 listed.

Table 2

Mixed polymer and and N-Vmylcnrbu-
zol in mol% Copolymer made from N-vinylcarbazole
Vinylidene chloride and and 85 ,. Copolymer made from N-vinylcarbazole
3,3 ', 5-trimethylisononyl ether and and 93 Copolymer made from N-vinylcarbazole
Vinyl acetate and and 88.6 Copolymer made from N-vinylcarbazole
Isopropenyl acetate and and 94.5 Copolymer made from N-vinylcarbazole
Vinyl stearate and and - 37.5 Copolymer made from N-vinylcarbazole
Methyl acrylate and and 67.6 Copolymer made from N-vinylcarbazole
Ethyl acrylate Graft copolymer made from N-vinylcarbazole and
Ethyl acrylate 41 Emulsion polymer made from N-vinylcarbazole and
Polyacrylate 90.3 Copolymer made from N-vinylcarbazole
n-butyl acrylate 94.5 Copolymer made from N-vinylcarbazole
2-ethylhexyl acrylate 58.3 Micchpolymerisat made from N-vinylcarbazole
Acryloxyethyl diethylamine 51.6 Copolymer made from N-vinylcarbazole
Vinyl cinnamate 76.6 Copolymer made from N-vinylcarbazole
Methyl methacrylate 92.5 Copolymer made from N-vinylcarbazole
Isobutyl methacrylate 62.7 Copolymer made from N-vinylcarbazole
Lauryl methacrylate 51.8 77.4

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Copolymer of N-vinylcarbazole and methylaeryloxyethyl diethylamine

Copolymer of N-vinyl carbazole and Acrylonitrile

Graft copolymer from N-vinylcarbazole and butyialdehyde acetal of polyvinyl alcohol Copolymer of N-vinylcarbazole and D i (2-di chloroethyl) vinylphosphonate Mixed polymer of N-vinyl carbazole and styrene

Propfmischpolymerisat.aus N-vinylcarbazole and Polystyrene

Copolymer of N-vinyl carbazole and vinyl naphthalene

Copolymer, made of N-vinylcarbazole and anthracene9,10)

Copolymer of N-vinyl carbazole and 2-vinyl pyridine

Mixed polymer; from N-vinylcarbazole and 4-vinylpyridine -

Copolymer of N-vinyl carbazole and N-vinyl! Pyrrolidine -

Terpolymer made from N-vinylcarbazole, -acrylonitrile and Styrene

Graft copolymer of a terpolymer Vinyl chloride, vinyl acetate and vinyl alcohol with N-vinyl carbazole

Graft copolymer of a terpolymer from Vinyl chloride, vinyl acetate and maleic anhydride with N-vinyl carbazole

9.7 88

30th

82.4 49

.27.3

91 , 5 31 ,8th 32. , 4 69 ,1 20th 29 , 4 55 ,1

A preferred photosensitive recording material According to the present invention, the spiropyran contains · "■ = compound (s) and poly-N-vinylcarbazole in a weight ratio within 80: 100 to 10: 100.

The poly-N-vinyl carbazole is still mixed with carbon tetrabromide or iodoform or a mixture of both polyhalogen compounds is used. The polyhalogen compounds are preferred with respect to the poly-N-vinylcarbazole used in a weight ratio of 160: 100 to 20: 100.

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■ (D) Organic, nitrogenous compounds that have a thiol group or have a thione group in their tautomeric form, as in the following tautomeric structural formula parts is pictured :

Il Il

HS-C = NS = C-NH

Preferred organic, nitrogen-containing compounds correspond to the following, general, tautomeric formulas:

, '- Xs, -X _n

Z C-SH * ZC = S

in which mean: ι

X is oxygen, sulfur, selenium or the group -NR, in which κ is hydrogen or an organic group, e.g. an alkyl group or a substituted alkyl group, preferably a C ^ -C ^ -alkyl group,

Z those for closing a 5- or 6-membered, substituted or unsubstituted heterocyclic, nitrogen-containing ring or ring system necessary Aüome e.g. the necessary atoms to close a Bonzthiazole, bengselenazole, benzoxazole or benzimidazole ring.

Preferred compounds which correspond to the scheme of class (D), are e.g.

KJ

&> S "C- SH ·

ι Il "

^ vJ ' ^IJ

(iv .'...- ι 309810/1000

N-

S / "^ C-SH

J = C ^ ^Χ Ν

HN N

(CII ₂ )

NH

CH ₀ -CH = CH ₀ , i.e. d.

ν - Ο

I ₀ C -MI

\ sf ^s c = s

'-ι I.

UC Nile

Imidazolidine-4-011-2-thione, e.g.

II N

O = C-Nile

3 09810/1000

^l i'etrahydropyrimidin-2-thione, ζ.Β,

II

^N c = s t

* NH

rotrahydiv.-Uiione, ζ.

and dihydrooxazine-2-thione and thiazi.n-2-

H N

H,

' H ₂ C-HC C = S

H ₀ G NH ^ά C "H-,

- 1,3 ₅ 4 ~ Dihydrotliiadiazin-2-thione, aB,

ι HIl

I ¹ I

Thiourrrtoffvorbindim ^ xn and their substituted derivatives 'to ^ HV / eifie N-PhenylthJohrvrn:' toff compounds, e.g.

CII ₇ £ J I ■> Il

, -N - C- NfI.

t; v. μ> ι

3098 10/1000

- 51 -

? 2A1563

- thioamides, e.g.
'Λ.

It is noteworthy that most of the appropriate sensitizing Hercapto compounds generally known picture tone influencers from the silver complex diffusion transfer process are.

(E) inorganic compounds that, under the influence of activating, electron magnetic radiation photoelectrons and have a basic or amphoteric character, e.g. photoconductive zinc oxide and lead oxide.

Pur in the event that photoconductive zinc oxide is used as an additional Sensitizer is used, the recording layer preferably contains 5 to 50 parts by weight of zinc oxide, dispersed in 100 parts by weight of a binder containing the spiropyran compound (s) preferably in an amount of 1 to Contains 50 parts by weight, and the photosensitive reagent for the formation of the dye salt, e.g. a photosensitive, organic halogen compound such as carbon tetrabromide and / or iodoform in an amount of 10 to 250 parts by weight.

The photosensitive recording layer can be used as a further constituent according to the present invention a film-forming one Contain binders. For this purpose are preferred hydrophobic polymers, which are the ingredients used so far aJ κ inöpHich against direct contact with the ambient air and y n: -. shield special ones with oxygen.

rs suitable binders for use according to the pre-Ii cf: or-ion invention are hydrophobic polymers and copolymers at ο the z.E. Styrene, vinyl acetate, acrylonitrile, acrylic acid ester, Methacrylic acid ester, !! - vinyl carbazole or butadiene units onlliaü.Um, hydrophobic cellulose derivatives, phenoxy resins or PolyJ'.ondon.sato of the polyester type e.g. polycarbonates.

(; v. '.. i 309810/1000

These polymers can be used in a mixture to improve the mechanical strength or adhesive force of the recording layer can be used to support them if no self-supporting layer is made.

To reduce the proportion of spontaneous, thermal color formation over long periods of time, as is necessary for storage and processing of the photographic material is desired, so-called anti-fog agents can be added to the photo-sensitive composition are given. Suitable antifoggants include triaryl compounds of Group V elements from the Table of the Periodic Table of the elements, e.g. triphenylstibine and sterically hindered phenols, e.g. 2,6-di-tert-butyl-p-cre3ol and other reducing or agents that absorb the oxygen in the air. Triphenylstibine and analogous compounds for use in accordance with the present invention are described in British Patent 1,071,104.

Preferred amounts of an anti-fog agent such as triphenyletibine vary in photosensitive carbon tetrabromide and / or iodoforms within the weight ratios of 1: 100 to 2.5: 100.

A dry photographic layer containing the aforementioned Containing ingredients can be formed by dissolving the binder (s) in a suitable inert solvent, as a dispersion or solvent for the other ingredients serves and that by evaporation of the casting composition is removed leaving a solid photographic recording layer on a selected support. The supports can be of any type found in photography Encounters silver logistical materials, e.g. paper and film supports.

In order to achieve the highest sensitivity, it is desirable to apply the recording layers in the absence of oxygen or to keep them in an oxygen-free environment from exposure.

The photosensitive, organic polyhalogen compounds, the GV.5G1 309810/1000

in the exposed state, a dye salt with a spiropyran compound are normally only sensitive in a wavelength range between 250 and 400 mn.

The recording materials according to the present invention which contain spirodiarylpyrans and sensitizers of the general formula show, especially in connection with polymers and copolymers, which contain N-vinylcarbazole units and serve as binders, a remarkable, high sensitivity to white and especially to red light. Djese unexpectedly high sensitivity in the visible spectrum is increased when the temperature of the recording layer composition is raised above 40 ⁰ C during the exposure to visible light. A very suitable working temperature is in the range from 40 to 70 ^° C.

By sharing the media of general awareness Formula with organic, spectral, sensitizing dyes, e.g. those of class (A), it is possible to use the spectral Increase sensitivity in the visible spectrum and create synergistic, to achieve sensitizing effects. So if you use a recording material that is superimposed Contains recording layers which are sensitized in the red, green or blue region of the spectrum and which are suitable color-forming combination contain »can produce superimposed blue-green, purple and yellow line pictures which result in a full-fledged reproduction of the multicolored original that is used for the information-wise exposure had been.

The recording materials sensitized according to the present invention, are suitable for copying images of different colors depending on the type of spiropyran compound used to surrender.

The stabilization of the copies obtained can take place by using the remaining free radical generator a suitable solvent or solvent

washes out mixture, e.g. with a hydrocarbon liquid, like petroleum ether, optionally mixed with acetone, or by simply evaporating it by increasing the Temperature if the compound in question is sufficiently volatile. For the latter purpose and because of the high photo sensitivity carbon tetrabromide or a mixture with iodoform is preferred.

According to a preferred recording and reproducing process In the present invention, the information-wise exposure is carried out in such a way that a latent image is first produced, which is converted into a visible dye image by means of a so-called "optical development".

Optical development is carried out by making the Recording layer showing the latent or barely visible Contains image, over its entire surface with visible Radiation exposed in the spectral Absorptionbaii.de of the products, which by the "bilürsHssige exposure and the pictorial interaction of the photo-exposed ingredients (1) and (2) the heated photosensitive composition are formed. In the uniform exposure, no light is used for which the photo-sensitive polyhalogen compound is intrinsically sensitive, since doing the effect of the image-wise exposure masked by a uniform! "ärtnang will. It is advantageous in optical development]> e ~ use a blocking filter that absorbs all the light that corresponds to the wavelength range, which are naturally not beneficial to the ingredients Recording layer is absorbed.

■■ ■■ ' By supplying heat, for example through contact with a hot body or by exposure to infrared radiation during uniform exposure to visible light, the optical development is noticeably accelerated and the image density is accelerated

The increase in optical development is particularly evident when using "van allyCl" iriisiyfcertoazci) or the copolymers, such as N-vinylcarbic solids

30S910 / 10Q0

in connection with the present amide, acylamine or ureido \ ί bindings. The. Addition of a triaryl stibine such as triphenyl stibine Such a mixture enhances the image density achieved by the optical development process.

It is believed that when used for optical development Exposure at least a part of the evenly applied Radiant energy is visible light, absorbed by a dye salt, which has a pyrylium structure, when using a diarylspiropyran, or an indolinium salt structure if one uses an indolinarylspiropyran. These salts appear to be spectral sensitizers for a chemical reaction between the spiropyran and the photosensitive To act polyhalogen compound or the radicals formed therefrom.

In a particularly preferred composition for formation A mixture of carbon tetrabromide, carbon and iodoform is used for both copy and optically developable images. which gives a super additive sensitizing effect.

According to another embodiment of optical development technology, the recording material is initially uniform exposed to electromagnetic radiation in order to undifferentiate latent dye centers over the entire recording layer to form which, later in terms of information by a sufficiently strong informational exposure in the absorption band of the EarstoffZentren are optically developed. The information-based exposure is optionally carried out at the same time as uniform heating, e.g. through uniform infrared exposure is effected.

Instead of evenly pre-exposing to form dye centers these dyes can e.g. be added to the drawing layer in small quantities by suction (diffusion)

GV. ^ 61 309810/1000

'Admit composition to act as optical development cores for dye imaging by serving imagewise exposure.

According to a particular embodiment, the spiropyrans in the unexposed recording layer composition Formed "in situ" by the corresponding pyrylium and Indolinium salts is assumed and the pH in a Manner is adapted to obtain the spiropyrans, which he regards as the dye precursors of the pyrylium and indolinium salts can be.

The information-based exposure according to the present invention can be a contact exposure of the direct or reflex type and also an optical projection exposure, as used in an optical enlarger, for example. The informational exposure does not need to be in all parts of the recording material at the same time to take place. It can be progressive in a single stage, e.g. in the case of soundtrack recording, or in successive, interrupted stages, provided that the required informational change is achieved. Thus, the recording material can be image-wise modulated High intensity beam, e.g. with a laser beam, can be scanned, or the material can progressively through a slit can be exposed, e.g. when it is exposed to copy light from a tube lamp running along the original is moved in parallel.

A recording material of the present invention which is used for Recording of information-based modulated UV radiation suitable can be used in X-ray and electron-beam recording. X-rays can be in Highly energy-absorbing substances are absorbed and thereby generate so-called secondary photons, e.g. from the band of UV radiation energy, and photoelectrons absorbed by the photoemic polyhalogen compound,

c, V. '; Eq

309810/1000

which, through its photo radicals, forms a dye salt with the spiropyran Substances incorporated into the recording material contain the elements lead, mercury, bismuth, barium and / or tungsten. Lead compounds are preferred, e.g. lead monoxide, lead bromide and lead iodide, which are photosensitive themselves are.

Suitable light sources for use in the recording method according to the present invention are UV radiation sources, xenon gas lamps, incandescent lamps, sunlight and flash lamps. I ^{1 For} the uniform exposure of the optical development, an infrared lamp is preferably used, which also emits in the visible spectrum.

Electron beam and laser beam recording are made with the apparatus suitable for this purpose, which are well known to those skilled in the art. *

Recording materials of the present invention are very versatile in that they can be used to reproduce halftone or linework through the use of a suitable sensitizer. You can very devoted to high-contrast images, making them suitable for the reproduction of line and screen templates are very useful and can be used successfully in the graphic arts "Thanks to the very high resolution of the recording materials (the dyes are formed in molecularly divided form), the recording materials The present invention is particularly suitable for microfilm reproduction and precision image reproduction, for example in the production of optical micromask templates that are used in the production of microelectronic circuits.

The Rol'lex exposure properties of the present recording materials the latter are very suitable for document reproduction, as copy-out images are never included in a reflex contact exposure m'l int-enrjiver Spoktraldiehte surrender.

¹ 309810/1000

According to a particular application, a recording layer is as described herein, used in conjunction with a magnetic recording layer especially on the back of a flexible tape carrying the magnetic recording layer. When using of such a material, a sound track is formed in the magnetic recording layer, and becomes a visible text image, that corresponds to the sound track on the recording layer copied according to the present invention.

Such a recording material therefore allows storage of optical and acoustic signals and enables the synchronous reproduction of both information.

The following examples illustrate the invention. The proportions are weight ratios unless otherwise stated.

example 1

- H £ rj; tellung_von_Probe_A

A mixture of 120 mg carbon tetrabromide, 120 mg iodoform, 100 mg 3-methyl-di »y5-naphthospiropyran and 8 ml of a 5% A solution of polystyrene in methylene chloride is 0.1 mm thick on an unsubstrated polyethylene terephthalate carrier applied.

The layer is dried in the dark and at room temperature.

- Production of sample B

A mixture of 120 mg carbon tetrabromide, 120 mg iodoform, 100 mg 3-methyl-di - ^ - naphthospiropyran, 60 mg acetanilide and 8 ml of a 5% solution of polystyrene in methylene chloride is applied to an unsubstrated polyethylene terephthalate carrier.

The layer is dried in the dark and at room temperature.

Samples A and B are marked by a gray wedge with a con

309810/1000

Constant of 0.15 ΡΐΌ level using a 3-line 1000 watt mercury vapor lamp "exposed, placed at a distance of 5 cm is. . -

The following table shows the exposure times and the number of directly reproduced wedge steps.

Tabel

Exposure time in sec.

Amount of levels reproduced

Sample A

Sample B

5 2

10 6 O

16 9 5

If you do the contact exposure in a 3M-? H0T0C0PIER 179 (Copier sold by Minnesota Mining and Manufacturing Co., St. Paul, Minn./USA) and at full intensity works, 0 steps with sample A and 2 steps with sample B are reproduced for an exposure time of 30 seconds.

The temperature of the recording materials during their exposure is about 50 ^° C.

The image obtained is stabilized by heating the recording material at 140 ^° C. for one minute.

Beis piel 2

A mixture of 120 mg carbon tetrabromide, 120 mg iodoform, 100 mg 3-methyl-di - ^ - naphthospiropyran, 20 mg triphenylstibine and 8 ml of a 5% solution of poly-N-vinylcarbazole in Mothylon chloride is 0.1 mm thick on an uncubstricrt.cn Polyethylene terephthalate carrier applied.

- Manufacture unj3_von_Probe_B >

A Mis RECOVERY from 120 mg of carbon tetrabromide, 120 mg of iodoform, 100 mg of 3-methyl-di- / 3 _v naphthospi _ropy: ran, 20 mg triphenylstibine, 60 mg acetanilide and 8 ml of a 5% solution of poly-N-

GV.561

98107

Vinyl carbazole in methylene chloride is 0.1 mm thick applied to an unsubstrated polyethylene terephthalate carrier.

The layer is "dried" in the dark and at room temperature.

Samples A and B are contact-exposed through a gray wedge with a constant 0.15 per step in a 3M-PH0T0C0PIER 179 (trade name). The exposure lasts 30 seconds, and the temperature of the recording materials during the exposure is about 50 ^° C.

An image of the wedge with 4 visible steps is applied to sample A and an image of the wedge with 12 visible steps is applied to sample B reproduced.

The same recording materials are used for manufacture of copy images used by means of a diazo copier, which is available under the name ACTINA SH from La Cellophane, Paris, France, and by working with a UV radiation source of 1000 watts.

The following table shows the exposure times and the number of directly reproduced wedge steps.

Recovery time
in sec.

Number of levels reproduced Sample A Sample B

19th

The stabilization of the images is carried out by darr. Recording material is heated for one minute at 18O ⁰ C.

- il2- ££ ili £ llH2ü_ ^ 2i * _ Recording material for comparison tests 120 inr; Carbon tetrabromide, 120 mg iodoform, 100 mg 3-Mothy] -

GV.'r ι 309810/1000

di- / S-naphthospiropyran, 30 mg triphenylstibine and 60 mg of a Sensitizer, which is indicated by a number in Table 1 of the description, is in 8 ml of a 5% Solution of poly-N-vinylcarbazole dissolved in methylene chloride.

The solutions are applied in a thickness of 0.1 mm; the recording layers are dried at room temperature and in the dark and exposed for 30 seconds with a gray wedge (constant 0.15) in a 3M PHOTOCOPIER 179 (trade name). The temperature of the exposed recording material is about 50 ^° C.

The following table shows the number of wedge steps you can use at the various materials received.

Tabel

Number of the sensitization compound of the general formula (I.

Number of reproduced

The images are stabilized by heating the recording materials for one minute at 180.degree.

Bui; ψ LοI 4

JSino mixture of 120 carbon tetrabromide _T 120 mg iodoform »100 mc; i-Mothyl-cli- ^ iiaphthospiropyran, J50 mg triphenylstibine,

CiV.% 1

309810/1

_ 42 -

60 mg of p-isopropylacetanilide and 8 ml of a 5% solution of Poly-N-vinylcarbazole in methylene chloride is in a strength of 0.1 mm on an unsubstrated polyethylene terephthalate carrier applied. The obtained layer is at room temperature and Darkness dries.

The recording layer is replaced by a transparent line original exposed in a 3M-PH0T0C0PIER 179 (trade name), by working at full intensity with an exposure time of 5 seconds. An image density of over 1 is obtained.

The image is stabilized by moving the recording material treated in a solution consisting of tolupl, acetone, n-hexane (1: 1: 4 parts by volume).

Boi r. Game 3

A mixture of 120 mg carbon tetrabromide, 120 mg iodoform, 100 mg 3-methyl-di-yfJ-naphthospiropyran, 60 mg acetanilide, 20 mg Triphenylstibine is dissolved in 8 ml of a 5% poly-N-vinylcarbazole solution dissolved in methylene chloride.

The solution is 0.1 mm thick on an unsubstrated Polyethylene terephthalate applied. The applied layer is dried in the dark and at room temperature.

The recording material is stored in a 3M-PH0T0C0FIER 179 (Trade name) exposed through a step wedge with the constant 0.15. The exposure lasts 30 seconds and results in a Auskopicx'bild that contains 11 visible steps.

Developmental errors
The recording material is exposed in the same way as described for preprocessing, but through a transparent line original and with an exposure time of only 2 seconds, so that no directly visible image is obtained.

309810/1000

The image-wise exposed recording layer then becomes uniform exposed with a 250 watt infrared lamp, which in one Distance of 20 cm is set up and the recording layer Irradiated through a narrow band filter for 25 seconds and mainly Light emits in the wavelength range from 600 to 610 nm.

The density of the cyan image obtained is over 1.

Example 6

A mixture of JOO mg carbon tetrabromide, 100 mg iodoform, 100 mg J-methyl-di-zS-naphthospiropyran, 30 mg triphenylstibine, 60 mg phenacetin, 5 mg Thio-Michler's ketone and 8 ml a 5% poly-N-vinyl carbazole solution in methylene chloride is 0.1 mm thick on an unsubstrated polyethylene terephthalate carrier applied. The layer obtained is dried in the dark and at room temperature.

The dry recording layer is left through for 3 seconds transparent line original in a 3M-PHOrOCQPIER 179 (trade name) exposed. A copy image with a neutral color and a density of over 1 is obtained.

Example 7

A mixture of 120 mg carbon tetrabromide, 120 mg iodoform, 100 mg 3-methyl-di7S-naphthospiropyran, 60 mg acetanilide, 30 mg Triphenylstibine and 8 ml of a 5% solution of poly-N-vinylcarbazole is 0.1 mm thick on a Polyäthylenter ephthalatt rager applied. The layer is dried in the dark and at room temperature.

The recording material obtained is divided into 6 strips, the one with a 100 watt incandescent lamp from a distance of 15 cm be exposed. During the exposure, the strips are exposed to different temperatures in order to get an impression to preserve the influence of heat during exposure.

In dor following table shows the temperatures are listed undeontiiprochon- (\ (exposure times to achieve a density D =. 1

GV.

209810 / TOöo

Tabel

Temperature, ⁰ C Exposure time (sec.) To Er
range of D = 1 37
48
55
63
70 10
6th
3
1
3

GV.561

309810/1000

Claims (1)

Claims A photographic recording method by imagewise exposure of a recording material "which .in intimate mixture contains: (1) at least one spiropyran compound, and (2) at least one UV-sensitive compound that is involved in Exposure to UV light is able to form a dye salt with the spiropyran compound, creating a visible image in the recording material will • - - either by imagewise exposure to UV light in one Dose sufficient to form a visible image, - or by imagewise exposure with. UV light of a first wavelength range in a dose that is sufficient to form a latent or barely visible image, the image parts of which have a spectral sensitivity, in a second wavelength range outside the intrinsic sensitivity range. of the UV-sensitive connection _t! and subsequent uniform exposure to light of the second wavelength range ,. - or by uniform exposure to UV light of a first wavelength range in a dose that is sufficient to increase the spectral sensitivity to light of a second wavelength range outside the inherent sensitivity range of the UV-sensitive compound, vxiä subsequent imagewise exposure to light of the second Wavelength range ;, characterized,; that the Ai ^ ze: ißJii »angsmaterial besides / the mixture from (1); and (Zl & to & organic compound; with: an amide or Earnstöffgr, u | ipi © ru »g contains; that of the following general formula, ι J ₁ a in which: R _{1 is} an alkyl group, an aryl group or a heterocyclic group, including these groups in substituted form, an -NHFU group or an -N '3 group »in which ^R 4 R, and Rl represent an alkyl group or an aryl group, including these groups in substituted form, and R _{2 is} hydrogen or an organic group. 'Δ. Photographic process according to claim 1, characterized in that the recording material is heated uniformly after the formation of a visible image in order to achieve image stabilization. 3- The method according to claim 1 or 2, characterized in that that the organic compound of the general formula acetanilide or an acetanilide derivative and the spiropyran compound is a spiropyran that is in ortho and meta positions with respect to the oxygen atom of at least one fyran ring contains a condensed benzene ring or a polycyclic, aromatic, condensed ring system, including these condensed rings or ring systems in substituted form. 4. Experience according to claim 3, characterized in that the spiropyran compound a spirodibenzopyran »a spirodinaphthopyran, a spirobenznaphthopyran, a 1,3,3-trimethylindoline-beiizspiropyran, a 1,3,3-trimethylindoline naphthospiropyran or is a spiropyran, which has a condensed » aromatic ling of the anthracene or fhenantine type contains 5- Working according to each of the preceding claims, thereby marked that in the recording material as OT- 30 9810 / T000 _ 47 - sensitive compound an organic polyhalogen compound is used, which corresponds to the following general formula: AX B'S in which: A, B, X and Y each represent a halogen atom or one of the radicals A, B, X and Y is an alkyl group or a substituted alkyl group, an aryl group, a substituted aryl group or an aroyl group, and the other radicals chlorine, bromine or iodine, or where at least two of the radicals A, B, X and Y are an aromatic acyl group and the other radicals are chlorine, bromine or iodine are. 6. The method according to claim 5, characterized in that the UV sensitive compound is carbon tetrabromide or iodoform. 7 · Method according to claim 5? characterized in that a mixture of carbon tetrabromide in the recording material and iodoform is used. 8. The method according to any one of the preceding claims, characterized characterized in that the mixture is used together with at least one compound which is one of the following Belongs to classes: (A) organic compounds that contain two radicals of different electron affinity, where the expression Radical includes group and atom, and the radical by a conjugated. System are tied to each other, (B) organic compounds that have an aromatic nucleus ouor contain an aromatic ring system in which 7.WOi "adjacent carbon atoms to this nucleus or · Ring system and an adjacent ring are common, which has no conjugate character and which is on one End is bound to the aromatic nucleus or the ring system by a carbon-carbon bond and 'V.501 30 98 tO Λ _ 48 - is bound at the other end to this nucleus or this ring system through an electron donating group, wherein the core or the ring system of these organic compounds can be substituted, (C) polymeric compounds that contain recurring units of the following general formula: ι ι -C - CH- n-1 in which: Z " sulfur or a simple bond, A is a single bond or a divalent hydrocarbon group, R ^ and R2 each hydrogen or a lower alkyl group, Q _-1 and ζ> 2 on the one hand, and Q * and Q ^ on the other hand are each hydrogen or in pairs together the necessary atoms to close an adjacent carbocyclic ring or a substituted adjacent carbocyclic ring, 1 od ex 2, (D) organic nitrogen-containing compounds that have a thiol group or have a thione group in their tautomeric form, as shown in the following tautomeric structural parts is : HS - C = N C - NH (E) inorganic compounds that, under the influence of activating, electromagnetic radiation produce photoelectrons and have a basic or amphoteric character, 9 · Verfaliron gcm according to each of the preceding claims, characterized characterized in that in the recording material together with 309810/1000 _ 49 - the mixture is a triaryl compound of an element of the Group V and / or a sterically hindered phenol is used as an anti-fog agent, 10. The method according to any one of the preceding claims, characterized characterized in that the mixture is used in one or more polymers and copolymers as binders the styrene, vinyl acetate, acrylonitrile, acrylic acid ester, methacrylic acid ester, N-vinylcarbazole or butadiene units contained, or in a hydrophobic cellulose derivative, a phenoxy resin or a · polycondensate of Polyester type including a polycarbonate resin. 11. The method according to any of the preceding claims, characterized in that highly energy-absorbing in the recording material Substances are used by means of which so-called secondary photons and photoelectrons are generated if hit by X-rays * - fen, and that the information-wise irradiation by means of X-rays is effected. 12. The method according to any one of the preceding claims, characterized in that the exposure is a direct exposure is. 15 · The method according to any one of claims 1 to 10, characterized characterized in that the exposure is a reflex exposure is. 14. A process according to any of the preceding claims, characterized in that the recording material is heated during the exposure at 40-70 ⁰ C. 15 »Photosensitive recording material containing an intimate mixture of (1) at least one spiropyran compound, and (2) at least one UV-sensitive compound used in Exposure to UV light is able to form a colored salt with the spiropyran compound, ^{GVr / 1} 309810/1000 characterized in that, in addition to the mixture of (1) and (2), there is an organic compound with an amide or urea grouping that corresponds to the following general formula R ₁ -C-NH-R ₂ 0 in which: R _{1 is} an alkyl group, an aryl group or a heterocyclic group, including these groups in substituted form, an -NHR ₇ .- or N "3 group, in . χ which R, and R ^ represent an alkyl group or aryl group, including these groups in substituted form, and
Rp is hydrogen or an organic group. 15. Photosensitive recording material according to claim 15, characterized in that the organic compound is acetanilide or an acetanilide derivative. 17- photosensitive recording material according to claim 15, characterized in that the spiropyran compound is a spiropyran which is in the ortho- and meta-position of the Oxygen atom of at least one pyran ring, one condensed bensol ring or a polycyclic, aromatic, condensed ring system including this condensed Contains rings or ring systems in substituted form. 18. Photosensitive recording material according to claim 15, characterized in that the spiropyran compound is a Spirodibenzpyran, a Spirodinaphthopyran, a Spirobenznaphthopyran, a 1,3,3-trimethylindoline-benzspiropyran, a 1,5,3-trimethylindoline naphthospiropyran or a Spiropyran lot containing a condensed aromatic ring of the Anfchracen or phenanthrene type. 309810/1000 19- photosensitive recording material according to claim 15, characterized in that the mixture is a spiropyran compound according to one of the following general formulas: H_C CH, ³ V i GV.5G1 309810/1000 in which mean: E, R ₁ , E ¹ ^, R ₂ , R ' ₂ , R ₅ and R ¹ , each hydrogen, an aliphatic group, a substituted, aliphatic group, a halogenated, nitro, hydroxy, an alkoxy or aryloxy group, a phenyl group , a substituted phenyl group, piperidyl, an alkylene ester, alkylenecarboxyl, carbonamide or substituted carbonamide group, or R ^ and Ε ',, together form a - (CH ^^ - chain, where η is 2 or 3, to the carbon atoms in the Tie 3 and 5 'positions together. 20. Photosensitive recording material according to claim 15> characterized in that the UV-sensitive compound is an organic polyhalogen compound corresponding to is the following general formula: B 'Y in which: A, B, X and Y each represent a halogen atom or one of the radicals A, B, X and Y is an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aroyl group, and the other radicals are chlorine, bromine or iodine, or where at least two of the radicals A, B, X and Y an aromatic acyl group and the other radicals are chlorine, bromine or iodine. 21. Photosensitive recording material according to claim 15 characterized in that the UV sensitive compound is carbon tetrabromide or iodoform. 22. Photosensitive recording material according to claim 20, characterized in that the recording material nine mixture of carbon tetrabromide and iodoform. 25.] hotoompfindlichos recording material according to claim 15, characterized in that the recording material ; uKiätz] icli for the mixture contains at least one compound, ilie belongs to one of the following classes: ^Gv - ^ ¹ 309810/1000 (A) organic compounds that have two radicals different from each other Electron affinity included, the term radical Comprises group and atom and the radicals are bound to one another by a conjugated system, (B) organic compounds containing an aromatic ring or an aromatic ring system in which two adjacent carbon atoms to this ring or the Ring system and an adjacent ring are common, which has no conjugate character., And the at one end to the aromatic ring or to the ring system through a carbon-carbon bond and is bound at the other end to this ring or this ring system through an electron donating group, where the ring or the ring system of these organic compounds can be substituted, (C) polymeric compounds containing repeating units of the following general structure; in which: Z is sulfur or a single bond, A is a single bond or a divalent hydrocarbon group. IL · and R ₀ each hydrogen or a lower alkyl group, Q ^ l and Qp oinerseibs, and Qz and Q ^ on the other hand each Wufjr, nrr; Loff or in pairs together the necessary atoms for closing an adjacent carbocyclic nucleus or a substituted, adjacent carbocyclic nucleus Kerns,
η 1 odor 2,. GV.5G1 30981071000 _ 54 - (D) nitrogen-containing compounds that have a thiol group or have a thione group in their tautomeric form, as in the following tautomeric structural parts is shown: HS - C = NS = C - NH (E) inorganic compounds that, under the influence of activating, Electromagnetic radiation producing photoelectronon and a basic or amphoteric Have character. 24 ·. Photosensitive recording material according to claim 25, characterized in that the compound corresponds to one of the following general formulas: D-Z-G = X (I) ι
R. D-Z-Y-Z-D (II) Q ₁ C = X (III) Q ₅ C = L ₁ -L ₂ -L ₃ = C _n (V) R.
U μ \ ^N v IL ₁ C-GH GV.561 309810/1000 in which mean: D is an electron donating group, Z is a conjugated system, R is hydrogen, a hydrocarbon group or the to close a homocyclic or heterocyclic Ring with an atom of group Z necessary atoms, Q ,. the non-metallic atoms that are necessary to to complete a ring or a ring system in which the group C = X is connected by a conjugated system an electron donating substituent is bound, X is an electronegative atom or group, Qo the non-metallic atoms that are 'necessary to to complete a ring or ring system, wherein the group D-Z-C ^ by a conjugated system to a electron withdrawing group is bonded, or the atoms necessary to match with the carbon atom of the group B-Z-C ^ to form a heterocyclic ring, the has an electronegative character with regard to group D, Y is an electron-withdrawing group, Qx a heterocyclic nucleus that is an electron donating Contains group linked by a conjugate system to the group = cCq, wherein "P and Q each contain one represent electron-attracting substituents, or in which P and Q together represent those to close a heterocyclic Represent the necessary atoms in a ring with an electronegative character, L ^ and L, each a methine group or a substituted one Something group, a simple chemical bond, a '5, / S -äthylenisch unsaturated, divalent group, or Im, Lp and L, together form a double bond, the group Q' _x C to the group "= CQ binds; 309810/1060 GH. CH -C- 3 H. - η in the : R is hydrogen or an alkyl group including one substituted alkyl group; C-SH η C = S ι in which mean:, X oxygen, sulfur, selenium or the group -N-R, in which R is hydrogen or an organic group, and Z the atoms necessary for closing a five- or six-membered heterocyclic, nitrogen-containing ring or ring system which substitutes can be, or a polymer containing N-vinyl carbazole unit or copolymer, or is photoconductive zinc oxide or lead (II) monoxide. 25. Photosensitive recording material according to claim 23, characterized in that the material contains the aforementioned mixture and poly-N-vinylcarbazole in one layer or a copolymer with poly-N-vinylcarbazole units as the only binder content. 309810/1000 26. Photosensitive recording material according to each of claims 15 to 25, characterized in that the recording material highly energy-absorbing substances contains, by means of which so-called secondary photons and "photoelectrons are generated. -u can if they be hit by x-rays. 27- Photosensitive Axif drawing material, according to each of claims) 15 to 26, characterized in that it ■ a triarylvr-r bond as anti-fog agent Element of group V and / or a historically hindered Contains phenol. 28. Photosensitive recording material according to 'everyone of claims "15 to 27, characterized in that Recording material the spiropyran compound in a mixture with a 1 to 50-fold weight merige photosensitive, contains organic polyhalogen compound. 2 ⁽ j. Photosensitive recording material according to any one of claims 15 to 28, characterized in that the recording material contains the spiropyran compound C en) and poly-N-vinylcarbazole in a weight ratio within 80: 100 to 10: 100. · 50. Photosensitive recording material according to claim 2 ^c j, characterized in that the recording material photosensitive.es carbon tetrabromide or iodoform odf i? contains a mixture of both polyhalogen compounds in a weight ratio within 16:10 to 2:10 with respect to the poly-N-vinylcarbazole. JI. Photoenipfiri'll-j ches drawing material according to each dor Claims' 5 to 50 ,. marked by "that the Aiii'i'.elchnupgümabepiar Ti'iplienylstibin in one weight ratio: contains within 1: 100 to 2.5: 100 with regard to the phot; ci ('! ii [) sensitive polyhalogen compound (s). 309810/1000 BATH ORIGINAL 2. Iho t ο sensitive s A11 ί " ζ e ic hnunß π mat ο ria 1 {■; em ä ssjcd ο m der Aru'.pL'üchc 15 to 31» thereby i "; ok ';nm',<- Lean, dao. ^r j -.Ia :; Aui'zeii'.hnnnGi;ni;ü; (jri.aL the organic; compound dor a'll- ^ ci ^ ioi new Formol, \ iou_ An.siJi-uch I ^ in einci · Ηοη ^ ο within the Gfn. Light ratio from 1: 1 to 0.1: 1 h: in particular the. ^c '[) i. popyranvorbindun ^ Cori) cnLhä.l t. 30 9 8 10 /! Π 0 O ^