DE2126187A1 - Anti-fading agent for color photographs - Google Patents

Description

Applicant: Konishiroku Photo Industry Co. ,, Ltd., 1-1o, 3 ~ Chome, Nihonbashi-Muro-machi, Chuo-ku, Tokyo (Japan)

Sankyo Company Limited, 1-6, 3-Chome, Kihonbashi-Hon-cho, Chuo-ku, Tokyo (Japan)

Anti-fading agent for color photographs

The present invention relates to an anti-fading agent of color photographs. In such color photographs, the colors are produced by azomethine, indoaniline, and indophenol paraffin educated. The means according to the invention largely prevents these colors from fading.

It is known that color photographs can be obtained in light-sensitive silver halide-containing color photographic recording materials that are formed from azoniethin-y indoanilin-y indophenol and similar dyes by color development by oxidative condensation of aromatic primary amino groups with color couplers. In this sense, subtractive color photography leads to good color reproduction, and the color development usually produces cyan, magenta and yellow dyes. The purple color ~ materials are usually with a coupler of the phenol or naphthol type cyan dyes having a coupler of the pyrazolone type, and the yellow Ftirbetoffe formed with a coupler of the acylacetamide type. These couplers are added to the developer solution or previously incorporated into a photographic silver halide emulsion. However, a color image obtained according to this color development process is not satisfactory.

109850/1674

lend with regard to the fastness to ultraviolet or visible light (hereinafter referred to as "light fastness ¹¹ ), and it fades relatively quickly when it is irradiated with ultraviolet or visible light. As a measure to eliminate this disadvantage, a method is known, according to which an ultraviolet absorber is incorporated into the light-sensitive color photographic silver halide-type recording material in order to reduce the amount of light which radiates on the color image obtained. However, in order to impart sufficient lightfastness to the color image, the ultraviolet absorber should be used in a relatively large amount. However, when the ultraviolet absorber is used in a large amount, the thickness of the photosensitive layer must necessarily be increased, which leads to undesirable deterioration in photographic properties such as developability and resolution in the so-called method with protected dispersion, in which an oil-soluble ultraviolet absorber is used in the form of a solution in an organic solvent, the additional disadvantage that the solution of the ultraviolet absorber is poorly compatible with the gelatin solution. In order to make the thickness of the emulsion layer smaller, the amount of the so-called high-boiling solvent used should be extremely small so that the ultraviolet absorber often crystallizes out. Based on these facts, an upper limit was set on the amount of the ultraviolet absorber used. In addition, the use of an ultraviolet absorber is not effective in preventing the color images from being faded by visible light. In this sense, too, the use of an ultraviolet absorber set a limit with regard to the improvement in light fastness. In addition, color images formed using pyrasolone or phenol type couplers tend to be streaked during storage and thereby deteriorate in quality. "

109850/1674

In view of this prior art, extensive Research carried out over several years with the aim of to further improve the lightfastness of color images. It has now been surprisingly found in the wake of such research found that the light fastness and the prevention of fogging in color images are significantly improved can without resorting to only the ultraviolet absorbing effect of ultraviolet absorbers when in the developed disgusting color images together with the dyes InuG & zojidin or oxazolidine derivative of the following general Formula is available.

The present invention accordingly relates to a gown against the fading of color photographs, which is characterized in that it contains at least one compound of the formula

O / η

where X is an oxygen atom or an imino group (-NH-

means; Y for a carbonyl group (-C-), an imino

methylene group (-C-) or an aminomethylene group

(-CH-) stands; R ₁ and R ₂ , which may be the same or different, each represent an alkyl group, a phenyl group or an aralkyl group, or R ₁ and R ₂ together with the carbon atom on which these symbols are attached represent a 5- to 7-membered saturated alicyclic Ring or a group of the formula

109850/1674

where Z represents an hydrogen atom, a hydroxyl group or an oxygen radical (-0), and E. and Rp. each represent a lower alkyl group, or one of these symbols represents a hydrogen atom and the other represents a lower alkyl group, or R and R ₁ - together with the carbon atom on which these symbols are located, a 5- to 7-membered saturated alicyclic group or a group of the formula

form, 'η stands for the number 1 or 2 and R ^ then, when η denotes the number 1, a hydrogen atom, a Alkyl group ,, a cycl oalkyl group, 'an aryl group, an aralkyl group or a group of the formula

CH,

represents, and when η is the number 2, an alkylene group, an arylene group or a group of formula

109850/1674

Rrj Rrj

represents -wherein Eg represents an oxygen atom, a methylene group or a group of the formula

0 0

"I!

-NH-C-NH-CH ₂ -CH ₂ -Mi-C-NH-

stands; and Er _{7 represents} a hydrogen atom or an alkyl group,
contains.

Alkyl groups represented by the symbols R ₁ and R ₂ are, for example, a methyl, ethyl, isobutyl, dodecyl or stearyl group. The benzyl group is mentioned as an aralkyl group, for example. If the symbol E stands for an alkyl group, it stands, for example, for a methyl, ethyl, dodecyl or octadecyl group, if it stands for a cycloalkyl group, it stands, for example, for a cyclopentyl or cyclohexyl group, when it is an aryl group it is, for example, a phenyl, naphthyl, tolyl or chlorophenyl group, and when it is an aralkyl group it is, for example, a benzyl group. The alkylene group is, for example, the ethylene or hexamethylene group and the arylene group, for example, the phenylene or tolylene group.

The term "lower" denotes in the sense of the present Invention in particular groups having 1 to 6, preferably 1 to 4 carbon atoms.

The means ge;: cn the fading of color photographs according to the hrfindum .; is am.erordentj I effective in £ ei or light üchthe.it of cyan, magenta and GeIb-

109850/1674 bad original

Color images obtained by color development of indoaniline, indophenol and azomethine dyes. It can exhibit an effect equivalent to that of an ultraviolet absorber even if it is used in a smaller amount. The effect providing the light fastness is further increased by using eS in combination with an ultraviolet absorber. The cyan, magenta and yellow couplers used to form the aforesaid color images are not limited in kind. It can be any of the types that are alkali soluble and that are incorporated into a silver halide photographic enzyme after being dissolved in alkali. They can also be of the type dissolved in a high-boiling organic solvent, dispersed in an aqueous gelatin solution and then incorporated into a photographic silver halide emulsion

The anti-fading agent according to the invention may be previously incorporated into any of the elements constituting the silver halide photographic light-sensitive material, e.g. In a photographic emulsion layer in which the cyan, magenta and gel "b dyes are formed by color development, or in an interlayer or protective layer color development are carried out, and it can be a stabilizer may be added preferably, is used in the final treatment. If the diffusion transfer method is used, the agent may be incorporated to the bleaching not only in such a photographic emulsion layer, but also in a receiving layer. course said it is sufficient that the anti-fading agent according to the invention is present together with the dyes which form one or more of the color images of the color photograph finally obtained.

.109850 / 1674

The compounds of formula I are hardly soluble in water, and they are in a low-boiling solvent such as methyl acetate, Ethyl acetate, carbon tetrachloride, chloroform, methanol, ethanol, n-butanol, dioxane, acetone, benzene, dimethylformamide or dimethyl sulfoxide, a high-boiling organic Solvents such as tricresyl phosphate, di-n-butyl phthalate or Ethyl-ii-diphenylcarbamate, or a mixture of solvents the low-boiling and high-boiling organic ones mentioned Dissolved solvents, and the resulting solution becomes a protective colloid solution such as an aqueous gelatin solution given, dispersed by means of a colloid mill or a homogenizer and then in, for example, a photographic Incorporated silver halide emulsion containing couplers. Depending on the kind of couplers used, the anti-fading agent of the invention and the couplers may be used together dissolved in an organic solvent or alkali and then added to an aqueous gelatin solution, etc. If the anti-fading agent is soluble in a lower alcohol, alkali or water, it can / the finishing bath are given.

Typical examples of compounds of the above general formula I are the following compounds:

109850/1674

(1) 5> 5-dimethylhydantoin O

Η, 0 ^Λ

F. 176 ⁰ C

(2) 4-Imino-5-ethyl-S-methyl - ^ - phenyl ^ -imidazolidinone NH

H ₃ C

P. 124-126 ° 0

Λ ο

(3) 5-ethyl-5-methyl-3-phenylhydantoin

H ₃ C

H _C O ' ^Χ ΙΙ— ^{b 2} H

■ "Ο

109850 / 167Α

NH

^H 5 ° 2!

N-CH

· ^H

(5) 2-Benzyl-5-ethyl ~ 5 ~ methylhydantoln O

_Η0 Λ _Ν

-O

.F. 88-89 σ

(6) 5-isobutyl-5-methyl-3-phenylhydantoin

H ₃ C ^ JH

³ *> CH - CH / ^ N

P. 98-99 ⁰ C

(7) 5-18obutyl-4 ~ iraino-5-methyl-3-c <-naphthyl-2-imidazolldinone

NH

p. 206.5-208 ⁰ C.

(8) 4-A ^ alno-5-isotfutyl-5-methylthyl -3-dt-naphthyl ~ 2-imidazolidine «!

HC ¹ ^ TO

⁵ > CH - CH ^ Nl 1 ( \ F. 1OS-IlO ⁰ C

HC ^{X 2} H ^ ₀ V /

- 10 -

H, C

109850/1874 ORIGINAL INSPECTED

(9) 5-Isobutyl-5-methyl-3-J.-naphthylhydantoin

H, C

195-196 ° C

(10) 4-Imino-5-methyl-3,5-diphenyl-2-iraidazolidinor

F. 176-177 ⁰ G

Λ O

(11) 5-methyl-3,5-diphenylhydairtoin . O

. 146-147 ° C

(12) 3-Gycloliexyl-4-imino-5-methyl-5-phenyl-2-imidazolidinone

N-H

(13) 3-Cyclohexyl-5-methyl-5-phenylhydantoin O

OsJ- _τ -

H 0

.F. 173-174 ° C - 11 -

1098B0 / 167A

(14) 5,5-dibenzyl-4-imino-3 "phenyl-2-imidazolidinor

NH

ο-

-N

. F. 246.5-247.5 G

(15) 5,5-dibenzyl-3-phenylhydantoin

—Ν

N-H

Λ.

184-185 ° C

(16) 5,5-Dibenzyl-4-imino-3-stearyl-2-imidazolidinori

NH CH .. ^ N - (CH ₀ ),

92-93 ° C

(17) 5, 5-dibenzyl-3-stearylHydantoin

Y-N

. 119-12CTC

(IS) 1,3-Diaza-3-cyclohexyl-4-imino-2-oxo ~ spi.ro [4.4] nonane

NH

F. 147-148 ° C - 12 -

109850/1674

-Ht- (19) 1,3-Diaza -3-cyclohexyl-2,4-dioxo-spiro [4,4jnonane

N-H

-N - (H

187-188 ⁰ C

(20) 1,3-Diaza-'4-imino-2-oxo-3-p-chloro * phenyl-spiro [A. 4 y nonane

N-H

Eq

: * F, 214-215 ° C

(21) 1,3-Diaza-2,4-dioxo-3-p-chloro-phenyl-spiro [4 »4] nonane O

Cl

F. 212-213 C

H \,

(22) 1,3-diaza-2,4-dioxo-spiro [4, O

--NH

. Mp 217-218 ° C

(23) 1,3-Diaza-4-imino-2-oxo-3-stearyl-spiroj / 1,5] decane NH

-Ν - (CH) CH m.p. 93-5 ° C

(24) 1,3-Diaza-2,4-dioxo-3-stearyl-spiro [4,5] decane O

-N - (CH ")," CH- τ? 90-91 ⁰ C

109850/1674

(25) 1> 3-Diaza-3-cyclohexyl-4-iraino-2-oxo-spiro [4 x 5 decane

NH

M.p. 247-248 ° C

(26) 1,3-Diaza-r3-cyclohexyl-2,4-dioxo-spiro [4,5J decane

OC

-N

M.p. 243-244 ° C

"ό

(27) 1,3-Diaza-4-imino-2-oxo-3-p-tolyl-spiro [4 _r 5] decane

NH

F, 232-233 ° C

N-H

(28) 1,3-Diaza-2,4-dioxo-3-p-tolyl-spiro [4 # 5] decane O

OC

• IT

CH,

247-248 "C

(29) α, 3-Diaza-4-imino-2-oxo-3-o-chlorophenyl-spiro [4.5I-decane

NH

N-H

F. 218-219 C

Cl

(30) 1,3-Diaza-2,4-dioxo-3-o-chloi-phenyl-spiro [4. ^] Decane

^{/ = r} "p. 242-243 ⁰ C

-—I

Cl

II

109850/1674

•! Τ

- 14 -

(31) 1,3-Diaza-4-inirio-2-oxo-3 "- ^ - napiithyl-spiro [4,5 j decane

NH

F. 234-235.5 ⁰ C

(32) 4-Benzoyl ~ 5-h: hydroxyphenyl-4-methyl-3- (1,3-diaza-4-imino-2-oxo-spiro [4x5J-3-decyl) phonyl carbamate

NH

N-

N-H

^m -

HO

P. 217-219 ⁰ G

(33) 1,6-bis (1,3-diaza-2,4-dioxo-spiro

o ■■ o

-N - (CH ₂ ) ₆ _

Cr H

t 240 ~ 241 ° C

(34) 4,4 ^f -Bis (1,3-diaza-4-imino-2-oxo-spiro [4.5-j-3-decyl) · diphenylmethane

NH

-N- <

• N-H

-N
H

F. 249-25CTC

(35) 1,3-Biaza-4-imino-2-oxo-3-stearyl-spiro [4. 6] undecane HH

-N - (0H ₂ ) ₁₇ 0H _v J m.p. 74-75 ° C

109850/1674

(36) 1,3 ~ Diaza-2,4-dioxo-3-stearyl-spiro [4 * 6] undecar
O

N-H

- (CH ₂ ) ₁₇ CH,

.F. 69-7O ⁰ C

(37) 1, ^ -Diaza ^ -cyclohexyl ^ -imino ^ -pxo-spiro [4,6] \ mdecane NH

-N / ΐΓ \, F.- 180 ⁰ C

(38) 1,3,8-Triaza-7,7,9,9-tetramethyl-2,4-dioxo-spiro [4.5] -decane

. 360-365 ⁰ C {(dec.)

(39) 1,3,8-Triaza-8-hydroxy-7,7,9,9-tetramethyl-2,4-dioxospiro [4. 5y decan

CH,

OH,

NH

CH

F .. over 36 ° C

(40) 1,3,8-Triaza-7,7,9,9-tetramethyl-2 _f 4-dioxo-spiro f4.51 decane-8-oxyl

CH

-NH

0 - IJ CH

• H— H

F.

«Dec. )

3 ^N CH

109850/1674

- 16 (41) Cyclohexane- ¹ -spiro-2 1 - (6 ', 6'-dimethylpiperidine) -4 ^! -

spiro-5 "hydantoin
GH,

CH

HU λ

O ^H

-NH

J * 280.5-

(Decomposition.)

(42) Cyclohexane -l-spiro-2 '- (6'-6'-dimethylpiperidine) -4 ^! - spiro-5 "-hydantoin-l'-oxyl

CH ₃
0 - N

- ITH

-F. 282-283.5 ⁰ C

"X

(43) 2,2,6,6-tetramethylpiperidine -4-spiro-2 ^! - (6'-6'-dimethylpiperadir.) -4 ^r - * spiro ~ 5 "-hydantoin

-NH

F. 243 C

(44) 2,2,6,6-tetramethylpiperidine -4-spiro-2 ^! - (6 «-6 '-

dimethylpiperidine) -4'-spiro-5 "-hydantoin-1,1 ^! -dioxyl

-KH

^F x 212-213 ° C

- 17 -

109850/1674

(45) 1,3, S-trifa-jS-eth, yl-4-imino-7,7,9,9, 9-tetramethyl-2-oxo-8piro [4,5jdecane

■ Ν -

F.

(46) 1,3,8-Triaza-3-ethyl-7,7,9,9, 9-tetramethyl-2,4-dioxospiro [4. 5_ | decan

CH,

N - C ₂ H ₅

.P. 165-166 ⁰ C.

(47) 1,3,8-Triaza-3-afchyl-4-imino-7 »7,9,9-tetramethyl-2-oxo-spiro [4» 5-decane -8-oxyl

CIL

OH,
O - N

NH

Ij

¹¹ - N - C ₂ H ₅

CH

-N-H

_{F #}

(48) 1,3, S-Triaza-4-imino-7,7,9,9-tetraraethyl-2-oxo-3-stearyl-spiro14 * 5 jdecan

CH,

3 NH m_ \

CII

Ν - II

-N -

CH ,,
'j

F.

109850/1674

(49) 1,3,8-Triaza-7,7, 9,9-tetramethyl-2,4-dioxo-3-stear? Lspiro (4,5 jdecan

CH

(50) 1,3,8-triaza-3-cyclohexyl-4-imino-7,7,9,9-tetranethyl-

2-oxo-spiro [4 ^ 5] decane

M.p. 2U-212 ° C

CH-CH 3

(51) 1,3,8-Triaza-3-cyclohexyl-7,7> 9,9-tetramethyl-2,4-dioxo-spiro [4 »5jdecane

CH ₃ CH ₃ O CH ₃ CH ₃

186-187 ° C

(52) 1,3,8-Triaza-3-cyclohexyl-4-imino-7,7,9,9,9-tetramethyl-2-oxo-spiro [4 # 5J decane-8-oxyl

. M.p. 242-243 ° C

CH ₃ CH ₃ NH

• 0-N

CH ₃ CH ₃

(53) 1,3,8-Triaza-3-cyclohexyl-7,7,9,9-tetramethyl-2,4-dioxo-spiro [4.5] deeari -8-oxyl

CH "CH,

184-185 ° C - 19 -

109850/1674

(54) I, 3,8-Triaza-4-imino-7,7,9,9-tetramethyl-2-oxo-3-phenyl-spiro [4.5 j decan

CH, CH _x NH

^ / ³ Γ

176-177 ° C

(55) 1,3,8-Triaza. ~ 4-imino-7,9,9-trimethyl-2-oxo-3-phenyl spiro [4.5j decan

CH, NH

P. 201-202 ^ C

(56) 1,3,8-triaza · ^,?, 9,9-tetramethyl-2, 4-dioxo-3-phenyl spiro [4 '5y decan

CH, O

F. 148-149 ⁰ C.

(57) 1,3,8-Triaza-4-imino-7,7,9,9-tetramethyl-2-oxo-3-phenyl-spiro [4 * 5] decar -8-oxyl

.CH, CH, NH .3 / 3

• 0-N

189-19O ⁰ C

CH ₅ CH ₅

(58) 1,3, e-Triaza-e-hydroxy-A-imino - ?, 7,9,9-tetramethyl-2 oxo-3-ph.enyl-spiro [4.5 J decane

CH, CH, HH

_# 184-186 ° C - 20 -

109850/1674

! 126187

-3-phe

y 12fi187

(59) 1 , 3, 8-Τγ1 & 2ε-7, 7,9,9-te traraeth.yl. ~ 2,4-dioxo-3-pnenyl-Bpiro [4,5-decane-8-oxyl

CH

. F,. 181-182 ° C

(60)! ^, E-Trlaza- ^ imlno-TiT ^ f
tolyl-spiro [4, 5} decan

NH

: Ό

M.p. 182 ~ 183 ° C

(61) 1,3,8-Triaza-7,7,9,9-tetramethyl-2,4-dioxo-3-p-tolyl-Bpiro [4 * 5jdecane

CH, CH, 0 .5, 3,

. F »202-203 C

(62) 1,3 »8-Triaaa-3 ~ o-chloro-phenyl-4 ~ iraino-7,7,9,9-tetramethyl-2-oxo-epiro {4 # 5jdecane

• F. 209.5-210.5 ⁰ C

CH ₃ CH ₃

(63) 1,3,8-Triasa-3-m-ehlor ~ phenyl-4 ~ iraino-7,7,9,9-

XT 'Γ

tetyaoethyl-2-oxo-spirq | 4.51decane . CH, CH, NH

V- / F .. 156.5-157.5 ° C

0 '- 21 -

109850/1674

· - 21 '■

(64) 1,3,8-Triaza-'j5-n-cih: lor-phenyl ~ 7,7,9,9-tetramethyl-2,4-dioxo-opiro [4.5 j decan

p. 162-165

CH _x CH,
3 3

(65) 1,3,8-Triaza-3-m-chloro «« pheiiYl-4-imlno ~ 7.7 _r 9,9-tetramethyl-2-oxo-spiro [4 <5J decane-8-oxyl

EH

Ό-ΪΙ

N-H

F. 195.5-196.5

"Ό

CH ₃ CH

(66) 1,3,8 ~ Triasa ~ 3-m-chloro-phenyl-7,7,9,9-tetramethyl-2,4-dioxo-spiro [4.5] decane -8-oxyl

, F. 197-198 ⁰ C.

(67) 1,3,8-Triaza-3-p-chloro-1-phenyl-4-iraino-7,7, 9,9-. tetramethyl-2-oxo-spiro [4,5jdecane

225-226 ⁰ C.

CH “CH ^ NH _{χ 3/3}

(68) 1,3,8-Triaza-3-p -chlorophenyl-7,7,9,9-tetramethyl-2,4-dioxo-opiro [4/3 jdecan

CH, CH, O

HN

JL · - η.-.

Λ H- -O

^CIT 3 ^οπ -; I 0 9 8 E 0/1 6

p. 200-201 ° C - 22 -

(69) 1 »3, 8 ~ Triaza-3 ~ p-chloro-plaenyl-4 ~ imino-7, 7,9,9 tetramethyl-2-oxo-spiro [4 »5j decai-8-oxyl

2 125 1ST

CH ₃ CH, ¹ ON

NH

-N

f. 213-214 σ

(70) 1,3,8-Triaza-4-imino-7,7,9,9-tetramethyl ~ 5-ohnaphthyl ~ 2-oxo-spiro [4 * 5] decane

F, 251 ~ 252 ° C

(71) 1,3,8-Triaza-7,7,9,9, 9-tetramethyl-3-c \ -napht- ¹ nyl-2,4-dioxo-spiro [4 »5j decane

CH ₃ 0 Λ
K F. 237-238 ° 0 HN
v_ ^ - I
^ N J Λ
CH / 3 T- W. V
0

(72) 1,3,8-Triaza-4-imino-7,7,9,9-tetramethyl-3-oinaphthyl-2-oxo-spiro [4.5-decane-8-oxyl

F .. 203-204

CH, CH-3 3

(73) 1,3,8-Triaza-7,7,9,9-1 etramethyl-3-4-naplithyl-2,4-dioxo-spiro [4.5] decane -8-oxyl

GH, 0 i

0/1674

F. 213-214 C - 23 -

INSFECTSD

(74) 1,3 »3-Triaza-4-imino-7,7,9,9-tetramethyl-3-onitrophenyl-2-oxo-spiro [4 * 5jdecane

CH,

HH

HN) <f ca, CH,

F. 189-190 ⁰ C.

NO,

(75) 1,3,8-Triaza-7,7,9,9-tetramethyl-3 ~ o-nitroph.enyl-2,4-dioxo-spiro [4,5 Jdecan

CH, CH,

230-232 ⁰ C.

0 ^N0 2

(76) 1,3,8-Triaza-4-imino-7,7,9,9-tetramethyl-3-onitrophenyl-2-oxo-spiro [4 * 5] decane -8-oxyl

CH "CH_ NH

^ ³

. 214-215 ° C

CH, CH,

(77) 1,3,8-Triaza-7,7,9,9-tetrameth.yl-3-o-nitroph.enyl-2,4-dioxo-spiro J4 «5] decane-8-oxyl

CH, CH, \ 3/3

yx j!

• 0-N) <

F. 229-230 "C

CH, CH,

(78) 3,8-Diaza-3-ethyl-4-imino-7,7,9,9-tetramethyl-1-oxa-2-oxo-spiro [4 » 5 jdecan

CH, ^ CH, NH HN

C :: _v CIL,

0 k

109850/1674

66-67 ° C
- 24 -

(79) 3,8 ~ Diaza-3-cyclohexyl ~ 4-imino-7,7,9,9-tetraiaethyl-loxa-2-oxo-spiro [4 «5 years decan

NH

CH-? , "H-Z

F. 181-182 ^OC

CH ₃ CH ₃

(80) 3,8-Diaza-3-cyclohexyl-7,7,9,9-tetrameth.yl-1-oxa-2,4-dioxo-spiro [4 * 5] decane

CH »OH- 0

^ ⁵

F. 173-174 ⁹ O

GH CH ₃

(81) 3,8-diaza-4-imino-7,7,9,9-tetramethyl-1-oxa-2-oxo-3-plienyl-spiro [4.5] decane

_F. 135-136 ° C

CH ₃ CH ₃

(82) 3,8-Diaza-4-imino-7,7,9,9-tetramethyl-l ~ oxa-2-oxo ~ 3-phenyl-spiro [4 * 5] decane -8-oxyl

F. 226-227 C.

CH-CH, NH -txrt

CH ₃ CH ₃

(83) 3,8-Diaza-3-p -chlorophenyl-4-imino-7,7,9,9-tetramethyll-oxa-2-oxo-spiro [4.5] decane

CH-CH-NH 3/3 π

HN

\ J "

-N-

- Cl

^CII 3 ^C1I 3 10

0/1674

F. 161-162 ⁰ C - 23 -

(84) 3,8-diaza ..- 3-p ~ chloro "phenyl-7,7, 9, 9-tetramethyl-l-oxa-2,4-dioxo-SPII ⁱ o [4. 5 decan j

CH, CH, O 3/3

-N-

ο
.F. 182-183 ° 0

(85) 3,8-Diaza-4-imino-7,7,9,9, 9-tetramethyl-3-o-naphthyl-loxa-2-oxo-spiro [4,5jdecar.

ClU CH "NH

(86) 3,8-Diaza-7,7,9,9, 9-tetramethyl-3-o (-naphthyl-1-oxa-2,4-dioxo-spiro [4.5] decane

CH, CH, 0 \ 3/3 ii

Mp 237-238 ° C

"0

(87) 1, 6-Bis (1,3,8-triaza-4-imino-7,7,9,9-tetramethyl-2-oxo-spiro [4.5] -3-decyl) -n-hexane

JH N- (GH ₂ ) NH CH GH
/ HN
\ Λ
0 /
\ NH
/ Λ
CH "
3 /H CH ₃ f
\ -ν / ι
" ¹ GH

M.p. 259-260 ° C - 26 -

109850/1674

(88) 1,6-bis (1.3, S-triaza-7,7,9,9-tetramethyl-2,4-dioxospiro [4,5I-3-decyl) -n-hexane

_, CH, O

mi χ

'VT

T- (CH

O CH, CH,

NH

O O

CH ₃

M.p. 254-255 ° C

(89) 2,4-Bis (1,3,8-triaza-4-iniino-7,7,9,9-tetramethyl-2-oxo-spiro [4 »5I-3-decyl) tol" U ol

CEL CH "TiH

- P.

(90) 2,4-bis (1,3,8-triaza-7,7,9,9-tetramethyl-2,4-dioxo spiro [4,5J-3-decyl] tolTLiol

^ 0 CH, CH-,

CH CH

F. over 250 ° C - 27 -

109850/1674

(91) 4,4'-Bis (1,3,8-triaza-4-imino-7,7,9,9-tetramethyl-2-oxo-spiro [4 # 5] -3-decyl) diphenylmethane

CH ₃ CH ₃

CH 'CH

.F. 218-219 ° G

(92) 4,4'-bis (1,3,8-triaza-7,7,9,9-tetramethyl-2,4-dioxospiro [4c5J-3-decyl] diphenylmethane

CH, O

J — iM

0 CH-CH, "3/3

CH ₃ CH ₃

CH ₃ CH ₃

.F. 232-234 ^u C

(93) 4,4'-Bis (1, ^, 8-triaza-4-imino-7,7,9,9-tetramethyl-2-oxo-spiro [4,5] -3-decyl) diphenyl ether

CH, CH, NH

NH CH, CH,

CH CH

CH ₃ CH ₃

Mp 224-226 ° C

- 28 -

109850/1674

(94) 4,4'-BiS (1,3,8-triaza-7,7,9,9, 9-tetramethyl-2,4-dioxospiro [4.5 J -3-decyl) dipheny] ^ ether

CH, CH O

CH ₅ CH ₅

CH

F. about

(95) Ιί, ΕΓ «-Bis [2-methyl-4- (1,3,8-triaza-4-imino-7,7,9,9-tetramethyl-2-oxo-8-oxyl-spiro [4.5] -3-decyl) phenylcarfeamoyl] ethylene ^ dianiin

NH CH, CH,

H ^ CH_

228-229 C

(96) 1,6-Bis (3,8-diaza-4-imino-7,7,9,9-tetramethyl-1-oxa-2-oxo-spiro [4-5 J -3-decyl] -n-hexane

CH, CH, HH NH CH "CH.,

T- (CH ₀ ), -N-

O O

NH

CH ₅ CH ₅

'. 102-104 C
- 29 -

109850/1674

(97) 1,6-Bis (3,8-diaza-7,7,9 _f 9-tetramethyl-1-oxa-2,4-dioxo-spiro [4,5j-3-decyl) -n -hexane

CH., CH, 0

CH

_{p #} 116-118 ⁰ C

(98) 4,4'-Bis (3,8-diaza-4-iraino-7,7,9,9-tetramethyl-loxa-2-oxo-spiro [4,5] -3-decyl) diphenyl. _w £ ther

OH, CH, NH 3/3 H.

NH CH, CH

-N

N-

CH ₃ CH ₃

CH ₃ CH ₃

(99) 4,4'-bis (3,8-diaza-7,7,9.9-tetramethyl-1-oxa-2,4 dioxo-spiro [4,5] -3-decyl) diphenyl ether

0 OH, CH,

CH, OH 3

CH ₃ CH ₃

. F; Above 26O ° C - 30 -

109850/1674

Processes for the preparation of compounds of the formula I are mentioned below by way of example.

Manufacturing example 1

- 'NH

Warming * S ^ \ S ι>

■ ν XT U-

A solution of 7 g of 1-cyclohexyl-3- (i-cyano-1-phei2ylethyl) urine in 100 ml of 50% ethanol was refluxed for 8 hours. The reaction liquid was then concentrated and the residue was treated with petrol, which caused crystals to separate out. The crystals were collected by filtration and then recrystallized from 50% ethanol, whereby 3.8 g of 3-cyclohexyl-4-imino-5-methyl-5-phenyl-2-imidazolidine were obtained in the form of white crystals. P. 142-144 ° C.

Elemental analysis for C _{1 /:} H ₀₁ N, 0:

Calculated (#) C 7o.82 _t H 7.8ο, Η 15.49 Found (£) C 71.1o, H 7.62, N 15.77

Production example 2 CN

Heat

A solution of 6 g of 1- (p ~ chlorophenyl) -3- (1-cyanocyclopentyl) urea in a LÖ8Un (* sraittelgemiBch from 50 ml hydrochloric acid and 50 ml of 50% ethanol was refluxed for 0 hours. Then the reaction liquid was concentrated, and the residue was washed with a 7 '.-' aqueous

o98B0 / -? 7i

ORIGiMAL INSPECTED

Sodium carbonate solution is added, with crystals separating out. The crystals were collected by filtration, washed with water and then recrystallized from ethanol, whereby 3.3 g 1,3-diaz: a-3- (p-chlorophenyl) -2,4-dioxo-spirdr4,4] nonane in the form of white crystals. F. 21 2 - 213 ° C.

Elemental analysis for C ₁ JH ₁₄ N-OCl:

Calculated CfS) C 58.98, _t H 4.96, N 10.58, Cl 13.39 Found ($) C 58.79, H 4.9o, N I0.86, Cl 13.21

Preparation Example 3 O

+ HaCM + (NH,

A solution of a mixture of 33.ο g cyclohexanone, 16.5 g urodium cyanide and 99.ο g ammonium carbonate in 78o ml 50 ^ strength ethanol was? Left to react for 8 hours at 50 to 55 ° C with stirring. Thereafter, the reaction liquid was concentrated, whereby crystals separated out. The crystals were collected by filtration and then recrystallized from dilute ethanol, 46.0 g of 1,3-diaza-2,4-dioxo-spiro | 4.5jdecane being obtained as white crystals. M.p. 217-218 ° C, yield M, 0 ^c />.

Elemental analysis for CgH ₁₂ ^N 2 ° 2 ^:

Calculated ($) C 57.13, H 7.19, N 16.66 Found (^) C 57.21, H 7.22, N 16.54

109850/1674

Production example 4

H ₂ O ₂ .

To a solution of 2o g of 1,3,8-Triaza-7,7,9,9-tetramethyl-2,4-dioxo-spiroJ4.5jdecane in 8o ml of acetic acid were ο.5 g of ethylenediarainetraacetate, ο.4 g of sodium tungstate and 40 ml of a 3o dilute aqueous hydrogen peroxide solution are given and the result The mixture was allowed to react for 7 days at room temperature with stirring. Subsequently, the reaction liquid became concentrated under reduced pressure and the residue was saturated with potassium carbonate and then at room temperature for 1 hour stirred, crystals separating out. The crystals were collected by filtration and then from dilute Recrystallized ethanol, 1,3 »8-triaza-7,7,9i9-tetramethyl-2,4-dioxo-spiro [4.5I-decane-8-oxyl with a decomposition point of 331 ° C.

Elemental analysis for

IL

Calculated (#) C. 54. 98 H 7th 55, H 1 7th 49 Found ( C. 55. 19 H 7th 67, 1 7th 45

Production Example 5 NC

Heat

IBT

109850/1674

A solution of 5 g of 4-cyano-4- (3-phenylureid) -2,2,6,6-tefcramethylpiperidine in 1oo ml of 50 tiger. Jithanol was refluxed for 5 hours and then concentrated and crystals separated out. The crystals were collected by filtration
and then recrystallized from benzene, 1,4-iinino-7,7,9,9-tetramethyl-2-oxo-3-phenyl-spiro ^r A.5J eecane being obtained as white crystals. P. 176 - 177 ° C.

Elemental analysis for C ₁₇ Hp ₄ O: calculated ($) C 67.97, found (^) C 68.12,

Production example 6

NC

H 8.o5,
H 8.08,

N 18.65 N 18.48

CII

Säiire

Heat

CH,

A solution of 4,4'-bio (4-cyano-2,2,6,6-tetramethyl-4-piperidylureylen) diphenylether in 15 ml of 95 inferred ethanol was gradually added at room temperature with stirring to 15 ml of 35% Ea] Acid was added, and the mixture obtained was then refluxed for 6 hours. The heating liquid was then

- 34 -

109850/1 67

It was then cooled down, crystals separating out, which were collected by filtration and dissolved in 30 ml v / water. the Solution was obtained by adding a 5% aqueous sodium carbonate solution neutralized, whereby crystals separate out. These crystals would be collected by filtration, with water / water washed, dried and then recrystallized from benzene to give 4,4'-bis (1,3,8-triaza-2,4-dioxo-7,7,9,9-tetramethyl-'J-.5J -3-decyl) -diphenylether obtained as white crystals

became. P. over 26o ° C.

Elemental analysis for C,, H. , Or-N, -:

^v 34 44 ο ο

Calculated (#) C 66.21, H 7.19, N 15.63

Found (#) C 66.11, H7.o5, N 15.69

Production example 7

NQ OH

H ₁ -C ₀ NCO

Heat

To a solution of 3.5 g of 4-cyano-4-hydroxy-2,2,6,6-tetramethylpiperidine in a solvent mixture axis 80 ml Benaol and 1 ο ml dimethylformamide was added at room temperature with stirring 1.5 g of ethyl isocyanate, and the resulting (Jemisch was allowed to react with stirring for 2 days at 30 to 40 ° C. The reaction liquid was then purified by distillation

Γ / 1 ß "

freed from solvent ", and the residue was diluted with Methanol is added, with crystals separating out. These were then collected by filtration, whereby 1-oxa-3,8-diaza-3-ethyl-4-imino-7,7,9,9-tetramethyl-spiro | 4 ·. 5jdecan-2-one was obtained in the form of colorless column-like crystals M.p. 66-67 ° C

Elemental analysis for C. ^, Hp, IT., Op J

Calculated (£) C 61.63, 'H 9.15, N 16.59 Found (ίό) C 61.56, H 9.21, N 16.55

Production example 8

acid

Heat

To 20 ml of a 50 ^ igen ethanol solution of 3.1 g of 1-0xa-3,8-diaza-3-cyclohexyl-4-imino-7,7,9 »9-tetramethyl-spiro ⁷ A .5Ϊdecan-2-one were under 5 ml of hydrochloric acid followed by stirring were added, and the resulting mixture was allowed to react for 8 hours at 8 ° to 85 ° C. with stirring. Subsequently, the reaction liquid was freed from the solvent by distillation, and the remaining crystals were dissolved in water. This solution was neutralized by adding sodium carbonate, crystals separating out, which were then collected by filtration, washed with water / water and recrystallized from benzene. Permanently obtained 1-oxa-3,8-diaza-3-cyc: ohexyl-7,7,9,9-tetramethyi-spiro 14,5-decane-2,4-dione in the form of white crystals. 173-174 ° C.

109850/1674

Elemental analysis for ^

Calculated {%) C. 66. 2o, H 9. 15, N 9. o8 Found ( ^C J>) C. 66. 16, H 9. 21 N 9. 00

The amount of the agent against the fading to be incorporated varies depending on the kind thereof and the kind of the coupler used and to which the Ui is given · xtel against the fading of the layer. Preferably, however, the amount is in the range of 1 to 2oo wt. Calculated on the coupler used. If desired, an ultraviolet absorber can be added to the photographic silver halide emulsion layer containing the anti-fading agent according to the invention containing couplers, or incorporated into any layer adjacent thereto, whereby the lightfastness of the color image obtained can be further improved. Examples of ultraviolet absorbers which can be used in the above sense are compounds of the benzophenone, acrylonitrile, thiazolidone, benzotriazole, oxazole, thiazole and imidazole dye type. This list is of course not exhaustive.

As already stated, the color images obtained have a greatly improved fastness to ultraviolet and visible light when the dyes providing the color photographic images are present together with the anti-fading agents according to the invention. This is explained further using the following examples. In addition, the anti-fading agents according to the invention are essentially colorless and therefore do not stain the color images. Incidentally, the incorporation of the anti-fading agents according to the invention does not adversely affect the color development of the photographic recording materials, and the presence of the agents together with color-forming dyes does not cause any change in the hue of the color images obtained . Has. kei-e

109850/1 674

adverse interactions with other photographic additives.

The result of tests with regard to the effect of the means, against fading according to the invention is described below.

Trial method:

Dyes corresponding to the color-developing dyes of a color photographic material have been synthesized. A solution of in each case one of the dyes prepared in this way was admixed with the compounds listed in the table and then applied to a photographic support to prepare samples. These samples were taken in a fade-ometer Exposure was made using a carbon arc lamp, and the color density after exposure was expressed as a percentage of the color density before the exposure indicated.

109850 / 167Λ

Test results:

Synthesized
dye

! For example, named "
Connection no.

Yellow color enxwicieLnder dye formed from coupler from acylacetamide-T} ^?

To
Hours.

After hours

Purple color developing dye formed from pyrazolone type coupler

After hours

After hours

Cyan color developing dye formed from phenol type coupler

After 32 hours

After 58 hours

Connection ²

58 73

52

91

71

91

61 78

48

93

73

"16

93

55 69

51

90

68

20th

90

53 75

45

96

70

30th

91

62 77

49

93

75

No addition

65

22nd 55

17th

76

45

_ -zn _

The present invention is further illustrated by the following examples. However, the invention is not based on limited these examples. In the examples, the numbers of the test compounds given are those of the examples above mentioned. Links.

example 1

To a blue-sensitive, highly sensitive color photographic Silver iodobromide emulsions were made per liter of emulsion 2 g of oaponin and a solution of 20 g of the yellow coupler «. £ - (4-stearoylamide-benzoyl) -3t5-dicarboxyacetanilide in 8o ml of a 1N sodium hydroxide solution, and the emulsion was by addition adjusted by citric acid to pH 6.8. Then was divided the emulsion into 18 servings. One portion was left without any additive. The other 17 servings were each mixed with the test compounds mentioned in Table 1. Subsequently, these portions were each photographic Baryta papers applied and dried, taking color photographic Papers were received. The color photographic papers were exposed to white light and then subjected to color development subjected, stopped, fixed, bleached, washed with water and dried. The received developed Samples of yellow color were exposed to sunlight. The exposure was for 42, 92 and 148 hours with the samples to the south with an angle of inclination of 45 °. The percentage of color density after exposure (D) of each sample based on the color density before exposure (Do) was calculated. The results obtained are shown in Table 1 compiled.

- Ao - 109850/1674

- No. lot
mg / 1 oo Table 1 2 _ 87 (° / o) To (D / Thu χ 1oo) 5 300 100 92 hours To Experimental No. Fade ratio 12th It 98 67 ( ^c / o) 148 h link It ml After 16 «T ■ 100 90 43 ($) No addition ti Emulsion 42 hours 24 Il 100 91 78 link Il 38 ti 96 93 76 It It 42 Il 100 90 81 Il Il 48 If 98 87 80 ti It 57 It 99 89 74 It dd 69 I! 100 87 78 It dd 76 Il 100 90 72 It It 82 dd 92 91 80 Il dd 87 Il 99 90 80 It dd 90 1t 100 87 78 Il II 92 Il 96 91 69 It ti 95 Il 94 90 78 It dd 97 It 100 88 76 dd It dd 100 82 75 Il It 90 72 It 91 85 It 87 Il

Example 2

A mixture of 12 g of the yellow coupler tt-jj5 - (<X-2,4-di-tertamylphenoxy) butylamide-benzoy \] "2-methoxyacetanilide, 6 g each of the test compounds mentioned in Table 2 and 3.0 g of the ultraviolet absorber 2- (2'-hydroxy- :? ', 5'-di-tert-butylphenyl) -benstriazole was dissolved in a solvent mixture of 8.0 g of tricresyl phosphate and 2o g of ethyl acetate. The received Solutions were added to 2oo ml of a 5 '...' strength aqueous Gelatin solution containing baponin given, and the mixed solutions were dispersed by means of a homogenizer. Me dispersions formed in this way containing the respective named

109850/1674

Test compounds were added to 400 ml of a red sensitive Silver iodobromide emulsion, which is then applied to photographic Baryta papers were applied and dried. In this way, samples according to the invention were made. "

For comparison, a control sample (A) containing no test compound and none was prepared in the same way Ultraviolet absorber, and a control sample (B) containing only the ultraviolet absorber were prepared.

Each of the samples thus prepared and the control samples were exposed to white light, subjected to color development, stopped, fixed, bleached, washed with water and dried. They were then measured in a Pade-Ometer using a carbon arc lamp for 80, 150 and 250 hours, respectively long exposed. The 'parb density after each exposure time (D) was measured and the percentage (D / Do χ 1οο) based on the density before exposure (Do) was calculated. the The results are compiled in Table 2.

- 42 -

t08850 / 167A

(B) 9 3 - 42 - - 2126187 To To To 3 mentioned test connections as he in] W) 32 (5i) g of ethyl acetate solved. the 8.0 g tricresyl phospha Connection No. 4. 17th A mixture of 8.0 g Table 2 80 hours 150 hours 250 hours Ultraviolet absorber 61 to 2oo ml one; solutions obtained were Il 23 75 (*) 55 91 "5% aqueous gelatin solution It 33 Fade ratio (D / Do χ I00) 88 76 78 Given saponin, and the solution Il 35 100 97 81 mixes were on Il 43 · 96 83 79 It 49 98 87 76 Il 59 100 90 80 Experimental Il 66 93 83 79 Connection no. Il 74 98 88 81 Control (A) Il 80 96 87 78 Il It 88 100 91 82 Il 91 98 90 80 Il 96 99 93 75 It 97 100 94 81 Il 99 94 85 79 Il 98 87 74 - Il 100 89 78 example 97 83 75 98 85 98 84 2- (p-tert-amylphenoxy- , 3 g each of the in of the purple coupler and 3.0 g of the same p-benaoyl) -amino-4-chloro-5-methyl-phenol 3example 2 was used, Tabel were made in a mixed solvent and 2o.o respectively holding

109850/1674

INSPECTED

photographic barite papers applied and then dried. In this way, samples according to the present invention became manufactured.

For comparison, in the same manner as described above, a control sample (A) containing no test compound and no ultraviolet absorber and a control sample were made (B) containing only the ultraviolet absorber.

Each of the samples thus prepared was subjected to the same treatments as described in Example 2 and then 85, Illuminated for 16 and 300 hours in a Pade-Ometer using a charcoal arc lamp to determine the change in parb density of the samples before and after exposure. The results obtained are summarized in Table 3.

- 44 -

109850/1674

• Experimental - 44 - 3 2126187 To To To was in a were each 4 named Ver solved. Which he- Connection no, Tabel 85 hours 160 hours 300 hours 5.0 g of dibutyl phthalate and 2o.o g containing gelatin solution Solvent mixture from to 2oö ml of a 5 # aqueous - Control (A) 82 (<? O) 64 {fo) 48 (^) holding solutions Ethyl acetate Given saponin, and the 3 ö- Control (B) Fading ratio (D / Do χ 1oo) 95 87 65 Mixtures were dispersed using a homogenizer.
-. - - - -., - - -. ......... J Connection No. 3 100 95 83 "6 98 94 87 "10 95 92 85 "16 95 87 82 ¹¹ 24 97 88 85 "32 98 90 86 ¹¹ 36 100 92 83 «44 100 94 82 47 96 87 79 55 95 88 80 ¹¹ 67 97 90 86 77 100 89 81 89 100 88 80 ¹¹ 92 100 90 82 ¹¹ 94 98 91 83 π 97 99 92 80 Example 4 A mixture of 1 < D.o jg of the purple coupler 1- (2,4-dimethyl 1-6- chlorophenyl) -3- {3- [iC- (3-pentadecyiphenoxy) butylamide] benzarid} - 5-pyrazolone and 7.5 g each of the in table Search connections

1098 50/167

The dispersions produced in this way were each 35o ml given to a green-sensitive silver iodobromide emulsion, which are then transferred to photographic barite papers to form Emulsion layers were applied. On the other hand, 7.o g of the same ultraviolet absorber as used in Example 2 was used in a mixed solvent 7.0 g tricresyl phosphate and 2o.o g ethyl acetate dissolved. The obtained solution became 300 ml of a 5 point gelatin aqueous solution containing saponin and the solution mixture was given by means of a homogenizer to form an ultra- ' violet absorber dispersion dispersed. The dispersion was applied to the above mentioned silver iodobromide emulsion layers containing the magenta coupler and the test compound applied so that the amount of the dispersion was 7 mg per 100 cm. Then it was dried. In this way, samples were prepared, each of the test compounds mentioned contained.

For comparison, a control sample (A) having an emulsion layer was prepared in the same manner as described above, which contained no test compound and had no ultraviolet absorber in the upper layer, as well as a control sample (B), which has an emulsion layer with no test compound and in the upper layer the ultraviolet absorber contained.

The samples and control samples thus prepared were subjected to the same treatments as described in Example 2 and then exposed for 32, 85 and 120 hours in a Pade-Ometer using a carbon arc lamp, to determine the change in color density of the samples in the same manner as described in Example 2. The received The results are shown in Table 4.

109850/1674

Table 4 Fading ratio (D / Do χ 1oo)

Experimental . 2 • To To To Link. No 5. 32 hours 85 hours 120 hours Control (A) 14th 78 ($) 53 (#) 25 (*) Control (B) 17th 92 78 57 Connection no 23 98 82 75 Il 34 96 83 72 Il 38 99 86 73 Il 48 100 87 75 fl 57 98 81 70 Il 61 100 86 78 Il 79 100 85 74 Il 87 97 82 70 Il 90 100 85 72 Il 93 95 80 69 Il 95 98 82 71 It 98 96 84 73 Il 98 83 70 Il 99 87 77 Il 97 84 73 Il 100 86 72 Example 5

In this example, the test compounds listed in Table 5 were used each used in the final stabilizing bath for a color paper after color development.

For this purpose, a multilayer color photographic paper containing the yellow, magenta and cyan couplers, respectively
in Examples 2, 3 and 4 were subjected to color development (22 ° C., 10 min.) by customary methods. Then it was stopped, fixed, bleached and with

109850/1674

Washed with water to obtain a test sample which was not subjected to treatment with a final stabilizing bath had been.

Separately from this, 5.ο g of those listed in Table 5 were added Test compounds dissolved in a stabilizing bath which had the composition of solution A mentioned below. To the For comparison, a stabilizing bath was prepared which contained solution A without the addition of a test compound. Farther a stabilizing bath was prepared which contained the solution B according to the composition given below.

Composition of the stabilizing baths:

Solution A Solution B

Sodium metaborate 12 g / liter 12 g / liter borax. 6.5 g / liter 6.5 g / liter

Citric acid 0 10 g / liter

pH 8.0 pH 3.6

Parts of the test sample described above were in each case for 3 minutes at 25 ° C. in the stabilizing baths produced in this way immersed, dried and then exposed to direct sunlight for 12 or 24 hours in the manner described in Example 1, to determine the change in blue, green and red color densities of the sample before and after exposure. aside from that The fog density of the non-image part of the sample after 240 hours of exposure was measured (expressed as blue color density) and compared to the density before exposure. The results obtained are summarized in Table 5.

- 48 -

109850/1674

Blue color To
.'240 hours TABLE 5 38 '· To
240 hours Haze density after
24 hours' Bfiliehimisr Nacb / ße-
clearing To
120 hours 55 Green color 48 Red color
eit ohtß ^ 76 Voi / be
clearing 0.18 Experimental ver
binding no. 66 75 To. To.
120 hours 240 hours To.
120 hours
*** "I Il ^ ₀₁ M. '88 0.05 0.08 Control,
Solution A alone 85 55 55 92 0.04 Control,
Solution B alone 83 74 52 98 90 0.08 60 Solution a
offset with: 92 81 50 92 0.03 0.06 Connection No. 1 91 79 86 51 100 91 0.03 0.05 Connection No. 4 94 80 83 53 100 88 0.04 0.06 Compound # 18 92 78 82 57 100 92 0.04 0.05 j
Enmity Ni ¹ 1 Ii 90 79 80 58 98 93 0.04 0.04 Compound number 37 93 83 79 51 100 90 0.03 0.07 Compound # 42 92 77 80 53 100 90 0.04 0.08 ¹ ^ ⁰ Compound 50 91 79 81 50 100 92 0.05 £ 0.07 Compound 64 89 78 83 99 94 • 0.04 0.06 ^ Compound # 72 88 78 100 0.04 Compound # 86 79 98

It can be seen from the results compiled in Tables 1 to 5 that the lightfastness of the color images obtained can be significantly improved if the means against fading according to the invention together with the the color images of color photographs forming dyes are used.

Claims

109850/1674

Claims (5)

Claims; wherein X represents an oxygen atom or an irino group (-NH-); Y for a carbonyl group O, (-C-) an iminomethylene group NH or an aminomethyl (J-) len group is HH ₂ ; R ₁ and R ₂ which are the same or (-CH-) can be different, each represent an alkyl group, a phenyl group or an aralkyl group, or R ₁ and R ₂ together with the carbon atom on which these symbols are attached form a 5- to 7-membered saturated alicyclic ring or a group of the formula CH ₃ CH ₃ NZ form, wherein Z is a hydrogen atom, a hydroxyl represents a group or an oxygen radical (-0), and R. and Rj- each be a lower alkyl group 109850/1674 interpret, or one of these symbols is a hydrogen atom and the other represents a lower alkyl group, or R. and Rr- together with the carbon atom 4 5 ' where these symbols sit, a 5- to 7-part saturated alicyclic group or a group of the formula N-Z CH ₃ CH ₃ form; η stands for the number 1 or 2 and R-, then, when η denotes the number 1, a hydrogen atom, a An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a group of the formula represents, and when η is the number 2, an alkylene group, an arylene group or a group of formula represents where Rg is an oxygen atom, a methy- 109850/1674 lengruppe or a group of the formula P 0 I! | t -NH-O-KII-CH ₂ -CH ₂ -IiH-O-NH- stent; and R _{17 represents} a V hydrogen atom or an alkyl group,
contains. 2. Means according to claim 1, characterized in that it
one or more of the connections Wr. 1 to 99 contains. 3. Means according to claims 1 to 2, characterized in that that there are also known ultraviolet absorbers contains. 4. Means according to claims 1 to 3, characterized in that that it is used in combination with conventional ultraviolet absorbers. 5. Color photographic material with at least one silver halide emulsion layer, characterized in that
it contains at least one compound of the formula I as an anti-fading agent. Dr. T / l-M 109850/18