DE2165371A1 - Color photographic material - Google Patents

Description

TELEGRAMS: KARPATENT NUSSBAUMSTRASSEIO

December 29, 1971 W 40 950/71

Fuji Photo Film Co., Ltd. Ashigara-Kamigun, Kanagawa (Japan)

e ■ 3 € payments and their use

The invention relates primarily to new dihydroxyspirochroma compounds.

An object of the present invention is to provide dihydroxyspirochroman compounds indicate those as heat stabilizers for polyester and as color image stabilizers for color photographic Materials can be used. The dihydr "O3cyspirochr Cyano compounds of the invention can be represented by the following general formula:

209841/0989 BAD ORfGlNAL

- 2 - 2 1 δ ο V / 1

where mean:

R _x . an alkyl, alkenyl, aryl, alkoxy, alkenoxy, aryloxy, acylamino or acylaminoaralkyl group, each with 1 to 18
Carbon atoms and

Rp is a hydrogen atom, a halogen atom, an alkyl, alkenyl or alkoxy group.

Specific examples of the compounds of the present invention
of the formula given above are the following:

209841/0989

BAO OFJföihÄt.

Compound I.

CH

HO i

6,6'-IflhjrcIroxy-7,7'-dimethyl-4 ', 4,4', 4 '· tetr & rr.ethyl-bis-2,2'-spirochroriari

Compound II

CH,

tetrarcethyl-bis-2,2 ¹ -spirochrornari

Compound III "

C ₅ H ₁₁ Ct)

HO

6,6 · -Iihyircxy-7,7 '-ai-t-aruyl-4,4,4', 4 '■ ΓΓ-: Γ.6ίϊ ¹ .ν · 1 ^ ί3-2, 2' -. "Pirochroni 'Ln

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_ Ii-

Compound IV

\ CH

HO

.2Ί65371

6,6'-Dihydroxy-7t7 ^1. -Di-n-octyl-4,4,4 ', 4'-jfcetramethyl-bis-2,2'"rS ^ irochroman

Compound V

CH

CH

6,6'-D ihycLroxy-7, 7'-di-n-pentadecyl-4, 4, 4 ', 4 »-tetranethyl-" bis-2, 2'-

spirochroman

CH

Compound VI

HO

6, 6 "-dihydroxy - ?, 7'-diphenyl -. *" 4, 4 ^T , 4 'tetrarr.ethyl-bis-2, 2'-spirochroman

20984 1/09 89

OH

BAD ORIdWAt "

Compound VII ^v

CH ₂ CH =

CH

= CHCH ₂ ■ ·

»- 6, - 6'-dihydroxy-7, 7'-diallyl-4, 4, 4 ', 4'-

tetreir.eth.yl- "bis-2j 2 '-spirochroman

OCH,

Compound VIII

CH

OH

6, 6'-dihydroxy-7, 7'-dimethoxy-4, 4 »4 '» 4 ¹ -tetranethyl-bis-2, 2'-spirochrcman

CH,

^OC 2 ^H 5

Compound IX

CH, .— -L-

6, 6 ^f -dihydroxy-7, 7'-diathoxy-4, "4. 4 ^1. 4 ¹ -tetramethyl-bis-2, 2'-spirochroman

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BATH ORIGINAL

Compound X _v

HO

6, 6 · -D ihydroxy-7, 7'-diphenoxy-4, 41 4 * »4 '· tetrair: ethyl-bis-2, 2 '-s ^ irochroman

OCH ₂ CH

Compound XI

CH

HO

CH ₂ = CHCH ₂ C

6, 6 '-Dihyarcxy-J7, 7'-diallyloxy-4, 4, 4 ¹ 1 tetraethyl bis-2, 2' -srirochi-oinan

2098A1 / 09 89

BATH ORIGINAL

link

CH ^ CHKHCGCH,

CILCON HC HCH;

⁵ -ι

CK,

6, o'-Dihydroxy-T »7'-CLi- β. -Acetyl ^ raincpropyl ^ ₍ '4, 4Ί 4'-tetraaiethyl-bis-2, 2'-spircchronane

Compound ZIII

CH

CH CONH-

NHCCCH,

6, 6 '-D ihydroxy-71 7' -di- -ß ". .- (p-acetylaniinophenyliethyl-

4, 4, 4 ', 4'-tetraethyl-bis-2, 2'-spirochromane

0 9-8,417 09 89 BAD ORIGINAU

Compound XIV

CH

CH

jyy ^, ^, ^ ¹ , ^^ ¹ , 8,8'-octamethylbis-2,2'-spiroehroman

Compound XV

CH

Cl

CH,

CH

8.8 ^f -Dichloro-6,6'-dihydroxy - ^ -, 4,4 ', 4', 7.7L hexamethyl-bis-2.2 ^f -spirochroman

The above dihydroxyspirochroman compounds are new compounds and they can be made by condensation of hydroquinone derivatives can be made with acetone:

209841/0989

CCH,

Synth es e a g e 1

620 g (5> 0 mol) of methyl hydroquinone, 150 ml of glacial acetic acid, 580 g (10 _{t of} 0 mol) of acetone and 850 ml of concentrated hydrochloric acid were placed in succession into a 5 liter three-necked flask equipped with a stirrer and a high flow condenser. The resulting mixture warmed up a little, gradually melted evenly, and turned slightly brown. Then it was heated under reflux in an oil bath with stirring and the reaction liquid turned blackish-brown within about 30 minutes. The reaction liquid was further heated under reflux in this state for 7 to 8 hours and then allowed to stand at room temperature. A black precipitate separated out within a few pages and about 5 3 years later the separated crystals were filtered and, after washing well with water, recrystallized twice from ethanol. Colorless needle-shaped crystals with a melting point of 145 to 14-9 ° C were obtained in an amount of 220 g *

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Other spirochromes can be made in the same way been.

Compound used in the synthesis of hydroquinone derivative

II butyl hydroxyquinone

III t-amyl hydroxyquinone

IV. n-octyl hydroxyquinone

V n-pentadecyl hydroxyquinone

VI phenyl hydroxyquinone

VII allyl hydroxyehinone

VIII methoxyhydroxyquinone

IX ethoxy hydroxyquinone

X phenoxyhydroxyquinone

XI aryloxy hydroxyquinone

XII ß-acetylaminopropyl-hydroxychxnon

XIII ß- (acetylaminophenyl) ethyl-hydroxyquinone

XIV 2,3-dimethyl-hydroxyquinone

XV 2-methyl-3-chloro-hydroxyquinone

The dihydroxyspirochroman compounds of the invention are very effective as a heat stabilizer for improvement the heat resistance of polyesters.

The invention also relates to polyester compositions comprising the dihydroxyspirochroman compounds of the generic ones given above Formula I contain as a heat stabilizer, it concerns especially polyester compositions with excellent Heat resistance suitable for fibers, films and strips.

The term "polyester" used here includes those compounds the reaction of polybasic carboxylic acids, in particular dibasic carboxylic acids, with polyhydroxy alcohols, in particular E'ihydroxyalkoholen can be obtained. Although these

209841/0989

Polyester having various excellent properties and are used in various fields, they are d ^ rch action of heat or ultraviolet rays USW ₀ affected (deteriorated), where they will discolor and reduced degree of polymerization and its mechanical strength. In particular, due to the discoloration and reduction in mechanical strength due to thermal degradation, the fibers, films and strips lose a considerable amount of their technical value.

So far there are already many types of phosphorus compounds, aromatic Amine compounds and phenols have been proposed to cause such degradation (deterioration) of the polyester impede. It is true that phosphorus compounds effectively prevent those caused by decomposition under the action of heat This cannot prevent discoloration, the disintegration of the polymer chains and the decomposition itself. on the other hand The aromatic amine compounds sometimes decompose with heat and cause discoloration. They also have Phenols have the disadvantage that they cause the polyesters to become cloudy, many of them have poor compatibility with the polyesters.

Accordingly, the aim of the present invention is to provide a stabilizing agent for polyester, in which the disadvantages of the known stabilizers are eliminated. Another one The aim of the invention is to provide heat-resistant polyester compositions.

!! Oh, extensive research into a process to improve the. V'äria resistance of the polyester has now been found that the 'hydroxyspirochromanverbindungen of the above General For ja el I are effective in improving heat resistance d - .; r polyester. Preferred examples of the above-mentioned dihydroxyspirochroman compounds, which are used as heat rods

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BATH ORIQINAL

izing agents for the polyesters are preferably used, are the compounds I to XV described on pages 5 to 8.

An example of the polyesters used according to the invention is polyethylene terephthalate, which is obtained by polycondensation of terephthalic acid with ethylene glycol, dimethyl terephthalate with ethylene glycol, terephthalic acid with ethylene oxide, or bis-β-hydroxyethyl terephthalate, which is obtained by a known method. The polyesters include those in which terephthalic acid is the main acid component and ethylene glycol is the main glycol component. Accordingly, may be replaced some of the acid component by one or more dicarboxylic acids, such zBIsophthalsäure, sebacic acid and adipic _$ and their Esterderivate and part of the glycol component may by one or more bifunctional alcohols such as trimethylene, hexamethylene and polyethylene glycol, etc., be replaced. The proportions of acid component and glycol component, apart from terephthalic acid and ethyl glycol, are each less than 40%.

When the amount of the dihydroxyspirochroman compounds of the present invention is too little, a sufficient effect is not obtained, while if the amount is too large, tanning discoloration sometimes occurs the polyester occurs. Accordingly, the amount to be added is from 0.005 "to 1, preferably from 0.01 to 0.2% by weight, based on on the acid component. These compounds can be used individually or two or more of them can be used together be used.

A method for adding the compounds according to the invention to the polyesters, for example, is a process in which dJo ^ e before in the synthesis of the polyester the starting materialion and a method of adding after completion an ester interchange reaction and a method of addition

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bath

to the pellets / from the manufactured polyesters. Though after the heat resistance of the polyester is improved in any process, the addition is in a polycandensation stage the ester interchange reaction is generally most preferred, because they do not decrease through volatilization and dispersed and mixed homogeneously in the polyesters.

The polyester compositions according to the invention can be catalysts such as calcium acetate, cobalt chloride, zinc chloride, magnesium oxide and antimony oxide, stabilizers such as phosphoric acid, phosphorous acid and their esters, matting agents such as titanium oxide, pigments such as carbon black etc., colorants such as dyes, and known additives such as branching agents, chain terminators, ultraviolet absorbers and antistatic agents, etc. } .

The Dihydroxyspirochromanverbindungen of the invention may itself be heated ₀ The polyester containing these compounds v / iron excellent in heat resistance and maintain high transparency. Therefore they are particularly suitable for the production of films and strips. The heat resistance of the polyesters is not impaired by the fact that they are used in conjunction with many known additives.

The invention is explained in more detail below using examples, but without being restricted thereto. In the examples, Lind comparative examples, all parts are by weight, [^] is the intrinsic viscosity of the polyester, a '' verb, the (60 / 4-0) mixture at 30.0 ⁰ G in a phenol / Tefcrachloräthan as solvent was determined.

ispiol_J_

A mixture of 100 parts of dimethyl terephthalate, 80 parts

209841/09 89 BAD ORtOINAi,

_. ■ 2165 3

Ethylene glycol, 0.15 part calcium acetate and 0.03 part antimony trioxide were heated to 150-220 ° C. for about 3 hours in order to remove a stoichiometric amount of methanol. Then 0.1 part of öje'-dihydroxy ^^ '- di-tert-butyl-4.4.4% 4 ^l -tetrajEuäthyl-bis-2.2 ^l -spirochroman were added. The mixture was polycondensed under a pressure of 1 ramtlg at 270 to 280 ° C. for 2 hours. The polyester obtained was colorless and transparent, [ij] = 0.650.

After treating this polyester by heating it in nitrogen to 300 ° C. for 1 hour, the viscosity was determined; ίηΐ ~ 0.590 and the ratio of decrease in the internal viscosity was 9.2 %.

Comparative example 1

A polyester was produced by the same method as in Example 1, except that no spirochroman compound according to the invention was used was used. This polyester was colorless and transparent, [> 1] = 0.650. When this polyester deEi was subjected to the same heating procedure as in Example 1, 0 /] = 0.515 and the ratio of decrease in Intrinsic viscosity was 20.7%

Example 2

After conducting an ester interchange reaction using the same raw materials and applying the same reaction conditions as in Example 1, polycondensation was carried out by the same method as in Example 1 by adding 0.1 part of öjG'-dihyaroxy-4,4,4 · , 4 ^l -7,7'-hexamethyl-bis-2.2 ^l > -spirochroraan and 0.03 parts of phosphorous acid. The polyester obtained was colorless and transparent, ίηΐ = 0.645. The viscosity [η! after carrying out the same Y / änne treatment as in Be: Lr; r> ie \ i 1 was 0.56t "),

203841/0989

BATH

the ratio of the decrease was 13 »2%. Comparative example 2

A polyester was prepared by the same procedure as in Example 2, except that no spirochroman compound according to the invention was used. This polyester was colorless and transparent, Oi] = 0.658. The viscosity [Jj] after the heat treatment was 0.520, the ratio of decrease was 21.0 %.

Example ^

A polyester was prepared by the same process as in Example 1, but this time instead of the sjiirochroman compound of Example 1, 6,6'-dihydroxy-7.7 ^l -di-noctyl-4,4,4 ', 4'-tetramethyl -to ^^ '-spirochroman was used. The viscosity [>?] Was 0.650. After the heat treatment, the viscosity was 0.59 % and the decrease ratio was 8.6%.

Be i play 4

A polyester was produced by the same process as in Example 2, but this time instead of the spirochroman compound of Example 2, 6.6 ^l -dihydroxy-7 _i 7 ^l -d-ipkenyl-4,4,4 ', 4 ^l -tefcrainehtyl- up to-2.2 ^t -spirochroiaan used vmrde, [']] = 0.640. The viscosity after the heat treatment was 0.570, the ratio of decrease was 10.9 %

Example 5

A mixture: rras 100! 'Eilen dimethyl terephthalate, 50 parts of ethylene glycol, 90 parts of trilite, vlenglykol, 0.15 part of calcium cctate υ.ικ; O ₅ CJ parts of antimony trioxide was used to achieve this

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BATH

an ester interchange reaction. Wake addition of 0.05 part of phosphoric acid (phosphorus acid) and 0.1 part of 6,6'-dihydroxy-7,7'-n-octyl-4,4,4 ', 4 · -tetramethyl-bis-2, 2 In spirochroman, the polycondensation was carried out by the same method as in Example 1. The polyester obtained was colorless and transparent, the viscosity oil] was 0.451. After the heat treatment was carried out by the same procedure as in Example 1, the viscosity [j] was 0.370. The ratio of decrease in intrinsic viscosity was 17.9 %.

For comparison, the viscosity ίηΐ of a polyester produced without adding the Spiroehr Oman compound was 0.445, after the heat treatment the viscosity C-Ti] was 0.333, the ratio of the decrease was 25.1 %.

As can be seen from the above examples and comparative examples, is the decrease in molecular weight by heat in the dihydroxyspirochroman compounds of the present invention containing polyesters is low and the durability is markedly improved. Accordingly, they are particularly preferably used for fibers, films and strips. The dihydroxyspirochroman compounds of the present invention are very effective as color image stabilizers of color photographic materials.

The invention also relates to color photographic materials comprising the dihydroxyspirochroman compounds of the above general formula I contain as color image stabilizer, which are excellent stabilizers for magenta color images and the properties given in the following description in comparison to those mentioned above, commonly used Have funds.

The inventive Dihydroxyspirochronanverbindungen the general formula I and. those on Seiton 3 to 8. submitted Examples, Compounds I through XV, have the following

2 09 aA1 / 0989

BAD ORfGfNAL

- ■ 17 -

Characteristics:

(1) The dihydroxyspirochroman compounds of the present invention suppress the degree of fading (degree of fading) the action of light to which the magenta color image obtained from the pyrazolone coupler is subjected is considerably reduced. In comparison to the previously known dye stabilizers, they can have an equivalent effect in smaller amounts exhibit.

(2) The dihydroxyspirochroman compounds of the present invention are themselves very stable and do not tend to take part in the color-forming reaction or during color development using primary aromatic amine compounds as well as in a bleach bath containing a strong oxidizing agent such as ferricyanide or bichromate, to one Lead to discoloration. They do not give discoloration even if they are after development in the color photographic Material are left.

(3) The dihydroxyspirochroman compounds of the present invention prevent the undesirable change resulting from the 5-pyrazolone coupler copied out or yellowing or discoloration of the images occurs when exposed to light or heat.

(4) The dihydroxyspirochroman compounds of the present invention are readily soluble in organic solvents and they can be readily and consistently used in color photographic materials incorporated.

(5) The bihydroxyspirochroman compounds of the present invention can be easily synthesized in one step from inexpensive starting materials which are readily available.

(6) The compounds according to the invention are not disadvantageous

209841/0989

Effect on the photographic emulsion in which they are incorporated and they interfere with the color formation of the Pyrazolone coupler not.

On the other hand, the magenta coupler used in the present invention can can be selected from a wide variety of structures. Under these structures give the 5-pyrazolone compounds particularly excellent results when used together with the Dihydroxyspirochromanverbindungen of structural formula I given above can be used, the 5-pyrazolone compounds belong to the groups represented by the following structural formulas II and III can be represented:

. R ₅ -C-CH-X

Il I

N C = O

\ / ^ Structural formula II

B ₅ -C- CH- CH - CH - C - R ₅ structural formula III

K C = ο 0 = C N

K _N

■ h V

In the above formulas, R represents an aryl group or a substituted aryl group. A suitable substituent for the Aryl group is an alkyl, aryl, alkoxy, aryloxy, alkylthio, Arylthio group, a halogen atom, a trifluoromethyl, ·

209841/0989

Cyano, acyl, sulfonyl, acylamino, sulfonatnino, ureido, Amino, carboxyl, alkoxycarbonyl or carbamyl group and R, preferably denotes one through these substituent groups substituted phenyl group.

R ₁ . means an alkyl group, a substituted one. Alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, an amino group, a substituted amino group, an acylamino group, a substituted ureido group, a sulfonamide or alkoxy group

R represents a lower alkyl or aryl group.

X represents those radicals which can be split off by the oxidation product of the primary aromatic amine developer compound, for example a hydrogen atom, an ilalogen atom, a cyano, arylthio, aryloxy, arylazo, heteroazo and acyloxy group. At least one of the radicals R 1 and R _r contains a hydrophobic radical having 8 to 30 carbon atoms. This hydrophobic residue tends to increase the affinity between the coupler molecules as well as between the coupler molecules and the coupler-solvent molecules and keeps the coupler inside and in vengeance on the solvent particles that are in close contact with one another. This hydrophobic residue also gives the coupler solvent an affinity for the dyes derived therefrom and tends to enhance the effect of the coupler solvent. This hydrophobic residue is in R ₇ or R ₁ . contain that dii ~ ect or indirectly through

H- -5

a diva 1 en-.en organic residue with an amine, ether,

2 09841/0989

BATH ORIGINAL

2Ί65371

Ester, urea or sulfonamide bond are linked to the coupler radical. A hydrophobic one suitable according to the invention
The remainder can be selected from the group of straight-chain or branched alkyl, alkenyl, alkoxyalkyl, alkoxyaryl, aryl, aryloxyalkyl, aryloxyaryl and acylaminoalkyl groups. Specific examples of the hydrophobic residue are the following:

(i). ⁿ ~ ^C 17 ^H 35 ~ (ii) nC ₁₆ H ₃₃ CH = CH- (iü) nC ₁₂ H ₂

(vii)

(iv) ⁿ ~ ^C 18 ^H 37 °

η -

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BATH ORIGINAL

'2Ί65371

(viii) tert. - C, H _Q // \ S OCH -

4 9

tert, -C ₄ H ₉

(ix) n-C H _ / V-O- / \

(χ) η - C ₁₅ H ₃₁ r

N - CH ₂ CH ₂ -

In practicing the present invention, one can a dispersion product in which a dihydroxyspirochroman compound separately emulsified to form a silver halide photographic emulsion having a diffusion-sensitive Pyrazolone coupler contains, or the diffusion-sensitive pyrazolone coupler and the dihydroxyspirochroman compound are dissolved in the same solvent to form a mixed solution, which is then in an aqueous medium is dispersed and the dispersion obtained wix'd the photographic Emulsion added.

The amount of the dihydroxyspirochroman compound used in the present invention varies depending on the purpose for which the color photographic material is to be used, depending on the type of 5-pyrazolone coupler and also depending on the structure of the one to be used Dihydroxyspirochraiuanverbindungen, an amount within the Range from 0.05 to 5.0 moles per mole of 5-pyrazolone coupler however effective, a particularly preferred amount is 0.1 to 2.0Hol

209841/0989

Specific examples of 5-pyrazolone compounds which can be used in the present invention which can be used with particularly satisfactory results are the following:

Coupler melting point

cjl

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- B.

KC- C ₁₇ H ₃₅

-C-- 'CK ₀ · -.

Cl

Cl

Cl

100-102 ^° C

IO4-?

"H / 7-λ

■ * ■ €>

₅ H _n (t)

174-175 ° C

C - CiL

C ₅ H _n Ct)

KHCOCHO

20984170989

BAD ORIQfNAL '; "

ο-.

N »= C— NHCOCH ₀ __

C-CH ₂ O ■ CH ₂ -N

125 ° C

Cl

Cl-5

N = C- NKCOCH ₀ CH ₀ N ^

/ r ..- ²² \

., C-CH ₀

1 M 2

87 -

C - NHCOCHO

-TX

- CK, 96 -9e ° C

. J

= C-NKCO

C - CH.

NHCOCH ₀ O

140-142 C

C ₅ H _{1] L} (sec)

209841/0989

C ~ NHCC-

CH ₂ :

WcCCH ₂ C

176-17 7 ° c

^C 5 ^H H (t)

= C -KHCO

-CH,

NHCCCH

141 ° C

^C 5 ^H H (t)

~ C - NHCC

= -C - NHCC

NHCOCHO

HECCCH ₂ O

'15Ο-152Ό

^C 5 ^H ll (t)

2098 A 1/09 89

8AD OBlGlMAL.

N = C-NHCO

175 ° C

KHCOCHO

V'nfe)

N = C ~ NHCO-

. C _ CH,

2. KIICOCHO

106-100 ⁰ C

° 15 ^H 3l (n)

C- KHCCNHC _1n H ₂

Cl

Il

■ 103 ° C

- NHCONH

' - ' Up

KHCOCHO-

129 -

^C 5 ^H H (t)

^C 5 ^H li (t)

2098A1 / .0989

^: copy, BAD ORIGINAL

Cl

N "= C-NHCCNH

15O-15l ° c

CH ,.

Cl

NHCfCH ₂ O

Cl

A- ν N r = r ■ N \ C - C - NHCONH CH ₅ O_ (Γ K < O V - \
Cl CH ₀ .. 2 .. -

* ^ i 62 ° c

^C 2 ^H 5

NHCOCHG

'· ^C 5 ^H H (t)

/ N

150 -

NHCOCH ₂ O

- .. 0CH, ^C 5 ^H n (t)

NHCCCH 0

OCH,

2098 A 1/09

. '. COPY ^ - 'BATH

C ₅ H

165-16 6 ⁰ C

C ₅ H ₁₁ CtKV

OCH ₂ CONH

(t)

CONH - C. CH -

II. I.

- κ- c-o

209841/0989

171-17 5 ° C

COOH

C ₁₇ H ₃₅

Il

f \

N-C- NHCOCHCH «CHC, Λ

CH ₂ COCIi

Il ο

C-NHCO

ti

COCHCH « ti

CH ₂ COOH

B ¹

HiCOCHCH = CHgCOCH

41/0989

BAUOR (QrNAt

/ Λ

N = C-NHGO- ' ^{7 νλ} 196-199 C

NHGOCHCh = CH-G ₁₆ H

^cl 'rl CH ₂ COOH

The dihydroxyspirochroman compounds of the above Structural formula I has a clear stabilizing effect on the couplers incorporated with a 5-pyrazolone ring derived azomethine dyes and sometimes they also have a stabilizing effect on color images, the of magenta color couplers with other structures, such as 5-

en
.Pyrazolobenzimidazoles, Indazolon / or 2-Cyanoacet-y-Ichromanen, are derived. In addition, the dihydroxyspirochroman compounds to be used according to the invention have the effect of improving the lightfastness even in color images which are impaired by yellow color couplers consisting of acylacetanilides and cyan color couplers consisting of phenols or α-naphthols.

Dissolve the dihydroxyspirochroman compounds according to the invention easily in many organic solvents. These compounds are finely dispersed in an aqueous medium after they have been dissolved in an organic solvent. The emulsion thus obtained then becomes the photographic emulsion added. One embodiment of the invention consists in using the dihydroxy spirochromic "omanver" compounds with oil-soluble 5-parazolone couplers to mix and then add the mixture in the medium or disperse the dye stabilizer and coupler in Form of a solution or a dispersion separately; r-'ti of the emulsion admit.

209841/0 9 89.

BAD Ol

For the purpose of adding the coupler and the dye stabilizer, to be used in the present invention, a wide variety of organic compounds can be added to the photographic emulsion Solvents can be used, but the solvents described below are particularly suitable for this purpose:

(1) Virtually water-insoluble and non-volatile solvents with a boiling point at normal atmospheric pressure of not less than 200 G, e.g. di-n-butyl phthalate, tri-o-kres} ^ - phosphate, tri-n-hexyl phosphate, Ν, Ν-diethyl capryiamide, di-n-butyl succinate, p-nonylphenol and chlorinated paraffins;

(2) partially water-soluble and volatile solvents having a boiling point at normal atmospheric pressure not higher than 120 C; this type of solvent is used during the manufacturing process the photographic material completely removed, e.g., ethyl acetate, cyclohexyl alcohol and cyclohexanone;

(3) water-miscible solvents; this solvent tyρ is used during the manufacturing process of the photographic Material removed by washing or dialysis, e.g. methanol, ethanol, dioxane, tetrahydrofuran, acetone, methyl ethyl octone, Diine thyl sulfoxide, dimethyl formamide, hexamethyl phosphorylamide and MethylcQjlosolve.

209841/0989

These dihydroxyspirochroman compounds dispersed in an aqueous medium for photographic use are in water insoluble and furthermore not in any of the other developing agents used for photographic processing containing developer solutions with a high pH and it does not happen that they by flowing out during the Development or that they diffuse into other layers of the photographic material.

In practicing the invention, only one can Type of the dihydroxyspirochroma compound indicated by the general formula I. either individually or in groups the same structural formula can be used in combination. Also, by using the connection in conjunction with a dye stabilizer other than one of the general ones Formula I the dye stabilizing effect according to the invention can be increased even further. For example, are suitable the alkyl hydroquinones described in U.S. Patents 2,336,327, 2,403,721 and 2,728,659 for use in conjunction with Dihydroxyspirochromans of the general formula I. As a result, not only is the magenta color image produced by the pyrazolone coupler made clearly lightfast, but also that remaining in the color photographic material after development Pyrazolone coupler can be effectively prevented from yellowing or discoloration (staining) upon exposure of heat or light. Specific examples of such compounds include 2,5-di-t-octy! Hydroquinone, 2,5-di-n-octy! Hydroquinone, 2-methyl-5-t-octy! Hydroquinone and 2-methyl 5-n-octy! Hydroquinone.

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BATH ORIGINAL

The use of an acid buffer solution as a final bath for development of the photographic material of the present invention is preferred in order to further improve the durability of the image. This is in Japanese Patent Application '82 769/1970 described in more detail.

For the I ¹ arbentwicklung Dihydroxyspirochromanverbindungen of the invention containing photographic material, the usual general procedure can be used. To produce a color image and a silver image, substituted p-phenylenediamines are used for color development and the silver is oxidized to the silver salt in the subsequent bleaching bath.The remaining silver halide and other silver salts are then removed by dissolving them in a fixer, leaving only the color image. When the magenta color image obtained from the diffusion-sensitive 5-pylazolone is treated in a bleaching bath containing a strong oxidizing agent such as bichromate and ferricyanide, it tends to fade upon exposure. For this reason, a magenta color image developed in a weak oxidizing agent and a strong silver complexing agent, e.g. thiosulfate and a mixture of ethylenediaminetetraacetic acid with a ferric salt-containing bleach bath, is lightfast and the use of such a bleach bath of a weakly oxidizing nature is for the implementation of the present Invention particularly suitable. As the p-phenylenediamine derivative to be used for the development of the color photographic material of the present invention, there can be used many already known compounds. Specific examples are Ν, Ν-diethyl-p-phenylenediamine., Έ , N-diethyl-3-methyl ~ 4-aniinoaniline, N-ethyl-N »(ß-hydroxyethyl) -p-phenylenediamine, N-ethyl-W- (ß-hydroxyethyl) -3-meth, yl- ^/ i ~ aminoaniline ₁ N-ethyl-N ~ (ß-methyl-sulfonara.idoethyl) -3 ~ methyl-4-aminoaniline, N, N »diethyl-3- ( methyl sulfonamidoethyl) -4-aininoaniline, etc. The color photographic material of the invention is advantageous when it is with aldehydes such as formaldehyde, either during or after

209841/0989

-34 "- 2Ί65371

Color development "is treated", this is not only used to to harden the hydrophilic film of the color photographic material, it also improves the heat resistance of the Color image. It is advantageous if the inventive color photographic In the final stage of the color development process, material is treated in a stabilizing bath. This Bath contains an acidic substance, a substance soluble in water with the effect of stabilizing the color image Ultraviolet absorbent and a fluorescent brightener. As a color image stabilizer added to the stabilizing bath Hydroquinone or its substituted derivatives, urea or its substituted derivatives are suitable and p-alkoxyphenol or its substituted derivatives. It is advantageous if the color photographic material according to the invention contains a substance which is practically non-visible Absorbs rays, but which strongly absorbs ultraviolet rays. Such an ultraviolet ray absorbing one Material protects the color image and the remaining coupler from exposure to ultraviolet rays after color development and further prevents the color photograph from becoming yellow, discolored (blotched), or faded. the Dihydroxyspirochroman compound used in the present invention particularly effectively prevents the color image protected by the ultraviolet absorbent from being faded by light. Ultraviolet absorbents found to be particular in practicing the invention in the specific form stilbene derivatives have proven suitable (cf. e.g. the known Japanese patent applications 9 585/1970 and 9 586/1970), 2-arylimino-5-arylmethylene thiazolidone or 2-arylimino-3-alkyl-5-heteromethylene thiazolidone (cf. the well-known Japanese Patent application 29 627/1969) and the 2-benzotriazolyl-4-alkylphenols, as described, for example, in published Japanese patent application 19 299/1968. the The present invention is applicable to various types of color photographic materials. It is particularly

209841/0989

-35- 216537Ί

Applicable to color negative films, positive color images, photographic Color paper, color reversal and color films for enlargement (e.g., Fuji Golor G Print). The support of the color photographic material of the present invention Materials can consist of a wide variety of materials and the most varied Have shapes. Sheets made of glass or plastics, soft flexible films or paper made of cellulose acetate, polyethylene terephthalate or polystyrene or resin coated paper can be used. In the case of practical implementation The photographic emulsion used in the invention is one in which a silver halide is dispersed in fine grains in the hydrophilic colloid and a suitable silver halide is silver chloride, silver bromochloride, Silver bromide or silver iodobromido examples of suitable hydrophilic colloids are water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone Polyacrylamide, polyacrylamide exposed to the Hoffmann reaction and copolymers of acrylic acid, acrylamide and N-vinylimidazole.

The following examples are intended to illustrate the invention on the basis of application examples explain in more detail, but without restricting them to them.

Application example 1

17 g of 1- (2, 6 ^l -dichloro-4 ^t -methoxy) phenyl-3-C3 "{a- (2 ^tl1 , 4"'- dit-amylphenoxy) butylamide} benzamide] -5-pyrazolone (compound example O ) as magenta couplers, the dye stabilizers given in the table below in the amounts also given and a solution obtained by heating 3 ^ g of tricresyl phosphate and 1 o ml of ethyl acetate were mixed with an aqueous solution of 50 ° C., 1.0 g of itatrundodecylbenzenesulfonate and 25 g Gelatin contained, mixed and placed in a high speed mixer . finely dispersing the same of a strong

0 9 8 41/0989

- ⁵⁶ - ■ 2 1 G F>: ■; 7 1

subjected to mechanical agitation.

To the obtained coupler dispersion product, 500 g of a photographic emulsion containing 6.7% silver o'odobromide and 45 g of gelatin were added. 15 ml of an acetone solution of 3 % triethylenephosphamide was added as a hardening agent. The mixture obtained in this way was applied to baryta paper to a dry layer thickness of 5 microns. This color photographic paper was exposed to green light through a step wedge with the aid of a sensitometer and developed at 30 ° C. as indicated below.

1. Color developer 7th Minutes 2. Stop fixer bath 2 «T 3. To wash 2 Il 4th Bleach solution 2 II 5. To wash 2 It 6th Hardening and fixing bath 2 Il 7- To wash 2 Il 8th. dry

Each of the treatment solutions described above had the following composition:

Color £ iybwi.ckler_

Sodium metaborate Sodium sulfite hydoxylamine sulfate Potassium bromide 6-nitrobenzimidazo] nitrate Sodium hydroxide

209841/0989

ORIGINAL WSPECTED

Treatment_1 S. ε 25.0 S. 2.0 S ^λ 5.0 ε 0.5 0.02 g 4.0

Benzyl alcohol Diethy1 glycol 4-Amino-3-methyl-N-ethyl - N- (ß-methylsulfonamide ethyl) aniline-3 / 2H ₂ O-HSO water pH 10.6 15.8 ml 20.0 ml

8.0 g ad 1 1

Treatment_2_

Ammonium thiosulphate sodium metabisulphite Glacial water

pH *, 5 bleach bath

Potassium nitrate Potassium ferricyanide Potassium bromide Boric acid borax

Water pH 7.2 120.0 g 20.0 g 10.0 g ad 1 1

BetLändlung_4_

25.0 g 20.0 g 8.0 g 5.0 g

2.5 S ad 1 1

Hardening and fixing bath

Ammonium Thiosulphate Sodium Sulphite Boric Acid Formalin (38 %) Water pH 9.5 Treatment_6_

120.0 g 5.0 g

2.5 S 40.0 ml ad 1 1

209841/0989

These developed samples were passed through a filter (Fuji Film Filter ITV-4G0) that was practically all ultraviolet for 10 days Absorbed rays with a wavelength of less than 400 microns, exposed with a daylight fluorescent layer. The light intensity of the emitted light at this point in time was 10,000 lux. Changes in green density (fading of the magenta dye image) and changes in blue density (yellow / earth the bright image areas) were measured before and after exposure. The results thereby obtained are as follows Given in the table.

209841/0989

Table I.

Changes in the developed samples upon exposure to light

rehearse

Dye stabilizer Degree of fading of the magenta contamination or

φ ranσρ dye image (decrease in discoloration in the

^{i / p} . ωtight green light density, initially bright picture areas

^ S / THfT-IIO - Ί ΓΛ f 7.TiMnViTMeI A ar * T) I eliTv

'o Ver, x, equals
co sample

not
added

invent

1st verb, I

2.

Comparative sample

Comparative

according to the invention
Verb. II

acquaintance
Link*

Density = 1.0)

3.4
3.4

(Increase in blue light density)

Duration of light exposure

.Days

0.35

0.09

0.09
0.10

6.8 0.10

10 days

0.67

0.18

0.17 0.21

0.20

* 2,2, ^ - trimethyl ^ -t-octyl-G-hydroxychroiaan

1.0., Days 0.10

0.08

0.08 0.09

0.09

From the results given in the table above, it can be seen that the compounds according to the invention in the Are capable of fading of the magenta dye image to prevent effectively and their improving effect exceeds that of the dye stabilizers known heretofore. In addition, the compounds of the present invention can effectively prevent that in the formation of the dye image unused remaining coupler on exposure or heating to yellowing or staining (discoloration) and this shows that they extend the life of the color photography and improve the dye image stabilizers can.

Application at ₁ sp_iel_2_

A- (4-methoxybenzoyi) - [2 ^l -chlor-5 '> - (2 ¹¹ , 4 "- disec.-amylphenoxyacetamido)] acetoanilide as yellow coupler containing blue-sensitive emulsion layer and applied in the form of a second layer (1 micron) an intermediate layer consisting of gelatin.

One obtained by melting by heating to 55 ° G of the mixture of 32 g of the magenta coupler 1- (2 ', 4', 6 ^l -trichlorophenyl-i5- [3 "fa- (2 '", 4 "' - di-t_amylphenoxy) butylamide] benzamide] -5-pyrazolone (compound example L), 63 ml of tri-n-hexyl phosphate, ^ O ml of ethyl acetate and the dye stabilizers indicated below were added to 700 ml of an aqueous solution containing 45 g of gelatin and 3.0 g of liatrium dodecyl sulfate The solution was added and stirred. They were vigorously mechanically stirred in a high-speed mixer for 30 minutes.

841/0989

BATH ORIGINAL

medium finely dispersed. All of the emulsified dispersion solution was added to 1 kg of a green-sensitive photographic emulsion containing 0.27 mol of silver iodobromide and? 0 g of gelatin. After adding 50 μl of an acetone solution of 3 % triethylenephosphaide as a hardening agent, the photographic emulsion was applied in the form of a third layer on the above-mentioned color photographic paper to give a dry film thickness of 3 microns. A gelatin layer containing 2-benztriazo-4-sec-butyl-6-t-butylphenol as an ultraviolet absorbent to a dry film thickness of 2 microns and then a 1-hydroxy-4-chloro-2- The red-sensitive emulsion layer containing dodecylnaphthamide as an oyan coupler was applied to a dry film thickness of 3 microns and then a 1 micron thick gelatin layer was applied as a protective layer to complete the color photographic paper.

This color photographic paper was exposed to green light through a step wedge and in a manner similar to that

. Application-7,. -r -.- uj .-- iT a. * -uta / Example Ί subjected to an IP color development, whereby a magenta dye image was obtained which had a gradually varying dye density. These developed samples were exposed directly to the light of a daylight fluorescent lamp with a light intensity of 10,000 lux and the results obtained are given in the following table.

209841/0989

Table II

Fading of the magenta dye images and discoloration (staining) of the light image areas
when the developed samples are irradiated with light

sample

Dye stabilizer

Type

O CO OO

O CO OO CO

Comparative not added sample

3. Invention. Verb. I

4-. according to the invention Verb. II

^Ver: known equal connection α ürobe

Amount (g)

6.4 6.4 12.8 Degree of fading of the magenta color contamination of the fabric image (decrease in the green and light image areas light density at an initial (increase in blue density of 1.0) "light density)

(this is the absolute value of the blue density, measured by a blue filter)

Duration of light exposure

ΊΟ days 0.31

0.09 0.08 0.10

20 Page 0.45

0.17 0.17

0.20

20 days

0.25

0.14 0.14 0.17

As can be seen from the above results, the compounds of the invention are both capable of a Effective fading of the magenta dye image to prevent as well as to give a more effective improvement than with the usual dye stabilizer. It was found that the compounds according to the invention are effective in preventing the bright image areas of the color copy Exposure to turn yellow.

Application example 3

To prepare the dispersion solution with the emulsified coupler, that of the green-sensitive emulsion on the in the application example 2 is to be added in the manner indicated, except for the coupler, the solvent and the Dye stabilizer the hydroquinone derivatives given below admitted. In all other points, the example mentioned was repeated and the results obtained are given in the following table.

209841/0989

Table III

Combined improvement effects through dihydroxyspxrochroman derivatives and hydroquinone derivatives (Light exposure time 20 days)

lot

(ε)

Sample dye stabilizer hydroquinone derivative degree of fading of gastric discoloration

_{φ M} ta dye image (decrease (stain

^IYP iv.enge _the G _r ü _c h _n ii-tdichte in formation) of

^ ° 'an initial density of light image of 1.0) districts (increase in blue light density)

2,5-di-t-octyl hydroquinone

2,5-3i-rL-octylhydroquinone

2098. 5 according to the invention
Compound I. 6.4 .F- 6th according to the invention
Compound II 6.4 6860 7th inventive gene.
Compound I. 6.4 8th· according to the invention
Compound II 6.4

3.2 0.14 0.10 I.
$
I. 3.2 0.14 0.11 3.2 0.12 0.12 3.2 0.13 0.13

When these results are compared with those of Table II, it can be seen that if the present invention Compounds, namely the dihydroxyspirochroman compounds, used in combination with alky! hydroquinone They cause the fading of the magenta dye image and, at the same time, the contamination of the bright areas of the image effectively prevent.

Use for example 4

To an existing cellulose triacetate film base, a sodium salt were used as first layer, 1-hydroxy-4-sulfo-2-octadecylnaphthoamid as a cyan coupler-containing red-sensitive emulsion layer to a dry film thickness of 5 microns, and as a second layer, a 1.5 micron thick G _e latinezwischenschicht applied one after the other.

The solution obtained by dissolving the dye stabilizers and hydroquinone derivatives given in Table IV below in 10 ml of tri-0-cresyl phosphate and 1.0 ml of ethyl acetate at 50 ° C. was added to 200 ml of 15 S gelatin, 0.5 g of sodium p- dodecylbenzenesulfonate and 0.5 g of sodium bisulfite-containing aqueous solution were added and the mixture was stirred. They were finely dispersed by vigorous mechanical stirring for JO minutes using a high speed mixer. All of the emulsified dispersion solution was added to 1 kg of a green-sensitive emulsion containing 0.27 mol of silver iodobromide and 70 g of gelatin. It was then added to an aqueous solution containing 21.8 g of 1-phenyl-3-ij5 '- (<% - oleylsuccinamide) bonzamide | -5-pyrazolone (compound example A ¹ ) and 1.5 g of sodium hydroxide, and the pH was adjusted the emulsion was adjusted to 6.0 using an aqueous solution of 5% acetic acid. 20 ml of an aqueous solution of 4 % of the sodium salt of 1-hydroxy-3,5-dichloro-S-triazine were added to this solution as a hardening agent added, which then refer to the above-mentioned color film sub-

209841/0989 ORiGiNAL BATHROOM

lay as a third layer up to a dry film thickness of 5 microns was applied. A gelatin layer containing a yellow colloid was also applied to the third layer of the film to a dry film thickness of 2 microns, one of the 2-sodium salt of α- (4--01eylsuccinamidobenzoyl) -2 '~ methoxy-5-carboxyacetoanilide blue-sensitive layer containing yellow coupler as a fifth layer up to a thickness of 6 Microns and a gelatin layer containing a high molecular weight ultraviolet absorbent having the structure shown below applied up to a thickness of 2.5 microns to complete the color film,

CH - CH-

KHSO

'SO-

SO _{x well}

where m is a large positive integer.

This film was exposed to green light through a step wedge and then in the color developing solution the following

O,

specified composition developed for 18 minutes at .20 C.

water

lY, N-diethyl-p-phenylenediamine sulfate Sodium sulfite

sodium

Hydroxylamine hydrochloride potassium bromide

1,000 ml 2.8 g 2.5 g 65.0 g 1.0 g 1.2 g

209841/0989

Then, 2 minutes, washed at 17 ° C for 5 minutes and treated in a bleach fixing solution of the following composition at 20 ⁰ C and finally 10 minutes, washed in running water of 17 ° C to produce a magenta image.

Bleach and fix solution_

Water 1 1

EDTA-2Na salt 35 B.

Sodium hydroxide 18 g

Ferric chloride 25 g

Hyposulfite ('5 ^ 0) 170 g

Borax 10 g

Potassium bromide 30 g

Potassium thiocyanate 10 g

The colored samples were developed with light from a xenon lamp with a light intensity of 50,000 lux through a heat-absorbing Filter exposed for 5 days The results obtained are shown in the table below.

209841/0989

Table IV

Fading of the magenta dye images and discoloration (flaking) of the bright ones Image areas when irradiated with light

Sample dye stabilizer hydroquinone derivative Degree of fading of the impurity

Type

Amount of type (c amount of magenta dye of the light image [g) image (decrease in the areas (increase in green light density in the case of blue light of an initial density)
of 1.1)

NJ Ver not O O equal added CO
OD sample 9 inventive 2.2 according to Verb. I O CD
OO 10 inventive 2.2 CD according to Verb. I V inventive 2.2 yes. Verb. II 12th inventive 2.2 according to connection II

not added O

2.2 2.5 M t-octyl hydroquinone

■ II 0.55

O 0.12 1.1 0.09 O 0.11 1.1 0.07

0.15

0.09 0.05 0.10 0.07

From the results of the table above, it can be seen that the compounds according to the invention cause bleaching (lading) the magenta dye image to a considerable extent Levels can be reduced in that they prevent the non-exposed, non-colored light image areas from being removed turn yellow on exposure and that their effects are further intensified by the joint use of dialky / hydroquinone will.

Application example 5

To 200 g of an emulsion containing 0.27 mol of silver iodobromide and 70 g of gelatin in 1 kg, the following solutions with a dispersed magenta coupler and the following dispersion solutions of dye stabilizers were added. After the further addition of 3 ml of an acetone solution of 3 % triethylenephosphamide, they were applied to a polyethylene terephthalate film to a dry film thickness of 5 microns.

Coupler dispersion solutions: the couplers given in Table V below were refluxed in 10 ml of tri-n-hexyl phosphate and 15 ml of ethyl acetate dissolved »The resulting solution was added to 70 ml of 0.5 g of sodium cetyl sulfate and 5.0 g of gelatin containing aqueous solution added »They were mechanically stirred vigorously in a homomixer in order to disperse them

Dispersion solutions of the dye stabilizers: those by dissolving of the dye stabilizer given in Table V below solutions obtained in a mixed solvent of 2 ml of di-n-butyl phthalate and 5 ml of ethyl acetate were obtained to 30 ml of 0.1 g of sodium cetyl sulfate and 2.0 g of gelatin containing aqueous solution added. She got strong under mechanical stirring in a homomixer.

209841/0989

These film samples were sensitometrically, exposed and as in in Application Example 1, treated to form magenta dye images and passed through an ultraviolet absorption filter with light from a fluorescent lamp? Light intensity of 10,000 lux exposed for 10 days for determination the fading of the dye images <, the resulting Results are given in Table V below.

As indicated in the following table, make the according to the invention used dihydroxyspirochromanverbinaungen that from 5-pyrazolone couplers Azomethine dye image produced with various substituent groups is lightfast.

209841/0989

Table V

Magenta dye images fade on exposure

sample MaE ent acuOplers lot Dye stabilizer added lot Type 4.52 Type 0 Ver
equal
sample A. 4.52 not 0.5 13th ti 4.52 I. 0.5 14th Il 4.52 II added 0.5 15th Il 5.80 V 0 Ver
equal
sample H 5.80 not 0.6 16 Il 5.80 VII added 0.6 17th Il 5.11 IX 0 Ver
equal
sample J 5.11 not 0.5 18th ti 5.11 II added 0.5 19th It 6.15 VIII 0 Ver
equal
sample W. 6.15 not 0.6 20th It 6.15 I. 0.6 21st dd V

Degree of fading (decrease in green light density at an initial density of 1.0) _

0.27

0.09

0.10 0.12

0.70 0.25 0.19

0.45 0.10

0.08

0.51 0.15 0.18

CJl CO

Claims (1)

W, am PATENTANWÄLTE DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C. GERNHARDT MDNCHE.N .. HAMBURG TELEPHONE: SS 5476 TELEGRAMS: CARPATENT 8000 MÖNCHEN 15, NUSSBAUMSTRASSE 10 June 13, 1972 ¥. 40 950/71 13 / We P 21 371.4 New patent claims 1. A color photographic material, characterized in that it consists it and at least one silver halide emulsion layer on the support from a Trä _G, which contains a 5-Pfrrazolonkuppler with at least one hydrophobic group having 8 to ^ O carbon atoms, and a color image stabilizing agent of the general formula OH CH 20 υ 841/0989 received mJÄ., £ $ L ·. Where mean: E _{1 is} an alkyl, alkenyl, aryl, alkoxy, alkenoxy, aryloxy, acylaminoalkyl or acylaminoaralkyl group with not more than 18 carbon atoms and Ep is ^a hydrogen atom, a halogen atom, an alkyl, alkenyl or alkoxy group. 2. A color photographic material according to claim 1, characterized in that it contains as Farbbildstabilisierungsnittel e ^ -dihydroxy ^^ - dimethyl - ^, ^ ^1, 4'-tetramethyl-2,2-bis -spiroehroman ·, 6,6'-dihydroxy-7 , 7'-di-t-butyl-4,4,4 ', V-tetramethyl-bis-2,2'-spiroehroman, 6,6'-dihydroxy-7,7'-di-tamyl-4,4, 4 ', 4'-tetramethyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-n-octyl-4,4,4', 4'-tetramethyl-bis-2 , 2'-spirochroman, 6,6'-dihydroxy-7.7 ^l -di-n-pentadecyl-4,4, V, 4'-tetramethyl-bis-2,2 · -spiroehroman, 6,6 * -dihydroxy -7,7'-diphenyl-4,4,4 '^' - tetramethyl-bis-S ^ '- spirochroman, 6,6'-dihydroxy-7,7'-diallyl-4,4,4 ·, 4'-tetramethyl-bis-2,2'-spiroehroman, '^', 4'-tetramethyl-bis- 2,2'-spirochroman, 6,6'-dihydroxy-7,7'-diethoxy-4,4,4 ', 4'-tetramethyl-bis-2,2 ^ spirochroman, 6,6'-dihydroxy-7,7'-diphenoxy-4,4,4 ', 4-tetramethyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-diallyloxy-4,4,4 ', 4'-tetramethyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-β-acetylaminopropyl-4,4,4 ', 4'-tetramethyl-bis-2 , 2'-spirochroman, 6,6 * -dihydroxy-7> 7'-di-ß- (p-acetylaminophenyl) ethyl-4,4,4 ·, 4'-tetramethyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-4,4,4 ·, 4 ', 7,7', 8,8'-octamethylbis-2,2'-spirochroman and 6,6'-dihydroxy-4,4,4 ', 4', 5,5 *, 7,7 ', 8,8'-decamethyl-bis-2,2'-spirochroman. 2098 41/0989 3. Color photographic material according to claim 11 or 2, characterized in that it contains the color image stabilizer in an amount of 0.05 to 5 moles per mole of 5-& ζο1οη couplers contains. 4. Farbphotographiscb.es material according to claim 3, characterized characterized in that it detects the color image stabilizer in an amount of 0.1 to 2 moles per mole of fj-I ^ razolone coupler \ holds. '- 5 · color photographic material according to claim 1, characterized labeled it as silver halide. Contains silver chloride, silver bromochloride, silver bromide or silver iodobromachloride. 6th A color photographic material according to Claim 1, characterized characterized in that there is also an alkylhydroquinone from the group of 2,5-di-t-octy! hydroquinone, 2,5-di-n-octylhydroquinone, 2-methyl-5-t-octyl hydroquinone and 2-methyl-5-n-octyl hydroquinone contains. 1 . Color photographic material according to claim 1, characterized in that it is also used as an ultraviolet absorption medium stilbene derivatives, 2-arylimino-3-arylmethylene-thiazoline, 2-arylimino-3-alkyl-5-heteromethylene-thiazoline and 2-benzotriazolyl-4-alky! Phenol contains. 209841/0989