CN100406457C

CN100406457C - Arylene compound, azomethine compound and silver halide photographic materials

Info

Publication number: CN100406457C
Application number: CNB00120839XA
Authority: CN
Inventors: 木村桂三; 荻山勝志; 矢吹嘉治; 川岸俊雄; 中峰猛; 水川裕樹
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2000-08-02
Filing date: 2000-08-02
Publication date: 2008-07-30
Anticipated expiration: 2020-08-02
Also published as: CN1336374A

Abstract

The present invention discloses an arylidene compound shown as structural formula (I). In the formula, L1 and L2 respectively represent divalent aliphatic radicals, divalent aromatic radicals or divalent heterocyclic radicals; L3 represents trimethyl, pentamethyl or heptamethyl; Y is equal to O, S or N-R10; R1 represents hydrogen, halogen atoms, cyano, nitryl, aliphatic radicals, aromatic radicals, heterocyclic radicals, -O-R<11>, -S-R<12>, -CO-O-R<13>, -O-CO-R<14>, -NR<15>R<16>, -CO-NR<17>R<18>, -SO2-R<19> or -SO2-NR<20>R<21>; R2, R3, R6 and R7 respectively represent hydrogen, halogen atoms, cyano, aliphatic radicals, aromatic radicals, -O-R<22>, -CO-R<23>, -CO-O-R<24>, -NR<25>R<26>, -NHCO-R<27>, -NH-CO-O-R<28>, -SO2-R<29> or -NH-SO2-R2-R<30>; R4 and R5 respectively represent hydrogen, aliphatic radicals, aromatic radicals, -CO-R<31> or -SO2-R<32>. in addition, the present invention also discloses azomethine compounds and silver halide photographic materials.

Description

Arylene compound, azomethine compounds and photographic silver halide material

Technical field

The present invention relates to arylene compound and azomethine compounds.In addition, the invention still further relates to and comprise as the arylene compound of photographic dye or the photographic silver halide material of azomethine compounds.

Background technology

Arylene compound and azomethine compounds are used as the dyestuff of fiber, or are used for paint or photographic silver halide material.

Dyestuff is added in the silver halide emulsion liquid layer or non-photosensitivity hydrophilic colloid layer of photographic silver halide material, so that absorb the light of specific wavelength.The dyestuff that is included in the photographic silver halide material must satisfy the condition of following (1)-(5).

(1) suitable spectral absorption effect

The absorbing wavelength scope is determined according to used dyestuff.

(2) photographic chemistry inertness

Dyestuff should not produce the chemical affect performance of silver halide emulsion liquid layer (particularly to) to the performance of photographic material.In more detail, dyestuff must not damage susceptibility, must sub-image be weakened, and must not produce photographic fog.

(3) be easy to bleaching or removing

In principle, dyestuff works between the imaging exposure period.After exposure, dyestuff must be removed from photographic material or bleach.If dyestuff is retained in the image that obtains, so, image will be by dyeing.Therefore, dyestuff should be easy to processed liquid (as developing solution, sodium hypochlorite solution) bleaching or remove.

(4) rapid diffusion

Dyestuff works in the certain layer of photographic material.Dyestuff should not diffuse in other layer.For example, be diffused in the susceptibility that antihalation (should be included in the non-photosensitivity colloid layer) in the emulsion layer will reduce emulsion layer.

(5) stability

When photographic material or dye solution storage, the color of dyestuff must not can change or weakens.

Usually be difficult to satisfy (3) and (4) individual condition.Satisfy condition (3), be easy to the dyestuff bleaching or remove, also be easy to diffuse in other layer.On the other hand, the dyestuff that satisfy condition (4), is difficult to spread will be difficult to bleaching or removing.

Suggestion is used: the photographic silver halide material that comprises satisfy condition (3) and (4).This material comprises: the solid fine particle that has the dyestuff of slightly acidic group (for example carboxyl).Because the not disassociation in the coating fluid (normally acidity or neutral) of each layer for preparing described material of slightly acidic group, therefore, dyestuff is insoluble in the described coating fluid.Therefore, dyestuff will mix wherein with the fine grain form of solid, and these particles will be difficult to diffuse in other layer.The slightly acidic group will dissociate in treatment solution (normally alkalescence), so dyestuff will be dissolved in the treatment solution.Therefore, utilize treatment solution, be easy to from photographic material, remove dyestuff.

Japanese patent provisional publication numbers 3 (1991)-7931,4 (1992)-37841,4 (1992)-37842 and 4 (1992)-45436 has disclosed and has comprised the arylidene dyestuff that is the solid fine particulate or the photographic silver halide material of azomethine dyes.

The applicant studies the known arylidene dyestuff and the azomethine dyes that disclose in the prior art.The applicant finds as a result: these dyestuffs need be aspect stable, be that condition (5) is improved.

Summary of the invention

The purpose of this invention is to provide a kind of arylene compound and azomethine compounds as stabilizing dye.

Another object of the present invention provides the photographic silver halide material that comprises stabilizing dye.Described dyestuff spreads hardly and is easy to be removed by treatment solution.

The invention provides arylene compound by structural formula (I) expression:

In the formula: each L ¹And L ²Be aliphatic divalent group independently, divalent aromatic radical or divalent heterocyclic group; L ³Be cyclonite, five methynes or seven methynes; Y is=0 ,=S or=N-R ¹⁰, R wherein ¹⁰Be hydrogen, aliphatic group, aromatic group or heterocyclic group; R ¹Be hydrogen, halogen atom, cyano group, nitro, aliphatic group, aromatic group, heterocyclic group ,-O-R ¹¹-,-S-R ¹²,-CO-O-R ¹³,-O-CO-R ¹⁴,-NR ¹⁵R ¹⁶,-CO-NR ¹⁷R ¹⁸,-SO ₂-R ¹⁹Or-SO ₂-NR ²⁰R ²¹, R wherein ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Be hydrogen independently of one another, aliphatic group or aromatic group; R ², R ³, R ⁶And R ⁷Be hydrogen independently of one another, halogen atom, cyano group, aliphatic group, aromatic group ,-O-R ²²,-CO-R ²³,-CO-O-R ²⁴,-NR ²⁵R ²⁶,-NHCO-R ²⁷,-NH-CO-O-R ²⁸,-SO ₂-R ²⁹Or-NH-SO ₂-R ³⁰, wherein, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰Be hydrogen independently of one another, aliphatic group or aromatic group; R ⁴And R ⁵Be hydrogen independently of one another, aliphatic group, aromatic group ,-CO-R ³¹Or-SO ₂-R ³², wherein, R ³¹And R ³²Be aliphatic group or aromatic group independently of one another; R ²And R ³, R ³And R ⁴, R ⁴And R ⁵, R ⁵And R ⁶, or R ⁶And R ⁷, can be bonded to each other forms a ring.

In addition, the present invention also provides and comprises carrier, the photographic silver halide material of silver halide emulsion liquid layer and non-photosensitivity hydrophilic colloid layer; Wherein silver halide emulsion liquid layer or non-photosensitivity hydrophilic colloid layer comprise the arylidene dyestuff by structural formula (I) expression.

The present invention also provides the azomethine compounds by structural formula (II) expression:

In the formula: each L ¹And L ²Be aliphatic divalent group independently, divalent aromatic radical or divalent heterocyclic group; Y is=0 ,=S or-N-R ¹⁰, R wherein ¹⁰Be hydrogen, aliphatic group, aromatic group or heterocyclic group; R ¹Be hydrogen, halogen atom, cyano group, nitro, aliphatic group, aromatic group, heterocyclic group ,-O-R ¹¹-,-S-R ¹²,-CO-O-R ¹³,-O-CO-R ¹⁴,-NR ¹⁵R ¹⁶,-CO-NR ¹⁷R ¹⁸,-SO ₂-R ¹⁹Or-SO ₂-NR ²⁰R ²¹, R wherein ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Be hydrogen independently of one another, aliphatic group or aromatic group; R ², R ³, R ⁶And R ⁷Be hydrogen independently of one another, halogen atom, cyano group, aliphatic group, aromatic group ,-O-R ²²,-CO-R ²³,-CO-O-R ²⁴,-NR ²⁵R ²⁶,-NHCO-R ²⁷,-NH-CO-O-R ²⁸,-SO ₂-R ²⁹Or-NH-SO ₂-R ³⁰, wherein, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰Be hydrogen independently of one another, aliphatic group or aromatic group; R ⁴And R ⁵Be hydrogen independently of one another, aliphatic group, aromatic group ,-CO-R ³¹Or-SO ₂-R ³², wherein, R ³¹And R ³²Be aliphatic group or aromatic group independently of one another; R ²And R ³, R ³And R ⁴, R ⁴And R ⁵, R ⁵And R ⁶, or R ⁶And R ⁷, can be bonded to each other forms a ring.

In addition, the present invention also provides and comprises carrier, the photographic silver halide material of silver halide emulsion liquid layer and non-photosensitivity hydrophilic colloid layer; Wherein silver halide emulsion liquid layer or non-photosensitivity hydrophilic colloid layer comprise the azomethine dyes by structural formula (II) expression.

Embodiment

Arylene compound is represented by structural formula (I):

In the structural formula (I), each L ¹And L ²Be aliphatic divalent group, divalent aromatic radical or divalent heterocyclic group independently.

Preferably, each L ¹And L ²Be aliphatic divalent group or divalent aromatic radical; Divalent aromatic radical more preferably.

Aliphatic divalent group refers to: alkylidene group, the alkylidene group of replacement, alkenylene group, the alkenylene group of replacement, the alkynylene group of alkynylene group or replacement.

Alkylidene group can have branched structure.Preferably, alkylidene group has 1-20 carbon atom, and 1-18 carbon atom more preferably arranged.

The alkylene moiety of the alkylidene group that replaces is identical with above-mentioned alkylidene group.

The alkenylene group can have branched structure.Preferably, the alkenylene group has 2-20 carbon atom, and 2-18 carbon atom more preferably arranged.

The alkenylene part of the alkenylene group that replaces is identical with above-mentioned alkenylene group.

The alkynylene group can have branched structure.Preferably, the alkynylene group has 2-20 carbon atom, and 2-18 carbon atom more preferably arranged.

The alkynylene part of the alkynylene group that replaces is identical with above-mentioned alkynylene group.

The alkylidene group that replaces, alkenylene and alkynylene group, its substituent example comprises: halogen atom, cyano group, nitro, carboxyl ,-O-R ³³,-S-R ³⁴,-CO-O-R ³⁵,-NR ³⁶R ³⁷,-CO-NR ³⁸R ³⁹,-SO ₂-R ⁴⁰Or-SO ₂-R ⁴¹R ⁴²R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁸, R ³⁹, R ⁴⁰R ⁴¹And R ⁴²Be hydrogen, aliphatic group or aromatic group independently of one another.Aliphatic group, aromatic group and heterocyclic group be R below ¹Definition in describe.

Divalent aromatic radical refers to the arylene group of arylene group or replacement.

Arylene group is phenylene or naphthylidene preferably, more preferably is phenylene, most preferably to phenylene.

The arylidene part that replaces arylene group is identical with above-mentioned arylene group.

The substituent example that replaces arylene group comprises: halogen atom, cyano group, nitro, carboxyl ,-O-R ⁴³,-S-R ⁴⁴,-CO-O-R ⁴⁵,-NR ⁴⁶R ⁴⁷,-CO-NR ⁴⁸R ⁴⁹,-SO ₂-R ⁵⁰Or-SO ₂-R ⁵¹R ⁵²R ⁴³, R ⁴⁴, R ⁴⁵, R ⁴⁶, R ⁴⁷, R ⁴⁸, R ⁴⁹, R ⁵⁰R ⁵¹And R ⁵²Be hydrogen, aliphatic group or aromatic group independently of one another.Aliphatic group, aromatic group and heterocyclic group be R below ¹Definition in describe.

Divalent heterocyclic group preferably includes heterocycle 5-unit or 6-unit, saturated or undersaturated.Heterocycle can with aliphatic series ring, aromatic ring or other heterocyclic fused.Heteroatomic example comprises in the heterocycle: B, N, O, S, Se, and Te.Heteroatoms preferably includes: N, O or S.Heterocycle preferably has at least two and is with free univalent carbon atom.In other words, divalent heterocyclic group preferably connects at two carbon atom places.The example of saturated heterocyclic comprises: pyrrolidine ring, morpholine ring, 2-boron-1,3-dioxolane and 1,3-thiazoles alkane.The example of unsaturated heterocycle comprises: imidazole ring, thiazole ring, benzothiazole ring, benzoxazoles ring, benzotriazole ring, benzo selenazoles ring, pyridine ring, pyrimidine ring and quinoline ring.

Divalent heterocyclic group can have substituting group.Substituent example comprises: halogen atom, cyano group, nitro, carboxyl ,-O-R ⁵³,-S-R ⁵⁴,-CO-O-R ⁵⁵,-NR ⁵⁶R ⁵⁷,-CO-NR ⁵⁸R ⁵⁹,-SO ₂-R ⁶⁰Or-SO ₂-R ⁶¹R ⁶²R ⁵³, R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷, R ⁵⁸, R ⁵⁹, R ⁶⁰R ⁶¹And R ⁶²Be hydrogen, aliphatic group or aromatic group independently of one another.Aliphatic group, aromatic group and heterocyclic group be R below ¹Definition in describe.

In structural formula (I), L ³Be cyclonite, five methynes or seven methynes.

Preferably, L ³Be cyclonite or five methynes, more preferably cyclonite.

Methyne can have substituting group.Have only under the substituent situation at methyne, described substituting group preferably is connected to (meta) on the methyne of center.In addition, also can two substituting groups in conjunction with forming 5-unit or 6-unit unsaturated aliphatic ring (for example, cyclopentenes ring, cyclohexene ring).Substituent example comprises: halogen atom, cyano group, nitro, carboxyl, aliphatic group, aromatic group, heterocyclic group ,-O-R ⁶³,-S-R ⁶⁴,-CO-R ⁶⁵,-CO-O-R ⁶⁶,-NR ⁶⁷R ⁶⁸,-CO-NR ⁶⁹R ⁷⁰,-NH-CO-R ⁷¹,-NH-CO-NH-R ⁷²,-NH-CO-O-R ⁷³,-SO ₂-R ⁷⁴,-SO ₂-NR ⁷⁵R ⁷⁶,-NH-SO ₂-R ⁷⁷,-CO-NH-SO ₂-R ⁷⁸Or-SO ₂-NH-CO-R ⁷⁹R ⁶³, R ⁶⁴, R ⁶⁵, R ⁶⁶, R ⁶⁷, R ⁶⁸, R ⁶⁹, R ⁷⁰, R ⁷¹, R ⁷², R ⁷³, R ⁷⁴, R ⁷⁵, R ⁷⁶, R ⁷⁷, R ⁷⁸And R ⁷⁹Be hydrogen, aliphatic group or aromatic group independently of one another.Aliphatic group, aromatic group and heterocyclic group be R below ¹Definition in describe.

In structural formula (I), Y is=0 ,=S or=N-R ¹⁰R ¹⁰Be hydrogen, aliphatic group, aromatic group or heterocyclic group.Aliphatic group, aromatic group and heterocyclic group be R below ¹Definition in describe.

Y is preferably=and 0.

In structural formula (I), R ¹Be hydrogen, halogen atom, cyano group, nitro, aliphatic group, aromatic group, heterocyclic group ,-O-R ¹¹,-S-R ¹²,-CO-O-R ¹³,-O-CO-R ¹⁴,-NR ¹⁵R ¹⁶,-CO-NR ¹⁷R ¹⁸,-SO ₂-R ¹⁹Or-SO ₂-NR ²⁰R ²¹R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ₂₀And R ²¹Be hydrogen, aliphatic group or aromatic group independently of one another.

Preferably, R ¹Be hydrogen, aliphatic group, aromatic group ,-O-R ¹¹-,-CO-O-R ¹³,-CO-NR ¹⁷R ¹⁸, hydrogen more preferably, alkyl group, the alkyl group that replaces, the aromatic yl group of aromatic yl group or replacement, especially preferred is hydrogen, the alkyl group of 1-10 carbon atom,, the alkyl group of the replacement of 1-10 carbon atom, the aromatic yl group of the replacement of the aromatic yl group of 6-10 carbon atom or 6-10 carbon atom, hydrogen most preferably, the alkyl group of 1-4 carbon atom, the alkyl group of the replacement of 1-4 carbon atom, the phenyl of the replacement of phenyl or 6-10 carbon atom.

In the application's specification sheets, " aliphatic group " refers to: alkyl group, the alkyl group of replacement, alkenyl group, the alkenyl group of replacement, alkynyl group, the alkynyl group of replacement, the aromatic alkyl group of aromatic alkyl group or replacement.

Alkyl group can have branched structure.Described alkyl group preferably has the 1-20 carbon atom, and the 1-18 carbon atom is more preferably arranged.

The moieties of the alkyl group that replaces is identical with the abovementioned alkyl group.

Alkenyl group can have branched structure.Preferably, alkenyl group has 2-20 carbon atom, and 2-18 carbon atom more preferably arranged.

The alkenyl part of the alkenyl group that replaces is identical with above-mentioned alkenyl group.

Alkynyl group can have branched structure.Preferably, alkynyl group has 2-20 carbon atom, and 2-18 carbon atom more preferably arranged.The alkynyl part of the alkynyl group that replaces is identical with above-mentioned alkynyl group.

The moieties of the aromatic alkyl group of aromatic alkyl group and replacement is identical with abovementioned alkyl.The aryl moiety of the aromatic alkyl group of aromatic alkyl group and replacement is identical with following aromatic yl group.Preferably, aromatic alkyl group comprises moieties with 1-20 carbon atom and the aryl moiety that is selected from phenyl or naphthyl.

The substituent example of the moieties of the alkynyl group of the alkyl group that replaces, the alkenyl group of replacement, replacement and the aromatic alkyl group of replacement comprises: halogen atom, cyano group, nitro, carboxyl ,-O-R ⁸⁰-,-S-R ⁸¹,-CO-O-R ⁸²,-NR ⁸³R ⁸⁴,-CO-NR ⁸⁵R ⁸⁶,-SO ₂-R ⁸⁷Or-SO ₂-NR ⁸⁸R ⁸⁹R ⁸⁰, R ⁸¹, R ⁸², R ⁸³, R ⁸⁴, R ⁸⁵, R ⁸⁶, R ⁸⁷, R ⁸⁸And R ⁸⁹Be hydrogen, aliphatic group or aromatic group independently of one another.

The substituent example of the aryl moiety of the aromatic alkyl group that replaces is identical with substituting group in the aromatic yl group of following replacement.

In the application's specification sheets, " aromatic group " refers to the aromatic yl group of aromatic yl group or replacement.

Aromatic yl group is preferably phenyl or naphthyl, more preferably phenyl.

The aryl moiety of the aromatic yl group that replaces is identical with above-mentioned aromatic yl group.

The substituent example of the aromatic yl group that replaces comprises: halogen atom, cyano group, nitro, carboxyl ,-O-R ⁹⁰-,-S-R ⁹¹,-CO-O-R ⁹²,-NR ⁹³R ⁹⁴,-CO-NR ⁹⁵R ⁹⁶,-SO ₂-R ⁹⁷Or-SO ₂-NR ⁹⁸R ⁹⁹R ⁹⁰, R ⁹¹, R ⁹², R ⁹³, R ⁹⁴, R ⁹⁵, R ⁹⁶, R ⁹⁷, R ⁹⁸And R ⁹⁹Be hydrogen, aliphatic group or aromatic group independently of one another.

Heterocyclic group in this manual preferably includes heterocycle 5-unit or 6-unit, saturated or undersaturated.Heterocycle can with aliphatic series ring, aromatic ring or other heterocyclic fused.Heteroatomic example comprises in the heterocycle: B, N, O, S, Se, and Te.Heteroatoms preferably includes: N, O or S.Heterocycle preferably has the carbon atom of at least two band freedom-valencys.In other words, divalent heterocyclic group preferably connects at two carbon atom places.The example of saturated heterocyclic comprises: pyrrolidine ring, morpholine ring, 2-boron-1,3-dioxolane and 1,3-thiazoles alkane.The example of unsaturated heterocycle comprises: imidazole ring, thiazole ring, benzothiazole ring, benzoxazoles ring, benzotriazole ring, benzo selenazoles ring, pyridine ring, pyrimidine ring and quinoline ring.

Heterocyclic group can have substituting group.Substituent example comprises: halogen atom, cyano group, nitro, carboxyl ,-O-R ¹⁰⁰,-S-R ¹⁰¹,-CO-O-R ¹⁰²,-NR ¹⁰³R ¹⁰⁴,-CO-NR ¹⁰⁵R ¹⁰⁶,-SO ₂-R ¹⁰⁷Or-SO ₂-NR ¹⁰⁸R ¹⁰⁹R ¹⁰⁰, R ¹⁰¹, R ¹⁰², R ¹⁰³, R ¹⁰⁴, R ¹⁰⁵, R ¹⁰⁶, R ¹⁰⁷R ¹⁰⁸And R ¹⁰⁹Be hydrogen, aliphatic group or aromatic group independently of one another.

In structural formula (I), R ², R ³, R ⁶And R ⁷Be hydrogen independently of one another, halogen atom, cyano group, aliphatic group, aromatic group ,-O-R ²²,-CO-R ²³,-CO-O-R ²⁴,-NR ²⁵R ²⁶,-NHCO-R ²⁷,-NH-CO-O-R ²⁸,-SO ₂-R ²⁹Or-NH-SO ₂-R ³⁰Wherein, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰Be hydrogen, aliphatic group or aromatic group independently of one another.

Preferably, R ²And R ⁷The hydrogen of respectively doing for oneself, halogen atom, aliphatic group or-O-R ²², hydrogen more preferably, chlorine, fluorine, alkyl group, the alkyl group of replacement, the alkoxy base of alkoxy base or replacement, especially preferred is hydrogen, chlorine, fluorine, the alkyl group of 1-10 carbon atom, the alkyl group of the replacement of 1-10 carbon atom, the alkoxy base of the replacement of the alkoxy base of 1-10 carbon atom or 1-10 carbon atom, hydrogen most preferably, the alkoxy base of the alkyl group of 1-5 carbon atom or 1-8 carbon atom.

Preferably, R ³And R ⁶Respectively do for oneself hydrogen or aliphatic group, hydrogen or alkyl group more preferably, especially preferred is the alkyl group of hydrogen or 1-8 carbon atom, most preferably hydrogen.

In structural formula (I), R ⁴And R ⁵Be hydrogen independently of one another, aliphatic group, aromatic group ,-CO-R ³¹Or-SO ₂-R ³²R ³¹And R ³²Be aliphatic group or aromatic group independently of one another.

Preferably, R ⁴And R ⁵The hydrogen of respectively doing for oneself, aliphatic group or aromatic group, hydrogen more preferably, alkyl group or aromatic yl group, especially preferred is the hydrogen or alkyl group, most preferably the alkyl group of hydrogen or 1-18 carbon atom.

In structural formula (I), R ²And R ³, R ³And R ⁴, R ⁴And R ⁵, R ⁵And R ⁶, or R ⁶And R ⁷, can be bonded to each other forms a ring.Preferably, R ³And R ⁴Or R ⁵And R ⁶Form a ring.

By R ²And R ³, or R ⁶And R ⁷The ring that forms is preferably 5-unit ring or 6-unit ring.Described ring is preferably aromatic ring (for example phenyl ring) or unsaturated heterocycle (for example pyridine ring, imidazole ring, thiazole ring, pyrimidine ring).

By R ³And R ⁴, or R ⁵And R ⁶The ring that forms is preferably 5-unit ring or 6-unit ring.The example of described ring comprises: tetrahydroquinoline ring and indoline ring.

By R ⁴And R ⁵The ring that forms is preferably 5-unit ring or 6-unit ring.The example of described ring comprises: pyrrolidine ring, piperidine ring and morpholine ring.

Azomethine compounds is represented by structural formula (II):

In structural formula (II), L ¹And L ²Be aliphatic divalent group, divalent aromatic radical or divalent heterocyclic group independently of one another.

Preferably, L ¹And L ²Be aliphatic divalent group or divalent aromatic radical, more preferably divalent aromatic radical independently of one another.

Aliphatic divalent group, the definition of divalent aromatic radical and divalent heterocyclic group is identical with the definition in the said structure formula (I).

In structural formula (II), Y is=0 ,=S or=N-R ¹⁰R wherein ¹⁰Be hydrogen, aliphatic group, aromatic group or heterocyclic group.

Preferably Y is=0.

In structural formula (II), R ¹Be hydrogen, halogen atom, cyano group, nitro, aliphatic group, aromatic group, heterocyclic group ,-O-R ¹¹-,-S-R ¹²,-CO-O-R ¹³,-O-CO-R ¹⁴,-NR ¹⁵R ¹⁶,-CO-NR ¹⁷R ¹⁸,-SO ₂-R ¹⁹Or-SO ₂-NR ²⁰R ²¹R wherein ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Be hydrogen, aliphatic group or aromatic group independently of one another.

Preferably, R ¹Be hydrogen, aliphatic group, aromatic group ,-O-R ¹¹-,-CO-O-R ¹³, or-CO-NR ¹⁷R ¹⁸, more preferably be hydrogen, alkyl group, the alkyl group that replaces, the aromatic yl group of aromatic yl group or replacement, especially preferred is hydrogen, the alkyl group of 1-10 carbon atom, the alkyl group of the replacement of 1-10 carbon atom, the aromatic yl group of the replacement of the aromatic yl group of 6-10 carbon atom or 6-10 carbon atom, most preferably, hydrogen, the alkyl group of 1-4 carbon atom, the alkyl group of the replacement of 1-4 carbon atom, the phenyl group of the replacement of phenyl or 6-10 carbon atom.

In structural formula (II), R ², R ³, R ⁶And R ⁷Be hydrogen independently of one another, halogen atom, cyano group, aliphatic group, aromatic group ,-O-R ²²,-CO-R ²³,-CO-O-R ²⁴,-NR ²⁵R ²⁶,-NHCO-R ²⁷,-NH-CO-O-R ²⁸,-SO ₂-R ²⁹Or-NH-SO ₂-R ³⁰Wherein, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰Be hydrogen, aliphatic group or aromatic group independently of one another.

In structural formula (II), R ⁴And R ⁶Be hydrogen independently of one another, aliphatic group, aromatic group ,-CO-R ³¹Or-SO ₂-R ³²R ³¹And R ³²Be aliphatic group or aromatic group independently of one another.

In structural formula (II), R ²And R ³, R ³And R ⁴, R ⁴And R ⁵, R ⁵And R ⁶, or R ⁶And R ⁷, can be bonded to each other forms a ring.Preferably, R ³And R ⁴Or R ⁵And R ⁶Form a ring.

Example and the definition of ring identical with described in the said structure formula (I).

By the arylene compound of structural formula (I) expression and as follows by the example of the azomethine compounds of structural formula (II) expression:

Arylene compound and azomethine compounds can be synthetic with reference to Japanese patent provisional publication numbers 52 (1977)-135335 and 3 (1991)-7931.

When arylene compound or azomethine compounds during as dyestuff, preferably, they are to be the solid fine particle state that is scattered in the medium.The example of dispersion medium comprises water and alcohols.Can be by use dispersion machine such as ball mill, vibromill, planetary ball mill, sand mill, colloidal mill, micronizer mill, roll mill mechanically prepare dye dispersion.In addition, also can use dispersion agent.In this case, dyestuff is dissolved in the appropriate solvent, adds the poor solvent of dyestuff then, thereby make the fine crystallization throw out deposition of dyestuff by dispersion agent.In addition, also can make these two steps of crystallization deposition thereby regulate the pH value then, and obtain the dyestuff of fine crystallization by dissolving dye in the solvent of proper pH value.

Suitable adhesive is added in the dye dispersion, so that preparation comprises the coating fluid of the layer usefulness of dyestuff.In addition, also can prepare this layer, carry out acidifying then so that the solid fine particle deposition of dyestuff according to the coating fluid of the salt of dissolving dye.In this case, the acidifying degree depends on the pka of the dissociation group (being carboxyl) of dyestuff.Can be by primary coat acid material in advance or by on described layer, applying acid material, and make this layer acidifying.

Tackiness agent as the layer that comprises dyestuff preferably uses hydrophilic natural or synthetic polymer.

Natural polymer is protein and polysaccharide.Proteinic example comprises: gelatin, albumin, casein and derivative thereof.The example of gelatine derivative comprises the graftomer of gelatin.The example of polysaccharide comprises: Mierocrystalline cellulose, dextrin, sodiun alginate, pectin, starch, gum arabic, and derivative.The example of derivatived cellulose comprises: Natvosol, Walocel MT 20.000PV, hydroxypropylcellulose, carboxymethyl cellulose, ethyl cellulose, methylcellulose gum, soluble cotton, and cellulose sulfuric acid ester.The example of starch derivative comprises: carboxymethyl starch.

The example of synthetic polymer comprises: polyalkylene oxide, polyvinyl alcohol, the polyvinyl alcohol of part acetalation; modified polyethylene alcohol, polyvinyl butyral, poly--the N-V-Pyrol RC; poly-ethyl oxazoline, polyvinyl methyl oxazoline, polyacrylic acid; polymethyl acrylic acid, acryl methyl propane sulfonic acid multipolymer, polymethyl acrylic acid; the multipolymer of maleic acid ester or toxilic acid acid amides; polyacrylamide, polyvinyl imidazol, and polyvinyl pyrazoles.Modified polyethylene alcohol is described in the Japanese patent provisional publication numbers 7 (1995)-219113, and other synthetic polymer is described among the EP678770 A2.

Natural or synthetic polymer also can play following dispersion agent.

As dispersion agent, can use tensio-active agent.The example of tensio-active agent comprises: anion surfactant (is described in US4,006,025; 5,104,776; EP678771 A2; With Japanese patent provisional publication number 62 (1987)-215272,63 (1988)-11935,63 (1988)-60446,1 (1989)-201655,4 (1992)-125548 and 4 (1992)-324858), nonionogenic tenside, amphoterics (is described in US3,542,581; With EP569074 A1), and fluorochemical surfactant (being described in EP602428A1).Preferably anion surfactant and nonionogenic tenside.Can be used in combination two or more tensio-active agents.

Natural or synthetic polymer also can be used as dispersion agent.Preferably be described in low-molecular weight polymer in the Japanese patent provisional publication numbers 60 (1985)-158437 (preferred, 1,500-2,000), and be described in US3, the non-ionic polymers in 860,425.

In the weight of dyestuff, the consumption of dispersion agent is preferably in the 1-200% weight range.

The fine grain median size of dyestuff is preferably from the 0.005-10 micron, more preferably from the 0.01-1 micron, especially preferably from the 0.01-0.5 micron, most preferably from the 0.01-0.1 micron.

Dyestuff (preferably being the solid fine particulate) is being mixed under the situation in the photographic silver halide material, and dyestuff will be included in the silver halide emulsion liquid layer or in the non-photosensitivity hydrophilic colloid layer.Which layer comprises dyestuff and will depend on purposes.

The colloid layer that comprises dyestuff plays antihalation layer or filtering layer.Antihalation layer is arranged between carrier and the emulsion layer, or is arranged on the carrier surface opposite with emulsion layer and (promptly is arranged on the back side of carrier).Yellow filtering layer is arranged between the emulsion layer of blue responsive emulsion layer and green sensitive, and the magenta filtering layer is between the emulsion layer of the emulsion layer of green sensitive and red sensitive.

In each above-mentioned layer (being antihalation layer, yellow filtering layer and magenta filtering layer), can comprise the dyestuff (preferably being the solid fine particulate) of structural formula (I).

Photographic silver halide material of the present invention preferably comprises: arylidene dyestuff or azomethine dyes, its consumption is from 5.0 * 10 ^-5To 5.0 gram/rice ², more preferably from 5.0 * 10 ^-4To 2.0 gram/rice ², especially preferably from 5.0 * 10 ^-3To 1.0 gram/rice ²Can be with two or more dye compositions in conjunction with being added in one deck, and can make a kind of dye composition be included in two-layer or multilayer in.The arylidene dyestuff of structural formula (I) can be used in combination with known dyestuff.

One of silver halide emulsion liquid layer in photographic material and non-photosensitivity hydrophilic colloid layer are prepared by hydrophilic colloid.Typical colloid is a gelatin.

Preferably the emulsion with Silver monobromide, iodine Silver monobromide, chlorine iodine Silver monobromide, chlorine Silver monobromide or silver chloride is used as silver halide emulsion.

Silver halide particle can be a particle diameter (diameter of view field) less than 0.1 micron superfine particle.In addition, described particle also can be a particle diameter greater than sizable particle of 10 microns.

It is monodispersed that preferable particle size distributes.In detail, in the particle gross weight, the particle of particle diameter in median size ± 20% scope preferably is no less than 60% weight, more preferably is no less than 80% weight.Monodispersed emulsion is described in US3, and 574,628; 3,655,394 and GB 1,413,748 in.

The silver halide particle of crystal habit can be regular shape (for example cube, octahedron, the tetrakaidecahedron), and difform (for example spheric is tabular) or its mix shape.In addition, crystallization has lattice imperfection (for example twin plane).

In the silver halide particle gross weight, comprise plain film shape particulate emulsion and preferably comprise: its amount is no less than 50%, and long-width ratio (corresponding circular diameter is divided by thickness) is 3 or bigger particle (according to shadow area).Plain film shape particle and preparation method thereof is described in Gutoff's " Photographic Science and Engineering " the 14th volume (1970), 248-257 page or leaf; US4,434,226; 4,414,310; 4,433,048; 4,439,520; And GB2, in 112,157.

Can prepare silver halide emulsion by known method, described method is described in: ResearchDisclosure (RD), and № 17,643,22-23 page or leaf (in December, 1978), (emulsion preparation and kind); Research Disclosure (RD), № 18,716, the 648th page (in November, 1979); Research Disclosure, № 307,105,863-865 page or leaf (in November, 1989); " the Chemie et Physique Photographique " of P.Glafkides publishes (1967) by Paul Montel; " the photograph emulsion chemistry " of G.F.Duffin published (1966) by Focal Press; With people's such as V.L. Zelikman " preparation of photograph emulsion and coating ", publish (1964) by Focal Press.

With regard to preparation includes the emulsion of wishing big or small silver halide particle, carry out nucleation and grain growth according to the bi-injection method of pAg control.In the method, under the condition that nucleogenesis does not take place again, under the supersaturation scope, control pAg.

In addition, also can prepare emulsion according to the method described in the Japanese patent provisional publication numbers 54 (1979)-48521.This method comprises the steps: the aqueous solution adding of potassiumiodide-aqueous gelatin solution and ammonium nitrate silver is comprised in the aqueous gelatin solution of silver halide particle.Add the speed time to time change.By this method,, can obtain highly monodispersed emulsion by making each condition optimizing (as adding the time dependence of speed, pH, pAg, and temperature of reaction).These conditions are described in the following document: " Photographic Science and Engineering " the 6th volume (1962), 159-165 page or leaf; " photograph science magazine " the 12nd volume (1964), the 242nd to 251 page; US3,655,394; And GB1,413,748.

With regard to the crystalline texture of silver halide particle, each particle has uniform halogen component or uneven halogen component.In inhomogeneous component, this component does not wait to inside from outer surface part.Described particle can have multilayered structure.Particle with inhomogeneous halogen component is described in GB1, and 027,146; US3 is in 505,068 and 4,444,877.In addition, by the epitaxy keying action, silver halide particle can with other silver halide particle combination with different halogen components.Described particle can combine with compound except that silver halide such as thiocyanation silver and plumbous oxide.

Preferably, particulate halogen component is distributed or described component just like core/shell structure or the such structure of bilayer structure.Particle with described structure is described in Japanese Patent publication number 43 (1968)-13162, in the Japanese patent provisional publication numbers 60 (1985)-222845,61 (1986)-75337 and 61 (1986)-215540.

In addition, described particle can also have three-decker (be described in Japanese patent provisional publication number 60 (1985)-222844) or multilayered structure.Also spendablely in addition be: the core/shell type particle, described particle has: the surface that covers with the silver halide thin layer of different halogen components.

Described particle can have composite structure and above-mentioned closing structure.Composite structure is described in Japanese Patent publication number 58 (1983)-24772; Japanese patent provisional publication numbers 58 (1983)-108526,59 (1984)-16254 and 59 (1984) 133540; In EP199290A2.In having the particle of composite structure, object (being compound) crystal has the halogen component different with host crystal.The object crystal is connected to the edge, the turning, or on the face of host crystal, described host crystal can have uniform halogen component or uneven halogen component, as core/shell structure.

Having the rock salt class can combine with the halogenation angle with the silver salt of outer structure (for example thiocyanation silver, silver carbonate) and form composite structure.In addition, non-silver salt such as Pb0 also can combine with silver halide.

In core/shell type iodine silver bromide grain, the content of Silver iodide can be higher or lower than the content of the Silver iodide in the shell part in the nuclear part.Similarly, in compound iodine silver bromide grain, the content of silver halide can be higher or lower than the content of silver halide in the object crystal in host crystal.

In the particle with even halogen component, the border between the halogen component can be clearly or spread.Diffusion term is made up of mixed crystal.For example can adopt the halogen component that changes gradually.

Can carry out various processing to silver halide emulsion.For example, EP0136727 B1 and 0064412 B1 have disclosed and have rounded the various processing of particulate, and DE2306447 C2 and Japanese patent provisional publication numbers 60 (1985)-221320 disclosed the various processing of particle surface being carried out modification.

In the present invention, use the silver halide emulsion of surperficial sub-image type usually.Yet,, also can adopt the emulsion of inner sub-image type by the developing solution of optimizing or the development conditions of optimization.Inner sub-image type emulsion is described in the Japanese patent provisional publication numbers 59 (1984)-133542.In addition, also can use particle wherein that the surperficial sub-image type silver halide emulsion (be described in Japanese patent provisional publication number 63 (1988)-264740 in) of shell is arranged.

For promoting the maturation of silver halide emulsion, the solvent that can use silver halide to use.In addition, it is ripe to be known that excessive halogen ion will promote, therefore, also can replace solvent, comes accelerates maturing in the reaction vessel by halogen is added into.Also can use the maturing agent beyond desolventizing, and can before silver salt and halogenide interpolation, be added in the reaction vessel.In addition, maturing agent can also be poured in the container with one or more silver salt, halogen or protective colloid.In addition, can irrespectively maturing agent be introduced in the container with silver salt and halid interpolation.

The example of the maturing agent except that the halogen ion comprises: ammonia, amine compound, and thiocyanate-such as ammonium thiocyanate and thiocyanic acid an alkali metal salt (particularly Sodium Thiocyanate 99 and potassium sulfocyanate).

Silver halide emulsion will stand chemical sensitization (sensibilized of chalcogen, precious metal sensibilized, or reduction sensibilized) usually.

(it is measured more than 1 * 10 being mixed with polyvalent metal ion ^-4Moles/mole silver) in the silver halide particle, the influence that causes by doping did not observe before chemical sensitization.Yet after chemical sensitization, this influence will be extremely tangible.According to the particulate terms and conditions, as component, structure and shape, and, the position of chemical sensitization nuclear is set also according to the purposes of emulsion.For example, can be with renucleation particulate centre portions or surface portion.In addition, nuclear can also be formed on the particulate surface.If nuclear is arranged near surface, so, can expect has tangible influence.Therefore, the mixing of polyvalent metal ion, surperficial sub-image type emulsion will be more more effective than inner sub-image type emulsion.

Chemical sensitization can be according to the photograph procedural theory (The Theoryof the Photographic Process) of T.H.James the 4th edition, and 67-76 page or leaf (1977) utilizes active gelatin(e) to carry out.According to Research Disclosure the 120th volume, № 12010 (in April, 1974); Research Disclosure the 34th volume, № 13452 (in June, 1975); US2,642,361; 3,297,446; 3,772,031; 3,857,711; 3,901,714; 3,904,415; 4,266,018; And GB1,315,755, the condition of sensitizing can be adjusted at: pAg5-10, pH5-8 and 30-80 ℃.

The sensitizing agent that is used for the sensibilized of chalcogen is: the compound of sulphur, selenium and tellurium.For the sensibilized of precious metal, sensitizing agent is the compound of gold, platinum, palladium and iridium.Two or more sensitizing agents can be used in combination.In the sensibilized of gold, gold compound can be used in combination with sulfocyanate compound.The example (being sulfur sensitizer) that is used for the sulphur compound of sensitizing agent comprising: Sulfothiorine, thiourea compound and rhodanic acid compound.Sulfur sensitizer is described in US3, and 857,711; In 4,266,018 and 4,054,457.

Can carry out chemical sensitization in the presence of the chemical sensitization auxiliary agent, described auxiliary agent will suppress the photographic fog in the sensitizing.The sensitization auxiliary agent also will strengthen susceptibility.The example of chemical sensitization auxiliary agent comprises: azepine indenes, azepine pyridine, and aza-pyrimidine.Chemical sensitization auxiliary agent (or chemical sensitization properties-correcting agent) is described in US2,131,038; 3,411,914; 3,554,757; Japanese patent provisional publication numbers 58 (1983)-126526; With the 138th to 143 page of the photograph emulsion chemistry of G.F.Duffin.

The present invention can be used for color photographic material and monochrome photography material effectively.

The example of color photographic material comprises: chromatics paper, colorful film and colour reversal film.Monochrome photography examples of material: X ray film, black and white film and the film that is used to print.

Color photographic material has multilayered structure usually, and comprises: two or more silver halide emulsion liquid layers and two or more non-photosensitivity hydrophilic colloid layer.The non-photosensitivity hydrophilic colloid layer is the protective layer on the emulsion layer of top, the middle layer between the emulsion layer, and the undercoat between end emulsion layer and the carrier, and be provided at backing layer on the carrier basal surface (emulsion layer is not provided on it).Which the layer comprise dyestuff will according to dyestuff be used for determine.Play at dyestuff under the situation of spectral filter effect, dyestuff is mixed in protective layer or the middle layer.On the other hand, in the dyestuff adding undercoat or backing layer with antihalation, be included in the emulsion layer and suppress the radiating dyestuff.

Additive for photographic material of the present invention has no particular limits.The example of described additive is described in following Research Disclosure, the 176th volume, and № 17643 (RD17643) and Research Disclosure, the 187th volume is among the № 18716 (RD18716).

Dyestuff can be mixed in the photographic silver halide material that adds thermal development.The material that adds thermal development is described in US4, and 500,626; EP2 10660 A2; In the Japanese patent provisional publication numbers 59 (1984)-218443,60 (1985)-133449 and 61 (1986)-238056.

The present invention is particularly suitable for the wet developing method.

Utilize the wet developing method of automatic processing machine to be described in Japanese patent provisional publication number 3 (1991)-13937[20-21,25,30-33,40,45-46,52-53 page or leaf], 3 (1991)-171136[18-19 pages or leaves] and the 27th page of 6 (1994)-43583[] in.

Color photographic material will be by developing bleaching-photographic fixing or photographic fixing, and washing or static stabilization usually after the imaging exposure.

In 1 square metre of photographic material, develop or photographic fixing in the consumption of photographic developer be preferably the 25-200 milliliter, 30-180 milliliter more preferably, especially preferred is from the 60-150 milliliter.

The development treatment time preferably is lower than 5 minutes, and more preferably from 5-60 second, especially preferred is 5-30 second.

For conserving water, carry out washing process according to the countercurrent washing method usually.Substitute washing process, can carry out stabilization procedures according to multistage counter current stabilising method (be described in Japanese patent provisional publication number 57 (1982)-8543 in).

Color developer is preferably: comprise the basic solution as main color developer component, primary aromatic amine.In addition, aminophenol compound also can be used as color developer, but Ursol D compound preferably.The example of Ursol D compound comprises: 3-methyl-4-amino-N, the N-Diethyl Aniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-Toluidrin ethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-methoxy-ethylaniline, its vitriol, its muriate, with and tosilate.

Under the situation of carrying out reversal process, coupling development is carried out after black-and-white development usually.The example of black-and-white development agent comprises: dihydroxy-benzene (for example quinhydrones), 3-pyrazolidone (for example, 1-phenyl-3-pyrazolidone), and amino-phenol (for example, N-methyl-p-aminophenol).

The pH value of colour or black-and-white development agent is usually from 9-12.

Emulsion layer bleaching after developing usually.Bleaching process can carry out (i.e. bleaching-fixing) or irrespectively carry out with fixing with photographic fixing.In addition, be the accelerate process process, can after bleaching process, bleach-the photographic fixing processing.For bleaching bath or bleaching-fixing bath, useful is to use the amino polycarbonate complex salts of iron (III).The bleaching bath or the bleaching-fixing bath that comprise above-mentioned salt, its pH value be usually from 5.5-8, but be accelerate process, also can be lower than described pH scope.

If desired, bleach boosters can be used for bleaching bath, bleaching-fixing bath, or its pre-bath in (prebath).The example of bleach boosters is for having the compound of sulfydryl or dithio group (disulfido group).Bleach boosters can be mixed in the photographic material.

As fixing salt, use thiosulphate usually.

After the desilverization, photographic material will stand washing or stabilization procedures usually.The water yield of washing usefulness is determined (characteristic of photographic material and purposes, water temperature, the quantity of washing container, and the photographic developer system is as falling liquid system or counter current system) according to various conditions.In multistage counter current washing system, the relationship description between the washing container and the water yield is in Journal of the Societyof Motion Picture and Television Engineers, the 64th volume, 248-253 page or leaf (May nineteen fifty-five).

Embodiment 1

Synthesizing of compound (3)

1.2 liters of ethanol and 308 are digested compound (1) put into three-necked distilling flask.Under stirring at room, digest compound (2) with 10 minutes times with 228 and be added in this flask.After again this mixture being stirred 3 hours, with dropping in the 1 hour solution that dissolved 198 gram sodium hydroxide make in 1080 ml waters.When adding end, the temperature in the flask is 35 ℃.After restir 1.5 hours, reaction mixture is poured in 6 liters of methyl alcohol.With 412 milliliters of concentrated hydrochloric acids of dropping in 30 minutes, then mixture was stirred 1 hour.Under reduced pressure filter this mixture then, so that collect sedimentary crystalline deposit thing.Wash throw out with water and carry out drying, obtain 354 and digest compound (3) [yield: 95%].

400 milliliters of tetramethylene sulfones are put into three-necked distilling flask.In nitrogen atmosphere, stirring down, digest compound (3) with 310 to be added in this flask, and adding 268 digests compound (4) in proper order.With this mixture heating up to 90 ℃, and under this temperature,, drip 24.0 gram methylsulfonic acids with 3 minutes time.After 135 ℃ of heating and stirring 1 hour, make mixture cooling and pour in the methyl alcohol of 1.5 liters of stirrings.After again this mixture being stirred 1 hour, under reduced pressure filter this mixture, so that collect sedimentary crystalline deposit thing.This throw out is carried out drying, obtain 404 and digest compound (5) [yield: 88%].

420 gram acetate are put into three-necked distilling flask.Utilize ice bath to make the flask cooling, be not higher than 50 ℃, and drip 283 gram triethylamines to cause the temperature in the flask.In addition, add 257 in proper order and digest compound (5) and 109.3 gram methyl aceto acetates.This mixture after 90 ℃ of heating and stirring 5 hours, is made mixture cooling and pours in the methyl alcohol of 2 liters of stirrings.With 30 minutes time, 292 milliliters of concentrated hydrochloric acids are dropped in this mixture.This mixture was stirred 1 hour, and under reduced pressure filter, so that collect sedimentary crystalline deposit thing.This throw out is carried out drying, obtain 280 and digest compound (6) [yield: 92%].

Digest compound (6) and 1.2 liters of ethanol are put into three-necked distilling flask with 260.When stirring, will in 650 ml waters, dissolve 120 with 30 minutes times and restrain the drips of solution that sodium hydroxide make and add in this flask.Again this mixture was stirred 2 hours, pour 2.2 liters of methyl alcohol then into.Under agitation, with time of 20 minutes 330 milliliters of concentrated hydrochloric acids are dropped in this mixture.Again mixture was stirred 1 hour, under reduced pressure filter this mixture then, so that collect sedimentary crystalline deposit thing.Throw out is carried out drying, obtain 241 and digest compound (7) [yield: 99%].

Synthesizing of arylene compound compound (I-1)

Digest compound (7) with 109.4,56.8 digest compound (8) and 2.2 liters of acetate are put into three-necked distilling flask.Stir down, 193 gram diacetyl oxides are added in this flask.After 100 ℃ of heating and stirring 2 hours, make mixture be cooled to room temperature.Mixture is carried out filtration under diminished pressure, so that collect sedimentary crystalline deposit thing.Sequentially use acetate, acetone and methyl alcohol wash throw out, obtain the arylene compound (I-1) that 384 grams are the wet pie of methyl alcohol [yield: 97%, dyestuff content: 38.3%].

Embodiment 2

Synthetic (II-3) of azomethine compounds

Compound (7) 203 grams and 600 ml methanol that make among the embodiment 1 are put into three-necked distilling flask.70 milliliters of triethylamines are added in this flask in room temperature, stirring down.Again this mixture was stirred 10 minutes, add 100 then and digest compound (9).With 30 minutes, Dropwise 52 ml acetic anhydride sequentially.In room temperature this mixture was stirred 4 hours, carry out filtration under diminished pressure then, to collect sedimentary crystalline deposit thing.Sequentially use methyl alcohol, acetone and methyl alcohol wash throw out, obtain the azomethine compounds (II-3) that 488 grams are the wet pie of methyl alcohol [yield: 85%, dyestuff content: 48.3%].

Embodiment 3

Synthesizing of arylene compound (I-3)

The compound (7) that 109.4 grams are made among the embodiment 1,61.3 digest compound (10) and 2.5 liters of acetate are put into three-necked distilling flask.Stir down, 193 gram diacetyl oxides are added in this flask.Stir down, this mixture heating up was refluxed 4 hours, be cooled to room temperature then.Resulting mixture is carried out filtration under diminished pressure, so that collect sedimentary crystalline deposit thing.Sequentially use acetate, methyl alcohol, acetone and methyl alcohol wash throw out, obtain the arylene compound (I-3) that 350 grams are the wet pie of methyl alcohol [yield: 97%, dyestuff content: 43.0%].

Embodiment 4

Synthesizing of compound (12)

With the compound (5) that 100 gram embodiment 1 make, 62.8 digest compound (11), and 31 milliliters of acetate and 200 milliliters of ethylene glycol add in the three-necked distilling flask.In this flask, drip 310 milliliters of Tri-n-Propylamines under the room temperature.After 110 ℃ of heating and stirring 3 hours, this mixture is cooled to 40 ℃, and pours in the 1000 gram ice.Stir down, 280 milliliters of concentrated hydrochloric acids are dropped in this mixture with 10 fens clock times.Again mixture was stirred 1 hour, and carry out filtration under diminished pressure, so that collect sedimentary crystalline deposit thing.Throw out is mixed with 300 milliliters of acetonitriles, and under agitation refluxed 1 hour.Make this mixture be cooled to room temperature, and carry out filtration under diminished pressure, so that collect sedimentary crystallized product.Finally obtain 115.3 and digest compound (12) [yield: 85%].

Synthesizing of compound (13)

Digest in compound (12) and the 250 ml methanol adding three-necked distilling flask 49.5.In room temperature, stir down, will in 40 ml waters, dissolve 20 with 5 minutes times and restrain the solution that sodium hydroxide make and add in the flask.After stirring 2 hours in addition, mixture is poured in the 400 gram ice.Stir down, 86 milliliters of concentrated hydrochloric acids are added in this mixture.Again this mixture was stirred 10 minutes, and concentrate, obtain remaining compound (13) by rotary evaporator.Product is not further purified and be used for following synthetic.

Synthetic (I-12) of arylene compound

With top compound (13), 21.0 digest compound (8), 150 milliliters of acetate, and 66.0 milli diacetyl oxides add in the three-necked distilling flask.In 90 ℃ this mixture heating up was stirred 4 hours, be cooled to 50 ℃ then.After adding 150 ml methanol, mixture is cooled to room temperature, and carries out filtration under diminished pressure, to collect sedimentary crystalline deposit thing.Sequentially throw out is washed, obtain 130.1 arylene compounds (I-12) [yield: the amount with compound (12) counts 95%, dyestuff content: 45.6%] that are the wet pie of methyl alcohol with methyl alcohol, acetone, water and methyl alcohol.

Embodiment 5

The fine grain dispersion of dye solids

With 21.7 ml waters, 3 milliliter of 5% weight to Octylphenoxy oxyethyl group ethyl sulfonic acid sodium water solution and 0.5 gram, 5% weight (polymerization degree: 10) aqueous solution adds in 700 milliliters the ball mill to the Octylphenoxy Soxylat A 25-7.5.0 gram arylene compounds (I-1) and 500 milliliters of zirconium white beads (diameter: 1 millimeter) are added in this ball mill, then by using the vibration ball mill to mix 2 hours (BO type, Chuo-Koki Co.Ltd.).The mixture that collection obtains, and with 8 the gram, 2.5% weight aqueous gelatin solution add in this mixture.The mixture that obtains is filtered, so that remove bead.So, made the gelatin dispersion [median size of dyestuff: 0.36 micron] of arylene compound (I-1).

The preparation of photographic silver halide material

Preparation has the color silver halide photographic material (be described in Japanese patent provisional publication number 11 (1999)-38568) of following laminate structure.The second layer (second antihalation layer) comprises the fine grain dispersion of arylene compound (I-1) solid, and its content is 0.10 gram/rice ²

The component of the 2nd layer (second antihalation layer) is as follows.Each layer except that the 2nd layer all comprises: with the identical component of common known color silver halide photographic material.

The assessment of photographic material

Make photographic material carry out white light exposure by wedge, handle by automatic processing machine in the following manner then.In advance developing machine is adjusted, is carried out described treating processes, when photographic developer builds up to three times more than of mother liquor tank photographic developer volumes till.

Photographic density to the material handled is measured, with the density [DR (min)] in the grey fog-zone of determining the red sensitive emulsion layer.According to based on following Comparative Examples 1 relative value of consequence, the DR (min) that obtains is assessed.According to resulting DR (min) value, the decolouring of dyestuff is assessed.Usually, the DR in the grey fog-zone (min) value is little, represents dye decolored good.

In addition, according to relative value, the susceptibility of red sensitive emulsion layer is assessed.By measuring the light quantity that produces+0.2 Fog density, calculate the logarithm inverse of measured amount, this calculated value is converted to based on following Comparative Examples 1 relative value of consequence then, and determine described relative susceptibility value.Usually, high susceptibility relatively refers to, and the dyestuff in second antihalation layer diffuses in the red sensitive emulsion layer hardly.

In addition, also utilize following method, the stability of dyestuff is assessed.At first, under the IR lamp, measure the exposure reflection spectrum (in the wavelength region may of 400-700 sodium rice) of photographic material before.Then, under 50 ℃ and 80% relative humidity, this material is stored 10 days in black box.After storing 10 days, under the IR lamp, measure the reflection spectrum in the above-mentioned wavelength region once more.Calculate the ratio of 550 nanometers and 650 nanometers absorbancys according to following formula, so that assess the stability of dyestuff.

Dye stability (absorbancy ratio)=

100 * (absorbancy before storing)/(storing the back absorbancy)

The results are shown in Table 1.

Embodiment 6-12

Repeat the step of embodiment 5, so that the fine grain dispersion of preparation dye solids, different is, with 5.0 gram arylene compounds (I-3), (I-6), (I-12), (I-14), (I-16), or azomethine compounds (II-3) or (II-9) substitute 5.0 gram arylene compounds (I-1).The median size of each dispersion is listed in the table 1.

Except that using each dispersion that makes, repeat the step of embodiment 5, so that the preparation siliver halide photosensitive material.With the method identical, the material that makes is assessed with embodiment 5.

The results are shown in Table 1.

Comparative Examples 1-6

Repeat the step of embodiment 5, so that the fine grain dispersion of preparation dye solids, different is, with the 5.0 gram oxonol compounds of listing below (X-1), (X-2), azomethine compounds (Y-1), (Y-2), or arylene compound (Z-1) or (Z-2) substitute 5.0 gram arylene compounds (I-1).The median size of each dispersion is listed in the table 1.

In the Japanese patent provisional publication numbers 3 (1991)-7931, with azomethine compounds (Y-1), (Y-2), and arylene compound (Z-1) and (Z-2) be described as compound (5) respectively, (7), (27) and (6).

Except using each dispersion that makes, repeat the step of embodiment 5, so that the preparation siliver halide photosensitive material.With the method identical the material that makes is assessed with embodiment 5.

The results are shown in Table 1.

Table 1

Annotate)

*: red sensitive silver halide emulsion liquid layer,

*: relative sensitivity,

The standard of * *: D (min) and relative sensitivity.

Embodiment 13

The preparation of photographic silver halide material

Preparation has the X-roentgenogramX material (be described in Japanese patent provisional publication numbers 3 (1991)-7931, embodiment 5) of following laminate structure.Dye coating comprises: the fine grain dispersion of arylene compound (I-1) solid of preparation among the embodiment 1.

Sealer

The silver halide emulsion liquid layer of X-radiation-sensitive

Dye coating (comprises content and is respectively 0.12 gram/rice ²With 50 milligrams/meter ²Gelatin and dye dispersion)

Carrier (dye blueness and thickness be 175 microns polyethylene terephthalate)

The silver halide emulsion liquid layer of X-radiation-sensitive

Sealer

The assessment of photographic material

Photographic material is placed between two coverts (G-3, Fuji Photo Film Co.Ltd), and carries out the X-x ray exposure x by the water phantom (water phantom) of 10cm.

By automatic processing machine (FPM-4000, Fuji Photo Film Co.Ltd) material that exposes is carried out processing treatment.

Determine susceptibility according to relative value, precondition is not have the sample susceptibility of dyestuff to be set in 100.

In optical density(OD) is 1.0 zone, also bright acutance (MTF) is assessed [aperture: 30 microns * 500 microns, spatial frequency: 1.0 circle/millimeters].

In addition, unexposed material is handled, so that its decolourising property is assessed by developing machine.With five grades of A-E bleaching level is assessed.Grade A represents: dyestuff decolours fully, and grade E represents that dyestuff keeps its color substantially.Grade B-D represents: the degree between grade A and E.

The results are shown in the row 2.

Embodiment 14-20

Repeat the step of embodiment 1, so that the fine grain dispersion of preparation dye solids, different is, with 5.0 gram arylene compounds (I-4), (I-18), (I-25), or azomethine compounds (II-1), (II-6) or (II-11) alternative 5.0 restrain arylene compounds (I-1).The median size of each dispersion is listed in the table 2.

The arylene compound (I-12) that in using prepared each dispersion and embodiment 8, makes, repeat the step of embodiment 13, so that the preparation photographic silver halide material.With the method identical, the material that makes is assessed with embodiment 13.

The results are shown in Table 2.

Comparative Examples 7

The fine grain dispersion of solid of the azomethine compounds (Y-2) that in using Comparative Examples 4, makes, repeat the step of embodiment 13, so that the preparation photographic silver halide material.With the method identical, the material that makes is assessed with embodiment 5.

The results are shown in Table 2.

Table 2

Embodiment 21

The preparation of photographic silver halide material

Preparation has the photographic material (be described in Japanese patent provisional publication numbers 3 (1991)-7931, embodiment 7) of following laminate structure.Antihalation layer comprises the fine grain dispersion of arylene compound (I-1) solid, and its content is 0.10 gram/rice ²

The 7th layer (protective layer)

The 6th layer (UV absorption layer)

The 5th layer (the responsive blue milk liquid layer of IR-)

The 4th layer (UV absorption layer)

The 3rd layer (the responsive magenta emulsion layer of IR-)

The 2nd layer (preventing the layer of blend of colors)

The 1st layer (the responsive yellow emulsion layer of IR-)

Antihalation layer (comprise its content and be respectively 0.8 gram and 77 milligrams gelatin and dye dispersion)

Carrier (paper of the laminated polyethylene film in two sides)

The assessment of photographic material

Make photographic material carry out the imaging exposure, and handle by colored paper sheet handling machine.The pictorial display that so obtains goes out high resolving power and sharp keen edge.

Embodiment 22-27

Repeat the step of embodiment 1, so that the fine grain dispersion of preparation dye solids, different is, with 5.0 gram arylene compounds (I-8), (I-19), or azomethine compounds (II-4), (II-7) or (II-8) alternative 5.0 restrain arylene compounds (I-1).

Except that the arylene compound (I-12) that uses each dispersion that makes and embodiment 8 to make, repeat the step of embodiment 21, so that the preparation photographic silver halide material.With the method identical with embodiment 21 material that makes is assessed, the result proves that each material will provide the image of high resolving power and sharpened edge.

Claims

1. arylene compound by structural formula (I) expression:

In the formula:

L ¹And L ²Independently of one another for straight or branched alkylidene group, alkenylene with straight or branched of 2-20 carbon atom with 1-20 carbon atom, have straight or branched alkynylene, phenylene or the naphthylidene of 2-20 carbon atom, wherein at least two carbon atoms have the single bonded 5-unit of dissociating or the first saturated or unsaturated heterocycle of 6-, wherein, above-mentioned group can also have the halogen atom of being selected from, cyano group, nitro, carboxyl,-OR,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl;

L ³Be cyclonite, five methynes or seven methynes;

Y is=O ,=S or=N-R ¹⁰, R wherein ¹⁰Be hydrogen, aliphatic group, aromatic group or heterocyclic group as giving a definition;

R ¹Be hydrogen, halogen atom, cyano group, nitro, as the aliphatic group of giving a definition, aromatic group or heterocyclic group ,-OR ¹¹,-SR ¹²,-COOR ¹³,-OCOR ¹⁴,-NR ¹⁵R ¹⁶,-CO-NR ¹⁷R ¹⁸,-SO ₂R ¹⁹Or-SO ₂-NR ²⁰R ²¹, R wherein ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Be hydrogen, aliphatic group or aromatic group independently of one another as giving a definition;

R ², R ³, R ⁶And R ⁷Be hydrogen independently of one another, halogen atom, cyano group, as aliphatic group of giving a definition or aromatic group ,-O-R ²²,-CO-R ²³,-CO-O-R ²⁴,-NR ²⁵R ²⁶,-NHCO-R ²⁷,-NH-CO-O-R ²⁸,-SO ₂-R ²⁹Or-NH-SO ₂-R ³⁰, wherein, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ²⁹And R ³⁰Be hydrogen, aliphatic group or aromatic group independently of one another as giving a definition;

R ⁴And R ⁵Independently of one another for hydrogen, as the aliphatic group of giving a definition or aromatic group ,-CO-R ³¹Or-SO ₂-R ³², wherein, R ³¹And R ³²Be aliphatic group or aromatic group independently of one another;

Above-mentioned aliphatic group comprises straight or branched alkyl, the thiazolinyl with straight or branched of 2-20 carbon atom with 1-20 carbon atom, straight or branched alkynyl and the aralkyl with 2-20 carbon atom, described aralkyl comprises moieties with 1-20 carbon atom and the aryl moiety that is selected from phenyl or naphthyl, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl,-OR,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl;

Above-mentioned aromatic group comprises phenyl and naphthyl, and these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl;

Above-mentioned heterocyclic group comprises the saturated or unsaturated heterocycle group of 5-and 6-unit, and these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl;

Wherein, R ²And R ³, R ³And R ⁴, R ⁴And R ⁵, R ⁵And R ⁶, or R ⁶And R ⁷, can be bonded to each other forms a ring.

2. arylene compound as claimed in claim 1, wherein L ³Be cyclonite.

3. arylene compound as claimed in claim 1, wherein Y is=O.

4. arylene compound as claimed in claim 1, wherein, R ¹Be hydrogen, have 1-20 carbon atom the straight or branched alkyl, have the straight or branched of 2-20 carbon atom thiazolinyl, have straight or branched alkynyl, the aralkyl of 2-20 carbon atom, described aralkyl comprises moieties with 1-20 carbon atom and aryl moiety, the phenyl or naphthyl that is selected from phenyl or naphthyl, and these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl.

5. arylene compound as claimed in claim 1, wherein, R ²And R ⁷Be hydrogen independently of one another, have the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl; R ³And R ⁶The hydrogen of respectively doing for oneself; R ⁴And R ⁵Be hydrogen independently of one another, have straight or branched alkyl, the phenyl or naphthyl of 1-20 carbon atom, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl; And, R ³And R ⁴Or R ⁵And R ⁶Be bonded to each other and form a ring.

6. a photographic silver halide material comprises carrier, silver halide emulsion liquid layer and non-photosensitivity hydrophilic colloid layer, and wherein silver halide emulsion liquid layer or non-photosensitivity hydrophilic colloid layer comprise the arylidene dyestuff of structural formula (I) expression:

Wherein:

L ³Be cyclonite, five methynes or seven methynes;

7. photographic silver halide material as claimed in claim 6, wherein the arylidene dyestuff by structural formula (I) expression is the solid fine particulate, and described particles dispersed is in silver halide emulsion liquid layer or non-photosensitivity hydrophilic colloid layer.

8. photographic silver halide material as claimed in claim 6, wherein L ³Be cyclonite.

9. photographic silver halide material as claimed in claim 6, wherein Y is=O.

10. photographic silver halide material as claimed in claim 6, wherein R ¹Be hydrogen, have 1-20 carbon atom the straight or branched alkyl, have the straight or branched of 2-20 carbon atom thiazolinyl, have straight or branched alkynyl, the aralkyl of 2-20 carbon atom, described aralkyl comprises moieties with 1-20 carbon atom and aryl moiety, the phenyl or naphthyl that is selected from phenyl or naphthyl, and these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl.

11. photographic silver halide material as claimed in claim 6, wherein, R ²And R ⁷Be hydrogen independently of one another, have the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl; R ³And R ⁶The hydrogen of respectively doing for oneself; R ⁴And R ⁵Be hydrogen independently of one another, have straight or branched alkyl, the phenyl or naphthyl of 1-20 carbon atom, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl; And, R ³And R ⁴Or R ⁵And R ⁶Be bonded to each other and form a ring.

12. azomethine compounds by structural formula (II) expression:

In the formula: L ¹And L ²Independently of one another for straight or branched alkylidene group, alkenylene with straight or branched of 2-20 carbon atom with 1-20 carbon atom, have straight or branched alkynylene, phenylene or the naphthylidene of 2-20 carbon atom, wherein at least two carbon atoms have the single bonded 5-unit of dissociating or the first saturated or unsaturated heterocycle of 6-, wherein, above-mentioned group can also have the halogen atom of being selected from, cyano group, nitro, carboxyl,-OR ,-SR ,-COOR,-OCOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl;

13. azomethine compounds as claimed in claim 12, wherein Y is=O.

14. azomethine compounds as claimed in claim 12, wherein R ¹Be hydrogen, have 1-20 carbon atom the straight or branched alkyl, have the straight or branched of 2-20 carbon atom thiazolinyl, have straight or branched alkynyl, the aralkyl of 2-20 carbon atom, described aralkyl comprises moieties with 1-20 carbon atom and aryl moiety, the phenyl or naphthyl that is selected from phenyl or naphthyl, and these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl.

15. azomethine compounds as claimed in claim 12, wherein R ²And R ⁷Be hydrogen independently of one another, have the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl; R ³And R ⁶The hydrogen of respectively doing for oneself; R ⁴And R ⁵Be hydrogen independently of one another, have straight or branched alkyl, the phenyl or naphthyl of 1-20 carbon atom, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl; And, R ³And R ⁴Or R ⁵And R ⁶Be bonded to each other and form a ring.

16. a photographic silver halide material comprises carrier, silver halide emulsion liquid layer and non-photosensitivity hydrophilic colloid layer, and wherein silver halide emulsion liquid layer or non-photosensitivity hydrophilic colloid layer comprise the azomethine dyes by structural formula (II) expression:

17. photographic silver halide material as claimed in claim 16, wherein the azomethine dyes by structural formula (II) expression is the solid fine particulate, and described particles dispersed is in silver halide emulsion liquid layer or non-photosensitivity hydrophilic colloid layer.

18. photographic silver halide material as claimed in claim 16, wherein Y is=O.

19. photographic silver halide material as claimed in claim 16, wherein R ¹Be hydrogen, have 1-20 carbon atom the straight or branched alkyl, have the straight or branched of 2-20 carbon atom thiazolinyl, have straight or branched alkynyl, the aralkyl of 2-20 carbon atom, described aralkyl comprises moieties with 1-20 carbon atom and aryl moiety, the phenyl or naphthyl that is selected from phenyl or naphthyl, and these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl.

20. photographic silver halide material as claimed in claim 16, wherein R ²And R ⁷Be hydrogen independently of one another, have the straight or branched alkyl or the alkoxyl group of 1-20 carbon atom, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl; R ³And R ⁶The hydrogen of respectively doing for oneself; R ⁴And R ⁵Be hydrogen independently of one another, have straight or branched alkyl, the phenyl or naphthyl of 1-20 carbon atom, these groups can also have the halogen atom of being selected from, cyano group, nitro, carboxyl ,-OR ,-SR ,-COOR ,-NR ₂,-CO-NR ₂,-SO ₂R or-SO ₂NR ₂Substituting group, wherein R is C _1-4Alkyl; And, R ³And R ⁴Or R ⁵And R ⁶Be bonded to each other and form a ring.