CN1221852C - Silver halide photographic emulsions and photographic sensitive material using same - Google Patents

Abstract

An object of the present invention is to provide a silver halide photographic light-sensitive material which is reduced in the various problems ascribable to the multilayer adsorption of a sensitizing dye. A silver halide photographic emulsion comprising a silver halide grain having adsorbed on the surface thereof a sensitizing dye in multiple layers is described, wherein the variation coefficient of the light absorption strength distribution among the grains is 100% or less.

Description

The sensitive photographic material of silver halide photographic emulsions and this emulsion of use

Technical field

The present invention relates to use a kind of sensitive photographic material of spectral sensitization silver halide photographic emulsions.

Background technology

Up to now, for obtaining the more silver halide photographic sensitive material of ISO, people have done a large amount of work.In silver halide photographic emulsions, the sensitizing dye that is adsorbed on the silver halide particle surface absorbs the light that enters photosensitive material, and luminous energy is passed to silver halide particle, thereby obtains light sensitivity.Therefore, in the spectral sensitization of silver halide,, can increase the luminous energy that passes to silver halide, thereby improve spectral sensitivity by increasing the absorptance of silver halide particle per unit grain area.Be adsorbed on the quantity of the spectral sensitizing dye on the per unit grain area by increase, can improve the absorptance on silver halide particle surface.

Yet the quantity that is adsorbed on the sensitizing dye on silver halide particle surface is limited, and the dye chromophore of absorption can not surpass the saturated absorption of individual layer (being one deck absorption).Therefore, at present with regard to the incident light quantum in the spectral sensitization zone, the absorptivity of each silver halide particle is low.

For addressing these problems, following method has been proposed.

Photographic Science and Engineering, Vol.20, No.3, among the Page97 (1976), P.B.Gilmal, people such as Jr. disclose a technology, wherein utilize electrostatic force, and the dye of positive ion is adsorbed on ground floor, and anionic dye is adsorbed on the second layer.

Disclose a technology in the USP 3,622,316 of G.B.Bird etc., the form of wherein multiple dyestuff multilayer absorption is adsorbed onto on the silver halide; The transfer of Forster type excitation energy takes place for promoting sensitizing to make.

In people's such as Sugimoto JP-A-63-138341 (terminology used here " JP-A " meaning is " not examining disclosed Japanese patent application ") and JP-A-64-84244, disclose the energy that utilizes luminescent dye and shifted the technology of carrying out spectral sensitization.

Photographic Science and Engineering, Vol.27, No.2, among the Page59 (1993), people such as R.Steiger disclose and have utilized the energy of the cyanine dyes that is replaced by gelatin to shift the technology of carrying out spectral sensitization.

In JP-A-61-251842, people such as Ikegawa disclose the technology of being carried out spectral sensitization by the energy of cyclodextrin replacement dye transfer of utilizing.

In addition, in EP-A-0985964, EP-A-0985965 and EP-A-0985966, people such as Richard Parton disclose a kind of technology, wherein be transferred in the dyestuff in the ground floor and obtain ISO, the assembly of the dye of positive ion and anionic dye is adsorbed in the multilayer for the energy that makes the dyestuff in the second layer or the upper strata.

Yet in these methods, the degree of absorption of sensitizing dye is actually absorptance or all enough highland growths of light sensitivity of the per unit granule surface area of inadequate and silver halide particle in the multilayer on silver halide particle surface.Need a kind of technology that can strengthen the interaction between the dye molecule and in fact realize effective multilayer absorption thus.

On the other hand, when the interaction between the molecule is enhanced and in fact effectively multilayer absorption is implemented, find to have the following problem of not expecting to produce:

(1) make the reduction of light sensitivity and the softening of contrast owing to the non-uniform Distribution of dyestuff adsorbance in particle,

(2) because island absorption makes light sensitivity reduce and the deterioration of granularity and

(3) owing to the photographic first being processed and afterwards between the less variation of absorption spectrum make the quality of image reduce.

These phenomenons are described in down.

Interaction between dye molecule is to be enhanced so that realized multilayer absorption, and the distribution of finding the dyestuff adsorbance is the non-uniform Distribution that depends among the particle.In common monolayer adsorption, amount growth along with the sensitizing dye that adsorbs, the amount of dye of absorption be distributed in particle among become more even, therefore, the above-mentioned non-uniform Distribution of dyestuff adsorbance is the result of a unanticipated under the situation of multilayer absorption fully.In addition, than monolayer adsorption, the problem that is caused by the non-uniform Distribution of dyestuff adsorbance is extremely serious and this also is a unexpected phenomenon.

And the interaction between dye molecule is enhanced so that realized multilayer absorption, finds that dyestuff in the second layer and upper strata does not increase and fails with the form of layer to exist with layer state, but increases and exist with the island attitude with the island form.In common monolayer adsorption, be well known that the growth of the adsorbance of sensitizing dye, dyestuff increases on silver halide particle with the stratiform form and finally exists with layer state.Therefore, if make them increase and exist, then be a phenomenon that unanticipated arrives with the island attitude as island in the behavior of the dyestuff in the second layer and upper strata under the situation of multilayer absorption.And, the dyestuff in the second layer and upper strata as island increase and situation about existing with the island attitude under, find that not only optical absorption intensity and light sensitivity are lowered, and the quality of image worsens also, and has unexpected problem.The interaction that is used to set up the multilayer adsorption structure consists essentially of two kinds of interactions, promptly (1) between the dye molecule of the dye molecule of ground floor and the second layer interaction and the interaction between (2) dye molecule in the second layer.That analyzes found that, if the interactional ratio between the dye molecule (b) in the second layer increases, then being distributed in of dyestuff adsorbance widened in the particle and island absorption also is easy to take place.

In addition,, find to increase by multilayer absorption and to have under the situation of emulsion of high photon absorbing intensity though reason is ignorant, if in the photographic first being processed and the variation of the absorption waveform afterwards be little, the quality of image seriously reduces so.These phenomenons can not be anticipated, because they do not take place in the monolayer adsorption of routine.

Summary of the invention

The purpose of this invention is to provide silver halide photographic sensitive material, be minimized by the many problems that make sensitizing dye on the silver halide particle surface, can compensate entering of incident photon and to accompany with the multilayer absorption of sensitizing dye simultaneously with multilayer form absorption.

The result of research owing to take a broad survey, above-mentioned purpose can obtain by following item (1)-(21).

(1) a kind of silver halide photographic emulsions, it comprises that its surface goes up the silver halide particle that is adsorbed with sensitizing dye with multilayer form, wherein the coefficient of variation that optical absorption intensity distributes in particle be 100% or below.

(2) a kind of silver halide photographic emulsions, it comprises that its surface upward is adsorbed with the silver halide particle of sensitizing dye with multilayer form, the maximal value of wherein setting the spectral absorption that sensitizing dye causes is Amax, in particle, show the coefficient of variation that minimal wave length among the wavelength of 50% Amax and the wavelength distance between the long wavelength distribute and be 50% or below.

(3) a kind of silver halide photographic emulsions, it comprises the silver halide particle that is adsorbed with sensitizing dye from the teeth outwards with multilayer form, and wherein the change width of the spectral absorption maximum wavelength that has corresponding to 50% or above particle of the projected area of all silver halide particles in the emulsion is 10nm or littler.

(4) a kind of silver halide photographic emulsions, it comprises the silver halide particle that is adsorbed with sensitizing dye from the teeth outwards with multilayer form, wherein the sensitizing dye among the second layer and upper strata all is to exist with the stratiform form.

(5) a kind of silver halide photographic emulsions, it comprises that its surface upward is adsorbed with the silver halide particle of sensitizing dye with multilayer form, suppose that wherein optical density at the spectral absorption maximum wavelength place of photographic first being processed is that the optical density at G0 and the spectral absorption maximum wavelength place after photographic processing is G1, then the A value of being represented by A=G1/G0 is 0.9 or littler.

(6) silver halide photographic emulsions described in (5), wherein A is 0.5 or littler.

(7) a kind of silver halide photographic emulsions, it comprises the silver halide particle that is adsorbed with sensitizing dye from the teeth outwards with multilayer form, wherein the sensitizing dye among the second layer and upper strata all has 20kJ/mol or above energy of adsorption (Δ G).

(8) a kind of silver halide photographic emulsions, it comprises the silver halide particle that is adsorbed with sensitizing dye from the teeth outwards with multilayer form, wherein the interaction energy between sensitizing dye in ground floor and the sensitizing dye in the second layer or upper strata be dyestuff in the second layer and upper strata whole energy of adsorption 10% or more than.

(9) silver halide photographic emulsions described in (1) to (8), it comprises the silver halide particle that is adsorbed with sensitizing dye from the teeth outwards with multilayer form, and wherein the sensitizing dye in ground floor all is not the sensitizing dye that is connected by covalent bond with sensitizing dye in the second layer or upper strata.

(10) silver halide photographic emulsions described in (1) to (9), it comprises the spectral absorption maximum wavelength to be lower than 500nm and optical absorption intensity is more than 60 or the spectral absorption maximum wavelength is that the above and optical absorption intensity of 500nm is the silver halide particle more than 100.

(11) silver halide photographic emulsions described in (1) to (10), the maximal value of wherein setting the spectral absorptance of the described emulsion that is caused by sensitizing dye is Amax, and showing minimal wave length among the wavelength of 50% Amax and the wavelength distance between the long wavelength is 120nm or shorter.

(12) silver halide photographic emulsions described in (1) to (11), the maximal value of wherein setting the spectral sensitivity of the described emulsion that is caused by sensitizing dye is Smax, and showing minimal wave length among the wavelength of 50% Smax and the wavelength distance between the long wavelength is 120nm or shorter.

(13) silver halide photographic emulsions described in (11) or (12) wherein demonstrate long wavelength corresponding to the spectral absorption of 50% Amax at 460-510nm, in the zone of 560-610nm or 640-730nm.

(14) silver halide photographic emulsions described in (11) or (12) wherein demonstrate long wavelength corresponding to the spectral sensitivity of 50% Smax at 460-510nm, in the zone of 560-610nm or 640-730nm.

(15) silver halide photographic emulsions described in (1) to (14), wherein the excitation energy of the sensitizing dye within the second layer or upper strata with 10% or bigger efficient transfer the energy in the sensitizing dye in the ground floor.

(16) silver halide photographic emulsions described in (1) to (15), wherein sensitizing dye in ground floor and the sensitizing dye in the second layer or upper strata show the absorption of J-wavestrip.

(17) silver halide photographic emulsions described in (1) to (16), it comprises the sensitizing dye with at least one aryl.

(18) silver halide photographic emulsions described in (1) to (17), it comprises the sensitizing dye of the basic nuclear that obtains from three or more cyclic condensation.

(19) silver halide photographic emulsions described in (1) to (18), wherein radius-thickness ratio be 2 or above plain film shape particle be to think that 50% (area) of all silver halide particles in emulsion or above ratio exist.

(20) silver halide photographic emulsions described in (1) to (19), it has experienced the selenium sensibilization.

(21) silver halide photographic emulsions described in (1) to (20), it contains the silver halide adsorbability compound except that sensitizing dye.

(22) a kind of silver halide photographic sensitive material, it comprises the silver halide photographic emulsions of one deck described in (1)-(21) at least.

Embodiment

Describe the present invention below in detail.

The present invention relates to a kind of emulsion, it has exempted the problem of running in the multilayer absorption of the effective sensitizing dye of lip-deep reality of silver halide particle.

In the present invention, term " sensitizing dye in the second layer or upper strata is to exist with layer state " is meant that at least a portion sensitizing dye in the second layer and upper strata is to exist with layer state.In this case, preferred more than 10%, more preferably more than 30%, further more preferably more than 50%, further preferred more than 70% again, preferred especially is to exist with layer state with the sensitizing dye in the second layer and upper strata more than 100% most preferably 90% or more.

The condition that sensitizing dye exists with layer state is to be described in down.

Normally, when film when substrate surface increases, promptly when sensitizing dye adsorbs with multilayer form in the present invention, considered following three kinds of patterns.

1, layer increases (layer-layer increases, and Frank-van der Merwe type increases)

2, the island increases or increases (nucleation and growth, the Volmer-Weber type increases) by three nucleation

3, potpourri increases (nucleation and layer increase, and the Stranski-Krastanov type increases)

These growths are described in P.Bennema and G.H., Gilmer, Crystal Growth:AnIntroduction, edited by P.Hartman, North-Holland Publishing Company, Amsterdam, London, pp. 282-310 (1973), Yoshihiko Goto, Kotai Butsuri (Solid Physics), Vol.18, No.7, page 380 (1983), Yoshihiko Goto and ShozoIno, Kotai Butsuri (Solid physics), Vol.18, No.3, page 121 (1983), Akio Ito (compiler), Hakumaku Zairyo Nyumon (Introduction of Thin FilmMaterials), Shokabo (1998), mitsumasa Iwamoto, Yuki Cho-HakumakuElectronics (Organic Ultrathin Electronics), Baufukan (1993), Akira Yabe etal., Yuki Cho-Haumaku Nyumon (introduction of Organic Ultrathin Film), Baifukan (1989), Nippon Hyomen Kagakukai Shusai Dai 1-Kai HakumakuKiso Koza Yoshi Shu (Summary Collection of 1 ^StElemental Iecture on ThinFilm at Meeting by Japan Surface Science), November 12/13, Tokyo (1998) etc.

Layer growth is meant that among the sensitizing dye that forms multilayer absorption, it is according to successively superposeing with the stratiform form on the sensitizing dye in the ground floor on silver halide particle that the sensitizing dye in the second layer and upper strata increases.The sensitizing dye of this situation in bottom takes place when having strong adhesive power.

Island increases and to form nuclear on the sensitizing dye of aggregation in ground floor be meant the sensitizing dye in the second layer and upper strata and this nuclear increases as the island.It is that binding force than the sensitizing dye in bottom is when stronger that this situation occurs in bounding force between the second layer and the upper strata sensitizing dye.

Potpourri increases and to be meant that layer increased in the starting stage and to take place in which floor of the second layer and upper strata, and after this described growth becomes island and increases.This may be by the sensitizing dye in the second layer or upper strata and the inconsistency between the sensitizing dye in the lower floor and the distortion of accumulating in film can cause.

If the dyestuff in the second layer or upper strata has formed the bidimensional associated matter, this bidimensional associated matter itself is easy to increase with the stratiform form, and therefore, even the interaction energy of adjacent bottom dye coating is less, layer absorption also easily realizes.Therefore, be preferably formed bidimensional in conjunction with product.Bidimensional can have any aggregated forms in conjunction with product, yet, be preferably formed the J-that will describe the back in conjunction with product.

In the present invention, in order to make that the sensitizing dye in the second layer and upper strata is to exist with layer state, sensitizing dye preferably increases by the layer in the above-mentioned growth pattern or potpourri increases, and more preferably increases by layer.

In according to the absorption of the multilayer of common process method, the sensitizing dye in the second layer and upper strata is to exist and improve the effect of absorptivity and the effect of super-sens is not satisfied by any way with the island form.

Sensitizing dye in the second layer and upper strata is can observe by using any method with the situation what state exists, but preferably use microscpectrometry, STM method, AFM method, neighbor point optical microphotograph method, negative electrode brightness method, fluorescence microscopy method, image SIMS method, SEM method, TEM method etc.

Whether the dyestuff that adsorbs in multilayer can be by determining according to the position (point) or the amount of dye of a plurality of absorbing dye layers that form on the silver halide particle surface with the stratiform form.In the present invention, when the position of a plurality of absorbing dye layers (point) or amount of dye are within 5 times of fluctuation in monolayer adsorption the time, absorption is regarded as layer absorption.Certainly, littler fluctuation represents to have better layer absorption.Fluctuation can be represented by the dye coating number of each position on silver halide particle (point) absorption or the standard deviation or the coefficient of variation of amount of dye.When sensitizing dye is that the state how to exist is when observing by using above-mentioned measuring method, therefore by the fluctuation of measuring them the dye coating number or the amount of dye of each position on particle surface (point) absorption are carried out quantitatively, thereby can determine whether layer absorption.

About the absorption affinity between the sensitizing dye, preferred condition such as following.

The energy of adsorption of the sensitizing dye in the second layer and upper strata (Δ G) preferably 20kJ/mol or more than, more preferably 30kJ/mol or more than, more preferably 40kJ/mol or more than, further preferred 42kJ/mol or more than, still more preferably 50kJ/mol or more than, again more preferably 80kJ/mol or more than, also more preferably 70kJ/mol or more than, and again more preferably 80kJ/mol or more than.

The bonding on upper strata does not limit especially, but 5000kJ or following preferably is more preferably 1000kJ or following.

As the interaction in energy of adsorption source can be any cohesive force but its example comprises that Van der Waals force (more particularly, be divided into the dipole-dipole force that between permanent dipole and permanent dipole, produces, the induction force that between permanent dipole and induced dipole, produces, and the diffusive force that between transient doublet and induced dipole, produces), the electric charge metastatic capacity, Coulomb force (electrostatic force), hydrophobic bonding force, hydrogen bond force, chemical bonding force and coordination bonding force.Have only one can use and among these bonding forces to using a plurality of free options buttons to make a concerted effort.Only, do not contain covalent bond when the covalent bond energy of adsorption of the sensitizing dye of dyestuff is 20kJ/mol or above (this is one of feature of the present invention) quantitatively in the second layer and upper strata.Known covalent bond has 104kJ/mol or above energy of adsorption at least.Is situation about being connected by a covalent bond for the dyestuff in ground floor with dyestuff in the second layer, Japanese patent application No. 11-34444, and 11-34463 has introduced the dyestuff that is connected with ad hoc structure with 11-34462.Because the dyestuff in the second layer is to be connected by covalent bond with dyestuff in ground floor natch, these dyestuffs all have 104kJ/mol or above energy of adsorption at least.The present invention is based on following discovery and is achieved: when the covalent bond energy of adsorption of the sensitizing dye in the second layer or the upper strata is 20kJ/mol or when above, can obtain splendid effect.Yet, if the energy of adsorption of the covalency bonding force of the sensitizing dye in the second layer or the upper strata be 20kJ/mol or more than, also can use the connection dyestuff.Self-evident, connecting dyestuff is to comprise in the various factors of the present invention.For example, when among being described in particle, distributing preferred interactional factor or layer absorption, must comprise the covalency bonding force.

Among these, Van der Waals force preferably, electric charge metastatic capacity, the Coulomb force, hydrophobic bonding force, hydrogen bond force, chemistry bonding force and coordination bonding force, Van der Waals force more preferably, electric charge metastatic capacity, the Coulomb force, hydrophobic bonding force and hydrogen bond force, more preferably Van der Waals force, electric charge metastatic capacity and Coulomb force, preferred especially Van der Waals force and electric charge metastatic capacity and most preferably be Van der Waals force.

Dyestuff and stabilization energy (it is the interaction that preferably causes the energy of adsorption of the dyestuff in the second layer or upper strata) are described in down.

The situation of the R-layer absorption in the second layer or upper strata is described in down.

In this case, interactional stabilization energy as the absorption affinity of i layer dyestuff source can be divided into: interactional stabilization energy (Δ Gi (i-1)) between i layer dyestuff and (i-1) layer dyestuff, interactional stabilization energy (Δ Gii) between i layer dyestuff and the i layer dyestuff and interactional stabilization energy (Δ Gi (i+1)) between i layer dyestuff and (i+1) layer dyestuff (wherein i be 2 or more than).

At this moment, following 1,2 and 3 be preferred successively.Under the situation of i=R (that is, the superiors), Δ Gi (i+1) is non-existent.

1. kJ/mol and/or Δ Gi (i+1)＞(Xi (I+1)) kJ/mol of Δ Gi (i-1)＞(Xi (i-1)) kJ/mol and/or Δ Gii＞(Xii).

2. kJ/mol and/or Δ Gi (i+1)＞(Xi (i+1)) kJ/mol of Δ Gi (i-1)＞(Xi (i-1)) kJ/mol and/or Δ Gii＞(Xii).

3. in 1 and 2, also has Δ Gi (I-1)＞Δ Gii, Δ Gi (I+1)＞Δ Gii.

Xi (i-1), the value of Xii and Xi (I+1) all preferably is 10,20,30,40,50,60,70 and 80 successively.

At I layer dyestuff and (I-2) between the layer dyestuff, at I layer dyestuff and (I+2) between the layer dyestuff, also exist between I layer dyestuff and silver halide particle etc. and interact, yet these are long range interactions and can ignore.

Sensitizing dye in ground floor also preferably exists with layer state.Normally, the interaction between silver halide particle and ground floor sensitizing dye is strong, so ground floor is to increase so that exist with layer state in many cases with layer form.

The energy of adsorption of dyestuff and the interactional stabilization energy of originating as energy of adsorption can record by any means.

For example, the energy of adsorption of dyestuff can (use the method for dye sorbent to be described in people's such as Asanuma the report by the thermodynamics assay method that uses the dye sorbent that the back will describe, Journal of Physical Chemistry B, Vol.101, pp.2149-2153 (1997)), (for example this method sees Journal of PhysicalChemistry B by the method from the mensuration energy of adsorption of adsorption isothermal, Vol.56, pp.1054 (1952), yet as described later, the method of the silver halide particle of dissolution precipitation and mensuration dyestuff adsorbance is useful), method according to mensuration dyestuff adsorbance described later, or (for example this method sees people such as Asanuma to use the calorimetric instrumentation to decide the method for energy of adsorption, Journal of Physical Chemistry B, Vol.101, pp.2149-2153 (1997)) record.In addition, also can use chemistry for example to calculate molecular orbit and calculating molecular force field.

Interactional stabilization energy as the energy of adsorption source also can use said method to measure.

For example, under the situation of two-layer absorption, the energy of adsorption of second layer dyestuff can be measured by said method.Then, record interactional stabilization energy between second layer dyestuff.For used method, stabilization energy can be by for example using the method that is proposed by matsubara and Tanaka (referring to Nippon Shashin Gakkai Shi (Journal of Japan PhotographicSociety), Vol.52, page 395 (1989)) and the mensuration that experimentizes.More particularly, stabilization energy can dyestuff takes place each other from the second layer the variation of uniting the absorption that causes (when under different temperatures, changing widely in the concentration of second layer dyestuff at gelatin solution, wherein having only silver halide particle from used emulsion, to remove) and obtain.And, also can use the calculating of for example MO calculating of chemistry and molecular force field.

At this moment, the interactional stabilization energy between ground floor dyestuff and the second layer dyestuff can obtain from following formula: (energy of adsorption of second layer dyestuff)=(the interactional stabilization energy between ground floor dyestuff and the second layer dyestuff)+(interactional stabilization energy between the second layer dyestuff.

Under the situation of three layers of absorption, can measure by the same procedure of second layer dyestuff as the interactional stabilization energy that the energy of adsorption of the 3rd layer of dyestuff is originated.At this moment, obtain following formula (energy of adsorption of second layer dyestuff)=(the interactional stabilization energy between ground floor dyestuff and the second layer dyestuff)+(the interactional stabilization energy between the second layer dyestuff+(interactional stabilization energy between second layer dyestuff and the 3rd layer of dyestuff), and because (the interactional stabilization energy between second layer dyestuff and the 3rd layer of dyestuff) is to be equal to (the interactional stabilization energy between the 3rd layer of dyestuff and the second layer dyestuff), so can obtain all results.

Under four layers or situation with the absorption on upper strata, all results also can obtain according to identical mode.

The optimum condition of the energy of adsorption between sensitizing dye is to be described in down by other expression.

The surface energy density of supposing sensitizing dye in ground floor is that the surface energy density of sensitizing dye in the σ 1 and the second layer of growing on ground floor is σ 2, and bonding interfacial energy density σ 21 is defined as σ 21=σ 2+ σ 1-γ between them.γ is the adhesion energy density of sensitizing dye in sensitizing dye and the ground floor in the second layer.

If γ＜0, sensitizing dye is not adsorbed on the ground floor sensitizing dye in the second layer in many cases, fails to form multilayer absorption.If γ＞0, interfacial energy is owing to absorption reduces, so second layer sensitizing dye is grown on the ground floor sensitizing dye.When satisfying σ 21≤σ 1-σ 2, it is dominant that stratiform increases, and during σ 1-σ 2＜σ 21＜σ 2+ σ 1, island increases preponderates.Therefore, in the present invention, preferably satisfy σ 21≤σ 1-σ 2.

In the present invention, optical absorption intensity is the integrated intensity of the light absorption by per unit granule surface area sensitizing dye and is defined as a value that is obtained by following method: the light quantity that supposition enters the particle per surface area is I ₀, the light quantity that absorbs of sensitizing dye is I from the teeth outwards, by integration with respect to wave number (cm ^-1) optical density log[I ₀/ (I ₀-I)], the value defined that is about to obtain is a photon absorbing intensity, limit of integration is from 5000cm ^-1To 35000cm ^-1

Silver halide photographic emulsions of the present invention preferably contain silver halide particle with half of whole projected areas of all silver halide particles or bigger ratio, when this particle has 500nm or longer spectral absorption maximum wavelength, it has 100 or bigger photon absorbing intensity, or when this particle had spectral absorption maximum wavelength less than 500nm, it had 60 or bigger photon absorbing intensity.When particulate had 500nm or longer spectral absorption maximum wavelength, photon absorbing intensity was preferably 150 or bigger, and more preferably 170 or bigger, further more preferably 200 or bigger.When particulate had spectral absorption maximum wavelength less than 500nm, photon absorbing intensity was preferably 90 or bigger, and more preferably 100 or bigger, further more preferably 120 or bigger.Be not the special restriction upper limit, but it is preferably 2000 or still less, more preferably 1000 or still less, further more preferably 500 or still less.

The spectral absorption maximum wavelength is preferably 350nm or longer less than the spectral absorption maximum wavelength of the particle of 500nm.

An example measuring the photon absorbing intensity method is to use the measuring method of microspectrophotometer.Microspectrophotometer is the device that can measure the microcosmos area absorption spectrum, and it also can measure the transmitted spectrum of a particle.People such as Yamashita (Nippon Shashin Gakkai, 1996 Nendo Nenjj, Taikai Ko ' en Yoshi Shu (Lecture Summary at Annual Meeting of Japan Photographic Association in 1996), Page 15) report in the extinction spectrum of measuring particle by the micro-spectral method has been described.From this absorption spectrum, can obtain the absorption intensity of each particle, yet the light of particle transmission is absorbed on upper surface and lower surface, therefore each the particle absorption intensity that is obtained by method as mentioned above half (1/2) is exactly the absorption intensity of particle surface per unit area, at this moment, the integral part with absorption spectrum is limited in 5000 to 35000cm ^-1Yet in experiment, integral part can comprise the longer or shorter 500cm of part that absorbs by dye sensitization than having ^-1The zone.

Photon absorbing intensity is a numerical value, can indistinguishably measure by the molecular number that sensitizing dye oscillator strength and per unit area absorb, it is possible therefore obtaining the surface area of the quantity of oscillator strength, absorbing dye of sensitizing dye and particle and changing them into photon absorbing intensity.

As with the absorption integrated intensity (optical density * cm of sensitizing dye solution ^-1) proportional numerical value, the sensitizing dye oscillator strength can obtain by experiment.Therefore, the absorption integrated intensity of supposing every 1M dyestuff is A (optical density * cm ^-1), the quantity of the sensitizing dye of absorption is B (mol/mol-Ag), granule surface area is C (m ²/ mol-Ag), in about 10% error, can obtain photon absorbing intensity: 0.156 * A * B/C according to following formula.

The photon absorbing intensity that calculates gained by this formula with based on aforesaid definition (by with wave number (cm ^-1) relevant log[I ₀/ (I ₀-I)] a value obtaining of integration) measured photon absorbing intensity is roughly the same.

Be to increase photon absorbing intensity, can use with one deck or more multi-layered form dye chromophore is adsorbed onto the method for particle surface, increase the method for dye molecule extinction coefficient and reduce the method for dyestuff occupied area.Can use the arbitrary method in these methods, but preferably dye chromophore is adsorbed to the method for particle surface with one or more layers form.

Here, dye chromophore is adsorbed onto this state in one or more layers of particle surface and means that near the dyestuff that is adhered to the silver halide particle is present in one or more layers.This dyestuff does not comprise the dyestuff that is present in the dispersion medium.And, this situation that dye chromophore is linked to each other with the material that is adsorbed onto particle surface with covalent bond is not seen one or more layers form absorption as, because when dye chromophore is present in the dispersion medium, linking group is very long, and the effect that increases photon absorbing intensity is unconspicuous.In so-called multilayer absorption (promptly wherein dye chromophore is adsorbed onto in one or more layers of particle surface) in this case, the dyestuff that produces spectral sensitization by the dyestuff that directly is not adsorbed onto particle surface and never directly be adsorbed onto silver halide is necessary to the dyestuff transmission excitation energy that directly is adsorbed onto particle.In this sense, it is not preferred transmitting excitation energy through 10 stages, because the excitation energy transmission efficiency has reduced.An example of this situation is the polymeric dye of describing among the JP-A-2-113239, and wherein most of dye chromophore are present in the dispersion medium, must could transmit excitation energy through more than 10 steps.

Among the present invention, each molecular dye forms colored essential number of steps preferably from 1 to 3, is more preferably 1 to 2.

Rikagaku Jiten (Physicochemical Dictionary), PP 985-986,4th ed. has defined among the Iwanami Stoten (1987) used here " chromophore ", and it is meant the atomic group that mainly causes the molecule absorption bands of a spectrum.Can use chromophore arbitrarily, for example contain atomic group just like C=C or N=N and so on unsaturated link.

The example of dye chromophore has cyanine dyes, styryl color, hemicyanine dye, portion's cyanine dyes, three nuclear portion cyanine dyes, four nuclear portion cyanine dyes, if rhodacyanine dye, compound cyanine dyes, the composite part cyanine dyes, pole-changing dyestuff, oxonol dye, half oxonol dye, the Squarium dyestuff, gram dyestuff, azomethane dyestuff, coumarine dye, Asia-2-propylene dyestuff, anthraquinone dye, triphenyl methine dyestuff, azo dyes, azomethine dyes, spiral compound, metallocene dyestuff, fluorenes dyestuff, the fulgide dyestuff, pyrene dyestuff, phenazine dyes, the phenothiazine dyestuff, quinone dyestuff, bipseudoindoxyl dye, diphenylmethane dye, polyenoid dyestuff, acridine dye, the acridone dyestuff, diphenylamine dyestuff, quinacridone dyestuff, quinoline dai ketone dyes, phenoxazine dyestuff, phthalein pyrene dyestuff, porphyrin dye, chlorophile dyestuff, blue or green dyestuff of phthalein and metal complex dyes.

In these materials, preferred cyanine dyes, styryl color, hemicyanine dye, portion's cyanine dyes, three nuclear portion cyanine dyes, four nuclear portion cyanine dyes, if rhodacyanine dye, compound cyanine dyes, the composite part cyanine dyes, the pole-changing dyestuff, oxonol dye, half oxonol dye, the Squarium dyestuff, gram dyestuff and as the poly-polymethylene chromophore of azomethine dyes and so on, cyanine dyes more preferably, portion's cyanine dyes, three nuclear portion cyanine dyes, four nuclear portion cyanine dyes, if rhodacyanine dye, further cyanine dyes more preferably, portion's cyanine dyes and if rhodacyanine dye, most preferably cyanine dyes.

At F.M.Harmer, Heterocyclic Compounds-Cyanine Dyes ane Related Compounds,Joho Wiley ﹠amp; Sons (1964), D.M.Sturmer, Heterocyclic Compounds-Special topics in heterocyclic Chemistry, Chap.18, Section 14, and PP describes these dyestuffs in detail among the 485-515.If do not limit n12, n15, the number of n17 and n18, each respectively is 0 or the integer of more (preferred 4 or littler), and USP 5,340, molecular formula described in 694,20 to 21 row be (XI), cyanine dyes (XII) and (XIII), portion's cyanine dyes and be preferred as if rhodacyanine dye.

Be adsorbed on dye chromophore on the silver halide particle preferably 1.5 or more multi-layered, more preferably 1.7 or more multi-layered, further more preferably 2 or more multi-layered.Be not the upper limit of the special restriction number of plies, however 10 or the number of plies still less be preferred, more preferably 5 or the number of plies still less.

Among the present invention, this state that is adsorbed onto the silver halide particle surface with one or more layers form chromophore means that the absorption quantity of per unit layer dye chromophore is to a great extent based on the saturated coverage of individual layer when being defined as the saturated coverage of individual layer by the saturated absorption that a kind of dye sensitization was obtained when (this dyestuff is adding the silver halide surface occupied area that has minimum in the sensitizing dye of emulsion).The absorption number of plies is meant the adsorbance based on the monolayer adsorption coverage.In dye chromophore is in the dyestuff that connects by covalent bond, and the absorption number of plies can be based on every kind of dyestuff under not-connected status, the occupied area of dyestuff.

Can obtain the dyestuff occupied area from adsorption isothermal, adsorption isothermal has shown the relation of free dye strength and dyestuff absorption quantity and grain area.For example, with reference to A.Herz et al, Adsorption from Aqueous Solution, Advances in Chemistry Series, No.17, Page 173 (1968), can obtain adsorption isothermal.

Be adsorbed onto the quantity of the sensitizing dye of emulsion layer for measurement, can use two kinds of methods, a kind of method is to make in upper strata hydration gelatin solution that the emulsion with absorbing dye is centrifugal to become independent emulsion grain, the spectral absorption of measuring supernatant liquor obtains the concentration of non-absorbing dye, from the quantity of adding dyestuff, deduct this concentration, just obtain dyestuff absorption quantity; Another kind method is drying precipitated emulsion grain, the sediment of dissolving scheduled volume in 1: 1 mixed solution of hydration hypo solution and methyl alcohol, and measure spectrum absorbs, thereby determines dyestuff absorption quantity.When using composite dye, utilize the absorption quantity that also can obtain every kind of dyestuff as the method for high-speed liquid chromatography.W.West et al for example, Jounral of Physical Chemistry, Vol.56 has described the quantity by dyestuff in the quantitative supernatant liquor among the Page1054 (1952), measure the method for dyestuff adsorbance.Yet when used amount of dye is very big,, can not determine absorption quantity definitely by the dye strength in the quantitative supernatant liquor even non-absorbing dye can be precipitated out.On the other hand, according to the silver halide particle that dissolution precipitation goes out, measure the method for dyestuff absorption quantity, can determine the quantity that is adsorbed onto the dyestuff on the particle definitely, because the subsidence rate of emulsion grain is very high, the dyestuff of precipitation is easy to separate with emulsion grain.This method is the most reliable to measuring dyestuff absorption quantity.

The content that the compound that can be used for taking a picture in the particle is advanced in absorption also can record according to the method identical with sensitizing dye, yet, because the absorption in visibility region is little, the quantivative approach of using high performance liquid chromatography is than the quantivative approach of spectral absorption more preferably.

As an example of the method for measuring the silver halide particle surface area, can utilize by reproduction process and carry out the transmission electron microscopy photograph, and calculate the size of each particle and the method for shape.In this case, calculate the thickness of plain film shape particle from the length gauge of duplicate shade.For example reference Denshi Kenbibyo Shiryo Gijutsu Shu (Electron Microscopic Sample Technologies), Nippon Denshi Kenbikyo Gzkkai Kanto Shibu (Compiler), Seibundo shinko Sha (1970), P.B.Hirsch et al., Electron Microscopy of Thin Crystals, Butterworths, London (1965) can carry out transmission electron microscopy and take a picture.

At A.M.Kragin et al., The Journal of Photographic Science, Vol.14, page 185 (1966), J.F.Paddy, Transactions of the Faraday Society, Vol.60, page 1325 (1964), S.Boyer et al., Journal de Chimie Physique et de Physicochimie Biologigue, Vol.63, page 1123 (1963), W.West et al., Journal of Physical Chemistry, Vol.56, page 1054 (1952), E.Klein et al., International Cologuium, compiled by H.Sauvernier, and Scientific Phtotgraphy, other example of measuring method has been described among the Liege (1959).

Utilize the above method, can test the dyestuff occupied area that records each particle, however common used most likely about 80 of sensitizing dye molecule occupied area ², therefore utilize with 80 ²The straightforward procedure that the dyestuff occupied area calculates can the guestimate absorption number of plies.

In the present invention, when being adsorbed onto on the silver halide particle with the multilayer form dye chromophore, directly be adsorbed onto the dye chromophore of silver halide particle, promptly the dye chromophore in the ground floor and the second layer and subsequently the dye chromophore in each layer can have reduction potential and oxidizing potential arbitrarily arbitrarily.Yet, the reduction potential of dye chromophore in the ground floor, it is bigger preferably to deduct the value that 0.2V obtains than dye chromophore reduction potential in the second layer or the upper strata.Here used phrase " reduction potential of dye chromophore is higher " is meant " dye chromophore is to be easy to be reduced ".

Can utilize the whole bag of tricks to measure reduction potential and oxidizing potential, yet preferably measure exact numerical values recited by the phase identification type second resonance AC polarography. Journal of Imaging Science, Vol., 30, the method for measuring current potential by the phase identification type second resonance AC polarography has been described among the page 27 (1986).

Dye chromophore in the second layer or the upper strata is luminescent dye preferably.Luminescent dye preferably has as the skeleton of dye laser dyestuff (promptly basic) structure.For example, at Mitsuo Maeda, Laser Kenkyu (Study of Laser), Vol.8, page 694, page 803 and page 958 (1980), Ibid, vol.9, page 85 (1981) and F.Shaefer, Dye Lasers, Springer has described these dyestuffs in (1973).

The absorption maximum wavelength of ground floor dye chromophore in the silver halide photographic sensitive material, preferably longer than the absorption maximum wavelength of the second layer or upper strata dye chromophore.And the light emission of the second layer or upper strata dye chromophore absorption preferred and the ground floor dye chromophore is overlapping.In addition, the dye chromophore in the ground floor is preferably formed J-associated matter (being the J-aggregation).Absorb and spectral sensitivity in order to have in desired wavelength coverage, the dye chromophore in the second layer or the upper strata also is preferably formed the J-associated matter.

The excitation energy of second layer dyestuff to the ground floor dyestuff preferably have 30% or above, more preferably 60% or above, further more preferably 90% or above energy transfer efficiency.Here used term " excitation energy of second layer dyestuff " is meant because second layer dyestuff and upper strata dyestuff extinction energy make the energy of the dyestuff under the excited state.Divide the period of the day from 11 p.m. to 1 a.m when the excitation energy of certain molecule is transferred to another one, think that excitation energy is to shift by excitation electron transfer mechanism, Forster type energy transfer mechanism, Dextor type energy transfer mechanism etc.Therefore, multilayer absorption system of the present invention is further preferably satisfied and can cause the condition that effective excitation energy shifts by these mechanism, more preferably satisfy the condition that is used to cause Forster type energy transfer mechanism.In order to improve the efficient that Forster type energy shifts, the reduction of reflectivity is effective near the surface of emulsion grain.

The efficient that is transferred to the ground floor dyestuff from second layer dyestuff and upper strata dyestuff energy can be used as second layer dyestuff the spectral sensitization that excites efficient/ground floor dyestuff the spectral sensitization efficient that excites and obtain.

The meaning of used term among the present invention is described below.

The dyestuff occupied area:

The occupied area of each molecule of dyestuff.It can be recorded by the adsorption isothermal experiment.When use connected the dyestuff of dye chromophore with covalent bond, the dyestuff occupied area based on the every kind of dyestuff that does not connect (chromophore) recorded this area, briefly, is 80 ²

The saturated coverage of individual layer:

The dyestuff adsorbance of the saturated covering of individual layer time unit grain area.Add the inverse of minimum dyestuff occupied area in the dyestuff.

Multilayer absorption:

A kind of state, wherein the absorption quantity of dye chromophore is bigger than the saturated coverage of individual layer on the per unit grain area.

The absorption number of plies:

Based on the saturated coverage of individual layer, the absorption quantity of dye chromophore on the per unit grain area.

The distribution of photon absorbing intensity in particle can be expressed as the coefficient of variation of the photon absorbing intensity of 100 or the more a plurality of particles that record at random by microspectrophotometry.The coefficient of variation can 100 * standard deviation/and average (%) and obtain.Photon absorbing intensity is a value that is proportional to the absorbing dye amount, and therefore, in other words, the distribution of photon absorbing intensity in particle can be called the distribution of absorbing dye amount in particle.The coefficient of variation of the distribution of photon absorbing intensity in particle preferably 60% or below, be more preferably 30% or below, further be more preferably 10% or below.

At 50% the maximum wavelength that shows the absorption maximum of sensitizing dye (Amax) and show the coefficient of variation that the distance between 50% the long wavelength of Amax distributes in particle preferably 30% or below, be more preferably 10% or below, further be more preferably 5% or below.

For the absorption maximum wavelength of each particle of sensitizing dye, particle with projected area preferred 70% or above, more preferably 90 or above ratio in 10nm or following wavelength coverage, have the absorption maximal value.In a more preferred of the absorption maximum wavelength of each particle of sensitizing dye, particle with preferred 70% or above, more preferably 90 or above ratio in 5nm or following wavelength coverage, have the absorption maximal value.

Adsorption site is to be fixed under the lip-deep monolayer adsorption situation of silver halide particle therein, along with the dyestuff adsorbance increases, and the distribution of known optical absorption intensity (being the dyestuff adsorbance) in the particle homogeneous that becomes.Yet, under the situation of multilayer absorption of the present invention, when finding not only to obtain two-layer absorption but also which floor obtains simultaneously to adsorb, adsorption site is unrestricted and distributes is to produce in particle easy as can, for example, some particle is produced monolayer adsorption and other particles are produced three layers of absorption.By analyzing, confirmed that (in other words the interactional ratio between the dyestuff in the second layer increases based on the whole energy of adsorption of second layer dyestuff, the ratio of the interaction energy between ground floor dye molecule and second layer dye molecule reduces relatively), the multilayer absorption system is to have heterogeneity aspect the absorbing dye amount that is easy in particle.Interaction energy between ground floor dye molecule and the second layer dye molecule based on the whole energy of adsorption of second layer dyestuff preferably 20% or more than, more preferably 40% or more than.

In order to strengthen the interaction energy between ground floor dyestuff and the second layer dyestuff, preferably use electrostatic interaction, Van der Waals interaction, hydrogen bond, coordination bond or their compound interaction force between ground floor dye molecule and second layer dye molecule.Though the main interaction between the two-layer dyestuff preferably Van der Waals between the dye chromophore interacts, and further preferably uses electrostatic interaction, Van der Waals interaction, hydrogen bond, coordination bond or their compound interaction force.

Interaction energy between ground floor molecule and the second layer molecule can be by measuring at the same procedure of layer absorption to the ratio of the whole energy of adsorption of second layer dyestuff.

The distribution of absorbing dye amount is the influence that is subjected to the adding conditional of dyestuff in particle.Add dyestuff at low temperatures and the method for temperature that raises then is preferred.

Containing photon absorbing intensity is 60 or bigger, perhaps be 100 or the emulsion of bigger silver halide photographic emulsions particle in, show the spectral absorption by dye sensitization maximal value Amax 50% and spectral sensitivity maximal value Smax 50% o'clock minimal wave length and shown distance between the long wavelength of 50%Amax and 50%Smax and be preferably 120nm or still less, 100nm or still less more preferably.

Show the minimal wave length of 80%Amax and 80%Smax and show 80%Amax and the long wavelength of 80%Smax between distance be 20nm or longer, preferably 100nm or shorter is more preferably 80nm or shorter, further is more preferably 50nm or shorter.

Show the minimal wave length of 20%Amax and 20%Smax and show 20%Amax and the long wavelength of 20%Smax between distance 180nm or shorter preferably, be more preferably 150nm or shorter, further being more preferably 120nm or shorter, most preferably is 100nm or shorter.

The long wavelength who shows 50%Amax and 50%Smax is preferably from 460 to 510nm, from 560 to 610nm or from 640 to 730nm.

For silver halide particle is had less than the spectral absorption maximum wavelength of 500nm and 60 or more photon absorbing intensity, or having 500nm or longer spectral absorption maximum wavelength and 100 or more photon absorbing intensity, first kind of preferable methods is to use the method for unique dyestuff as described below.

JP-A-10-239789 for example, JP-A-8-269009, JP-A-8-328189 has described to use and has had a dyestuff of aryl or be used in combination the dye of positive ion with aryl and the method for anionic dye among the JP-A-10-123650, described among the JP-A-10-171058 and used dyestuff with multivalence electric charge, JP-A-10-104774 has described the method for using the dyestuff with pyridine group, JP-A-10-186559 has described the method for using the dyestuff with hydrophobic grouping, JP-A-10-197980 has described the method for using the dyestuff with coordination bond group, and these methods are preferred.

In these methods, preferably use the method for dyestuff or be used in combination the dyestuff that has only positive charge, more preferably only use the dyestuff of cancellation electric charge in positively charged dyestuff, the molecule or do not have the method for electric charge dyestuff or be used in combination the positively charged dyestuff and the method for electronegative dyestuff (wherein in positively charged dyestuff and the electronegative dyestuff at least a be to contain at least one aryl to make substituent dyestuff) with at least one aryl.

Describe aryl below in detail.Aryl comprises hydrocarbon aryl and heterocyclic aryl.This group can contain many cyclic condensations structure that forms by hydrocarbon aromatic ring and the mutual condensation of heterocycle aromatic ring or the many cyclic condensations structure that forms by aromatic hydrocarbon group and fragrant heterocyclic compound, also can be replaced by the V substituting group that the back can be described.The example of the aromatic ring that preferably contains in the aryl comprises benzene, naphthalene, anthracene, phenanthrene, fluorenes, benzophenanthrene, aphthacene, biphenyl, pyrroles, furans, thiophene, imidazoles, azoles, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, indoles, coumarone, benzothiophene, isobenzofuran, quinolizine, quinoline, 2,3-benzodiazine, naphthalene quinoline, quinoxaline, quinoline oxazoline, quinoline, carbazole, phenanthridines, bifurcation pyridine, phenanthroline, thianthrene, chromene, xanthenes, phenoxthine, phenothiazine and fen thiophene.

In these materials, preferably hydrocarbon aromatic ring, more preferably benzene and naphthalene, most preferably naphthalene.

The example of dyestuff comprises the dyestuff as the dye chromophore example recited above.In these materials, the dyestuff of the poly-polymethylene dye chromophore example of conduct preferably recited above.

Cyanine dyes more preferably, styryl color, hemicyanine dye, portion's cyanine dyes, three nuclear portion cyanine dyes, four nuclear portion cyanine dyes, if rhodacyanine dye, compound cyanine dyes, composite part cyanine dyes, the pole-changing dyestuff, oxonol dye, half oxonol dye, Squarium dyestuff, the gram dyestuff, the azomethane dyestuff, further cyanine dyes more preferably, portion's cyanine dyes, three nuclear portion cyanine dyes, four nuclear portion cyanine dyes are if rhodacyanine dye particularly preferably is cyanine dyes, portion's cyanine dyes and if rhodacyanine dye, most preferably cyanine dyes.

Describe particularly preferred method in detail below with reference to structural formula.

Method (1) and (2) they are preferred, among the two, and method (2) more preferably.

(1) use at least a below cationic shown in the molecular formula (I), the method for betaine or nonionic methine dyes.

(2) use the negative ion methine dyes shown in cationic methine dyestuff shown at least a following molecular formula (I) and at least a following molecular formula (II) simultaneously.

Wherein, Z ₁Expression forms nitrogenous heterocyclic necessary atomic group, supposes Z ₁On further cyclic condensation, R ₁The expression alkyl, aryl or heterocyclic group, Q ₁Expression makes the group of necessity of the compound formation methine dyes shown in the molecular formula (I), L ₁And L ₂All represent methine group, P separately ₁Be 0 or 1, suppose Z ₁, R ₁, Q ₁, L ₁And L ₂Substituting group is respectively arranged, and substituting group makes the methine dyes shown in the molecular formula (I) as the whole dye of positive ion, betaine dyestuff or the non-ionic dye of forming, when if molecular formula (I) is a cyanine dyes or during rhodacyanine dye, and Z ₁, R ₁, Q ₁, L ₁And L ₂Each preferably has substituting group, and substituting group makes the methine dyes shown in the molecular formula (I) as the whole dye of positive ion, the M of forming ₁The gegenion of expression balancing charge, m ₁In the expression and molecule in electric charge necessary 0 or bigger integer.

Wherein, Z ₂Expression forms nitrogenous heterocyclic necessary atomic group, supposes at Z ₂On further cyclic condensation, R ₂The expression alkyl, aryl or heterocyclic group, Q ₂Expression makes the group of necessity of the compound formation methine dyes shown in the molecular formula (II), L ₃And L ₄All represent methine group, P separately ₂Be 0 or 1, suppose Z ₂, R ₂, Q ₂, L ₃And L ₄Substituting group is respectively arranged, and substituting group makes the methine dyes shown in the molecular formula (II) as whole anionic dye, the M of forming ₂The gegenion of expression balancing charge, m ₂In the expression and molecule in electric charge necessary 0 or bigger integer.

When the compound that only uses shown in molecular formula (I), R ₁The group that preferably contains aromatic ring.

When the compound that is used in combination shown in compound shown in the molecular formula (I) and the molecular formula (II), preferred, R ₁And R ₂In at least one is the group that contains aromatic ring, more preferably, R ₁And R ₂It all is the group that contains aromatic ring.

The used dye of positive ion of the present invention can be arbitrarily, only otherwise when comprising gegenion, the electric charge in the dyestuff is a positive ion.But the dyestuff that does not preferably contain anion substituent.The used anionic dye of the present invention can be arbitrarily, only otherwise when comprising gegenion, and negative ion during electric charge in the dyestuff, but preferably contain the dyestuff of one or more anion substituents.The used betaine dyestuff of the present invention is the dyestuff that electric charge is arranged in the molecule, has wherein formed inner salt, and molecule does not have electric charge generally.The used non-ionic dye of the present invention is the dyestuff that does not at all have electric charge in the molecule.

Terminology used here " anion substituent " is meant the substituting group of negative charge.It is 5 to 8 o'clock that the example is included in pH value, and the rate of dissociation is the acid groups of 90% disassociation proton.Its instantiation comprises sulfo group, carboxyl, and sulfate, phosphate, boronate and according to its pKa and the group that has proton to dissociate out of the PH in the environment, for example-CONHSO ₂-Ji (as the sulfonamido formoxyl, the carbamyl sulfamoyl) ,-CONHCO-base (as the carboxyamino formoxyl) ,-SO ₂NHSO ₂-Ji (as the Herbicidal sulphonylamino sulfonyl) and phenolic hydroxyl group.Among these groups, preferably sulfo group and carboxyl ,-CONHSO ₂-Ji ,-CONHCO-base and-SO ₂NHSO ₂-Ji.

From-CONHSO ₂-Ji ,-CONHCO-base and-SO ₂NHSO ₂-Ji, according to its pKa and the PH in the environment, proton can not dissociate out.In this case, these groups are not included in the anion substituent.In other words, under the situation that proton does not dissociate, even two of this kind group are replaced to the dyestuff of for example being represented by following general formula (I-1), described dyestuff still can be considered the dye of positive ion.

The example of cationic substituent comprises amino replacement or unsubstituted and pyridine radicals.

Following molecular formula (I-1), (I-2) or (I-3) more preferably represented the dyestuff shown in the molecular formula (I):

L wherein ₅, L ₆, L ₇, L ₈, L ₉, L ₁₀And L ₁₁All represent methine group, P separately ₃And P ₄All represent 0 or 1 separately, n ₁Be 0,1,2,3 or 4, Z ₃And Z ₄Expression forms nitrogenous heterocyclic necessary atomic group, and its precondition is Z ₃And Z ₄But go up cyclic condensation, R ₃And R ₄The expression alkyl, aryl or heterocyclic group, M ₁And m ₁Have with molecular formula (I) in identical meaning, its precondition is when compound (I-1) when being the dye of positive ion, R ₃, R ₄, Z ₃, Z ₄And L ₅To L ₁₁All not having anion substituent, is the electric charge in the balance dye molecule when compound (I-1) is the betaine dyestuff, R ₃, R ₄, Z ₃, Z ₄And L ₅To L ₁₁Anion substituent is respectively arranged, a preferred anion substituent.

L wherein ₁₂, L ₁₃, L ₁₄And L ₁₅All represent methine group, P separately ₅Expression 0 or 1, n ₂Expression 0,1,2,3 or 4, Z ₅And Z ₆Expression forms nitrogenous heterocyclic necessary atomic group, and its precondition is Z ₅And Z ₆But go up cyclic condensation, R ₅And R ₆The expression alkyl, aryl or heterocyclic group, M ₁And m ₁Have with molecular formula (I) in identical meaning, its precondition is when compound (I-2) when being the dye of positive ion, R ₅, R ₆, Z ₅, Z ₆And L ₁₂To L ₁₅Cationic substituent is respectively arranged, and is balancing charge when compound (I-2) is the betaine dyestuff, R ₅, R ₆, Z ₅, Z ₆And L ₁₂To L ₁₅Cationic substituent and anion substituent are respectively arranged, a preferred cationic substituent and an anion substituent, when compound (I-2) when being non-ionic dye, R ₅, R ₆, Z ₅, Z ₆And L ₁₂To L ₁₅Both do not had cationic substituent and do not had anion substituent yet;

L wherein ₁₆, L ₁₇, L ₁₈, L ₁₉, L ₂₀, L ₂₁, L ₂₂, L ₂₃And L ₂₄All represent methine group, P separately ₆And P ₇All represent 0 or 1 separately, n ₃And n ₄All represent 0,1,2,3 or 4 separately, Z ₇And Z ₉All expression forms the essential atomic group of nitrogen heterocyclic ring, Z separately ₈And Z ' ₈All expression formation has (N-R separately ₈) _Q2The essential atomic group of heterocycle, its precondition be the ring can be condensed into Z ₇, Z ₈, Z ₈', R ₇, R ₈And R ₉All represent alkyl separately, aryl or heterocyclic group, and M ₁And m ₁Have with molecular formula (I) in identical meaning, its precondition is when dyestuff (I-3) when being the dye of positive ion, R ₇, R ₈, R ₉, Z ₇, Z ₈, Z ' ₈, Z ₉And L ₁₆To L ₂₄All there is not anion substituent, and when compound (I-3) is the betaine dyestuff, R ₇, R ₈, R ₉, Z ₇, Z ₈, Z ₈', Z ₉And L ₁₆To L ₂₄Have anion substituent,

Anionic dye shown in the molecular formula (II) is more preferably used following molecular formula (II-1), (II-2) or (II-3) expression:

L wherein ₂₅, L ₂₆, L ₂₇, L ₂₈, L ₂₉, L ₃₀And L ₃₁All represent methine group, P separately ₈And P ₉All represent 0 or 1 separately, n ₅Expression 0,1,2,3 or 4, Z ₁₀, Z ₁₁All expression forms nitrogenous heterocyclic necessary atomic group separately, and its precondition is Z ₁₀And Z ₁₁But go up cyclic condensation, R ₁₀, R ₁₁All represent alkyl separately, aryl or heterocyclic group, M ₂And m ₂Have with molecular formula (II) in identical meaning, its precondition is R ₁₀And R ₁₁Anion substituent is respectively arranged;

L wherein ₃₂, L ₃₃, L ₃₄And L ₃₅All represent methine group, P separately ₉Expression 0 or 1, n ₆Expression 0,1,2,3 or 4, Z ₁₂All expression forms the essential atomic group of nitrogen heterocyclic ring, Z separately ₁₃And Z ₁₃' all expression formation has (N-R separately ₁₃) _Q3The essential atomic group of heterocycle, its precondition is Z ₁₂, Z ₁₃And Z ₁₃But ' last cyclic condensation, R ₁₂, R ₁₃All represent alkyl separately, aryl or heterocyclic group, M ₂And m ₂Have with molecular formula (II) in identical meaning, its precondition is R ₁₂And R ₁₃In at least one has anion substituent;

L wherein ₃₆, L ₃₇, L ₃₈, L ₃₉, L ₄₀, L ₄₁, L ₄₂, L ₄₃And L ₄₄All represent methine group, P separately ₁₀And P ₁₁All represent 0 or 1 separately, n ₇And n ₈All represent 0,1,2,3 or 4 separately, Z ₁₄And Z ₁₆All expression forms nitrogenous heterocyclic necessary atomic group, Z separately ₁₅And Z ₁₅' all expression formation has (N-R separately ₁₅) _Q4The essential atomic group of heterocycle, Z ₁₄, Z ₁₅, Z ₁₅' and Z ₁₆But go up cyclic condensation, R ₁₄, R ₁₅And R ₁₃All represent alkyl separately, aryl or heterocyclic group, M ₂And m ₂Have with molecular formula (II) in identical meaning, its precondition is R ₁₄, R ₁₅And R ₁₆In at least two anion substituent is arranged.

When independent use molecular formula (I-1), (I-2) or during the compound (I-3), R ₃And R ₄In at least one, preferred two is the group that contains aromatic ring, R ₅And R ₆In at least one, preferred two is the group that contains aromatic ring, R ₇, R ₈And R ₉In at least one, preferred two, more preferably three all is the group that contains aromatic ring.

When be used in combination molecular formula (I-1), (I-2) or (I-3) shown in compound and molecular formula (II-1), (II-2) or (II-3) shown in compound the time, R ₃To R ₉Or R ₁₀To R ₁₆In, at least one, preferred two, more preferably three, further more preferably four or more be the group that contains aryl.

Utilize aforesaid method for optimizing, can obtain the spectral absorption maximum wavelength for being 60 or more, or the spectral absorption maximum wavelength is that 500nm, photon absorbing intensity are 100 or more silver halide particle less than 500nm, photon absorbing intensity.Yet the dyestuff in the second layer is usually with free state absorption, and in most of the cases, their absorption width and spectral sensitivity width are wideer than desirable separately scope.In order to realize the ISO in the desired wavelength coverage, the dyestuff that is adsorbed on the second layer must form J-associated matter (being the J-aggregation).The J-aggregation has high fluorescence efficiency and little Stokes displacement, so this helps in the second layer dyestuff and utilize Foster type energy to shift, and the luminous energy of absorption is transferred to the dyestuff of ground floor, and they are similar in the extinction wavelength.

Among the present invention, the dyestuff in the second layer and the upper strata is meant and is adsorbed onto on the silver halide particle, but directly is not adsorbed onto the dyestuff of silver halide.

Among the present invention, the J-associated matter of dyestuff in the second layer or the upper strata is defined as a kind of like this product, the absorption width that the more long wavelength direction that its makes the dye sheet be adsorbed onto the second layer or upper strata reveal absorbs is not take place between chromophore under the interactional free state, 2 times of the absorption width that the more long wavelength direction that dye solution shows absorbs or still less.The absorption width of used here more long wavelength direction is meant and is absorbing maximum wavelength and longer and show energy width between the wavelength that absorbs peaked 1/2 little absorption than absorbing maximum wavelength.As everyone knows, when forming the J-associated matter, and compare under the free state, more the absorption width of long wavelength's direction reduces.Still be in free state if be adsorbed onto the dyestuff of the second layer, absorb width and can be increased to 2 times of absorption width that dye solution showed under the free state more long wavelength direction absorbs or more, because absorption position and adsorbed state are inconsistent.Therefore, the dyestuff in the second layer or the upper strata can be by as above definition.

The spectral absorption that whole spectral absorption of emulsion deduct the ground floor dyestuff just obtains being adsorbed on the spectral absorption of the second layer and upper strata dyestuff.

Absorption spectrum when only adding dyestuff in ground floor by measuring can be measured the spectral absorption of the dyestuff in the ground floor.Adsorbed in the emulsion of sensitizing dye by dye sorbent is joined in multilayer, thereby, also can measure spectral absorption spectrum at the second layer and upper strata absorbing dye.

Using dye sorbent from the experiment of particle surface absorbing dye, after the dyestuff in the second layer and upper strata was adsorbed, the dyestuff in the ground floor was adsorbed usually.Therefore by selecting suitable acceptance condition, can obtain the spectral absorption of ground floor dyestuff, thereby obtain the spectral absorption of dyestuff in the second layer and the upper strata.Asanum et al. Journal of Physical Chemistry B, Vol.101, pp has described the method for using dye sorbent among the 2149-2153 (1997).

When using the dye of positive ion, betaine dyestuff or non-ionic dye shown in molecular formula (I) and the anionic dye shown in molecular formula (II), in order to form the J-associated matter of dyestuff, the preferred dyestuff of absorption formation ground floor and the dyestuff that absorption forms the second layer or upper strata of separately adding, preferred, the dyestuff that is used for ground floor has the structure that differs from one another with the dyestuff that is used for the second layer or upper strata.Dyestuff in the second layer or the upper strata preferably only contains the dye of positive ion, betaine dyestuff or non-ionic dye, or contains the dye of positive ion and anionic dye.

For the dyestuff in the ground floor, can use any dyestuff, molecular formula (I) or (II) shown in dyestuff be preferred, the dyestuff shown in the molecular formula (I) is preferred.

For the dyestuff in the second layer, preferably only use shown in the molecular formula (I) the dye of positive ion, betaine dyestuff or non-ionic dye.In another preferred embodiment of dyestuff of the second layer, be used in combination the dye of positive ion and anionic dye, used arbitrary dyestuff is the anionic dye shown in the dye of positive ion shown in the molecular formula (I) or the molecular formula (II) preferably, more preferably all contains the anionic dye shown in the dye of positive ion shown in the molecular formula (I) and the molecular formula (II).As the dyestuff in the second layer, the ratio of anionic/cationic dyestuff is 0.5 to 2, is more preferably 0.75 to 1.33, most preferably is 0.9 to 1.11.

Among the present invention, dyestuff except shown in molecular formula (I) and the molecular formula (II) also can add other dyestuff, however the dyestuff shown in molecular formula (I) or the molecular formula (II) preferably account for add the dyestuff total amount 50% or more, more preferably account for 70% or more, most preferably account for 90% or more.

By such adding second layer dyestuff, the interaction between second layer dyestuff can increase, and impels the dyestuff in the second layer to reset, thereby forms J-associated matter (being the J-aggregation).

When using as molecular formula (I) or the dyestuff (II) during as the ground floor dyestuff, Z ₁And Z ₂The basic nuclear that forms of basic nuclear that replaces by aryl or three or more cyclic condensation preferably.When using as molecular formula (I) and the dyestuff (II) during as the second layer or upper strata dyestuff, Z ₁And Z ₂The basic nuclear that forms by three or more cyclic condensations preferably.

For example, the number that is condensed into the ring of basic nuclear is 2 in the benzoxazoles ring, is 3 in the aphthothiazoles ring.Even the benzothiazole ring is replaced by phenyl, the number of the ring of condensation also is 2.What three or more cyclic condensations formed endorses substantially to be arbitrarily, as long as it is to be examined substantially by many cyclic condensations type heterocycle that three or more cyclic condensations obtain.Yet preferred three cyclic condensation type heterocycles and Fourth Ring condensed type heterocycle.The preferred embodiment of three cyclic condensation type heterocycles comprise naphtho-(2,3-d) oxazole, naphtho-(1,2-d) oxazole, naphtho-(2,1-d) oxazole, naphtho-(2,3-d) thiazole, naphtho-(1,2-d) thiazole, naphtho-(2,1-d) thiazole, naphtho-(2,3-d) imidazoles, naphtho-(1,2-d) imidazoles, naphtho-(2,1-d) imidazoles, naphtho-(2,3-d) selenazoles, naphtho-(1,2-d) selenazoles, naphtho-(2,1-d) selenazoles, indoles also (5,6-d) oxazole, indoles also (6,5-d) oxazole, indoles also (2,3-d) oxazole, indoles also (5,6-d) thiazole, indoles also (6,5-d) thiazole, indoles also (2,3-d) thiazole, coumarone also (5,6-d) oxazole, coumarone also (6,5-d) oxazole, coumarone also (2,3-d) oxazole, coumarone also (5,6-d) thiazole, coumarone also (6,5-d) thiazole, coumarone also (2,3-d) thiazole, benzothiophene also (5,6-d) oxazole, benzothiophene also (6,5-d) oxazole and benzothiophene also (2,3-d) oxazole.The preferred embodiment of Fourth Ring condensed type heterocycle comprise anthra (2,3-d) oxazole, anthra (1,2-d) oxazole, anthra (2,1-d) oxazole, anthra (2,3-d) thiazole, anthra (1,2-d) thiazole, phenanthro-(2,1-d) oxazole, phenanthro-(2,3-d) imidazoles, anthra (1,2-d) imidazoles, anthra (2,1-d) imidazoles, anthra (2,3-d) selenazoles, phenanthro-(1,2-d) selenazoles, phenanthro-(2,1-d) selenazoles, carbazole also (2,3-d) oxazole, carbazole also (3,2-d) oxazole, dibenzofurans also (2,3-d) oxazole, dibenzofurans also (3,2-d) oxazole, carbazole also (2,3-d) thiazole, carbazole also (3,2-d) thiazole, dibenzofurans also (2,3-d) thiazole, dibenzofurans also (3,2-d) thiazole, coumarone also (5,6-d) oxazole, dibenzothiophene also (2,3-d) oxazole, dibenzothiophene also (3,2-d) oxazole, tetrahydro carbazole also (6,7-d) oxazole, tetrahydro carbazole also (7,6-d) oxazole, dibenzothiophene also (3,2-d) thiazole and tetrahydro carbazole also (6,7-d) thiazole.The most preferred example of the basic nuclear that three or more cyclic condensations form comprise naphtho-(2,3-d) oxazole, naphtho-(1,2-d) oxazole, naphtho-(2,1-d) oxazole, naphtho-(2,3-d) thiazole, and naphtho-(1,2-d) thiazole, naphtho-(2,1-d) thiazole, indoles also (5,6-d) oxazole, indoles also (6,5-d) oxazole, indoles also (2,3-d) oxazole, indoles also (5,6-d) thiazole, indoles also (2,3-d) thiazole, coumarone also (5,6-d) oxazole, coumarone also (6,5-d) oxazole, coumarone also (2,3-d) oxazole, coumarone also (5,6-d) thiazole, coumarone also (2,3-d) thiazole, benzothiophene also (5,6-d) oxazole, anthra (2,3-d) oxazole, anthra (1,2-d) oxazole, and anthra (2,3-d) thiazole, anthra (1,2-d) thiazole, carbazole also (2,3-d) oxazole, carbazole also (3,2-d) oxazole, dibenzofurans also (2,3-d) oxazole, dibenzofurans also (3,2-d) oxazole, carbazole also (2,3-d) thiazole, carbazole also (3,2-d) thiazole, dibenzofurans also (2,3-d) thiazole, dibenzofurans also (3,2-d) thiazole, dibenzothiophene also (2,3-d) oxazole and dibenzothiophene also (3,2-d) oxazole.In these materials, further more preferably naphtho-(2,3-d) oxazole, naphtho-(1,2-d) oxazole, and naphtho-(2,3-d) thiazole, indoles also (5,6-d) oxazole, indoles also (6,5-d) oxazole, indoles also (5,6-d) thiazole, coumarone also (5,6-d) oxazole, coumarone also (5,6-d) thiazole, coumarone also (2,3-d) thiazole, benzothiophene also (5,6-d) oxazole, carbazole also (2,3-d) oxazole, carbazole also (3,2-d) oxazole, dibenzofurans also (2,3-d) oxazole, dibenzofurans also (3,2-d) oxazole, carbazole also (2,3-d) thiazole, carbazole also (3,2-d) thiazole, dibenzofurans also (2,3-d) thiazole, dibenzofurans also (3,2-d) thiazole, dibenzothiophene also (2,3-d) oxazole and dibenzothiophene also (3,2-d) oxazole.

Realize that a kind of like this dye chromophore is applied to the adsorbed state on silver halide particle surface with multilayer form the another kind of preferred embodiment of method is to use the dye composition that contains two or more dye chromophore parts, wherein dye chromophore links to each other with covalent bond by linking group.The dye chromophore that can use can be arbitrarily, and their example comprises aforesaid dye chromophore.In these dye chromophore, the as above poly-polymethylene dye chromophore described in the dye chromophore preferably, cyanine dyes more preferably, portion's cyanine dyes.If rhodacyanine dye and oxonol dye, if further cyanine dyes more preferably is rhodacyanine dye and portion's cyanine dyes, most preferably portion's cyanine dyes.

The preferred embodiment of method comprises the method for the described use of JP-A-9-265144 by the continuous dyestuff of methine chain as mentioned above, use described in the JP-A-10-226758 is connected to the method for the dyestuff on the oxonol dye, JP-A-10-110107, JP-A-10-307358, JP-A-10-307359 and the use described in the JP-A-10-310715 contain the method that is connected dyestuff of unique texture, described use has the method that is connected dyestuff of unique linking group to JP-A-9-189986 with JP-A-10-204306, Japanese patent application sequence number 11-34444,11-34463 has the method that is connected dyestuff of unique texture and the method for a kind of dyestuff of use described in the Japanese patent application sequence number 10-249971 with the use described in the 11-34462, this dyestuff has reactive group, produces to connect dyestuff in emulsion.

Connect the dyestuff shown in the preferably following formula of dyestuff (III):

D ₁-(La-(D ₂) _q) _r (III)

M ₃m ₃

D wherein ₁And D ₂All represent dye chromophore separately, La represents linking group or singly-bound, and q and r all represent from 1 to 100 integer, M separately ₃The gegenion of expression balancing charge, m ₃The expression neutralization divides the number of necessity of charge of the electron.

D is described below ₁, D ₂And La.

D ₁Or D ₂Shown chromophore can be arbitrarily.Its instantiation comprises aforesaid dye chromophore, in those chromophories, the preferred as above poly-polymethylene dye chromophore described in the dye chromophore, be more preferably cyanine dyes, portion's cyanine dyes, if rhodacyanine dye and oxonol dye, further cyanine dyes more preferably, portion's cyanine dyes and if rhodacyanine dye, most preferably cyanine dyes.

Among the present invention, when the connection dyestuff shown in the molecular formula (III) is adsorbed on the silver halide particle, D ₂Preferably directly be not adsorbed onto the chromophore of silver halide.

In other words, D ₂To the adsorption strength of silver halide particle preferably than D ₁Lower.To the most preferred order of the adsorption strength of silver halide particle is D ₁＞La＞D ₂

Like this, D ₁Preferably silver halide particle there is the sensitizing dye part of adsorbability, yet can be adsorbed onto on the silver halide by physisorption or chemisorption.

D ₂Preferably a little less than the adsorbability to silver halide particle, also luminescent dye preferably.As luminescent dye, be preferred for the dyestuff that contains skeleton structure (being basic structure) of dye laser.Mituo Maeda for example, Laser Kenkyu (study of laser), Vol.8, page 694, page 803and page 958 (1980), Ibid, Vol.9, page 85 (1981), and F.Shaefer, Dye Lasers, Springer has described these dyestuffs in (1973).

In silver halide photographic sensitive material, D ₁The absorption maximum wavelength preferably than D ₂The absorption maximum wavelength longer.And, D ₂The preferred and D of light emission ₁Absorption overlapping.In addition, D ₁Be preferably formed the J-aggregation.For being had, the connection dyestuff shown in the molecular formula (I) absorbs and spectral sensitivity D in desired wavelength coverage ₂Also be preferably formed the J-associated matter.

D ₁And D ₂Respectively have any reduction potential and any oxidizing potential, however D ₁Reduction potential preferably than D ₂Reduction potential to deduct the value of 0.2V gained bigger.

La represents linking group (preferred divalent linker) or singly-bound.Linking group is atom or the atomic group that has in carbon atom, nitrogen-atoms, sulphur atom and the oxygen atom at least one preferably.La preferably represents to contain the linking group of 0 to 100 carbon atom, more preferably contains 1 to 20 carbon atom, and be made of the one or two or more compound in the following groups: alkylidene (for example, methylene, ethylidene, propylidene, butylidene, pentylidene), arlydene is (for example, phenylene, naphthylene), alkylene thiazolinyl (ethenylidene for example, allylidene), alkylene alkynyl (for example ethynylene, inferior propinyl), acylamino-, ester group, sulfophenyl, sulfonate group, urea groups, sulfonyl, sulfinyl, thioester substrate, ester group, carbonyl ,-N (Va)-(wherein Va represents H atom or monovalence substituting group; The substituent example of monovalence comprises the represented group of describing later of V) and heterocycle divalent group (for example 6-chloro-1,3,5-triazines-2,4-two bases, pyrimidine-2,4-two bases, quinoxaline-2,3-two bases).

Aforesaid linking group respectively contains the substituting group that the described V in back represents.And these linking groups respectively contain the ring hydrocarbon or the heterocycle of non-aromatic (aromatic or).

La more preferably represents to contain the divalent linker of 1 to 10 atom, constitute by the one or two or more compound in the following groups: the alkylidene (methylene for example that contains 1 to 10 carbon atom, ethylidene, propylidene, butylidene), arlydene (the phenylene for example that contains 6 to 10 carbon atoms, naphthylene), the alkylene thiazolinyl (for example ethenylidene, allylidene) that contains 2 to 10 carbon atoms contains the alkylene alkynyl (ethynylene for example of 2 to 10 carbon atoms, inferior propinyl), ester group, amide group, sulfoamino-group and sulfonate group.These linking groups all can be replaced by the described V in back.

La is the interaction by connecting key, can carry out the linking group of energy transfer or electron transfer.The interaction of connecting key comprises that the tunnel interacts and hypermutation commutation interaction.Among both, be preferably based on the connecting key of hypermutation commutation interaction.Shammai Speiser, Chem.Rev.Vol.96 has defined connecting key and has interacted and hypermutation commutation interaction among the pp 1960-1963 (1996).As the linking group that energy transfer or electron transfer are taken place, Shammai Speiser, Chem.Rev.Vol.96, described in the pp 1967-1969 (1996) is preferred.

Q and r all represent 1 to 100 integer separately, and be preferred 1 to 5, more preferably 1 to 2, further more preferably 1.When q and r all represent 2 or more for a long time, the complicated linking group that contains La can be different mutually separately, the multiple dye chromophore that contains D2 also can be different mutually.

Dyestuff shown in the molecular formula (III) preferably has-1 charge number as an integral body.

Dyestuff is more preferably methine dyes, wherein the D in the molecular formula (III) ₁And D ₂Each (V) or (VI) is independently represented by following molecular formula (IV):

L wherein ₄₅, L ₄₆, L ₄₇, L ₄₈, L ₄₉, L ₅₀And L ₅₁All represent methine group, P separately ₁₂And P ₁₃All represent 0 or 1 separately, n ₉Expression 0,1,2,3 or 4, Z ₁₇And Z ₁₈All expression forms nitrogenous heterocyclic necessary atomic group separately, and its precondition is Z ₁₇And Z ₁₈But go up cyclic condensation, M ₄Expression balancing charge gegenion, m ₄In the expression and intramolecular charge needed 0 or bigger number, R ₁₇And R ₁₈All represent alkyl separately, aryl or heterocyclic group;

L wherein ₅₂, L ₅₃, L ₅₄And L ₅₅All represent methine group, P separately ₁₄Expression 0 or 1, n ₁₀Expression 0,1,2,3 or 4, Z ₁₉All expression forms nitrogenous heterocyclic necessary atomic group, Z separately ₂₀And Z ₂₀' all expression forms and has (N-R ₂₀) _Q5Heterocycle or acyclic acidic endgroups, its precondition is Z ₁₉, Z ₂₀And Z ₂₀But ' last cyclic condensation, M ₅Expression balancing charge gegenion, m ₅In the expression and intramolecular charge needed 0 or bigger number, R ₁₉And R ₂₀All represent alkyl separately, aryl or heterocyclic group:

L wherein ₅₆, L ₅₇, L ₅₈, L ₅₉, L ₆₀, L ₆₁, L ₆₂, L ₆₃And L ₆₄All represent methine group, P separately ₁₅And P ₁₆All represent 0 or 1 separately, n ₁₁And n ₁₂All represent 0,1,2,3 or 4 separately, Z ₂₁And Z ₂₃All expression forms nitrogenous heterocyclic necessary atomic group, Z separately ₂₂And Z ₂₂' all expression forms and has (N-R ₂₂) _Q6The necessary atomic group of heterocycle, its precondition is Z ₂₁, Z ₂₂, Z ₂₂' and Z ₂₃But cyclic condensation, M ₆Expression balancing charge gegenion, m ₆In the expression and intramolecular charge needed 0 or bigger number, R ₂₁, R ₂₂And R ₂₃All represent alkyl, aryl or heterocyclic group separately.

L wherein ₆₅, L ₆₆And L ₆₇All represent methine group, q separately ₇And q ₈All represent 0 or 1 separately, n ₁₃Expression 0,1,2,3 or 4, Z ₂₄And Z ₂₄' all expression forms and has (N-R ₂₄) _Q7The necessary atomic group of heterocycle, Z ₂₅And Z ₂₅' all expression forms and has (N-R ₂₅) _Q8The necessary atomic group of heterocycle, its precondition is Z ₂₄, Z ₂₄', Z ₂₅And Z ₂₅But ' cyclic condensation, M ₇Expression balancing charge gegenion, m ₇In the expression and intramolecular charge needed 0 or bigger number, R ₂₄And R ₂₅All represent alkyl, aryl or heterocyclic group separately.

D in molecular formula (III) ₁Preferably, be more preferably methine dyes by molecular formula (IV) expression by molecular formula (IV), (V) or (VI) methine dyes of expression.D in molecular formula (III) ₂Preferably by molecular formula (IV), (V) or (VII) methine dyes of expression, be more preferably by the molecular formula (IV) or (V) methine dyes of expression, further preferably by the methine dyes of molecular formula (IV) expression.

In use molecular formula (I) with in the method for dyestuff shown in the method for dyestuff (II) and the use molecular formula (III), it is preferred using the method for dyestuff shown in molecular formula (I) and the molecular formula (II).

Describe molecular formula (I) (comprise molecular formula (I-1), (I-2) and (I-3)) below in detail, molecular formula (II) (comprise molecular formula (II-1), (II-2) and (II-3)), (IV), (V) and the methylidyne compound (VI).

In molecular formula (I) with (II), Q ₁And Q ₂All represent to form the necessary group of methine dyes separately.Pass through Q ₁And Q ₂Group can form any methine dyes, but their example comprises as above as the described methine dyes of the example of dye chromophore.

In those dyestuffs, cyanine dyes preferably, if portion's cyanine dyes is rhodacyanine dye, three nuclear portion cyanine dyes, four nuclear portion cyanine dyes, pole-changing dyestuff, hemicyanine dye and styryl color, cyanine dyes more preferably, hemicyanine dye and if rhodacyanine dye, further cyanine dyes more preferably.F.M.Harmer, Heterocylic Compounds-Cyanine Dyes and Related Compounds, John Wiley ﹠amp; Sons, New York, London (1964), D.M.Sturmer. Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry, chap18, section 14, describe these dyestuffs among the pp 482-515 in detail.

To cyanine dyes, portion's cyanine dyes with if rhodacyanine dye, if do not limit n12, n15, the number of n17 and n18, and they all are 0 or bigger integer (preferably 4 or still less), USP 5,21 to 22 row described molecular formula (XI), (XII) and (XIII) be preferred in 340,694.

When by Q ₁Or Q ₂Form cyanine dyes or if during rhodacyanine dye, available following resonant expression molecular formula (I) and (II):

At molecular formula (I), (II), (IV), (V) and (VI) in, Z ₁, Z ₂, Z ₃, Z ₄, Z ₅, Z ₇, Z ₉, Z ₁₀, Z ₁₁, Z ₁₂, Z ₁₄, Z ₁₆, Z ₁₇, Z ₁₈, Z ₁₉, Z ₂₁And Z ₂₃Each represents a kind of formation nitrogen heterocyclic ring, the nitrogenous necessary atomic group of heterocycle of preferred 5-or 6-unit.Yet, but equal cyclic condensation on each of these atomic groups.Ring can be aromatic ring or non-aromatic ring, but aromatic ring is preferred, and its example comprises hydrocarbon aromatic ring (for example, phenyl ring and naphthalene nucleus) and hetero-aromatic ring (for example, pyrazine ring and thiphene ring).

Nitrogenous heterocyclic example comprises thiazoline nuclear, thiazole nucleus, benzothiazole nucleus, oxazoline nuclear, oxazole nucleus, benzoxazole nucleus, selenazoline nuclear, selenazole nucleus, benzo selenazole nucleus, 3,3-dialkyl group indolenine nuclear (for example, 3,3-dimethyl indolenine), imidazoline nuclear, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nuclei, the 4-quinoline nuclei, 1-isoquinoline nuclear, 3-isoquinoline nuclear, imidazo [4,5-b] quinoxaline nuclear, oxadiazoles nuclear, thiadiazoles nuclear, tetrazolium nuclear and pyrimidine nuclear.In above-mentioned heterocycle, benzothiazole nucleus preferably, benzoxazole nucleus, 3,3-dialkyl group indolenine nuclear (for example, 3,3-dimethyl indolenine), benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nuclei, 4-quinoline nuclei, 1-isoquinoline nuclear, 3-isoquinoline nuclear; Benzothiazole nucleus more preferably, benzoxazole nucleus, 3,3-dialkyl group indolenine nuclear (for example, 3,3-dimethyl indolenine), benzimidazole nucleus; Further benzoxazole nucleus more preferably, benzothiazole nucleus, benzimidazole nucleus; Most preferably benzoxazole nucleus and benzothiazole nucleus.

Suppose that the substituting group on nitrogen heterocyclic ring is V, the substituting group of V representative is not particularly limited, yet the example comprises halogen atom, alkyl (comprising naphthenic base and bicyclic alkyl); alkenyl (comprising cycloalkenyl group and bicycloenyl), alkynyl group, aryl, heterocyclic radical; cyano group, hydroxyl, nitro, carboxyl; alkoxy, aryloxy group, siloxy, heterocyclic oxy group; acyloxy, carbamoyloxy group, alkoxy carbonyl oxygen base, aryloxy group carbonyl oxygen base; amino (comprising anilino-), amide group, amino carbonyl amino, alkoxycarbonyl amino; aryloxycarbonyl amino, sulfamoyl amino, alkyl sulfonyl amino, Arenesulfonyl amino; sulfydryl, alkylthio group, artyl sulfo, heterocycle sulfenyl; sulfamoyl, sulfo group, alkyl sulphinyl; aryl sulfonyl kia, alkyl sulphonyl, aryl sulfonyl; acyl group, aryloxycarbonyl, alkoxy carbonyl; carbamyl, arylazo base, heterocycle azo base; inferior amide group, phosphino-, phosphinyl; phosphinyl oxygen base, phosphinyl oxygen base, phosphinyl is amino and silica-based.

More particularly, the example of V comprises halogen atom (for example chlorine atom, bromine atoms, iodine atom), alkyl [that is, line style, branching, replacement or unsubstituted ring alkyl; Described alkyl comprises the alkyl (alkyl that preferably has 1-30 carbon atom, methyl for example, ethyl, n-pro-pyl, isopropyl, the tert-butyl group, n-octyl, eicosyl, the 2-chloroethyl, the 2-cyano ethyl, the 2-ethylhexyl, naphthenic base (replacement or the unsubstituted ring alkyl that preferably have 3-30 carbon atom, cyclohexyl for example, cyclopentyl, the positive decyl cyclohexyl of 4-) and bicyclic alkyl (replacement or 2 that preferably has a 5-30 carbon atom is the substituted bicyclic alkyl not, promptly remove the singly-bound group that a hydrogen atom obtains from two cycloalkanes with 5-30 carbon atom, for example two encircle [1,2,2] heptan-the 2-base, two rings [1, oct-3-yl) and have a tricyclic structure of many ring structures 2,2]; Alkyl in the following substituting group alkyl of alkyl sulfenyl (for example) has such conception of species step of going forward side by side and comprises alkenyl], alkenyl [be line style, branching, ring-type replaces or substituted alkenyl base not; Alkenyl comprises that alkenyl (is preferably the replacement with 2-30 carbon atom or is substituted alkenyl base, for example vinyl; allyl; isopentyl; geranyl; oil base), cycloalkenyl group (replacement or the unsubstituted ring thiazolinyl that preferably have 3-30 carbon atom; promptly remove the unit price base of a hydrogen atom, 2-cyclopentene-1-base for example, 2-cyclohexene-1-yl from cyclenes with 3-30 carbon atom) and bicycloenyl (replace or unsubstituted bicycloenyl; preferably have the replacement of 3-30 carbon atom or substituted bicyclic thiazolinyl not, promptly remove the unit price base of a hydrogen atom, for example two rings [2 from two cyclenes with two keys; 2,1] hept-2-ene"-1-base, two rings [2; 2,2] alkynyl (replacement or the unsubstituting polysulfide yl that preferably have 2-30 carbon atom oct-2-ene-4-yl)]; ethinyl for example; propargyl; trimethyl silicon based ethinyl), aryl (replacement or the unsubstituting aromatic yl that preferably have 6-30 carbon atom, for example phenyl; p-methylphenyl, naphthyl, a chlorphenyl; neighbour-palmityl aminophenyl), heterocyclic radical (preferably replaces or unsubstituted fragrance or non-aromatic heterocycles are removed the unit price base that a hydrogen atom obtains from 5 or 6 yuan, more preferably has 5 or 6 membered aromatic heterocycle groups of 3-30 carbon atom; 2-furyl for example; the 2-thienyl; the 2-pyrimidine radicals; the 2-[4-morpholinodithio base), cyano group, hydroxyl; nitro, carboxyl, alkoxy (replacement or the unsubstituting alkoxy that preferably have 1-30 carbon atom; methoxyl for example; ethoxy; isopropoxy; tert-butoxy; n-octyloxy; the 2-methoxy ethoxy), aryloxy group (preferably has for example phenoxy group of the replacement of 6-30 carbon atom or unsubstituted aryloxy; the 2-methylphenoxy; 4-tert-butyl group phenoxy group; the 3-nitro-phenoxy, 2-tetradecane acyl group amino-benzene oxygen); siloxy (siloxy that preferably has 3-20 carbon atom, for example trimethylsiloxy group; the tertiary butyl dimethyl Si base), heterocyclic oxy group (replacement or the unsubstituting heterocycle oxygen base that preferably have 2-30 carbon atom; 1-phenyltetrazole-5-oxygen base for example, 2-four hydroxyl pyranose oxygen bases), acyloxy (preferred formyloxy; have the replacement of 2-30 carbon atom or substituted alkyl carbonyl oxygen base and have replacement of 6-30 carbon atom or unsubstituting aromatic yl carbonyl oxygen base not; formyloxy for example; acetoxyl group; new pentane acyloxy; stearoyl-oxy; benzoyloxy group; p-methoxyphenyl ketonic oxygen base), carbamyl oxygen base (preferably has the replacement of 1-30 carbon atom or does not replace for example N of carbamyl oxygen base, N-dimethyl methyl ammonia acyloxy; N; N-diethyl carbamyl oxygen base; morpholinyl carbon acyloxy; N; N-di-n-octyl amino-carbon acyloxy; N-octyl group carbamyl oxygen base), alkoxy carbonyl oxygen base (replacement or unsubstituting alkoxy carbon acyloxy, for example the methoxyl carbon acyloxy that preferably have 2-30 carbon atom; ethoxy carbon acyloxy; tert butoxy carbonyl oxygen base; n-octyl carbon acyloxy); aryloxy group carbon acyloxy (replacement or unsubstituted aryloxy carbon acyloxy, for example the phenoxy group carbon acyloxy that preferably have 7-30 carbon atom; to methoxyl phenoxy group carbon acyloxy; to n-hexadecane oxygen phenoxyl carbon acyloxy), amino (preferred amino; has the replacement of 1-30 carbon atom or substituted alkyl is amino and have the replacement or a unsubstituting phenenyl amido of 6-30 carbon atom; for example amino; methylamino; dimethylamino; anilino-methylphenylamine base; diphenyl amino), amide group (preferred formamido; have the replacement of 1-30 carbon atom or substituted alkyl carbonamido and the open-minded unsubstituting aromatic yl carbonamido in district with 6-30 carbon atom formamido for example not; acetamido and pivaloyl amido; the lauroyl amido; benzamido; 3,4; 5-three n-octyloxy phenyl carbons amide group); the amino-carbon amide group (preferably has the replacement of 1-30 carbon atom or substituted-amino carbonamido not, carbonamido for example, N; N-dimethylamino carbonamido; N; N-diethylamino carbonamido; the morpholine carbonamido), alkoxy carbonyl amido (replacement or unsubstituting alkoxy carbonamido with 2-30 carbon atom, for example methoxyl carbonamido; the ethoxy carbonamido; the tert butoxy carbonyl amido; n-octadecane oxygen base carbonamido; N-methyl methoxy base carbonamido); aryloxy group carbonamido (replacement or the unsubstituted aryloxy carbonamido that preferably have 7-30 carbon atom; phenoxy group carbonamido for example; to the chlorophenoxy carbonamido; between n-octyloxy phenoxy group carbonamido), the sulfonamide amido (preferably has the replacement of 0-30 carbon atom or does not replace the sulfonamide amido, for example the sulfonamide amido; N; N-dimethylamino sulfoamido; N-n-octyl sulfonamide amido); alkyl or aryl sulfonamide amido (preferably has the replacement of 1-30 carbon atom or substituted alkyl sulfonamide amido or have the replacement of 6-30 carbon atom or not substituted amido sulfoamido, for example sulfonyloxy methyl amido not; the butyl sulfonamide base; the phenyl-sulfamide base; 2,3; 5-trichlorobenzene base sulfoamido; the p-methylphenyl sulfoamido), sulfydryl; the alkyl sulfenyl (preferably has the replacement of 1-30 carbon atom or not substituted alkyl sulfenyl, for example methyl sulfenyl; the ethyl sulfenyl; the n-hexadecyl sulfenyl); artyl sulfo (replacement or the unsubstituting aromatic yl sulfenyl that preferably have 6-30 carbon atom; phenyl sulfenyl for example; the rubigan sulfenyl; the m-methoxyphenyl sulfenyl), heterocycle sulfenyl (replacement or the unsubstituting heterocycle sulfenyl that preferably have 2-30 carbon atom, for example benzothiazolyl sulfenyl; 1-phenyltetrazole-1-base sulfenyl); sulfamoyl (preferably has the replacement of 0-30 carbon atom or does not replace sulfamoyl; N-ethyl sulfamoyl for example; N-(3-dodecyloxy) sulfamoyl); N, N-benzoyl group sulfamoyl; N-(N '-phenyl-carbamyl) sulfamoyl), sulfonic group; alkyl-or the aryl sulfinyl (preferably have the replacement of 1-30 carbon atom or substituted alkyl sulfinyl and have the replacement or the unsubstituting aromatic yl sulfinyl of 6-30 carbon atom not; methyl sulfinyl for example; the ethylsulfinyl-1 base; the phenyl sulfinyl; the p-methylphenyl sulfinyl); the alkyl or aryl sulfonyl (preferably has the replacement of 1-30 carbon atom or substituted alkyl sulfonyl and have replacement or unsubstituting aromatic yl sulfonyl, for example methyl sulphonyl of 6-30 carbon atom not; ethylsulfonyl; phenyl sulfonyl; the p-methylphenyl sulfonyl), acyl group (preferred formoxyl; have the replacement of 2-30 carbon atom or substituted alkyl carbonyl not; replacement or unsubstituting aromatic yl carbonyl with 7-30 carbon atom; with replacement with 4-30 carbon atom or unsubstituting heterocycle carbonyl, wherein carbonyl is by carbon atom keyed jointing, for example acetyl group; valeryl; 2-chloro acetyl group; stearyl; benzoyl; align the octyloxyphenyl carbonyl; 2-pyranose carbonyl; the 2-furyl carbonyl); aryloxycarbonyl (preferably has for example phenyloxycarbonyl of the replacement of 7-30 carbon atom or unsubstituted aryloxy carbonyl; adjacent chlorophenoxy carbonyl; m-nitro oxygen base carbonyl; to tert-butyl group phenyloxycarbonyl); alkoxy carbonyl (replacement or unsubstituting alkoxy carbonyl, for example methoxycarbonyl that preferably have 2-30 carbon atom; ethoxy carbonyl; tert-butoxycarbonyl; n-octadecane oxygen base carbonyl), carbonamido (preferably has the replacement of 1-30 carbon atom or does not replace carbonamido; carbonamido for example; N-methyl carbonamido; N; N-dimethyl carbonamido; N, N-di-n-octyl carbonamido; N-(methyl sulphonyl) carbonamido), aryl or heterocycle azo base (replacement or the unsubstituting aromatic yl azo group and replacement or unsubstituting heterocycle azo group that preferably have 6-30 carbon atom with 3-30 carbon atom; phenylazo for example; the rubigan azo group; 5-ethyl sulfenyl-1; 3,4-thiadiazoles-2-base azo group), imino group (preferred N-succinimido and N-benzene diimide base); phosphino-(preferably has the replacement of 2-30 carbon atom or does not replace phosphino-; dimethyl phosphino-for example; diphenylphosphino; the toloxyl phosphino-), phosphinyl (preferably has the replacement of 2-30 carbon atom or does not replace phosphinyl, for example phosphinyl; two octyloxy phosphinyls; dioxy base phosphinyl); phosphinyl oxygen base (preferably has the replacement of 2-30 carbon atom or does not replace phosphinyl oxygen base; two phenoxy group phosphinyl oxygen bases for example; two octyloxy phosphinyl oxygen bases), phosphinyl amino (preferably has the replacement of 2-30 carbon atom or does not replace phosphinyl amino, for example dimethoxy phosphinyl amino; dimethylamino phosphinyl amino); (preferably have the replacement of 3-30 carbon atom or do not replace silica-based, for example trimethyl silicon based with silica-based; tert-butyl group dimethyl is silica-based; the phenyl dimethyl is silica-based).

And described substituting group can make ring (fragrance or non-aromatic hydrocarbon or heterocycle by having; These rings can be further combined with forming many cyclic condensations ring, the example comprises phenyl ring, naphthalene nucleus, anthracene nucleus, the quinoline ring, phenanthrene ring, the fluorenes ring, benzo [9,10] phenanthrene ring, the aphthacene ring, cyclohexyl biphenyl, pyrrole ring, furan nucleus, thiphene ring, imidazole ring, the oxazole ring, thiazole ring, pyridine ring, the pyrazine ring, pyrimidine ring, the pyridazine ring, the indolizine ring, indole ring, the coumarone ring, the benzothiophene ring, the isobenzofuran ring, the quinolizine ring, the quinoline ring, 2,3-diaza naphthalene nucleus, naphthalene quinoline ring, quinoxaline ring, quinoline oxazoline ring, the quinoline ring, the carbazole ring, the phenanthridines ring, bifurcation pyridine ring, the phenanthroline ring, the thianthrene ring, the chromene ring, the xanthenes ring, the phenoxthine ring, phenothiazine ring and azophenlyene ring) structure of condensation takes place.

When these functional groups had hydrogen atom, hydrogen atom can be removed and these functional groups can further be replaced by above-mentioned group.The example of this kind functional group comprises alkyl-carbonyl-amino sulfonyl, aryl-amino-carbonyl sulfonyl, alkyl sulfonyl-amino carbonyl and aryl sulfonyl amino carbonyl.Their example comprises methyl sulphonyl amino carbonyl, p-methylphenyl-sulfonyl amino carbonyl, acetyl-amino sulfonyl and benzoyl-amido sulfonyl.

In these substituting groups, alkyl preferably, aryl, alkoxy, halogen atom, aromatic ring condensation product, sulfo group, carboxyl and hydroxyl.

At Z ₁, Z ₂, Z ₃, Z ₄, Z ₅, Z ₇, Z ₉, Z ₁₀, Z ₁₁, Z ₁₂, Z ₁₄, and Z ₁₆Last more preferred substituents V is aromatic group and aromatic rings condensation product.

Use D in the molecular formula (III) ₁The chromophore of expression is with molecular formula (IV) (V), (VI) Biao Shi methine dyes, in this case, at Z ₁₇, Z ₁₈, Z ₁₉, Z ₂₁, and Z ₂₃Last more preferred substituents V is aromatic group and aromatic rings condensation product.

Use D in the molecular formula (III) ₂The chromophore of expression is with molecular formula (IV) (V), (VI) Biao Shi methine dyes, in this case, at Z ₁₇, Z ₁₈, Z ₁₉, Z ₂₁, and Z ₂₃Last more preferred substituents V is a carboxyl, sulfo group or hydroxyl, further sulfo group more preferably.

Z ₆, Z ₆' and (N-R ₆) _Q1, Z ₁₃, Z ₁₃' and (N-R ₁₃) _Q3, Z ₂₀, Z ₂₀' and (N-R ₂₀) _Q5, Z ₂₄, Z ₂₄' and (N-R ₂₄) _Q7And Z ₂₅, Z ₂₅' and (N-R ₂₅) _Q8Represent respectively by formation heterocycle or the necessary atomic group of acyclic acidic endgroups of mutually combining with triplets.Any heterocycle (preferred 5 or 6 yuan of heterocycles) all can form but acid core is preferred.Acid core and acyclic acidic endgroups are to be described in down.Each all can have any acid core or the acyclic acidic endgroups form of common cyanine dyes acid core and acyclic acidic endgroups.In a preferred form, Z ₆, Z ₁₃, Z ₂₀, Z ₂₄And Z ₂₅Be thiocarbonyl, carbonyl, ester group, acyl group, carbamyl, cyano group or sulfonyl, more preferably thiocarbonyl or carbonyl.Z ₆', Z ₁₃', Z ₂₀', Z ₂₄' and Z ₂₅' each all represents to form acid core or necessary all the other atomic groups of acyclic acidic endgroups.Under the situation that forms acyclic acidic endgroups, Z ₆', Z ₁₃', Z ₂₀', Z ₂₄' and Z ₂₅' each all preferably thiocarbonyl, carbonyl, ester group, acyl group, carbamyl, cyano group or sulfonyl.

q ₁, q ₃, q ₅, q ₇And q ₈Each all is 0 or 1, preferred 1.

Terminology used here " acid core and acyclic acidic endgroups " is for example James (editor), The Theory of the Photographic Process, 4th ed., page 198-200, definition to some extent among the Macmillan (1977).Here used acyclic acidic endgroups is meant acid, and what promptly form ring is subjected to the electronics end group.

The concrete example of acid core and acyclic acidic endgroups comprises USP 3,567,719,3,575,869,3,804,634,3,837,862,4,002,480,4,925,777, JP-A-3-167546 and USP5,994,051 and 5,747, those examples described in 236.

Acid core is preferably formed one and contains carbon, the 5-or the 6-member heterocyclic ring containing nitrogen of nitrogen and chalcogen (being typically oxygen, sulphur, selenium or tellurium) atom.Its example comprises following nuclear:

The 2-pyrazolin-5-one, pyrazolidine-3,5-diketone, imidazoline-5-ketone, hydantoins, 2-or 4-thiohydantoin, 2-imino group oxazolidine 4-ketone, 2-oxazoline-5-ketone, 2-sulfo-oxazoline-2,4-diketone, isoxazoline-5-ketone, 2-thiazoline-4-ketone, thiazolidin-4-one, thiazolidine-2,4-diketone, rhodanine, thiazolidine-2,4-diketone, different rhodanine, 1,2-dihydroindene-1,3-diketone, thiophene-3-ketone, thiophene-3-ketone-1,1-dioxide, Indolin-2-one, indoline-3-ketone, 2-oxygen indazole quinoline ion, 3-oxygen indazole quinoline ion, 5,7-dioxy-6, the 7-thiazoline is [3,2, a] pyrimidine also, cyclohexane-1,2-diketone, 3,4-dihydro-isoquinoline-4-ketone, 1,3-dioxan-4, the 6-diketone, barbituric acid, 2-Malony Ithiourea, coumaran-2,4-diketone, quinoline-2-one-, pyrido [1,2-a] pyrimidine-1, the 3-diketone, pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a] benzimidazole, Pyrazolopyridine ketone, 1,2,3,4-quinoline-2, the 4-diketone, 3-oxygen-2,3-dihydrobenzo [d] thiophene-1,1-dioxide and 3-dicyan methine-2,3-dihydrobenzo [d] thiophene-1,1-dioxide.

Comprise nuclear (carbonyl or the thiocarbonyl that wherein constitute above-mentioned nuclear are to be substituted in the active methylene group position of acid core) in addition with outer methylene structure and have outside the methylene structure nuclear (for example wherein have by interior methylene or cyano group methylene as the starting material of acyclic acidic endgroups and the activity methene compound of the structure that obtains is to be substituted in the active methylene group position).

These acid core and acyclic acidic endgroups each all can be by by above-mentioned or replace with substituting group that the V of cyclic condensation represents.

Z ₆, Z ₆' and (N-R ₆) _Q1, Z ₁₃, Z ₁₃' and (N-R ₁₃) _Q3, Z ₂₀, Z ₂₀' and (N-R ₂₀) _Q5, Z ₂₄, Z ₂₄' and (N-R ₂₄) _Q7And Z ₂₅, Z ₂₅' and (N-R ₂₅) _Q8Be preferably formed hydantoins respectively with triplets, 2-or 4-thiohydantoin, 2-oxazoline-5-ketone, 2-sulfo-oxazoline-2, the 4-diketone, thiazolidine-2,4-diketone, rhodanine, thiazolidine-2,4-diketone, barbituric acid or 2-Malony Ithiourea, be more preferably hydantoins, 2-or 4-thiohydantoin, 2-oxazoline-5-ketone, rhodanine, barbituric acid or 2-Malony Ithiourea further are more preferably 2-or 4-thiohydantoin, 2-oxazoline-5-ketone, rhodanine, barbituric acid.

Pass through Z ₈, Z ₈' and (N-R ₈) _Q2, Z ₁₅, Z ₁₅' and (N-R ₁₅) _Q4And Z ₂₂, Z ₂₂' and (N-R ₂₂) _Q6The example of the heterocycle that every triplets form be with to by Z ₆, Z ₆' and (N-R ₆) _Q1, Z ₁₃, Z ₁₃' and (N-R ₁₃) _Q3, Z ₂₀, Z ₂₀' and (N-R ₂₀) _Q5, Z ₂₄, Z ₂₄' and (N-R ₂₄) _Q7Or Z ₂₅, Z ₂₅' and (N-R ₂₅) _Q8The heterocycle that forms is described, and those are identical.In these, preferably to by Z ₆, Z ₆' and (N-R ₆) _Q1, Z ₁₃, Z ₁₃' and (N-R ₁₃) _Q3, Z ₂₀, Z ₂₀' and (N-R ₂₀) _Q5, Z ₂₄, Z ₂₄' and (N-R ₂₄) _Q7Or Z ₂₅, Z ₂₅' and (N-R ₂₅) _Q8The heterocycle (wherein oxo group or epithio base are removed) that forms and in above-mentioned acid core.

More preferably conduct is by Z ₆, Z ₆' and (N-R ₆) _Q1, Z ₁₃, Z ₁₃' and (N-R ₁₃) _Q3, Z ₂₀, Z ₂₀' and (N-R ₂₀) _Q5, Z ₂₄, Z ₂₄' and (N-R ₂₄) _Q7Or Z ₂₅, Z ₂₅' and (N-R ₂₅) _Q8The above-mentioned acid core of the instantiation of the ring that forms is wherein removed oxo group or epithio base.

Further more preferably preferred hydantoins, 2-or 4-thiohydantoin, 2-oxazoline-5-ketone, 2-sulfo-oxazoline-2,4-diketone, thiazolidine-2, the 4-diketone, rhodanine, thiazolidine-2, the 4-dithione, remove oxo group or epithio base on barbituric acid or the 2-Malony Ithiourea, more preferably from hydantoins, 2-or 4-thiohydantoin, 2-oxazoline-5-ketone, rhodanine removes oxo group or epithio base on barbituric acid or the 2-Malony Ithiourea, further more preferably from 2-or 4-thiohydantoin, 2-oxazoline-5-ketone removes oxo group or epithio base on the rhodanic acid.

Q ₂, q ₄And q ₆Each all is 0 or 1, preferred 1.

R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉, R ₁₀, R ₁₁, R ₁₂, R ₁₃, R ₁₄, R ₁₅, R ₁₆, R ₁₇, R ₁₈, R ₁₉, R ₂₀, R ₂₁, R ₂₂, R ₂₃, R ₂₄And R ₂₅Each represents a kind of alkyl, aryl or heterocyclic group.Their instantiation comprises and contain 1 to 18, and is preferred 1 to 7, and more preferably the non-substituted alkyl of 1 to 4 carbon atom (for example; methyl, ethyl, propyl group; isopropyl, butyl, isobutyl; hexyl, octyl group, dodecyl; octadecyl), contains 1 to 18, preferred 1 to 7; more preferably (for example, with above-mentioned substituting group V, preferably aralkyl (for example for the substituted alkyl of 1 to 4 carbon atom; benzyl, the 2-phenethyl), the alkyl of replacement); unsaturated alkyl (for example, allyl), hydroxyalkyl (2-hydroxyethyl for example; the 3-hydroxypropyl), carboxyalkyl (for example, 2-carboxyethyl; 3-carboxylic propyl group, 4-carboxylic butyl, ethyloic); alkoxyalkyl (for example, 2-methoxy ethyl, 2-(2-methoxy ethoxy) ethyl); aryloxy alkyl (for example, 2-phenoxy group ethyl, 2-(1-naphthoxy) ethyl); alkoxy carbonyl alkyl (for example; the ethoxy carbonyl methyl, 2-benzyloxycarbonyl ethyl), the aryloxycarbonyl alkyl is (for example; 3-phenyloxycarbonyl propyl group); acyloxy alkyl (for example, 2-acetoxyl group ethyl), acyl group alkyl (for example 2-acetyl ethyl); the carbamyl alkyl (for example; 2-morpholino carbonyl ethyl), sulfamoyl alkyl (for example N, N-dimethylamino sulfonyl methyl); sulfoalkyl (for example; the 2-sulfoethyl, 3-sulfopropyl, 3-sulphur butyl; 4-sulphur butyl; 2-[3-sulphur propoxyl group] ethyl, 2-hydroxyl-3-sulfopropyl, 3-sulphur propoxyl group ethoxyethyl group); the sulphur alkenyl; sulfato alkyl (for example, 2-sulfato-ethyl, 3-sulfato propyl group; 4-sulfato butyl); heterocyclic substituted alkyl (for example, 2-(pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl); alkyl sulfonyl-amino formoxyl alkyl (for example mesyl carbamyl ylmethyl); acyl amino formoxyl alkyl (for example, acetyl-amino formoxyl methyl), the acyl group sulfamoyl alkyl is (for example; acetyl group sulfamoyl methyl) and the alkyl sulphonyl sulfamoyl alkyl (for example; mesyl sulfamoyl methyl), contains 6 to 20, preferred 6 to 10; more preferably the non-substituted aryl of 6 to 8 carbon atoms (for example; phenyl, the 1-naphthyl), contain 6 to 20; preferred 6 to 10; more preferably the substituted aryl of 6 to 8 carbon atoms is (for example, with above-mentioned V substituting group, especially; right-methoxyphenyl; right-aminomethyl phenyl, to the chloro-phenyl, the aryl of replacement); contain 1 to 20; preferred 3 to 10, more preferably non-substituted heterocycle group (for example, the 2-furyl of 4 to 8 carbon atoms; the 2-thienyl; the 2-pyridine radicals, 3-pyrazolyl, 3-isoxazolyl; the 3-isothiazolyl; the 2-imidazole radicals, 2-oxazolyl, 2-thiazolyl; the 2-pyridazinyl; the 2-pyrimidine radicals, the 3-pyrazinyl, 2-(1; 3; the 5-triazolyl), 3-(1,2; the 4-triazolyl); the 5-tetrazole radical) and contain 1 to 20, preferred 3 to 10, more preferably the substituted heterocycle group of 4 to 8 carbon atoms (for example; the heterocyclic group that replaces with the substituting group example of above-mentioned V; particularly, 5-methyl-2-thienyl, 4-methoxyl-2-pyrimidine radicals).

R ₁, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈And R ₉Each all preferably contains the group of an aromatic ring.The example of aromatic rings comprises hydrocarbon aromatic ring and hetero-aromatic ring.These rings can be the cyclic condensation rings more than that forms by hydrocarbon aromatic ring or the mutual condensation of hetero-aromatic ring, or by an aromatic hydrocarbon ring and fragrant heterocycle cyclic condensation ring more than that is composited.These encircle each all available above-mentioned substituting group V or analog replaces.The preferred embodiment of aromatic ring comprises the aromatic ring example of the aromatic group of narrating above.

The group that contains aromatic ring can be expressed as-Lb-A ₁, wherein Lb represents singly-bound or linking group, A ₁The expression aryl.The preferred embodiment of the linking group that Lb represents comprises linking group and the analog thereof that above-mentioned La represents.A ₁The example of the aryl of expression comprises the above-mentioned examples of groups that contains aromatic ring.

Preferred embodiment with alkyl of hydrocarbonaceous aromatic ring comprises aralkyl (benzyl for example, 2-phenylethyl, naphthyl methyl, 2-(4-diphenyl) ethyl), aryloxy alkyl (for example, 2-phenoxy group ethyl, 2-(1-naphthoxy) ethyl, 2-(4-two phenoxy groups) ethyl, 2-(adjacent-,-or right-halogenated phenoxy) ethyl, 2-(adjacent-, between-or right-methoxyl phenoxy group) ethyl) and aryloxycarbonyl alkyl (for example, 3-phenyloxycarbonyl propyl group, 2-(1-naphthoxy carbonyl) ethyl); The band hetero-aromatic ring alkyl, 2-(2-pyridine radicals) ethyl for example, 2-(4-pyridine radicals) ethyl, 2-(2-furyl) ethyl, 2-(2-thienyl) ethyl and 2-(2-pyridine radicals methoxyl) ethyl; The hydrocarbon aryl, 4-methoxyphenyl for example, phenyl, naphthyl and diphenyl; Heteroaryl, 2-thienyl for example, 4-chloro-2-thienyl, 2-pyridine radicals and 3-pyrazolyl.

In these groups, more preferably have the alkyl group of replacement or non-replacement hydrocarbon aromatic ring or hetero-aromatic ring, further more preferably have the alkyl group of replacement or non-replacement hydrocarbon aromatic ring.

R ₂, R ₁₀, R ₁₁, R ₁₂, R ₁₃, R ₁₄, R ₁₅And R ₁₆Each preferably has the group of aromatic ring.R ₁₀And R ₁₁Both, R ₁₂And R ₁₃One of at least and R ₁₄, R ₁₅And R ₁₆One of at least have anion substituent.R ₂Preferably have anion substituent.The example of aromatic ring comprises hydrocarbon aromatic ring and hetero-aromatic ring.These rings can be the many cyclic condensations rings that forms by hydrocarbon aromatic ring or the mutual condensation of hetero-aromatic ring for every kind, or by aromatic hydrocarbon ring and fragrant heterocycle many cyclic condensations ring that is composited.These encircle each all available above-mentioned substituting group V or analog replaces.The preferred embodiment of aromatic ring comprises the aromatic ring example of the aromatic group of narrating above.

The group that contains aromatic ring can be expressed as-Lc-A ₂, wherein Lc represents singly-bound or linking group, A ₂The expression aryl.The preferred embodiment of the linking group that Lc represents comprises the linking group that La represents.A ₂The preferred examples of the aromatic group of expression comprises the example of above-mentioned aromatic group.Lc or A ₂Preferably replaced by at least a anion substituent.

Preferred embodiment with alkyl of hydrocarbonaceous aromatic ring comprises and passes through sulfo group, the aralkyl of phosphate or carboxyl substituted (for example, 2-sulphur benzyl, 4-sulphur benzyl, 4-sulphur phenethyl, 3-phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulphur butyl, 2-(41-sulfo group-4-diphenyl) ethyl, 4-phosphoric acid benzyl), sulfo group, the aryloxycarbonyl alkyl of phosphate or carboxyl substituted is (for example, 3-sulphur phenyloxycarbonyl propyl group) and sulfo group, the aryloxy alkyl of phosphate or carboxyl substituted (for example, 2-(4-sulphur phenoxy group) ethyl, 2-(2-phosphniline oxygen base) ethyl, 4,4-two phenoxy groups-3-sulphur butyl);

The preferred embodiment of the alkyl of band hetero-aromatic ring comprises 3-(2-pyridine radicals)-3-sulfopropyl, 3-(2-furyl)-3-sulfopropyl and 2-(2-thienyl)-2-sulfopropyl.

The preferred embodiment of the aryl of band hydrocarbon aromatic group comprises by sulfo group the aryl of phosphate or carboxyl substituted (for example, 4-sulfophenyl, 4-sulphur naphthyl); And aromatic heterocycle group, sulfo group for example, the aromatic heterocycle group of phosphate or carboxyl substituted (for example, 4-sulfo group-2-thienyl, 4-sulfo group-2-pyridine radicals).

In these groups, more preferably have sulfo group, the hydrocarbon fragrance of phosphate or carboxyl substituted or the alkyl of assorted aromatic group, further more preferably have sulfo group, the alkyl of the hydrocarbon aromatic ring of phosphate or carboxyl substituted, 2-sulphur benzyl most preferably, 4-sulphur benzyl, 4-sulfo group-phenethyl, 3-phenyl-3-sulfopropyl and 4-phenyl-4-sulphur butyl.

In molecular formula (III), use D ₁The chromophore of expression is with molecular formula (IV), (V), (VI) under the situation of Biao Shi methine dyes, uses R ₁₇, R ₁₈, R ₁₉, R ₂₀, R ₂₁, R ₂₂, R ₂₃, R ₂₄And R ₂₅Each non-substituted alkyl all preferably recited above of substituting group of expression or substituted alkyl (alkyl, carboxyalkyl for example, sulfoalkyl, aralkyl and aryloxy alkyl).

In molecular formula (III), use D ₂The chromophore of expression is with molecular formula (IV), (V), (VI) under the situation of Biao Shi methine dyes, uses R ₁₇, R ₁₈, R ₁₉, R ₂₀, R ₂₁, R ₂₂, R ₂₃, R ₂₄And R ₂₅Substituting group each non-substituted alkyl preferably recited above or substituted alkyl of expression are more preferably the alkyl (for example carboxyalkyl and sulfoalkyl) that has an anion substituent, further sulfoalkyl more preferably.

L ₁, L ₂, L ₃, L ₄, L ₅, L ₆, L ₇, L ₈, L ₉, L ₁₀, L ₁₁, L ₁₂, L ₁₃, L ₁₄, L ₁₅, L ₁₆, L ₁₇, L ₁₈, L ₁₉, L ₂₀, L ₂₁, L ₂₂, L ₂₃, L ₂₄, L ₂₅, L ₂₆, L ₂₇, L ₂₈, L ₂₉, L ₃₀, L ₃₁, L ₃₂, L ₃₃, L ₃₄, L ₃₅, L ₃₆, L ₃₇, L ₃₈, L ₃₉, L ₄₀, L ₄₁, L ₄₂, L ₄₃, L ₄₄, L ₄₅, L ₄₆, L ₄₇, L ₄₈, L ₄₉, L ₅₀, L ₅₁, L ₅₂, L ₅₃, L ₅₄, L ₅₅, L ₅₆, L ₅₇, L ₅₈, L ₅₉, L ₆₀, L ₆₁, L ₆₂, L ₆₃, L ₆₄, L ₆₅, L ₆₆And L ₆₇Each represents methine independently.L ₁To L ₆₇The methine of expression can have a substituting group.Substituent example comprises V recited above.For example contain 1 to 15, preferred 1 to 10, the more preferably replacement of 1 to 5 carbon atom or non-substituted alkyl (for example, methyl, ethyl, the 2-carboxyethyl), contain 6 to 20, preferred 6 to 15, the more preferably replacement of 6 to 10 carbon atoms or non-substituted aryl (for example, phenyl, neighbour-carboxy phenyl), contain 3 to 20, preferred 4 to 15, more preferably the replacement of 6 to 10 carbon atoms or non-substituted heterocycle group are (for example, N, N-dimethyl barbituric acid), halogen atom is (for example, chlorine, bromine, iodine, fluorine), contains 1 to 15, preferred 1 to 10, the more preferably alkoxy of 1 to 5 carbon atom (for example, methoxyl, ethoxy), contain 0 to 15, preferred 2 to 10, more preferably the amino of 4 to 10 carbon atoms (for example, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, the N methyl piperazine base), contain 1 to 15, preferred 1 to 10, more preferably alkylthio group (for example, the methyl mercapto of 1 to 5 carbon atom, ethylmercapto group), contains 6 to 20, preferred 6 to 12, the more preferably arylthio of 6 to 10 carbon atoms (for example, thiophenyl, right-the methylbenzene sulfenyl).Can form ring with another methine, perhaps can with Z ₁To Z ₂₃Or R ₁To R ₂₃Cheng Huan together.

L ₁, L ₂, L ₃, L ₄, L ₅, L ₆, L ₁₀, L ₁₁, L ₁₂, L ₁₃, L ₁₆, L ₁₇, L ₂₃, L ₂₄, L ₂₅, L ₂₆, L ₃₀, L ₃₁, L ₃₂, L ₃₃, L ₃₆, L ₃₇, L ₄₃, L ₄₄, L ₄₅, L ₄₆, L ₅₀, L ₅₁, L ₅₂, L ₅₃, L ₅₆, L ₅₇, L ₆₃And L ₆₄Each is the methine of a non-replacement preferably.

n ₁, n ₂, n ₃, n ₄, n ₅, n ₆, n ₇, n ₈, n ₉, n ₁₀, n ₁₁, and n ₁₂Each represents 0,1,2,3 or 4 independently, and is preferred 0,1,2 or 3, more preferably 0,1 or 2, further more preferably 0 or 1.

Work as n ₁, n ₂, n ₃, n ₄, n ₅, n ₆, n ₇, n ₈, n ₉, n ₁₀, n ₁₁, and n ₁₂Each is 2 or more for a long time, methine will repeat, but that these methines do not need is identical.

p ₁, p ₂, p ₃, p ₄, p ₅, p ₆, p ₇, p ₈, p ₉, p ₁₀, p ₁₁, p ₁₂, p ₁₃, p ₁₄, p ₁₅And p ₁₆Each represents 0 or 1 independently, is preferably 0.

M ₁, M ₂, M ₃, M ₄, M ₅, M ₆And M ₇Each all is included in the molecular formula, like this in order that in requiring and during the ionic charge of dyestuff, show kation or anionic existence.Cationic representative instance comprises inorganic cation, for example hydrogen ion (H ⁺), alkali metal ion (for example, sodion, potassium ion, lithium ion) and alkaline-earth metal ions is (for example, and organic cation, for example ammonium ion (ammonium ion, tetraalkyl ammonium ion calcium ion),, pyridinium ion, the ethylpyridine ion), 1,8-azabicyclo [5.4.0]-7-undecylene ion.Negative ion can be an inorganic anion, also can be organic anion, and the example comprises that halide ion (for example, fluorine ion, chlorion, iodide ion), substituted aryl sulfonate ion (for example, right-the toluenesulfonic acid salt ion, right-the chlorobenzenesulfonic acid salt ion), the aryl disulfonic salt ion (for example, 1,3-benzene sulfonate ion, 1,5-naphthalenedisulfonic acid salt ion, 2,6-naphthalenedisulfonic acid salt ion), the alkylsurfuric acid salt ion (for example, the methylsulfuric acid salt ion), sulfate ion, thiocyanic acid salt ion, the perchlorate ion, tetrafluoro boric acid salt ion, picrate ion, acetate ion and trifluoromethanesulfonic acid ion.And, can be with the ionomer or the another kind of dyestuff of electric charge that has and dyestuff opposite charge.When hydrogen ion is gegenion, CO ₂ ^-And SO ₃ ^-The available CO of difference ₂H and SO ₃H represents.

m ₁, m ₂, m ₃, m ₄, m ₅, m ₆And m ₇Each representative is used for balancing charge number required 0 or bigger number, and preferred numerical value is 0 to 4, and preferred numerical value is 0 to 1, and when forming inner salt, numerical value is 0.

To only describe the instantiation of the dyestuff in the optimization technique that is used in the detailed description of the present invention below, yet self-evident, the present invention never only limits to this.

The instantiation (comprising framework) of the compound of molecular formula among the present invention (I) representative

The instantiation (comprising framework) of the compound of molecular formula among the present invention (II) representative

The instantiation (comprising framework) of the compound of molecular formula among the present invention (III) representative

Dyestuff among the present invention can be according to F.M Harmer, Heterocyclic Compounds- Cyanine Dyes and Related Compounds, John Wiley ﹠amp; Sons, New York, London (1964); D.M.Sturmer Heterocyclic Compounds-Special topics in Heterocylic Chemistry, chap.18, Sec.14, pp.482-515, John Wiley ﹠amp; Sons, New York, London (1977); Rodd ' s Chemistry of Carbon Compounds, 2 ^NdEd., Vol.IV, Part B, Chap.15, p369-422; Method described in Elseiver Science Publishing CompanyInc. New York (1977) and (quoting to describe specific example) patent described above and the document is synthetic.

The present invention is not confined to the use of sensitizing dye of the present invention, and except those dyestuffs of the present invention, spectral sensitizing dye can also use with array mode.In spendable dyestuff, preferred cyanine dyes, portion's cyanine dyes, if rhodacyanine dye, oxonol dye, three nuclear portion cyanine dyes, four nuclear portion cyanine dyes, pole-changing dyestuff, styryl color and hemicyanine dye, cyanine dyes more preferably, portion's cyanine dyes, if rhodacyanine dye, further cyanine dyes more preferably.These dyestuffs (F.M.Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds, John Wiley ﹠amp; Sons, New York, Lodon (1964), and D.M.Sturmer, Heterocyclic Compounds-Special Topics in Hetero-Cyclic Chemistry, Chap.18, Sec.14 has a detailed description among the pp.482-515.

For cyanine dyes, portion's cyanine dyes with around the painting dyestuff, at USP 5,340, molecular formula (XII) described in the 694 21-22 pages or leaves and (XIII), be preferred, its precondition is n12, and n15, the number of n17 and n18 are unrestricted and each is 0 or above integer (preferred 4 or following).

These sensitizing dyes can single use or their two kinds or above being used in combination.The bond of sensitizing dye is generally used for the supersensitization effect.Their representative instance sees US2, and 688,545,2,977,229,3,397,060,3,522,052,3,527,641,3,617,293,3,628,964,3,666,480,3,673,898,3,679,428,3,303,377,3,769,301,3,814,609,3,837,862 and 4,026,707, GB1,344,281 and 1,507,803, JP-B-43-49336 and JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.

Itself do not have the dyestuff of spectral sensitization effect or do not absorb visible light basically but the material that shows the supersensitization effect can be included in the emulsion with sensitizing dye.

Can be used as case description that the example (for example pyrimidinyl-amino compound, triazine radical amido compound, pyrroles father-in-law's compound, aminobenzene vinyl cycloalkanes, fragrant organic formaldehyde condensation products, bifurcation acridine compound, cadmium salt) of the hypersensitizer in the spectral sensitization of the present invention and hypersensitizer and sensitizing dye be used in combination at US3,511,664,3,615,613,3,615,632,3,615,641,4,596,767,4,945,038,4,965,182,2,933,390,3,635,721,3,743,510 and 3,618,295.

Sensitizing dye of the present invention (equally applicable to other sensitizing dye and supersensitization dyestuff) also can be added in the silver emulsion of the present invention in any technology during the preparation emulsion, up to the present it is considered as useful.Add also can be at any time or step carry out, so long as before emulsion applies, for example between the silver halide particle shaping period and/or before the silver halide particle desalination, during desalination and/or after the desalination but before chemical slaking causes, as at US2,735,766,3,628,960,4,183,756 and 4,225,666, described in JP-A-58-184142 and the JP-A-60-196749, be right after before the chemical slaking or during, or after chemical slaking but before applying, for example be disclosed in JP-A-58-113920.And, as US4,225,666 and JP-A-58-7629 described, identical compound can add individually or in the compound combination with different structure in batches, for example during particle forms and during chemical slaking is finished or afterwards, or before the chemical slaking or during and during chemical slaking is finished.When adding, the kind of compound or the combination of compound can be changed in batches.

It is different and change that the addition of sensitizing dye of the present invention (being equally applicable to other sensitizing dye and supersensitization dyestuff) depends on the shape and size of silver halide particle, yet, sensitizing dye can every mole of silver halide to 1 * 10 ^-6To 8 * 10 ^-3The amount of mole is used.For example, when the silver halide particle size is 0.2-1.3 μ m, add measuring every mole of silver halide preferably 2 * 10 ^-6To 3.5 * 10 ^-3, be more preferably 7.5 * 10 ^-6To 1.5 * 10 ^-3Mole.

Yet under the situation of multilayer absorption, sensitizing dye of the present invention is to adsorb necessary amount interpolation to obtain multilayer.

According to the present invention, sensitizing dye of the present invention (being equally applicable to other sensitizing dye and supersensitization dyestuff) can directly be dispersed in maybe dyestuff can be dissolved in the emulsion a kind of suitable solvent for example methyl alcohol, ethanol, methyl cellosolve, acetone, water or pyridine or in their mixed solvent after and the form of the solution that obtains is added in the emulsion.At this moment, can add adjuvant for example alkali, acid or surfactant and they are combined.Also can use ultrasound wave to dissolve.Adding method for compound, can use at US3,469, described in 987 with compound dissolution at volatile organic solvent, solution is disperseed and dispersion liquid is added into method in the emulsion at the nucleophilicity colloid, described in the JP-B-46-24185 compound is being dispersed in water-soluble solvent and dispersion liquid is being added into method in the emulsion, described in the JP-A-51-74624 compound dissolution is being added into method in the emulsion at surfactant and with solution, and compound dissolution is being substantially free of water and solution is added into method in the emulsion in that JP-A-50-80726 is described.In addition,, can use at US2 for being added in the emulsion, 912,343,3,342,605,2,996,287 and 4,429, the method described in 835.

Utilization has the photographic silver halide particle (wherein sensitizing dye adsorbs with multilayer form) of high photon absorbing intensity, can obtain high sensitizing luminosity.Yet the problem of planting the emulsion initiation thus is ignorant so far at all.

By research widely, it has been observed by the present inventors that when will before the processing of photographic emulsion photographic, the optical density (OD) at spectral absorption maximum wavelength place being set at G0 and will being set at G1 in the optical density (OD) at the spectral absorption maximum wavelength place after the photographic processing, if the A value of being represented by A=G1/G0 surpasses 0.9, photograph ability so is badly damaged.When A be 0.9 or below, this problem is minimized.A preferably 0.7 or below, be more preferably 0.5 or below, further be more preferably 0.3 or below, especially preferably 0.1 or still less.

In above-mentioned, G1 and G0 all are meant the optical density (OD) that sensitizing dye produced of participating in spectral absorption.

For example, the optical density (OD) that is produced when the azomethine that makes by colour development by colour coupler or the superimposed sensitizing dye of coloring material, to absorb resulting optical density (OD) be G0 or G1 by deducting azomethine dyes or coloring material.

In order to eliminate the effect of azomethine dyes, can assess the G1 that does not carry out in the colored unexposed area that forms.In order to eliminate the effect of coloring material, after the photosensitive material that never adds sensitizing dye was estimated optical density (OD), the optical density (OD) of estimation can deduct from the optical density (OD) of the photosensitive material that is added with sensitizing dye.

Above-mentioned newfound problem is to be described in down.In the photosensitive material of routine, sensitizing dye has little photon absorbing intensity, therefore, in the optical density (OD) at spectral absorption maximum wavelength place before photographic and do not have big change afterwards.In other words, even A surpasses 0.9, following problem does not cause fatal problem.

Problem is in the dispersion of the quality of image of JP-A-11-160836 photosensitive silve halide material with from the printing of colored negativity photosensitive material the time, the dispersion in colour balance.

By research widely, it has been observed by the present inventors that when will before the processing of photographic emulsion photographic, being set at G0 and will being set at G1 in the optical density (OD) at the spectral absorption maximum wavelength place after the photographic processing in the optical density (OD) that the spectral absorption maximum wavelength goes out, if the A value of being represented by A=G1/G0 surpasses 0.9, photograph ability so is badly damaged.When A be 0.9 or below, this problem is solved.

For reduce A to 0.9 or below, can use any method.Yet, for example can use following method.

1. design the method for the structure of sensitizing dye

By the design sensitizing dye structure, A can be set in 0.9 or below.The example of this kind dyestuff comprises the dyestuff that has dissociation group and can cause hydrophilic/hydrophobic to change along with the change (for example PH) of environment.Can cause along with the change (for example PH) of environment the dyestuff that color status the changes dyestuff of the decolouring of predetermined temperature place (for example) and can with component reaction in the rinse solution and the dyestuff that changes at color status (dyestuff after for example decolouring).

The dyestuff that has dissociation group and can cause hydrophilic/hydrophobic to change along with the change (for example PH) of environment is to be shown in down but the present invention is not limited.

2. for example at Research Disclosure, the following method of describing among the Vol.207, No.20733 (July, 1981):

(1) adds water-soluble stilbene compound, non-ionics or both potpourris method to the developer;

(2) after bleaching and photographic fixing, handle photograph component to destroy the method for dyestuff with rigidizer; With

(3) use the method for persulfate bleaching bath as bleaching bath.

3. make dye decolored method

This method is described in JP-A-64-4739, JP-A-64-15734, and JP-A-64-35440, JP-A-1-21444 is among JP-A-1-35441 and the JP-A-1-159645.All these are to add the method for adjuvant to the develop solution etc.

4. destroy the method that sensitizing dye associates: this method is described among JP-A-2-50151 and the JP-A-2-71260.These are to destroy the method that sensitizing dye associates and obtains decolorization thus.

These methods 1 to 4 can be used in combination.

In the present invention, except that sensitizing dye, silver halide adsorption compound (a kind of available compound of photograph that is adsorbed on the silver halide particle) comprises anti-fog agent, stabilizing agent and nucleator.The example of spendable anti-fog agent and stabilizing agent is included in Research Disclosure, Vol.176, Item 17643 (RD17643), ibid., Vol.187, Item 18716 (RD18716), and ibid., Vol.308, item 308119 (RD308119).The example of spendable nucleator is included in US2, and 563,785 and 2,588, the hydrazine described in 982 is at US3, hydrazides and the hydrazone described in 227,552, at GB1,283,835, JP-A-52-69613, JP-A-55-138742, JP-A-60-11837, JP-A-62-210451, JP-A-62-291637, US3,615,515,3,719,494,3,734,738,4,094,683,4,115,122,4,306,016 and 4,471, the heterocycle quaternary salt described in 044.At US3,718, the 470 described substituent sensitizing dyes that in dye molecule, contain with nuclear activity, at US4,030; 925,4,031,127,4; 245,037,4,255,511; 4,266,013 and 4,276,364 and GB2; thiocarbamide bonding type acid hydrazide-alkali cpd described in 012,443 and at US4,080,270; 4,278,748 and GB2,011, having described in the 391B be bonded to thioamides ring on it or heterocyclic radical for example triazole or tetrazolium as the acid hydrazide-alkali cpd of absorption base.

In the present invention, the preferred embodiment of silver halide adsorption compound comprises nitrogen-containing heterocycle compound for example thiazole and benzothiazole, sulfhydryl compound, sulfide compound, sulfinic acid compound, thiosulfonic acid compound, thioamide compound, carbamide compound, selenourea compound and thiourea compound.Among these, more preferably nitrogen-containing heterocycle compound, sulfhydryl compound, sulfide compound and thiourea compound, and further nitrogen-containing heterocycle compound more preferably.The nitrogen-containing heterocycle compound that nitrogen-containing heterocycle compound is preferably represented by general formula (VIII) to (XI).

Compound by general formula (VIII) expression is the nitrogen-containing heterocycle compound that contains (tautomeric) imino group on heterocycle, compound by general formula (IX) expression is the nitrogen-containing heterocycle compound that contains (tautomeric) sulfydryl, compound by general formula (X) expression is the nitrogen-containing heterocycle compound that contains (non-tautomeric) thioketones base, and the compound of being represented by general formula (IX) is the nitrogen-containing heterocycle compound that contains the quaternary ammonium salt base base.These compounds all can be the acceptable acid addition salts forms.

Q1 in general formula, Q2, on behalf of nitrogen heterocyclic ring and its example, Q3 and Q4 all comprise imidazole ring, the benzimidazole ring, the naphtho-imidazole ring, thiazole ring, the benzothiazole ring, the aphthothiazoles ring, the oxazole ring, the benzoxazoles ring, the aphthoxazoles ring, benzo selenazoles ring, triazole ring, the benzotriazole ring, tetrazole ring, azepine indenes ring (diaza indenes ring for example, the benzotriazole ring, purine ring, pentaaza indenes ring), purine ring, the thiadiazoles ring, the oxadiazoles ring, the selenazoles ring, indole ring, triazine ring, pyrrole ring, pyridine ring, the pyridazine ring, the quinoline ring, the rhodanic acid ring, thiohydantoin, oxazolidinedione ring and 2,3-diaza naphthalene nucleus.

Among these, mutual-through type (VIII), preferred azepine indenes ring, (benzo) triazole ring, indole ring, triazine ring, purine ring and tetrazole ring, mutual-through type (IX), preferred tetrazole ring, triazole ring, (benzo) imidazole ring, thiadiazoles ring, azepine indenes ring and pyrimidine ring, mutual-through type (X), preferably (benzo) thiazole ring, (benzo) imidazole ring, (benzo) oxazole ring, triazole ring and tetrazole ring and mutual-through type (XI), preferred (benzo, naphtho-) thiazole ring and (benzo, naphtho-) oxazole ring." (benzo, naphtho-) thiazole ring " is meant " thiazole ring, benzothiazole ring or aphthothiazoles ring " (being equally applicable to other).

These heterocycles all can have suitable substituents for example hydroxyl, alkyl (for example methyl, ethyl, amyl group), alkenyl (as allyl), alkylidene (as ethinyl), aryl (as phenyl, naphthyl), aralkyl (as benzyl), amino, hydroxyl amino, alkylamino (for example ethylamino).Dialkyl amido (as dimethylamino), arylamino (for example phenyl amino), acylamino-(for example acetylamino), acyl group (for example acetyl group), alkyl sulfenyl (for example methyl sulfenyl), carboxyl, sulfo group, alkoxy (for example ethoxy), aryloxy group (for example phenoxy group), alkoxy carbonyl (for example methoxycarbonyl), can substituted carbamyl, can substituted amino-sulfonyl, can substituted urea groups, cyano group, halogen atom (for example chlorine, bromine), nitro, sulfydryl and heterocycle (for example pyridine radicals).

In general formula, R represents alkyl (for example methyl, ethyl, hexyl), alkenyl (as allyl, 2-butenyl group), alkylidene (as ethinyl), aryl (for example phenyl) or aralkyl (as benzyl), and they can have suitable substituents.

X ^-Expression negative ion (for example inorganic anion such as halide ion or organic anion for example p-toluenesulfonic esters).

In these compounds, preferably by general formula (VIII), (IX) and (XI) compound of expression, mutual-through type (VIII), the purine (it is tautomeric and can has imino group) that replaces of hydroxyl more preferably, mutual-through type (IX), mercapto-tetrazole (for example carbonyl, sulfo group) and mutual-through type (XI) with acidic-group, benzothiazole.

In these compounds; By general formula (VIII) and (IX) expression compound all in the silver ion bonding to form silver salt.In this case, nitrogen heterocyclic ring is preferably formed in that the solubility product in water is 10 near the room temperature ^-9To 10 ^-20, more preferably 5 * 10 ^-10To 10 ^-18Silver salt.

Taking a picture available compound can be before sensitizing dye adds, after interpolation is finished, or add beginning and add in time period between finishing at sensitizing dye and add, but take a picture available compound preferably before sensitizing dye adds, or add beginning and add in time period between finishing at sensitizing dye and add, more preferably add adding beginning and adding in time period between finishing.

The addition of available compound of taking a picture is different and different according to the kind of the function of adjuvant or emulsion, yet, normally 5 * 10 ^-5To 5 * 10 ^-3Mol/mol-Ag.

The instantiation that is adsorbed to the available compound of photograph on the silver halide particle is as follows.Self-evident, the present invention is not limited.

C-1 C-2 C-3

C-4 C-5

C-6 C-7 C-8

C-9 C-10 C-11

C-12 C-13 C-14

C-15 C-16

C-17

C-18

C-19

C-20

C-21

C-22 C-23

C-24

C-25

For the photographic emulsion that sensitization mechanism takes place in the present invention, can use any in silver bromide, iodo silver bromide, chloro silver bromide, silver iodide, iodo silver halide, iodine bromo silver halide and the silver halide.Yet the halogen component on the outermost layer of emulsion grain preferably contains 0.1mol% or more iodide, 1mol% or more more preferably, and therefore 5mol% or more more preferably can implement this multilayer adsorption structure securely again.

Particle size distribution can be wide can be narrow, but preferred narrow distributes.

The silver halide particle of photographic emulsion can be the particle with regular crystal formation such as cubic, octahedra crystal formation, tetrakaidecahedron crystal formation or prismatic dodecahedron crystal formation, it also can be particle with irregular crystal formation such as spherical crystal type or plain film shape crystal formation, also can be the potpourri that has high-order (hlk) crystal face or have these crystal particles, however preferred plain film shape crystal formation.To describe plain film shape crystal formation subsequently in detail.Particle with high-order crystal face exists Journal of Imaging Science, Vol.30, pp.247-254 has description in (1986).

For being used for silver halide photographic emulsions of the present invention, above-described silver halide particle can or use separately or uses with the form of mixtures of multiple particle.Silver halide particle has not homophase between nexine and superficial layer, have heterogeneous structure, for example overlaps heterogeneous structure, has local phase structure or have equal phase structure in whole particle at particle surface.These particles also can exist simultaneously.

Each can be surface latent image type emulsion for these different emulsions, and wherein latent image mainly forms on the surface; Or internal latent image type emulsion, wherein latent image forms in particle.

In the present invention, the preferred silver halide plain film shape particle that uses a kind of halogen component that contains silver halide, silver bromide, chloro silver bromide, iodo silver bromide, chlorine iodo silver bromide or iodo silver bromide.Plain film shape particle preferably has the particle of (100) or (111) principal plane.Plain film shape particle with (111) principal plane is referred to as (111) plain film shape particle hereinafter, and this particle has triangle or cube crystal face usually.Usually, when distribution became even, the plain film shape particle with hexagonal crystal face accounted for more at high proportion.JP-B-5-61205 has described single dispersed cubic plain film shape particle.

Have (100) crystal face and make the plain film shape particle of principal plane and be referred to as (100) plain film shape particle hereinafter, this particle has right angle or square crystal formation.In this emulsion, the adjacent edge ratio is called plain film shape particle rather than elongated piece less than 5: 1 particle.When plain film shape particle is the high particle of silver halide or silver halide content, (100) plain film shape particle aspect principal plane stability than the good stability of (111) principal plane.Therefore (111) plain film shape particle must carry out (111) principal plane stabilization processes, and its method is at JP-A-9-80660, and JP-A-80656 and USP5 have description in 298,388.

Be used for of the present inventionly containing silver halide or high (111) the plain film shape particle of silver halide content has report in following patent:

USP 4,414, and 306,4,400,463,4,713,323,4,783,398,4,962,491,4,983,508,4,804,621,5,389,509,5,217,858 and 5,460,934.

Be used for high (111) the plain film shape particle of bromide sliver content of the present invention and report arranged in following patent:

USP 4,425, and 425,4,425,426,4,434,266,4,439,520,4,414,310,4,433,048,4,647,528,4,665,012,4,672,027,4,678,745,4,684,607,4,593,964,4,722,886,4,755,617,4,755,456,4,806,461,4,801,522,4,835,322,4,839,268,4,914,014,4,962,015,4,977,074,4,985,350,5,061,609,5,061,616,5,068,173,5,132,203,5,272,048,5,334,469,5,334,495,5,358,840 and 5,372,927.

(100) the plain film shape particle that is used for the present invention has description in following patent:

USP 4,386, and 156,5,270,930,5,292,632,5,314,798,5,320,938,5,319,635 and 5,356,764, European patent 569,971 and 737,887, JP-A-6-308648 and JP-A-9-5911.

The silver emulsion that is used for the present invention preferably be adsorbed with on it open in the present invention sensitizing dye and the plain film shape silver halide particle with higher surface area/volume ratio, and preferably wherein radius-thickness ratio be 2 or above (preferred 100 or following), more preferably 5-80, more preferably the particle of 8-80 has accounted for 50% or above emulsion of all silver halide particles.

The thickness of plain film shape particle preferably is lower than 0.2 μ m, more preferably less than 0.1 μ m, further be more preferably and be lower than 0.07 μ m.In order to prepare plain film shape particle, use following technology with high radius-thickness ratio like this and little thickness.

Plain film shape particle used in this invention is at distribute in particle homogeneous preferably of dislocation line amount.In emulsion of the present invention, each particle have 10 or the silver halide particle of above dislocation line preferably account for all particles 50 to 100%, more preferably 70-100%, further preferably account for 90-100%.

If this ratio is to be lower than 50%, present the inhomogeneity unfavorable result among particle.

In the present invention, when the number of the ratio of the particle of determining to have dislocation line and dislocation line, dislocation line is preferably at least on 100 particles, be more preferably 200 particles or more than, further more preferably 300 particles or above observing directly.

As the protective colloid of preparation emulsion of the present invention with as the cementing agent of other hydrophilic colloid, preferably use gelatin, yet, also can use the hydrophilic colloid except that gelatin.

The example of other spendable hydrophilic colloid comprise protein for example gelatine derivative, gelatin to the graft polymer of other polymkeric substance, albumin and casein; Sugar derivatives is cellulose derivative (for example hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfuric acid ester), mosanom and starch derivative for example; With various synthesis hydrophilic polymeric materials for example polyvinyl alcohol (PVA), polyvinyl alcohol (PVA) part acetal, polyvinylpyrrolidone, polyacrylic acid, polymethylacrylic acid, polyacrylamide, polyvinyl imidazole and tygon pyrazoles.

Gelatin can be at Bull.Soc.Photo.Japan, No.16, the P.30 gelatin of the gelatin of the lime treatment of describing in (1966), acid-treated gelatin or enzyme processing.

Thereby emulsion of the present invention preferably washes with water with the desilverization and makes freshly prepd protective colloid dispersion.The water washing temperature can be selected according to purposes but select in the preferred scope between 5 ℃ to 50 ℃.PH during washing also can select according to purposes but be preferably 2-10, more preferably 5-10.Method for washing can be selected from emulsion bar WATER-WASHING METHOD, uses barrier film dialysis, centrifuging, solidifies precipitation and ion-exchange.Solidifying under the situation of precipitation, this method can be to use the method for sulfate, method with an organic solvent, use the method for water-soluble polymers and the method for use gelatine derivative.

In the process of preparation emulsion of the present invention, preferably make metal cation salt for example at grain forming, during in desalination, in chemical sensitization the time or before coating, keep suitable content according to concrete purposes.When metal cation salt is that it preferably adds during grain forming when being doped in the particle, when it is owing to the modified particles surface or is used as chemical sensitizer, preferably after grain forming or before the chemical sensitization effect, add.When mixing, metal cation salt can mix in the entire portion of particle or can be only partly mix at the core or the shell of particle.The example that can be used as metal of the present invention comprises Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Ti, In, Sn, Pb and Bi.If these metals are form for example ammonium salt, acetate, nitrate, sulfate, phosphate, oxyhydroxide, hexa-coordinate complex salt and the four-coordination complex salt of soluble salt, they all can add during grain forming so.Their example comprises: CdBr ₂, CdCl ₂, Cd (NO ₃) ₂, Pb (NO ₃) ₂, Pb (CH ₃COO) ₂, K ₃[Fe (CN) ₆], (NH ₄) ₄[Fe (CN) ₆], K ₃IrCl ₆, (NH ₄) ₃RhCl ₆And K ₄Ru (CN) ₆The part of coordination compound can be selected from halogen, aco, cyano group, cyanate, thiocyanate, nitrosyl radical, oxo group and carbonyl.These metallic compounds can use separately or the two or more of these metallic compounds are used in combination.

Metallic compound is preferably to be dissolved in them in the water or to add after for example in methyl alcohol and the acetone in the appropriate organic solvent again.For stabilizing solution, can use and add hydrogen halides (as HCl, HBr) or alkali halide (KCl for example, NaCl, KBr, the method for aqueous solution NaBr).If desired, also can be added into acid, alkaline metal etc.Also metallic compound can be added into before grain forming in the reaction vessel or also and can add during grain forming.And, metallic compound may be added in the water soluble silver salt (AgNO for example ₃) or the aqueous solution of alkali halide (for example NaCl, KBr, KI) in and in the silver halide particle forming process, add gained solution then continuously.In addition, solution can be can't help water soluble silver salt or alkali halide and be made, and adds continuously on suitable opportunity in the molding particles process.Preferred combination is used these various adding methods.

According to circumstances, at US3, the method for adding chalcogen compound in the emulsion preparation process described in 772,031 also can be used.Except S, outside Se and the Te, in system, also can add cyanogen salt, thiocyanate, selenocyanic acid, carbonate, phosphate or acetate.

Silver halide particle of the present invention can stand at least a in the following sensibilization in the arbitrary steps during the silver halide particle preparation: sulphur sensitizing, selenium sensitizing, golden sensitizing, palladium sensitizing, noble metal sensitizing and reduction sensitization.Preferred combination is used two kinds or above process for increasing sensitivity.Various emulsions can be prepared by the step that the effect of change chemical sensitization is carried out.Its example comprises that the nuclear of chemical sensitization wherein embeds the type that position in type in the particle, the shallow-layer that chemical sensitization nuclear is embedded in particle surface and chemical sensitization nuclear form at particle surface.The position of chemical sensitization nuclear can be selected according to concrete purposes.Normally, near preferred formation particle surface of at least a chemical sensitization nuclear.

A chemical sensitization effect can preferably implementing in the present invention is to use being used in combination of chalcogen process for increasing sensitivity or noble metal process for increasing sensitivity or they separately.As T.H.James, the Theory ofthe Photographic Process, 4 ^ThEd., pp.67-76, the described chemical sensitization effect of Macillan (1977) can use active gelatin to carry out or as Research Dislosure, Vol.120,12008 (April 1974), Research Dislosure, Vol.34,13452 (June 1975), US2,642,361,3,297,446,3,772,031,3,857,711,3,901,714,4,266,018 and 3,904,415, and GB1,315, use sulphur described in 755, selenium, tellurium, gold, platinum, palladium, iridium, or two kinds or above combination of these sensitizing dyes, PAg is 5-10, pH value is that 5-8 and temperature are 30-80 ℃.。When noble metal sensitizing, can use noble metal as gold, platinum, palladium and the salt of complying with.Among these, golden sensitizing, palladium sensitizing and being used in combination of they are preferred.In golden sensitizing, can use known compound for example gold chloride, potassium chloroaurate, golden thiocyanate, aurosulfo and Auric selenide.Palladium compound is meant divalence or tetravalence palladium salt.Preferred palladium compound is by R ₂PdX ₆Or R ₂PdX ₄Expression, wherein R represents hydrogen atom, alkali metal atom or amino, and X represents halogen atom for example chlorine, bromine and iodine.

More particularly, preferred K ₂PdCl ₄, (NH ₄) ₂PdCl ₆, Na ₂PdCl ₄, (NH ₄) ₂PdCl ₄, Li ₂PdCl ₄, Na ₂PdCl ₆And K ₂PdBr ₄Gold compound or palladium compound preferably are used in combination with thiocyanate or sulfo-selenate.

The example of spendable sulphur sensitizer comprises as US3,857,711,4,266,018 and 4,054, and the hypo described in 457 (hypo), thiourea compound, rhodanic acid compound and sulfocompound.The chemical sensitization effect also can be carried out in the presence of so-called chemical sensitization auxiliary agent.Knownly be used for suppressing atomizing and the compound of super-sens between action period for example azepine indenes, azepine pyridazine and aza-pyrimidine can be used as the chemical sensitization auxiliary agent in chemical sensitization.The example of chemical sensitization effect additive modification agent is at US2, and 131,038,3,411,914 and 3,554,757, JP-A-58-126526 and Duffin, Chemistry of photographic Emulsion, pp.138-143.

Emulsion of the present invention preferably also carries out golden sensibilization.The consumption of gold sensitizer preferably has 1 * 10 to every mole of silver halide ^-4To 1 * 10 ^-7Mole is more preferably 1 * 10 ^-5To 5 * 10 ^-7Mole.The consumption of palladium compound preferably 1 * 10 ^-3To 5 * 10 ^-7Mole.The consumption of thiocyanic acid compound or selenocyanic acid compound preferably 5 * 10 ^-2To 1 * 10 ^-6Mole.

The consumption that is used for the sulphur sensitizer of silver halide particle of the present invention preferably has 1 * 10 to every mole of silver halide ^-4To 1 * 10 ^-7Mole is more preferably 1 * 10 ^-5To 5 * 10 ^-7Mole.

The process for increasing sensitivity that is preferably used as emulsion of the present invention is the selenium sensibilization.Known unsettled selenium compound is used in the selenium sensibilization.More particularly, can use selenium compound for example colloidal metal selenium, selenourea (for example N, N-dimethyl selenourea, N, N-diethyl selenourea), selenium ketone and selenium acid amides.In some cases, the selenium process for increasing sensitivity is preferably to be used in combination with sulphur sensitizing, noble metal sensitizing or their combination.

Silver emulsion of the present invention preferably during the grain forming, after grain forming and before the chemical sensitization or during, or after chemical sensitization, carry out reduction sensitization,

Reduction sensitization can be undertaken by being selected from following any means: add the reduction sensitization agent to silver emulsion, the method that is called silver-colored slaking wherein silver halide particle be that the low pAg with 1-7 increases or slaking in atmosphere, with the method that is called high PH slaking, wherein silver halide particle is that the high pH value with 8-11 increases or slaking in atmosphere.Also can be used in combination two kinds or above method.

The method of adding the reduction sensitization agent is favourable, because the degree of reduction sensitization effect can be controlled consciously.

The well known examples of reduction sensitization agent comprises tin salt, ascorbic acid and their derivant, amine, polyamines class, hydrazine derivate, formamidine sulfinic acid, silane compound and borane compound.Reduction sensitization agent used in this invention can be selected from known reduction sensitization agent.And two or more of these compounds can be used in combination.Preferred compound as the reduction sensitization agent is stannous chloride, thiourea dioxide, dimethylamine borane and ascorbic acid and their derivant.The addition of reduction sensitization agent changes according to the working condition of emulsion is different, therefore, need select but suitable be to be 10 to every mole of silver halide ^-7-10 ^-3

The reduction sensitization agent is to be dissolved in the water or for example to add between the rise period of particle after ethanol, ethylene glycol, acetone, ester or the acid amides in the organic solvent.The reduction sensitization agent also can be added in the reaction vessel earlier, but preferably is chosen in suitable its method of time interpolation during the grain growth.The reduction sensitization agent also can be added in water soluble silver salt or the water-soluble alkali halogenide earlier and use aqueous solution, and silver halide particle also can be precipitated.In addition, the method for also preferably in the long period section, adding in batches or adding continuously the solution of reduction sensitization along with the growth of particle.

In the preparation process of emulsion of the present invention, the preferred oxygenant that uses silver.Terminology used here " to the oxygenant of silver " is meant to have and acts on the compound of argent with the function that is converted into silver ion.Specifically, can use the compound that the silver-colored particle of minute quantity can be transformed into silver ion during silver halide particle moulding and chemical sensitization.Can form the silver salt that is difficult to dissolve in the crafty water for example silver halide, silver sulfide and silver selenide at this silver ion that makes, perhaps can form for example silver nitrate of the silver salt that is easy to be dissolved in the water.Oxygenant to silver can be inorganic or organic compound.The example of inorganic oxidizer comprises ozone, hydrogen peroxide or their adduct (NaBO for example ₂.H ₂O ₂.3H ₂O, 2NaCO ₃.3H ₂O ₂, Na ₄p ₂O ₇.2H ₂O ₂, 2NaSO ₄.H ₂O ₂.2H ₂O), peracid salt (K for example ₂S ₂O ₈, K ₂C ₂O ₆, K ₂P ₂O ₈), peroxo-complex (K for example ₂[Ti (O ₂) C ₂O ₄] .3H ₂O, 4K ₂SO ₄.Ti (O ₂) OH.SO ₄.2H ₂O, Na ₃[VO (O ₂) (C ₂H ₄) ₂] .6H ₂O), oxysalt for example permanganate (as KMnO ₄) and chromate (as K ₂Cr ₂O ₇), halogen element is iodine and bromine for example, crosses halide salt (for example crossing potassium iodide), slaine (for example potassium hexacynoferrate) and thiosulfate with high price.

The example of organic oxidizing agent comprises for example para-quinone of quinone, organic peroxide power peracetic acid and benzylhydroperoxide and the compound (for example, N-bromo-succinimide, toluene-sodium-sulfonchloramide, chloramine B) that discharges reactive halogen.In these oxygenants, for example ozone, hydrogen peroxide and their adduct of inorganic oxidizer preferably in the present invention, halogen element and thiosulfate, organic oxidizing agent is quinone for example.In the preferred examples scheme, above-mentioned reduction sensitization effect is to be used in combination with oxygenant to silver.Described method can be selected from following method: use earlier oxygenant and carry out the method for reduction sensitization then, carry out reduction sensitization earlier and the method using the method for oxygenant then and both are carried out simultaneously.

Sensitizing emulsion of the present invention can comprise the various compounds except that aforesaid compound, makes to be adsorbed on the silver halide to prevent atomizing or be used for stablizing photographic property with preparation, storage or the photographic processing that is used at photosensitive material.Anti-fog agent and stabilizing agent can repeatedly add according to purposes, for example before the grain forming, during or afterwards, during washing, the washing after dispersed phase between, before the chemical sensitization, during or afterwards and the coating before.These anti-fog agents and stabilizing agent all are to add in the preparation process of emulsion, not only produced its intrinsic resistance to fogging and stability, and be used for that various uses is for example controlled the crystallization property of particle, reduced particle size, the solubleness, control chemical sensitization and the control dyestuff that reduce particle arranged.

If one of at least photographic layer among the blue layer of sense, green layer or the sense red beds provides on the sheet base, the photosensitive material that the silver emulsion that uses the present invention to obtain makes is enough.The number of silver halide emulsion layer and non-photographic layer and order are not restricted especially.Its representative instance is a kind of silver halide photographic sensitive material, and it comprises a slice base and forms thereon by having essentially identical spectral sensitivity but at least one sense chromatograph that the different a plurality of silver halide emulsion layers of light sensitivity are formed.This photographic layer is to the arbitrary unit photographic layer that all has spectral sensitivity among blue light, green glow and the ruddiness.Under the situation of multilayer silver halide colour photographic sensitive material, this unit sensitization material begins generally to feel red beds, the order arrangement of green layer and the blue layer of sense from sheet base side.Yet according to predetermined application, this ordering can change, and perhaps can be placed on ordering between the same spectra light sensitivity layer to different light sensitivity.

Non-photographic layer for example also can be between above-mentioned light-sensitive silver halide layer or as the superiors or the bottom in the middle layer between each layer.

The middle layer can be included in JP-A-61-43748, JP-A-59-113438, and JP-A-59-113440, colour coupler of describing among JP-A-61-20037 and the JP-A-61-20038 and DIR compound, and also can comprise normally used mixed color inhibitor.

The a plurality of silver halide emulsion layers that constitute each unit photographic layer preferably use the double-layer structure of being made up of high-sensitivity emulsion layer and low speed emulsion layer, as at DE No.1, and 121,470 or GBNo.923, described in 045.Normally, each layer preferred arrangement become light sensitivity is reduced successively towards sheet base direction.Non-photographic layer can be provided between silver halide emulsion layer.In addition, as JP-A-57-112751,62-200350,620206541 and 62-206543 described in, can make away from sheet base one adnation to become the low speed emulsion layer, and become the mode of high-sensitivity emulsion layer to arrange near sheet base one adnation.

The instantiation that layer is arranged is, from leaving sheet base farthest side, can dispose these photographic layers with the ordering (being BL/BH/GH/GL/RH/RL) of the blue layer of the blue layer of low speed sense (BL)/ISO sense (BH)/ISO green layer (GH)/low speed green layer (GL)/ISO sense red beds (RH)/low speed sense red beds (RL) with the ordering of BH/BL/GL/RH/RL or RH/BL/GH/GL/RL/RH.

Described in JP-B-55-34932,, dispose these photographic layers with the order of feeling blue layer/GH/RH/GL/RL from leaving sheet base far side.In addition, described in JP-A-56-25738 and 62-63936, from leave the sheet base far away from, can arrange these photographic layers with the order of feeling blue layer/GL/RL/GH/RH.

In addition, as described in the JP-B-49-15495, can use by three layers of different configuration of forming of light sensitivity, can wherein make the silver emulsion of top high photographic sensitivity be changed to the superiors, the silver halide emulsion layer that light sensitivity is lower than the upper strata is changed to the middle layer, and the silver halide emulsion layer that light sensitivity is lower than the middle layer is configured to lower floor so that light sensitivity reduces successively towards the sheet base.Even when this layer structure be to have different photosensitive three layers when constituting by above-mentioned, described in JP-A-59-202464, layer with same spectra light sensitivity is from leaving sheet base far side, can in the order of light sensitivity emulsion layer/high-sensitivity emulsion layer/low speed emulsion layer arrange.

In addition, can adopt the order of high-sensitivity emulsion layer/low speed emulsion layer/middle light sensitivity emulsion layer or low speed emulsion layer/middle light sensitivity emulsion layer/high-sensitivity emulsion layer to form layer structure.

In addition, as above-mentioned, under four layers of generations or situation, can change layer configuration with superstructure.

As above-mentioned,, can select various layer structure and configuration according to the purposes of separately photosensitive material.

In photosensitive material of the present invention, use above-mentioned various adjuvants but also can use various adjuvants except that these according to concrete purposes.

These adjuvants are more specifically to be described in Research Disclosure, Item 17643 (December, 1978), ibid, Item 18716 (November, 1979) and ibid., Item 308118 (December, 1989).Each relevant part is in together being listed in the table below.

Additive types	RD17643	RD18716	RD308119
				1, chemical sensitizer	23 pages	648 pages of right hurdles	996 pages
2, improve the light sensitivity agent		648 pages of right hurdles
				3, spectral sensitizer, hypersensitizer	The 23-24 page or leaf	Page right hurdle, 648 pages of right hurdles-649	Right hurdle, 996 pages of right hurdles-998
4, brightener	24 pages		998 pages of right hurdles
				5, antifoggant, stabilizing agent	The 24-25 page or leaf	649 pages of right hurdles	Page right hurdle, 998 pages of right hurdles-1000
6, light absorber, filter dye, ultraviolet absorber	The 25-26 page or leaf	Page left hurdle, 649 pages of right hurdles-650	Page right hurdle, 1003 pages of left hurdles-1003
				7, anti-color spot agent	25 pages of right hurdles	650 pages of left hurdle-right hurdles	1002 pages of right hurdles
8, dyestuff video stabilizing agent	25 pages		1002 pages of right hurdles
				9, film rigidizer	26 pages	651 pages of left hurdles	1004 pages of right hurdles, 1005 left hurdles
10, bonding agent	26 pages	651 pages of left hurdles	1004 pages of right hurdles, 1005 left hurdles
				11, plastifier, lubricant	27 pages	650 pages of right hurdles	1006 pages of left hurdle-right hurdles
12, coating additive, surfactant	The 26-27 page or leaf	650 pages of right hurdles	Page left hurdle, 1005 pages of left hurdles-1006
				13, antistatic agent	27 pages	650 pages of right hurdles	1006 pages of right hurdles, 1007 pages of left hurdles
14, matting agent			Page left hurdle, 1008 pages of left hurdles-1009

In addition, in order to prevent owing to formaldehyde gas makes photograph ability variation, preferably will be as US4,411,897 and 4,435, described in 503 can in formaldehyde reaction and therefore fixedly the compound of formaldehyde react and be added in the photosensitive material.

In the present invention, can use various colour couplers.Its instantiation is to describe to be aforementioned Research Disclosure No.17643, and VII-C to G, and ibid. are among the patent of being quoted among the NO.301705, VII-C to G.

The preferred embodiment of yellow colour former comprises those described in the following patent literature: US3,933,501,4,022,520,4,326,024,4,401,752 and 4,248,961, JP-B-58-10739GB1,425,0202 and 1,476,760 and US3,973,968,4,314,023 and 4,511,649 and EP-A-249473.

As magenta colour coupler, preferred 5-pyrrolinone and pyrrolin oxazole.Particularly, those described in the preferred following patent: US4,310,619 and 4,351,897, EP73,636, Us3,061,432 and 3,725,067, Research Disclosure, No.24220 (June, 1984), JP-A-60-33552, Research Discosure, No.24230 (June, 1984), JP-A-60-43659, JP-A-61-72238, JP-A-55-118034, JP-A-60-185951, US4,500,630,4,540,654 and 4,556,630 and WO 88/04795.

Cyan coupler comprises naphthols colour coupler and phenol colour coupler.Preferably be described in the following patent those: US4,052,212,4,146,396,4,228,233,4,296,200,2,369,929,2,801,171,2,2772,162,2,895,826,3,772,002,3,758,308,4,334,011 and 4,327,173, DE (OLS) 3,329,729, EP-A-121365, EP-A-249453, US3,446,622,4,333,999,4,775,616,4,451,559,4,427,767,4,690,889,4,254,212 and 4,296,199 and JP-A-61-42658.

The representative instance that the dyestuff of polymerization is molded into toner is described in US3, and 451,820,4,080,211,4,3677,282,4,409,320 and 4,576,910, GB2,102,173 and EP-A-341188.

Have suitable diffusible colour coupler as the dyestuff that makes development, those that describe in following patent are preferred: US4,366,237, GB2,125,570, EP96,570 and German patent application number (OLS) 3,234,533.

As the band look colour coupler of adjusting the unnecessary absorption of developed dye, preferably at ResearchDislosure, No.17643, Item VII-G, ibid, No.307105, Item VII-G, US4,163,670, JP-B-57-39413, US4,004,929 and 4,138,256, GB1, those described in 146,368.And, can preferably use at US4,774, described in 181 pass through quality the time fluorescent dye corrigendum developed dye that discharges unnecessary absorption colour coupler and at US4, described in 777,120 contain as the group that dissociates can with developer reaction colour coupler with the dyestuff former group that forms dyestuff.When quality, discharge and also can preferably use in the present invention the useful compound of taking a picture.For the DIR colour coupler that discharges development restrainer, its preferred embodiment is preferably at aforementioned RD17643, Item VII-F, and ibid, No.307105, Item VII-F, JP-A-57-151944, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, and US4,248,962 and 4,782,012.

Discharge the colour coupler of nucleator or development accelerant for imaging when developing, preferably at GB2,097,140 and 2,131,188, those that describe among JP-A-59-157638 and the JP-A-59-170840.And, at JP-A-60-107029, JP-A-60-252340, described in JP-A-1-44940 and the JP-A-1-45687 to pass through the developer that has that oxidation-reduction reaction discharges fogging agent, development accelerant, ag halide solvent etc. be preferred as the compound of formed oxidation product.

Except these, the examples for compounds that can use in photosensitive material of the present invention is included in US4,130, competition colour coupler described in 427, at US4,130,427,4,338,393 and 4,310, many equivalent colour couplers described in 618, be released into toner at the DIR redox compound described in JP-A-60-185950 and the JP-A-62-24252, the DIR colour coupler is released into toner, DIR colour coupler releasing redox compound and DIR redox releasing redox compound, and release can recover the colour coupler of the dyestuff of color after the release described in EP-A-173302 and the EP-A-313308, RD No.11449 and 24241 and JP-A-61-201247 described in bleach accelerator releasing coupler, US4, the part described in 555,477 is released into toner, be released into toner at the leuco dye described in the JP-A-63-75747, with at US4, the fluorescent dye described in 774,181 is released into toner.

Colour coupler used in this invention can be sneaked into to photosensitive material by various known process for dispersing.

The example that can be used on the high boiling organic solvent in the oil-in-water process for dispersing is for example to be described in US2,322,027.

The instantiation that can be used on high boiling organic solvent in the oil-in-water process for dispersing, have 175 ℃ or above boiling point under atmosphere comprises: phthalic acid ester (for example dibatyl phithalate, dicyclo-hexyl phthlate, phthalic acid two-2-2 Octyl Nitrite, phthalic acid ester in the last of the ten Heavenly stems, two (2,4-two-tertiary pentyl phenyl) phthalic acid ester, two (2,4-two-tertiary pentyl phenyl) isophthalic acid ester, two (1,1-diethyl propyl group) phthalic acid ester); Phosphoric acid or phosphate (triphenyl phosphate, tricresyl phosphate, phosphoric acid 2-ethylhexyl diphenyl ester, tricyclohexyl phosphate, tricresyl phosphate-2-Octyl Nitrite, tricresyl phosphate dodecyl ester, three butoxy ethyl ester of phosphoric acid, tricresyl phosphate chloro propyl diester, phosphoric acid 2-ethylhexyl phenyl ester), benzoic ether (for example benzoic acid 2-Octyl Nitrite, benzoic acid dodecyl ester, benzoic acid 2-ethylhexyl-to hydroxy ester); Amidate (for example N, N-diethyl laurylamide, N, N-diethyl lauramide, N-myristyl pyrrolidone); Alcohol or phenol (isostearoyl alcohol, 2,4-di-tert-pentyl phenol); Alphatic carboxylic acid ester (for example two (2-Octyl Nitrite), dioctyl azelates of decanedioic acid, tributyrin, the different hard acyl fat of lactic acid, trioctyl lemon acid); Anil (for example N, N-dibutyl-2-butoxy-uncle's 5-octyl group aniline); And hydro carbons (for example alkane, dodecyl benzene, diisopropyl naphthalene).As complementary solvent, for example can use boiling point for about 30 ℃ or above, preferred 50 ℃ to about 160 ℃ organic solvent.Their representative instance comprises ethyl acetate, butyl acetate, ethyl propionate, MEK, cyclohexanone, acetate 2-ethoxy ethyl ester and dimethyl formamide.

The instantiation of latex process for dispersing and effect and the latex that is used to flood is for example at US4,199,363, and German patent application number (OLS) 2,541,274 and 2,541,230.

Color sensitive material of the present invention can comprise various anticorrosion and germifuge and their example comprises that phenethyl is pure and mild at JP-A-63-257747, described in JP-A-62-272248 and the JP-A-1-80941 those, for example 1,2-benzisothiazole-3-ketone, normal-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-xylenol, 2-phenoxetol and 2-(4-thiazolyl) benzimidazole.

The present invention also can be applied to various color sensitive materials.Their representative embodiment comprises the colour negative or the film of common purposes, the colour reversal film that is used for magic lantern or TV, color photographic paper color photo paper, colour positive and color inversion photography paper.The present invention also can be particularly advantageously applied to the color dub film.

The example that can be used on suitable base of the present invention sees aforesaid RD No.17643, and page 28, ibid, and No.18716 is from 647 pages of right hurdles to 648 page left hurdle and ibid, No.37105,879 pages.

In photosensitive material of the present invention, at the 28 μ m or following preferably of the gross thickness with all hydrophilic colloid layers on the emulsion layer side, be more preferably 23 μ m or following, further be more preferably 18 μ m or following, especially preferably 16 μ m or following.Sheet expansion rate T1/2 preferably 30 seconds or below, be more preferably 20 seconds or below.Here used " sheet thickness " is meant in temperature is that 25 ℃ and relative humidity are (2 days) measured sheet thickness under 55% the humidity controlled condition.Sheet expansivity T1/2 can measure by known method in this technical field, for example by utilizing at A.Green et al., and photogr.Sci.And Eng., Vol.19, No.2, the dilatometer described in the pp.124-129 and measuring.Sheet expansion rate T1/2 is the required time that is defined as the sheet thickness that reaches capacity, and wherein saturated sheet thickness is to be 90% of the maximum swelling sheet thickness of handling to reach in 3 minutes 15 seconds with color developer flushing at 30 ℃.

Sheet expansion rate T1/2 can change aging condition adjustment to being used as in the gelatin of cementing agent or after applying by adding the sheet rigidizer.

In photosensitive material of the present invention, preferably be that the hydrophilic colloid layer (hereinafter referred to as " back sheet ") of 2-20 μ m is coated on the opposite sides with emulsion layer with total dry thickness.This back sheet preferably contains for example above-mentioned optical absorbing agent, filters dyestuff, ultraviolet light absorber, antistatic agent, rigidizer, cementing agent, plastifier, lubricant, coating aid and surfactant.Back sheet preferably has 150 to 500% percentage die swell ratio.

Colour photographic sensitive material of the present invention can pass through at aforesaid D No.17643, page 28-29, and ibid, No.18716,651 pages, left hurdle is right hurdle and ibid extremely, No.37105, the usual method described in the 880-881 page or leaf is developed.

Be used for the developer alkaline aqueous solution preferably of the develop processing of photosensitive material of the present invention, it mainly comprises aroma type primary amine color developer.As color developer, the amino-phenol compounds is available but the P-pHENYLENE dI AMINE compounds is preferred and their representative example comprises 3-methyl-4-amino-N, the N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-sulfonyl methane amino-ethyl aniline, 3-methyl-4-amino-N-ethyl-'beta '-methoxy ethylaniline and their sulfate, hydrochloride or tosilate.Among these, particularly preferably be 3-methyl-4-amino-N-ethyl n-beta-hydroxyethyl aniline.If desired, these compounds can they two or more be used in combination.

Color developer generally includes, for example for example chloride, bromide, iodide, benzimidazole, benzothiazole and sulfhydryl compound of for example alkali-metal carbonate of PH buffering agent, borate or phosphate and development restrainer or anti-fogging agent.Color developer also can comprise (if desired) various antiseptics, hydramine for example, diethyl hydroxylamine, sulphite, hydrazine (for example N, the two ethyloic hydrazines of N-), Carbaphen, triethanolamine and catechol sulfonic acid; Organic solvent is ethylene glycol and diethylene glycol for example; Development accelerant is benzylalcohol, polyglycol, quaternary ammonium salt and amine for example; Dyestuff is molded into toner; The competition colour coupler; Complementary developer is 1-phenyl-3-pyrrolidone for example; Viscosifying agent; With various Ao's mixture, comprise aminopolycanboxylic acid, amino polyphosphoric acid and phosphono-carboxylic acids.The representative example of Ao's mixture comprises ethylene diaminetetraacetic acid, nitrilotriacetic acid, diethylene triamine penta acetate, CDTA, hydroxyethyliminodiacetic acid, 1-hydroxyl ethylidene phosphoric acid, ethylene diamine-N, N, N, N-tetramethylene phosphoric acid, ethylene diamine-two (o-hydroxy guanidine-acetic acid) and their salt.

Under the situation of carrying out reverse developing processing, colour development is normally carried out after black-and-white development.The black-and-white development agent can be used for example known black-and-white development agent for example dihydroxy benzenes (for example quinhydrones), 3-pyrrolidone (for example 1-phenyl-1-pyrrolidone) and aminophenols (for example N-methyl-p-aminophenol class).Color developer and black-and-white development agent all have the pH value of 9-12 usually.Though the magnitude of recruitment of these developers is according to different two differences of the color photographic material that washed, it is to every square metre of photographic material normally 31 and during bromide ion concentration reduction in replenishing liquid, magnitude of recruitment can even be reduced to 500ml or following.When magnitude of recruitment has reduced, the contact area of rinse solution and air is component or the air oxidation that preferably reduces to prevent solution.

The contact area of photographic solution and air can be estimated by following exposure rate in flushed channel.

Exposure rate=[contact area (the cm of rinse solution and air ²)] ÷ [volume (cm of rinse solution ³)]

The exposure rate of above-mentioned definition preferably 0.1 or below, be more preferably 0.001 to 0.05.For example can reduce exposure rate: provide for example method of callow of shielding material on the surface of the photographic liquid in flushed channel by following method, use the method for the removable cap rock described in the JP-A-1-82033, or at the narrow slit developing method described in the JP-A-63-216050.Exposure rate preferably not only can two steps by colour development and black-and-white development reduce, and can by for example bleach in steps, bleach in institute subsequently-photographic fixing, photographic fixing, water washing and stabilization reduce.In addition, magnitude of recruitment also can reduce by using the method that suppresses the accumulation of bromide ion in the developer.

The colour development time normally is set at 2-5 minute.Yet the further reduction of flush time can be by setting high-temperature and high PH condition and using color developer to realize under high concentration.

After colour development, photographic emulsion layer is bleached usually.Bleaching can carry out with photographic fixing (bleaching-photographic fixing) simultaneously or these can carry out respectively.In order to increase flushing speed, also can use the purging method of bleaching and bleach then-photographic fixing.In addition, in bleaching-fixing bath of forming by two succeeding vats, carry out process of washing, can carry out freely selecting according to concrete purposes in the method for carrying out the method for photographic fixing before the bleaching-photographic fixing or after bleaching-photographic fixing, carrying out photographic fixing.The example of bleaching agent comprises: the compound of polyvalent metal is iron (III) for example, peracid (particularly, sodium peroxydisulfate is to be suitable for the film color negative film), quinone and nitro compound.The representative example of bleaching agent comprises the organic complex salt of iron (III), for example with aminopolycanboxylic acid such as ethylene diaminetetraacetic acid, diethylene-triamine pentaacetic acid, CDTA, methyliminodiacetic acid, 1, the complex salt of 3-diaminopropanetetraacetic acid or glycoletherdiaminotetraacetic acid and with the complex salt of citric acid, tartrate or maleic acid.Among these, consider under the fast and antipollution situation of flushing speed that aminopolycanboxylic acid's ferrate complex salt (comprising ethylene diaminetetraacetic acid ferrate complex salt and 3-diaminopropanetetraacetic acid ferrate complex salt) is preferred.

Aminopolycanboxylic acid's ferrate complex salt is to be specially adapted in liquid lime chloride and the bleaching-photographic fixing solution.The liquid lime chloride of suitable aminopolycanboxylic acid's ferrate complex salt and bleaching-photographic fixing solution have 4.0 to 8 pH value usually but wash and can carry out under lower pH value to increase flushing speed.

If necessary, can in liquid lime chloride, bleaching-photographic fixing solution or their prebath, use bleach boosters.The instantiation of useful bleach boosters is included in the compound of describing in the following explanation: for example at US3,893,858, DE1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-18426 and Research Dislosure, the compound described in the No.17129 (July, 1978) with sulfydryl or disulfide group; At the tetrahydrothiazole derivates described in the JP-A-51-140129; At JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and US3, the thiourea derivative described in 706,561; At DE1,127,715 and JP-A-58-16235 described in iodide salt; At DE966,410 and 2,748, the polyoxyethylene ene compound described in 430; At the many ammoniates described in the JP-B-45-8836; At JP-A-49-40943, JP-A-49-59664, JP-A-53-94927, JP-A-54-357727, the compound described in JP-A-55-26506 and the JP-A-58-163940; And bromide ion.Among these, have the compound of sulfydryl or disulfide group because their big facilitation effect is preferably and more preferably at US3,893,858, DE1,290,812 and JP-A-53-95630 described in compound.At preferred US4 also, the compound described in 552,884.Also bleach boosters can be sneaked into to photosensitive material.The color sensitive material that bleach boosters is used for taking a picture in bleaching-photographic fixing is effective especially.

Except above-mentioned compound, in order to prevent to bleach stain, liquid lime chloride or blix solution preferably contain organic acid.To be acid dissociation constant (pKa) comprise acetate, propionic acid and glycolic for the compound of 2-5 and their example to particularly preferred organic acid.

The example that is used in the fixer in photographic fixing solution or bleaching-photographic fixing solution comprises thiosulfate, thiocyanate, thioether-alkali cpd, thiocarbamide and a large amount of iodide.Among these, thiosulfate be use always and especially, ATS (Ammonium thiosulphate) can be used the most widely.Also preferred thiosulfate is used in combination with thiocyanate, thioether-alkali cpd and thiocarbamide.As the antiseptic of photographic fixing solution or bleaching-stop bath, preferably at the sulfide described in the EP-A-294769, disulfide, carbonyl disulfide adduction and sulphate.In addition, stop bath or bleaching-stop bath preferably contain various aminopolycanboxylic acid or the organic phospho acids that are used for the purposes of stabilizing solution.

In the present invention, photographic fixing solution or bleaching-photographic fixing solution preferably contain pKa be the compound of 6.0-9.0 to adjust PH, more preferably for example imidazoles, 1-methylimidazole, 1-ethyl imidazol(e) and glyoxal ethyline of imidazoles, content is 0.1-10mol/l.

Total desilverization time is preferably short as much as possible under the situation that does not cause desilverization failure.Preferably 1-3 minute this time, more preferably 1-2 minute.The flushing temperature is 25-50 ℃, preferably 35-45 ℃.In this preferred range, the pollution after desilverization speed is improved and can prevents effectively to wash.

In desilverisation, stir preferably strong as much as possible.The instantiation that strengthens stirring method is included in the method on the emulsion surface of the spray liquid flow bump photosensitive material that makes rinse solution described in the JP-A-62-183460, strengthens the method for mixing effect at the use whirligig described in the JP-A-62-183460, scraping blade contacts to cause the method for the turbulent flow on emulsion surface and to increase the method for the circulation flow-rate of rinse solution on the whole by mobile photosensitive material and in making the emulsion surface simultaneously and being distributed in solution.This kind mode that is used for strengthening stirring all is effective at all liquid lime chlorides, bleaching-photographic fixing solution and photographic fixing solution.The reinforcement of stirring is thought to increase bleaching agent or fixer be supplied to speed in the emulsion layer, and the result, desilverization speed improved.Under the situation of using bleach boosters, the said method that is used to strengthen stirring is more effective and in this case, promotes that effect can be increased significantly or the photographic fixing inhibiting effect can be eliminated by bleach boosters.

The automatic processing machine that is used for that photosensitive material of the present invention is developed preferably has as JP-A-60-191257, the device of the conveying photosensitive material described in JP-A-60-191258 and the JP-A-60-1912259.As described in top JP-A-60-191257, the amount of the rinse solution that this kind conveying device is carried can reducing from previous bath in the back bath widely, and have and place the advantageous effects that worsens on the rinse solution performance.This effect is effective especially for the magnitude of recruitment that reduces flush time or be reduced in rinse solution in per step.

Silver halide colour photographic sensitive material of the present invention is washed and/or static stabilization after the desilverization usually.In water-washing step the consumption of washings can according to the performance of photosensitive material (for example by material therefor for example colour coupler cause) or purposes and also according to the temperature of washings, the number of rinsing bowl (stage number), replenish system for example adverse current or following current system, or other various conditions are set within a wide scope.Among these, relation between the consumption of the water of the number of rinsing bowl and multistage counter current system can be according at Journal of the Society ofMotion Picture and Television Engineers, Vol.64, method described in the pp.248-253 (May, 1955) is determined.

According in the multistage counter current system described in the above-mentioned publication, the consumption of washings can reduce widely because the residence time of water in groove increases, and has caused vegetative problem and the floating material that produced is bonded on the photosensitive material.In the flushing of color sensitive material of the present invention, but be used to effectively address this problem at the method utmost point of reduction calcium ion described in the JP-A-62-288838 and magnesium ion.In addition, at isothiazolone compounds described in the JP-A-57-8542 and thiabendazole, chloro-alkali germifuge is chlorinated isocyanuric acid sodium and at HiroshiHoriguchi for example, Bokin, Bobai-Zai no Kagaku (Chemistry of Bactericides andFungicides), Sankyo Shuppan (1986), Biserbutsu no Mekkin, Sakkin, Bobai-Gijutsu (Strilizing, Disinfecting and Fungicidal Technology forMicroorganisms), compiled by Eisei Gijutsu Kai, issued by Kogyo Gijutsukai (1982), and Bokin-Bobai Zai Jiten (Handbook of Bactericides andFungicides), the germifuge described in the compiled by Nippon Bokin Bobai Gakkai (1986) for example benzotriazole also can use.

The PH of the washings in the flushing of photosensitive material of the present invention is 4-9, preferred 5-8.Temperature of washing water and wash time can be for example according to the performance of photosensitive material with purposes and different widely, but temperature and flush time are respectively 15-45 ℃ and 20 seconds-10 minutes usually, are more preferably 25-40 ℃ and 30 seconds-5 minutes.Photosensitive material of the present invention also can directly be handled two with stabilizing solution and replace above-mentioned washing.In the stabilization processes process of this kind, can use at JP-A-57-8543 any known method described in JP-A-58-14834 and the JP-A-60-220345.

In some cases, stabilization processes can be carried out after above-mentioned washing again.Its example is that the stabilization that contains dye stabilizers and surfactant is bathed, and it is used as the back and bathes in the washing processing of taking a picture with color sensitive material.The example of dye stabilizers comprises aldehydes for example formalin and glutaraldehyde, N-methylol compound and hexa-methylene four ' amine or aldehyde sulfide-addition compound product.This stabilization is bathed and also can be comprised various Ao's mixture and germifuge.

The halogen solution excessively that accompanies with additional washings and/or stabilizing solution can re-use in for example desilverization step in other washing processing step.

For example in using the washing processing of automatic processing machine, if each washing fluid is because evaporation two when concentrating, is preferably added water to adjust concentration.

In silver halide colour photographic sensitive material of the present invention, color developer can be sneaked into to simplify rinsing step and to increase flushing speed.In order to sneak into colour developing solution, the various precursors of color developer are preferred the uses.Their example is included in US3, the indoaniline described in 342,597, at US3,342,599, Researc Disclosure, No.14850 and ibid., the schiff bases compound described in the No.15159 is at ibid, aldol compound described in the No.13924, at US3, the metal salt complex described in 719,492 and at the urethane compound described in the JP-A-53-135628.

In silver halide colour photographic sensitive material of the present invention, if necessary, promote colour development thereby various 1-phenyl-3-pyrrolidone can be added.The representative instance of these compounds is stated among JP-A-57-144547 and the JP-A-58-115438 at JP-A-56-64339.

In the present invention, each washing processing solution is to use under 10-50 ℃ temperature.The temperature of standard or on the contrary, can use lower temperature to improve the quality of image or to improve the stability of rinse solution normally between 33-38 ℃ but can use higher temperature promoting flushing and to shorten flush time thus.

Photosensitive silve halide material of the present invention can be applied at US4, and 500,626, JP-A-60-133449, JP-A-59-218443, the photosensitive material of the heat-developable described in JP-A-61-238056 and the EP-A-210660.

In addition, silver halide colour photographic sensitive material of the present invention can be applied in the film device that has camera lens described in JP-B-2-32615 and the JP-B-U-3-39784 (used term " JP-B-U " is meant unexamined Japanese Utility Model publication) effectively here and if situation be that so effect is easier realization.

The present invention is also applicable to the diffusion transfer photosensitive material.

By reference the following example the present invention is described in more detail, yet the present invention will not be limited.

Embodiment 1

(preparation of master batch emulsion a)

To containing 0.017 gram KBr and 0.4 gram mean molecular weight is that 1164 ml water solution of 20000 oxidized gelatin stir, and holds them in simultaneously under 35 ℃.In 48 seconds, pass through the three-dimensional jetting method then with AgNO ₃(1.6g) aqueous solution, KBr aqueous solution and mean molecular weight are that the aqueous solution of 20000 oxidized gelatin (2.1g) is added into.At this moment, silver-colored electromotive force is to remain on 13mV based on saturated calomel electrode.Then, add KBr so that silver-colored electromotive force reaches-66mV and temperature is increased to 60 ℃ of degree.Being added into after 21 gram mean molecular weight are 100000 succinic acid gelatin, add NaCl (5.1g) aqueous solution again.In addition, by two to jetting method within 61 minutes with AgNO ₃(206.3g) turnover rate is quickened in aqueous solution, the adding of KBr aqueous solution simultaneously.At this moment, silver-colored voltage is to remain on-44mV based on saturated calomel electrode.After desalination is finished, be that 100000 succinic acid gelatin is added into and PH and pAg are adjusted to 5.8 to 8.8 respectively with mean molecular weight, thereby make master batch emulsion.Comprise 1 moles of silver and 80 gram gelatin in every kilogram of this master batch emulsion, and emulsion grain is that average equivalent diameter is that the coefficient of variation of 1.46 μ m, equivalent diameter is 28%, average thickness is that 0.046 μ m and radius-thickness ratio are 32 plain film shape particle.

(moulding of core)

The 1200 ml water solution that will contain the above-mentioned seed emulsion that makes of 134 grams, 1.9 gram KBr and 22g mean molecular weight and be 100000 succinic acid gelatin stir, and hold them in simultaneously under 35 ℃.Only before just will adding, with AgNO ₃(43.9g) aqueous solution, KBr aqueous solution and mean molecular weight are that the aqueous solution of 20000 gelatin is mixed in an insulated chamber that is equipped with magnetic coupling induction type stirrer and added within 25 minutes then.At this moment, silver-colored electromotive force is to remain on-40mV based on saturated calomel electrode.

(moulding of first shell)

After the sandwich layer grain forming, only before just will adding, with AgNO ₃(43.9g) to be 20000 aqueous gelatin solution mix in an insulated chamber that is equipped with magnetic coupling induction type stirrer and added within 20 minutes then for aqueous solution, KBr aqueous solution and mean molecular weight.At this moment, silver-colored electromotive force is to remain on-40mV based on saturated calomel electrode.

(moulding of second shell)

After the first shell moulding, only before just will adding, with AgNO ₃(42.6g) aqueous solution, KBr aqueous solution and mean molecular weight are that the aqueous solution of 20000 oxidized gelatin (2.1g) is mixed in an insulated chamber that is equipped with magnetic coupling induction type stirrer and added within 17 minutes then.At this moment, silver-colored electromotive force is to remain on-20mV based on saturated calomel electrode.After this, temperature is reduced to 55 ℃.

(moulding of the 3rd shell)

After the second shell moulding, only before just will adding, silver-colored electromotive force is adjusted to-55mv and then with AgNO ₃(7.1g) aqueous solution, KI (6.9g) aqueous solution and mean molecular weight are that 20000 aqueous gelatin solution mixes in insulated chamber same as described above and added within 5 minutes then.

(moulding of the 4th shell)

After the 3rd shell moulding, in 30 minutes by the bidirectional jet method with constant rate of speed with AgNO ₃(66.4g) aqueous solution and KBr aqueous solution are added into.In the process of adding, be added into the yellow prussiate of six potassium chloride iridium and potassium.At this moment, silver-colored electromotive force is to remain on 30mV based on saturated calomel electrode.Washing is to carry out in common mode, is added into gelatin and PH and pAg are adjusted to 5.8 to 8.8 respectively.The emulsion that obtains is appointed as emulsion b.Emulsion b is that average equivalent diameter is that the coefficient of variation of 3.3 μ m, equivalent diameter is 21%, average thickness is that 0.090 μ m and radius-thickness ratio are 37 plain film shape particle.In addition, 70% of whole projected area or more than be to be that 3.3 μ m or above and thickness are that 0.090 μ m or following plain film shape particle capture by average equivalent diameter.Suppose that the area that dyestuff occupies is 80 ², the saturated coverage of individual layer is 1.45 * 10 ^-3Mol/mol-Ag.

The temperature of emulsion b rises to 56 ℃, and first dyestuff described in the table 1 is added into, and adds C-1, potassium rhodanate, gold chloride, sodium thiosulfate and N then, N-dimethyl selenourea, and preferably carry out the chemical sensitization effect.Further add second kind of dyestuff and potpourri was stirred 60 minutes.This chemical sensitization method is to be appointed as dyestuff adding method A.In the process that dyestuff adds, the method that is lower than the temperature under the room temperature with wherein temperature being adjusted to and is added into sensitizing dye is appointed as dyestuff adding method B.

Sensitizing dye is used as the solid-state fine dispersions that use makes in the method described in the JP-A-11-52507.More particularly, be dissolved in 0.8 weight portion sodium nitrate and 3.2 weight portion sodium sulphate in 43 parts of ion exchange waters and add 13 weight portion sensitizing dyes and use the dissolving scraping blades to disperse 20 minutes to obtain the solid dispersion of sensitizing dye down with 2000rpm at 60 ℃.

Table 1

Emulsion number	The ground floor amount of dye (10 of adding -3Mole/every mole of Ag)	The second layer amount of dye (10 of adding -3Mole/every mole of Ag)	The dyestuff adding method	The dyestuff adsorbance 1)(10 -3Mole/every mole of Ag)	The number of plies of absorption 2)	The association state of second layer dyestuff 3)
							1	D-1：0.58 D-4：0.87	Do not have	A	1.39	0.96	-
2	″	D-1：1.45 D-21：1.45	A	3.48	2.40	M
							3	″	″	A	3.50	2.41	M
4	″	D-6：2.90	A	3.03	2.09	J
							5	″	D-7：2.90	A	3.11	2.14	J
6	D-2：0.58 D-3：0.87	″	A	3.18	2.19	J

1) total adsorbance of each dyestuff.

2) to be considered as be 1.45 * 10 when the saturated extent of adsorption with individual layer ^-3During mole/every mole of Ag, the number of the adsorbed layer of gained.

3) deduct the absorption of ground floor dyestuff after, the association state of the second layer and upper strata dyestuff.Identify according to the method described in the instructions.

Photon absorbing intensity to per unit area is to be performed as follows measurement.The emulsion of gained is coated on the glass sheet and by following method thinly uses the microspectrophotometer MSP65 that produces by Karl Zweiss that the transmitted spectrum and the reflectance spectrum of individual particle are measured with the spectrum that is absorbed.Area when being no particle as the reference of transmitted spectrum and as the reference of reflectance spectrum is that known silit is measured to reflectivity.The part of measuring is the circular holes part with diameter of 1 μ m.Adjust the position simultaneously so that the hole part is not overlapping with particle outline.Transmitted spectrum and reflectance spectrum be with at 14000cm-1 (714nm) to 28,000cm ^-1Measure in the wavenumber region (357nm).From the absorptivity by formula (1-T (transmitance)-R (reflectivity)) definition, spectrum can be absorbed.Use absorbs the absorptance A ' obtain by deducting silver halide, by general-Log (1-A ') with respect to wave number (cm ^-1) integration and with the result of gained divided by 2 photon absorbing intensities that obtain per unit area.Limit of integration is 14000cm ^-1To 28,000cm ^-1Between.At this moment, using tungsten lamp is 8V as light source and light source voltage.In order to dwindle the infringement of the dyestuff that causes owing to photoirradiation, use monochromatic filter and wavelength distance and gap width to be set at 2nm and 2.5nm respectively at major opposing side.Absorption spectrum and photon absorbing intensity are based on that 200 particles are measured and the coefficient of variation in particle is based on the photon absorbing intensity and the wavelength distance that show 50%Amax and measures.In addition, from the maximum absorption wavelength of individual particle, determined the ratio of the particle that in the wavelength coverage of the 10nm that is rendered as highest frequency, comprises.

Assessed the quality of image by granularity.In assessment during granularity, the sample of each Test No. is utilized the measuring method of RMS value, the use colour temperature is that the Halogen lamp LED of 3200 ° of K exposes as light source.After this, each sample is carried out photographic processing for example develop, measure by microdensitometer and (measure pore diameter: 48 μ m) to obtain the RMS value and to use zero △ * assess relatively.Have the poor quality of image be denoted as *, what have the viable quality of image is to be denoted as △, and have a good quality of image be denoted as zero.

The adsorbed state of sensitizing dye is to use the AFM that is made by Nanoscope to assess.The gelatin that is adsorbed on the particle surface is to degrade by proteolytic enzyme to be rendered as a kind of like this state to make sample, so that the structure of sensitizing dye adsorbed layer can be observed.Then, with spatial resolution be 2 nanometers noncontact casting pattern the damage of sample be reduced under the minimum situation sample observed and with particle surface on the standard deviation of rough degree as the index of adsorbed state.

Gelatin hardener and coating auxiliary agent are to be added into respectively in the above-mentioned emulsion that obtains and with the gelatin protective seam together to be coated on the cellulose ethanoate sheet base to obtain 3.0g-Ag/m ²Silver-colored coated weight.The film of gained is exposed to tungsten lamp (colour temperature: 2854K) following 1 second by continuous grating color filter.On sample, (by Fuji photo Film Co., Ltd) leaching 500nm or following light are used to subtract blue exposure, and it has activated the dyestuff side as colored filter to use Fuji Gelatin Filter SC-50 simultaneously with photoirradiation.Use Surface Developer MAA-1 as follows that the sample of exposure was developed 10 minutes down at 20 ℃.Be not referred to as A with wherein adding compound T-1 to the washing processing in the stop bath, the addition of T-1 is that the washing processing of 1.5g/l is referred to as B, is referred to as C and the addition of T-1 is the washing processing of 0.2g/l.

The prescription of surface development agent MMA-1

Mitouer 2.5g

L-ascorbic acid 10g

Nabox (by Fuji Photo Film Co., Ltd.) 35g

Potassium bromide 1g

Add water and make it to reach 1 liter

PH 9.8

After developing, carry out photographic fixing at 20 ℃ with following stop bath.

The prescription of stop bath

ATS (Ammonium thiosulphate) 170g

Sodium sulphite (anhydrous) 15g

Boric acid 7g

Glacial acetic acid 15ml

First alum 20g

Ethylene diaminetetraacetic acid 0.1g

Tartrate 3.5g

Add water and make it to reach 1 liter

Film after handling is carried out optical density (OD) by Fuji Automatic Densitometer to be measured.Light sensitivity be by the inverse of the desired light quantity of optical density (OD) that is used to obtain (photographic fog+0.2) represent and the light sensitivity that will test No.1 as 100.Gray scale is to represent by the inverse of the desired light quantity ratio of density difference that is used to obtain (photographic fog+0.2) to (photographic fog+1.2).With the gray scale of Comparative Examples 1 is as 100.In addition, the optical density (OD) of supposing maximum spectral absorption wavelength place the photographic processing development of the photosensitive material shown in the table 3 (for example) be before G0 and after photographic processing the optical density (OD) at maximum spectral absorption wavelength place be G1, so A is defined as A=G1/G0.

The result is presented in table 2 and 3.

Table 2

The emulsion numbering	Photon absorbing intensity 1)	Distance to 50%Amax 2)	Maximum absorption wavelength changes among particle; Particle ratio (%) within 10nm 3)	The standard deviation in slit (nm) on particle surface 4)
					1	89(5.7)	65(3.6)	98	0.4
2	215(132.1)	138(98.1)	46	2.8
					3	224(86.2)	128(45.4)	59	1.7
4	198(76.7)	101(48.9)	62	1.1
					5	202(59.9)	98(35.8)	74	0.8
6	208(31.2)	97(28.7)	87	0.7

1) the average photon absorbing intensity of 200 particles; Value in the bracket is the coefficient of variation.

2) mean value of 200 particles; Value in the bracket is the coefficient of variation.

When 3) showing maximum absorption wavelength at the highest frequency place of 200 particles, the ratio of the particle of absorption maximum in the wavelength coverage of 10nm.

4) when the factor of porosity of particle surface be when measuring by AFM, the standard deviation of factor of porosity; Space resolution is 2nm in AFM measures.

Table 3

Test No.	The emulsion numbering	The washing processing method	Energy transfer efficiency	A＝G1/G0 2)	Light sensitivity (photographic fog+0.2)	Gray scale	Granularity	Remarks
									1	1	A	-	100	100	100	○	Contrast
2	2	A	0.67	156	79	79	×	Contrast
									3	3	A	0.89	178	87	87	△	The present invention
4	4	A	0.92	199	94	94	△	The present invention
									5	4	B	0.92	199	94	94	○	The present invention
6	4	C	0.92	199	94	94	○	The present invention
									7	5	A	0.91	202	96	96	○	The present invention
8	6	A	0.94	204	99	99	○	The present invention

1) in the maximum absorption wavelength on the second layer and upper strata, the excitation energy that excites dyestuff in the second layer and upper strata is transferred to the energy ratio of ground floor dyestuff; Ratio in spectral sensitization between the relative quantum yields (φ r) of the relative quantum yields (φ r) at maximum wavelength place and ground floor dyestuff.

2) to set the optical density of sensitizing dye at the caused spectral absorption maximum wavelength of photographic first being processed place by sample application be G0 and be G1 by the optical density of sensitizing dye at above-mentioned wavelength place after photographic processing.

From these as can be seen, in the multilayer absorption system,, not only can obviously improve light sensitivity and gray scale, and can obviously improve the quality of image when sensitizing dye is when adsorbing with layer state and adsorbed state when being even in particle.In addition, when in the photographic first being processed with absorb afterwards when big change has taken place, be sure of to have improved significantly the quality of image.

Embodiment 2

Carry out according to the same way as among the embodiment 1 that dyestuff adds and the chemical sensitization effect, just will in the 14th layer of the sample 108 of Japanese patent application No. 11-168662, become the dyestuff shown in the table 4 by the sensitizing dye among the emulsion A-8.And, assess according to method identical among the embodiment 1.

Table 4

Emulsion number	The ground floor amount of dye (10 of adding -3Mole/every mole of Ag)	The second layer amount of dye (10 of adding -3Mole/every mole of Ag)	The dyestuff adsorbance 1)(10 -3Mole/every mole of Ag)	The number of plies of absorption 2)	The association state of second layer dyestuff 3)
						1	D-14：1.46	Do not have	1.34	0.92	-
2	D-15：1.46	Do not have	1.30	0.89	-
						3	D-14：1.46	D-20：3.10	4.22	2.89	J
4	D-15：1.46	″	4.30	2.95	J

1) total adsorbance of each dyestuff.

2) to be considered as be 1.45 * 10 when the saturated extent of adsorption with individual layer ^-3During mole/every mole of Ag, the number of the adsorbed layer of gained.

3) deduct the absorption of ground floor dyestuff after, the association state of the second layer and upper strata dyestuff.Identify according to the method described in the instructions.

The result is presented in table 5 and the table 6.

Table 5

The emulsion numbering	Photon absorbing intensity 1)	Distance to 50%Amax 2)	Maximum absorption wavelength changes among particle; Particle ratio (%) within 10nm 3)	The standard deviation in slit (nm) on particle surface 4)
					1	50(9.3)	53(4.5)	96	0.5
2	51(9.4)	54(4.7)	97	0.5
					3	121(105)	79(61.4)	45	2.9
4	130(43.1)	69(32.0)	89	1.3

1) the average photon absorbing intensity of 200 particles; Value in the bracket is the coefficient of variation.

2) mean value of 200 particles; Value in the bracket is the coefficient of variation.

When 3) showing maximum absorption wavelength at the highest frequency place of 200 particles, the ratio of the particle of absorption maximum in the wavelength coverage of 10nm.

4) when the factor of porosity of particle surface be when measuring by AFM, the standard deviation of factor of porosity; Space resolution is 2nm in AFM measures.

Table 6

Test No.	The emulsion numbering	Energy transfer efficiency	A＝G1/G0 2)	Light sensitivity (photographic fog+0.2)	Gray scale	Granularity	Remarks
								1	1	-	0.92	100	100	○	Contrast
2	2	-	0.96	99	100	○	Contrast
								3	3	0.78	0.99	219	86	×	Contrast
4	4	0.95	0.43	265	97	○	The present invention

1) in the maximum absorption wavelength on the second layer and upper strata, the excitation energy that excites dyestuff in the second layer and upper strata is transferred to the energy ratio of ground floor dyestuff; Ratio in spectral sensitization between the relative quantum yields (φ r) of the relative quantum yields (φ r) at maximum wavelength place and ground floor dyestuff.

2) to set the optical density of sensitizing dye at the caused spectral absorption maximum wavelength of photographic first being processed place by sample application be G0 and be G1 by the optical density of sensitizing dye at above-mentioned wavelength place after photographic processing.

3) assess by mode identical among the embodiment 1, just the Gelatin Filter SC-39 of film by being made by the Fuji Photo Film Co., Ltd. optical filter that sees through long wavelength light of leaching 390 nano wave lengths (can) and continuous grating were exposed 1/100 second and measure yellow density.

From these as can be seen, even in containing the colored negativity photosensitive material system of emulsion (wherein sensitizing dye is with multilayer absorption), when sensitizing dye is when adsorbing with layer state and adsorbed state when being even in particle, not only light sensitivity and gray scale can be obviously improved, and the quality of image can be obviously improved.In addition, when in the photographic first being processed with absorb afterwards when big change has taken place, be sure of to have improved significantly the quality of image.

Embodiment 3

By the X-ray photosensitive system among the embodiment 1 of color photographic paper color photo paper system among the embodiment 1 of the colour reversal photosensitive material system among the embodiment 1 of colored negativity photosensitive material system, JP-A-7-92601 and JP-A-11-160828 among the embodiment 5 of assessment JP-A-8-29904, JP-A-6-347944 and JP-A-8-122954 carry out with embodiment 1 and 2 in identical comparison.The result, similar to Example 1, confirmation can obtain a kind of like this photosensitive material, thus its in particle, have the sensitizing dye adsorbance of little distribution, advantageously have ISO and high-contrast, reduced by the absorption of the multilayer of sensitizing dye cause that optical density (OD) increases the problem that causes quality of image variation.

By the present invention, can obtain a kind of like this silver halide photographic emulsions and sensitive photographic material, it has for example reduced and is adsorbed the problem of caused quality of image difference and advantageously had ISO and high-contrast by the multilayer of sensitizing dye.

Though with reference to specific embodiment, the present invention is described in detail, those skilled in the art are apparent that, can carry out various changes and modifications within spirit of the present invention and scope.

Claims (21)

1, a kind of silver halide photographic emulsions, it comprises that its surface upward is adsorbed with the silver halide particle of sensitizing dye with multilayer form, the coefficient of variation that optical absorption intensity distributes in the wherein said particle be 100% or below, wherein the sensitizing dye among the second layer and upper strata all exists with the stratiform form, and formation J-associated matter, and described sensitizing dye uses kation betaine shown at least a following molecular formula (I) or nonionic methine dyes, perhaps use the negative ion methine dyes shown in cationic methine dyestuff shown at least a following molecular formula (I) and at least a following molecular formula (II) simultaneously

Wherein, Z ₁Expression forms the necessary atomic group of nitrogen heterocyclic ring, and its precondition is at Z ₁On can cyclic condensation, R ₁Expression alkyl, aryl or heterocyclic radical, Q ₁Expression makes the compound shown in the molecular formula (I) form the necessary group of methine dyes, L ₁And L ₂All represent methine, P separately ₁Be 0 or 1, but Z ₁, R ₁, Q ₁, L ₁And L ₂Substituting group is respectively arranged, and this substituting group makes the methine dyes shown in the molecular formula (I) as the whole dye of positive ion, betaine dyestuff or non-ionic dye, the M of forming ₁The gegenion of expression balancing charge, m ₁In the expression and molecule in electric charge necessary 0 or bigger integer;

Wherein, Z ₂Expression forms the necessary atomic group of nitrogen heterocyclic ring, and its precondition is at Z ₂On can cyclic condensation, R ₂The expression alkyl, aryl or heterocyclic radical, Q ₂Expression makes the compound shown in the molecular formula (II) form the necessary group of methine dyes, L ₃And L ₄All represent methine, P separately ₂Be 0 or 1, but Z ₂, R ₂, Q ₂, L ₃And L ₄Substituting group is respectively arranged, and this substituting group makes the methine dyes shown in the molecular formula (II) as whole anionic dye, the M of forming ₂The gegenion of expression balancing charge, m ₂In the expression and molecule in electric charge necessary 0 or bigger integer.

2, silver halide photographic emulsions according to claim 1, the maximal value of wherein setting the spectral absorption that sensitizing dye causes is Amax, then in particle, show the coefficient of variation that minimal wave length among the wavelength of 50% Amax and the wavelength distance between the long wavelength distribute and be 50% or below.

3, silver halide photographic emulsions according to claim 1, wherein the change width of the spectral absorption maximum wavelength that has corresponding to 50% or above particle of the projected area of all silver halide particles in the emulsion is 10nm or littler.

4, silver halide photographic emulsions according to claim 1, the optical density that wherein is set in the spectral absorption maximum wavelength place of photographic first being processed is that the optical density at G0 and the spectral absorption maximum wavelength place after photographic processing is G1, and then the A value of being represented by A=G1/G0 is 0.9 or littler.

5, silver halide photographic emulsions according to claim 4, wherein A is 0.5 or littler.

6, silver halide photographic emulsions according to claim 1, wherein the sensitizing dye among the second layer and upper strata all has 20kJ/mol or above energy of adsorption.

7, silver halide photographic emulsions according to claim 1, wherein the interaction energy between sensitizing dye in ground floor and the sensitizing dye in the second layer or upper strata be dyestuff in the second layer and upper strata whole energy of adsorption 10% or more than.

8, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, wherein the sensitizing dye in ground floor all is not the sensitizing dye that is connected by covalent bond with sensitizing dye in the second layer or upper strata.

9, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, it comprises the spectral absorption maximum wavelength to be lower than 500nm and optical absorption intensity is more than 60 or the spectral absorption maximum wavelength is that the above and optical absorption intensity of 500nm is the silver halide particle more than 100.

10, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, the maximal value of wherein setting the spectral absorption of the described emulsion that is caused by sensitizing dye is Amax, and showing minimal wave length among the wavelength of 50% Amax and the wavelength distance between the long wavelength is 120nm or shorter.

11, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, the maximal value of wherein setting the spectral sensitivity of the described emulsion that is caused by sensitizing dye is Smax, and showing minimal wave length among the wavelength of 50% Smax and the wavelength distance between the long wavelength is 120nm or shorter.

12, silver halide photographic emulsions according to claim 10 wherein show long wavelength corresponding to the spectral absorption of 50% Amax at 460-510nm, in the scope of 560-610nm or 640-730nm.

13, silver halide photographic emulsions according to claim 11 wherein show long wavelength corresponding to the spectral sensitivity of 50% Smax at 460-510nm, in the scope of 560-610nm or 640-730nm.

14, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, wherein the excitation energy of the sensitizing dye within the second layer or upper strata with 10% or bigger efficient transfer the energy in the sensitizing dye in the ground floor.

15, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, wherein sensitizing dye in ground floor and the sensitizing dye in the second layer or upper strata show the J-wavestrip and absorb.

16, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, it comprises the sensitizing dye with at least one aryl.

17, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, it comprises the sensitizing dye of the basic nuclear that obtains from three or more cyclic condensation.

18, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, wherein radius-thickness ratio be 2 or above plain film shape particle be to think that 50% or above area ratio of all silver halide particles exists in emulsion.

19, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, it has experienced the selenium sensibilization.

20, according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7, it contains the silver halide adsorbability compound except that sensitizing dye.

21, a kind of silver halide photographic sensitive material, it comprises one deck at least according to the silver halide photographic emulsions described in the claim 1-4, one of 6 and 7.