CN1273862C - Silver halide photographic emulsion and photosensitive material using said emulsion - Google Patents

Abstract

A silver halide photographic emulsion is disclosed, comprising a silver halide grain having a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more or having a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more, wherein assuming that a maximum value of the spectral absorption factor of said emulsion by a sensitizing dye is Amax, the distance between the shortest wavelength showing 80% of Amax and the longest wavelength showing 80% of Amax is 20 nm or more and the distance between the shortest wavelength showing 50% of Amax and the longest wavelength showing 50% of Amax is 120 nm or less.

Description

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

Technical field

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

Background technology

Up to now, for obtaining the more silver halide photographic sensitive material of high sensitivity, 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 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 Page 97 (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., wherein the multiple dyestuff in the composite bed is adsorbed onto on the silver halide; For promoting that sensitizing shifts Forster type excitation energy.

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.

Deposit Photographic Science and Engineering, Vol.27, No.2, among the Page 59 (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.

About so-called two the chromophoric connection dyestuffs of isolation (wherein two chromophories and non-conjugated but continuous by covalent bond) that contain, USP 2,393, and 351,2,425,772,2,518,732,2,521,944 and 2,592,196 and EP 565,083 in, their example has been described.Yet, they are not used to improve absorptance.Be the USP 3,622,317 and 3,976 of purpose to improve absorptance, in 493, G.B.Bird, people such as A.L.Borror disclose a technology, wherein, adsorbed a kind of chromophoric connection sensitizing dye of complicated cyanines molecule that has for increasing absorptance, and for promoting sensitizing that energy is shifted.In JP-A-64-91134, Ukai, Okazaki and Sugimoto disclose a technology, wherein are connected on the spectral sensitizing dye that can be adsorbed onto on the silver halide as cyanine dyes, portion's cyanine dyes and the dyestuff that does not have adsorbability substantially that contains the hemicyanine dye and so on of at least two sulfo groups and/or carboxyl at least a.

In JP-A-6-57235, L.C.Vishwakarama discloses a kind of dehydration condensation that passes through two kinds of dyestuffs, the synthetic method that connects dyestuff.And in JP-A-6-27578, what disclose methine cyanines and five first alkynes oxonols is connected the red property of dyestuff thoughts.Yet, in this example the absorption of the light of oxonols emission and cyanines not overlapping, utilize Forster type excitation energy to shift spectral sensitization do not take place, the light congregation owing to being connected oxonols can not obtain higher sensitivity.

At European Patent Publication No 887700A ₁In, people such as R.L.Parton disclose the connection dyestuff with specific linking group.

At USP 4,950, in 587, people such as M.R.Roberts disclose the spectral sensitization by the cyanine dyes polymkeric substance.

Like this, carry out a large amount of research for improving absorptance so far, but the improvement of absorptance has not been obtained sufficiently high effect, also do not obtained sufficiently high sensitivity.

In color sensitive material, in the target wavelength zone, must have spectral sensitivity especially.The spectral sensitization of photosensitive silve halide material does not use the absorption of sensitizing dye at free state usually, but utilizes the J-absorption band that forms when dyestuff is adsorbed on the silver halide particle surface.Have light absorption and spectral sensitivity for making in desired wavelength region may, the J-absorption band is very useful, because compare with the absorption under free state, it has the absorption of moving rapidly to long wavelength's direction.In this sense, even the sensitizing dye in the composite bed is adsorbed onto particle surface, also can increase absorptance.When dyestuff directly is not adsorbed onto on the silver halide particle, when promptly the dyestuff in the second layer or subsequent layer adsorbs with the monomer attitude, absorb and extend in the very wide scope, this spectral sensitivity for actual photosensitive material is inappropriate.

On the other hand, there is the width of about 100nm in each color sensitizing zone, causes that the unnecessary big-difference to the sensitivity of light in this scope is disadvantageous.

In this case, need a kind of technology that sensitizing dye in the composite bed is adsorbed onto the silver halide particle surface, this technology can satisfy following the requirement: the integrated intensity that increases the light absorption of per unit grain area, absorption and spectral sensitivity are limited in the required color sensitizing zone, reduce variation simultaneously as far as possible the spectral absorption and the sensitivity of that regional light.

And, found that when the sensitizing dye in the composite bed is adsorbed onto particle surface the amount of the gelatin that is adsorbed reduces, so in some cases, the defencive function of colloid weakens, and particle condenses easily.Therefore, need a kind of sensitizing dye in the absorption composite bed to stop the technology of particle aggregation simultaneously.

Summary of the invention

An object of the present invention is to provide a kind of prevention particle aggregation, and have the silver halide photographic emulsions of high sensitivity.

Another object of the present invention provides a kind of sensitive photographic material that uses this emulsion.

Can reach these purposes in the following manner.

(1) a kind of silver halide photographic emulsions, it contains a kind of silver halide particle, this silver halide particle is adsorbed with at least a spectral sensitizing dye of J-aggregate form in the above with one or more layers, this silver halide particle has less than the spectral absorption maximum wavelength of 500nm and 60 or bigger photon absorbing intensity, or have 500nm or longer spectral absorption maximum wavelength and 100 or bigger photon absorbing intensity, the maximal value of wherein setting the spectral absorption of the described emulsion that is caused by sensitizing dye is Amax, the distance that then shows the minimal wave length of 80%Amax and show between the long wavelength of 80%Amax is 20nm or longer, shows the minimal wave length of 50%Amax and the distance that shows between the long wavelength of 50%Amax is 120nm or shorter.

(2) a kind of silver halide photographic emulsions, it contains a kind of silver halide particle, this silver halide particle is adsorbed with at least a spectral sensitizing dye of J-aggregate form in the above with one or more layers, this silver halide particle has less than the spectral absorption maximum wavelength of 500nm and 60 or bigger photon absorbing intensity, or have 500nm or longer spectral absorption maximum wavelength and 100 or bigger photon absorbing intensity, the maximal value of wherein setting the spectral sensitivity of the described emulsion that is caused by sensitizing dye is Smax, the distance that then shows the minimal wave length of 80%Smax and show between the long wavelength of 80%Smax is 20nm or longer, shows the minimal wave length of 50%Smax and the distance that shows between the long wavelength of 50%Smax is 120nm or shorter.

(3) as (1) described silver halide photographic emulsions, the long wavelength who wherein shows the 50%Amax spectral absorption is at 460-510nm, in the zone of 560-610nm or 640-730nm.

(4) as (2) described silver halide photographic emulsions, the long wavelength who wherein shows the 50%Smax spectral sensitivity is at 460-510nm, in the zone of 560-610nm or 640-730nm.

(5) as arbitrary described silver halide photographic emulsions in (1), (2), (3) or (4), wherein contain dyestuff in the silver emulsion with at least one aryl.

(6) as arbitrary described silver halide photographic emulsions in (1)-(5), wherein sensitizing dye is adsorbed onto on the silver halide particle with composite bed, the second sensitizing dye layer has the structure that is different from the first sensitizing dye layer, and the second sensitizing dye layer contains anionic dye and contains the dye of positive ion.

(7) as arbitrary described silver halide photographic emulsions in (1)-(5), it contains the sensitizing dye with the basic nuclear that is formed by three or more cyclic condensations.

(8) as arbitrary described silver halide photographic emulsions in (1)-(7), wherein have less than the spectral absorption maximum wavelength of 500nm and 60 or bigger photon absorbing intensity, or have 500nm or longer spectral absorption maximum wavelength and 100 or the silver halide particle of bigger photon absorbing intensity be that radius-thickness ratio is 2 or bigger plain film shape particle.

(9) as arbitrary described silver halide photographic emulsions in (1)-(8), wherein have less than the spectral absorption maximum wavelength of 500nm and 60 or bigger photon absorbing intensity, or have 500nm or longer spectral absorption maximum wavelength and 100 or the silver halide particle of bigger photon absorbing intensity through selenium sensitizing.

(10) contain the silver halide photographic sensitive material of at least a silver halide photographic emulsions, wherein contain arbitrary described silver halide photographic emulsions in (1) to (9),

Description of drawings

Fig. 1 has shown the spectral absorption spectrogram that has only a kind of dyestuff.

Fig. 2 has shown the spectral sensitivity distribution.

Embodiment

Describe the present invention below in detail.

The present invention is to use the silver halide photographic sensitive material of the silver halide particle of dye sensitization, and it has big photon absorbing intensity, and suitable spectral absorption waveform and suitable sensitivity distribute.

In the present invention, photon absorbing intensity is the integrated intensity by the light absorption of the per unit grain area of dye sensitization, supposes that the light quantity that enters the particle per surface area is I ₀, the light quantity of sensitizing dye absorption is I from the teeth outwards, by integration and wave number (cm ^-1) relevant optical density log[I ₀/ (I ₀-I)], be photon absorbing intensity with the value defined that obtains, limit of integration is from 5000cm ^-1To 35000cm ^-1

Silver halide photographic emulsions of the present invention preferably contain silver halide particle, when this particle has 500nm or longer spectral absorption maximum wavelength, it has 100 or bigger photon absorbing intensity, or when this particle has spectral absorption maximum wavelength less than 500nm, it has 60 or bigger photon absorbing intensity, with half of whole projected areas of all silver halide particles or bigger ratio.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.

Do not use the micro-spectral method, particle is in line, and stop particle to be piled up mutually, measure the method for its transmitted spectrum, can obtain photon absorbing intensity yet but utilize.

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 in dye chromophore be 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 the dye chromophore in one or more layers is adsorbed to the method for particle surface.

Here, dye chromophore be adsorbed onto this state in one or more layers of particle surface mean near the dyestuff that is adhered to the silver halide particle exist with one or more layers in.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 regarded the absorption in one or more layers 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 composite bed 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 J-P-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 steps necessary number preferably from 1 to 3.

Rikagaku Jiten (Physicochemical Dictionary), PP 985-986,4th ed. has defined among the IwanamiStoten (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 chromophore in one or more layers is adsorbed onto the silver halide particle surface 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 obtained when (this dyestuff is adding the silver halide surface occupied area that has minimum in the sensitizing dye of emulsion).Absorb the number of plies and be meant the uptake that absorbs coverage based on individual layer.Connecting by covalent bond in the dyestuff of dye chromophore, absorbing the number of plies can be based on every kind of dyestuff under the state that does not connect these dye chromophore, the occupied area of dyestuff.

Can obtain the dyestuff occupied area from absorption isotherm, absorption isotherm 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 (1963), and isotherm can be absorbed.

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 Page 1054 (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.

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 with reference to 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 transmit the electronics microcosmic and take a picture.

At A.M.Kragin et al., The Journal of Photographic Science, Vol.14, page185 (1966), J.F.Paddy, Transactions of the Faraday Society, Vol.60, page1325 (1964), S.Boyer et al., Journal de Chimie Physique et de Physicochimie Biologigue, Vol.63, page1123 (1963), W.West et al., Journal of Physical Chemistry, Vol.56, page 1054 (1952), E.Klein et al., International Cologuium, compiled by H.Sauvemier, 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 guestimate absorb the number of plies.

In the present invention, when the dye chromophore in the composite bed is adsorbed onto on the silver halide particle, 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 subsequent layer.

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 page27 (1986).

Dye chromophore in the second layer or the subsequent layer 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 subsequent layer dye chromophore.And the light emission of the second layer or subsequent layer 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-association product (being the J-aggregation).Absorb and spectral sensitivity in order to have in desired wavelength coverage, the dye chromophore in the second layer and the subsequent layer also is preferably formed J-association product.

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 absorption isotherm 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 uptake 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.

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, IP-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, hexichol, 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, sulfate, phosphate; boronate; the amino formyl alkyl (for example, the sulfonyl methane carbamoyl methyl) of alkyl sulfonyl, acyl amino formyl alkyl is (for example; acetylamino formyl methyl); acyl group sulfonamide alkyl (for example, acetyl sulfonamide methyl) and alkyl sulfonyl sulfonamide alkyl (for example, sulfonyl methane sulfonamide methyl).In these groups, preferred sulfo group and carboxyl, more preferably sulfo group.

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

Following molecular formula (I-1) (I-2) or (I-3) has more preferably been 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 ₇, Z ₈And Z ₉All represent to form the atomic group of nitrogenous heterocyclic necessity separately, its precondition is Z ₇And Z ₉But go up cyclic condensation, R ₇, R ₈And R ₉All represent alkyl separately, aryl or heterocyclic group, M ₁And m ₁Have with molecular formula (I) in identical meaning, when compound (I-3) when being the dye of positive ion, R ₇, R ₈, R ₉, Z ₇, Z ₈, Z ₉And L ₁₆To L ₂₄All not having anion substituent, is electric charge in the balance dye molecule when compound (I-3) is the betaine dyestuff, R ₇, R ₈, R ₉, Z ₇, Z ₈, Z ₉And L ₁₆To L ₂₄Anion substituent is respectively arranged, a preferred anion substituent.

Following molecular formula (II-1), (II-2) or (II-3) more preferably represented the anionic dye shown in the molecular formula (II):

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 ₁₂, Z ₁₃All expression forms nitrogenous heterocyclic necessary atomic group separately, and its precondition is Z ₁₂And Z ₁₃But go up 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, if Z ₁₄And Z ₁₅But cyclic condensation, then Z ₁₄, Z ₁₅And Z ₁₆All expression forms nitrogenous heterocyclic necessary atomic group, R separately 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, to going on foot 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 high sensitivity in the desired wavelength coverage, the dyestuff that is adsorbed on the second layer must form J-association product (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 that absorbs 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 subsequent layer 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-aggregation of dyestuff in the second layer or the subsequent layer 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 subsequent layer 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-aggregation, 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 absorb the position and absorbing state inconsistent.Therefore, the dyestuff in the second layer or the subsequent layer 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 subsequent layer 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 at composite bed, thereby, also can measure spectral absorption spectrum at the second layer and subsequent layer absorbing dye.

Using dye absorbent from the experiment of particle surface absorbing dye, after the dyestuff in the second layer and subsequent layer 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 subsequent layer.Asanum et al. Jourmal of Physical Chemistry B, Vol.101, pp has described the method for using dye absorbent 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-aggregation of dyestuff, the preferred dyestuff of absorption formation ground floor and the dyestuff that absorption forms the second layer or subsequent layer 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 subsequent layer.Dyestuff in the second layer or the subsequent layer 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 dyestuff in such adding second layer, the interaction in the second layer between dyestuff can increase, and impels the dyestuff in the second layer to reset, thereby forms J-association product (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 subsequent layer 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 the another kind of preferred embodiment of method that dye chromophore in a kind of like this composite bed covers the adsorbed state on silver halide particle surface 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 11-24444,11-34463 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 absorption intensity of silver halide particle preferably than D ₁Lower.To the most preferred order of the absorption intensity 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 803 and page958 (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-aggregation.

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 pp1960-1963 (1996).As the linking group that energy transfer or electron transfer are taken place, Shammai Speiser, Chem.Rev.Vol.96, be preferred described in the pp 1960-1963 (1996).

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 _L2And 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 ₁₉And Z ₂₀All expression forms nitrogenous heterocyclic necessary atomic group separately, and its precondition is Z ₁₉But go up 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, its precondition is Z ₂₁And Z ₂₃But cyclic condensation, Z ₂₁, Z ₂₂And Z ₂₃All expression forms nitrogenous heterocyclic necessary atomic group, M separately ₆Expression balancing charge gegenion, m ₆In the expression and intramolecular charge needed 0 or bigger number, R ₂₁, R ₂₂And R ₂₃All represent alkyl separately, aryl or heterocyclic group;

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, chap 18, and 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 ₂₁, and Z ₂₃, each represents a kind of formation nitrogen heterocyclic ring, preferred 5-or the nitrogenous heterocycle in 6-position, necessary atomic group.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; Benzoxazole nucleus most preferably, 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 that halogen atom (for example; chlorine, bromine, iodine; fluorine), sulfydryl, cyano group; carboxyl, phosphate, sulfo group; hydroxyl contains 1 to 10, and preferred 2 to 8; the more preferably carbamyl of 2 to 5 carbon atoms (for example, methylamino formoxyl, ethylamino formoxyl; morpholino carbonyl), contains 0 to 10, preferred 2 to 8; the more preferably sulfamoyl of 2 to 5 carbon atoms (for example methyl sulfamoyl, ethyl sulfamoyl, piperidino sulfonyl); nitro contains 1 to 20, and preferred 1 to 10; the more preferably alkoxy of 1 to 8 carbon atom (for example, methoxyl, ethoxy; the 2-methoxyethoxy, the 2-phenyl ethoxy), contain 6 to 20; preferred 6 to 12, more preferably aryloxy group (for example, the phenoxy group of 6 to 10 carbon atoms; right-methylphenoxy, right-the chloro phenoxy group, naphthoxy); contain 1 to 20, preferred 2 to 12, more preferably the acyl group of 2 to 8 carbon atoms (for example; acetyl group, benzoyl, three chloro acetyl group); contain 1 to 20, preferred 2 to 12, more preferably the acyloxy of 2 to 8 carbon atoms (for example; acetoxyl group, benzoyloxy), contain 1 to 20; preferred 2 to 12; more preferably the acylamino-of 2 to 8 carbon atoms (for example acetylamino) contains 1 to 20, and preferred 1 to 10; the more preferably sulfonyl of 1 to 8 carbon atom (mesyl for example; ethylsulfonyl, benzenesulfonyl), contain 1 to 20; preferred 1 to 10; the more preferably sulfinyl of 1 to 8 carbon atom (for example, methanesulfinyl, second sulfinyl; the phenylsulfinyl base); contain 1 to 20, preferred 1 to 10, more preferably the sulfonamido of 1 to 8 carbon atom (for example; methanesulfonamido; the second sulfonamido, benzenesulfonamido-), amino; contain 1 to 20; preferred 1 to 12, more preferably substituted-amino (for example, the methylamino of 1 to 8 carbon atom; dimethylamino; dibenzyl amino, anilino-, diphenylamino); contain 0 to 15; preferred 3 to 10, the more preferably ammonium of 3 to 6 carbon atoms (for example trimethyl ammonium, triethyl ammonium); contain 0 to 15; preferred 1 to 10, more preferably the diazanyl of 1 to 6 carbon atom (for example front three diazanyl) contains 1 to 15; preferred 1 to 10; the more preferably urea groups of 1 to 6 carbon atom (for example urea groups, N, N-dimethyl urea groups); contain 1 to 15; preferred 1 to 10, more preferably the imino group of 1 to 6 carbon atom (for example succinimide base) contains 1 to 20; preferred 1 to 12; the more preferably alkylthio group of 1 to 8 carbon atom (for example, methyl mercapto, ethylmercapto group; the rosickyite base); contain 6 to 20, preferred 6 to 12, more preferably the arylthio of 6 to 10 carbon atoms (for example; thiophenyl; right-the methylbenzene sulfenyl, right-the chlorobenzene sulfenyl, 2-pyridine sulfenyl; the naphthalene sulfenyl) contains 2 to 20; preferred 2 to 12, more preferably alkoxy carbonyl group (for example, the methoxycarbonyl group of 2 to 8 carbon atoms; carbethoxyl group; the 2-benzyloxycarbonyl group) contain 6 to 20, preferred 6 to 12, the more preferably aryloxy carbonyl of 6 to 10 carbon atoms (for example phenyloxycarbonyl); contain 1 to 18; preferred 1 to 10, more preferably non-substituted alkyl (for example, the methyl of 1 to 5 carbon atom; ethyl; propyl group, butyl), contain 1 to 18; preferred 1 to 10; the more preferably substituted alkyl of 1 to 5 carbon atom (for example, methylol, trifluoromethyl; benzyl; carboxyethyl, ethoxycarbonylmethyl group, acetylamino methyl); contain 2 to 18; preferred 3 to 10, more preferably 3 to 5 carbon atoms, and the substituted alkyl that contains unsaturated alkyl is (for example; vinyl; ethinyl, 1-cyclohexenyl group, benzylidyne; benzal); contain 6 to 20, preferred 6 to 15, more preferably the replacement of 6 to 10 carbon atoms or non-substituted aryl are (for example; phenyl; naphthyl, right-carboxy phenyl, right-nitrobenzophenone; right-tolyl); contain 1 to 20, preferred 2 to 10, more preferably the replacement of 4 to 6 carbon atoms or non-substituted heterocycle group are (for example; pyridine radicals; the 5-picolyl, thienyl, furyl; morpholino, tetrahydrofurfuryl).Above-mentioned every kind of group can be just like the such structure of ring in the condensation thereon (fragrance or non-aromatic hydrocarbon or heterocycle, phenyl ring for example, naphthalene nucleus, anthracene nucleus, quinoline ring).

The substituting group that V represents can further replace with V.

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 ₁₃And Z ₂₀Each representative a kind of formation necessary atomic group of acid core, yet, the acid karyomorphism molecular formula of portion's cyanine dyes of any routine also can be formed.Terminology used here " sour part nuclear " is as at James (compiler), The Theory of the Photographic Process, 4thed., page 198, definition to some extent among the Macmillan (1977).Its concrete example comprises USP3,567,719,3,517,869,3,804,634,3,837,862,4,002,480,4,925,777 and JP-A-3-167546 described in those examples.

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 center.

Z ₆, Z ₁₃And Z ₂₀Each is hydantoins preferably, 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 ₁₅Or Z ₂₂The 5-or the 6-member heterocyclic ring containing nitrogen that form are from Z ₆, Z ₁₃Or Z ₂₀Remove in the heterocycle of representative that oxo group or epithio base form, preferably from hydantoins, 2-or 4-thiohydantoin, 2-oxazoline-5-ketone, 2-sulfo-oxazoline-2, the 4-diketone, thiazolidine-2,4-diketone, rhodanine, thiazolidine-2, the 4-dithione removes 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, remove 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 rhodanine.

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 ₂₂And R ₂₃Each 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 ₉, each 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 for every kind, 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 also 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.

The preferred examples that contains the group of the aromatic ring that does not contain anionic group comprises the alkyl of hydrocarbonaceous aromatic ring, aralkyl (benzyl for example for example, the 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-, between-or right-halogenated phenoxy) ethyl, 2-(adjacent-,-or right-methoxyl phenoxy group) ethyl) and the 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 also 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.

The preferred examples that contains the group of the aromatic ring that anion substituent replaces comprises the alkyl of band hydrocarbon aromatic ring, sulfo group for example, 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, aryloxycarbonyl alkyl of phosphate or carboxyl substituted (for example, 3-sulphur phenyloxycarbonyl propyl group) and sulfo group, the aryloxy alkyl of phosphate or carboxyl substituted is (for example, 2-(4-sulphur phenoxy group) ethyl, 2-(2-phosphniline oxygen base) ethyl, 4,4-two phenoxy groups-3-sulphur butyl);

The band hetero-aromatic ring alkyl, 3-(2-pyridine radicals)-3-sulfopropyl for example, 3-(2-furyl)-3-sulfopropyl and 2-(2-thienyl)-2-sulfopropyl;

The aryl of band hydrocarbon aromatic group, sulfo group for example, 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.

Use D in the molecular formula (III) ₁The chromophore of expression is that with molecular formula (IV) (V) (VI) Biao Shi methine dyes in this case, is used R ₁₇, R ₁₈, R ₁₉, R ₂₀, R ₂₁, R ₂₂And R ₂₃Each non-substituted alkyl preferably recited above of substituting group of expression or substituted alkyl (alkyl, carboxyalkyl for example, sulfoalkyl, aralkyl and aryloxy alkyl).

Use D in the molecular formula (III) ₂The chromophore of expression is that with molecular formula (IV) (V) (VI) Biao Shi methine dyes in this case, is used R ₁₇, R ₁₈, R ₁₉, R ₂₀, R ₂₁, R ₂₂And R ₂₃Substituting group each non-substituted alkyl preferably recited above or substituted alkyl of expression are more preferably the alkyl (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 ₆₃And L ₆₄Each represents a methine independently.L ₁To L ₆₄The 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, more preferably 1 to 5 the alkoxy (for example, methoxyl, ethoxy) of carbon atom, 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 ₅And M ₆Each all is included in the molecular formula, like this in order that in being necessary 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 (for example, calcium ion), and organic cation, for example ammonium ion (ammonium ion, tetraalkyl ammonium ion, pyridinium ion, ethylpyridine 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 ₅And m ₆Each 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 concrete enforcement of the dyestuff in the optimization technique used in this 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

Specific Examples of Compound Represented by Formula(II) of the Present Invention (including lower concept structures)

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

In the present invention, the method that has the sensitizing dye of maximum maximum wavelength of specific spectral absorption or spectral sensitivity distribution except use recited above, by using dyestuff with molecular formula (IV) expression that establishes an equation down, the mid point light sensitivity and the basic light sensitivity of characteristic curve can be improved, and a sharp-pointed spectral sensitivity spectrum can be obtained.

Wherein Z24 represents for forming 5 yuan or the necessary atomic group of 6 member heterocyclic ring containing nitrogens, Z25 represents for forming fat or aromatic rings is necessary and more a plurality of ring (comprising the nitrogen heterocyclic ring that is formed by Z24) of the necessary atomic group of many cyclic condensations structure comprise 3 or to(for) formation, Q represents to make the represented compound of molecular formula (IV ') to generate the necessary group of methine dyes, R24 represents alkyl group, aromatic yl group or heterocyclic group, L65 and L66 all represent a methine group separately, p17 represents 0 or 1, M7 represents to be used for the gegenion of balancing charge, and m7 represents to be used to neutralize necessary from 0 to 10 the number of branch charge of the electron.

Preferred embodiment in the application of the represented dyestuff of molecular formula (IV ') is described below.

(1) in the represented compound of molecular formula (IV '), used, also, had and be used to generate the substituent dyestuff of being with of the dye of positive ion (this dyestuff is defined as " dyestuff IV ' c ") generally not with the dyestuff of anion substituent.

But in the independent use of dyestuff IV ' c, R24 is preferably alkyl, aryl or the aromatic heterocycle group that aromatic group (aryl or aromatic heterocycle group) replaces.

(2) in the represented compound of molecular formula (IV '), used to be used to generate the substituent dyestuff of being with of anionic dye (this dyestuff is defined as " dyestuff IV ' a ") generally.

(3) to use represented methine dyes and at least a dyestuff IV ' a of at least a following molecular formula (IV '-1) simultaneously

Wherein Z26 represents to be used to generate the necessary atomic group of nitrogen heterocyclic ring, its precondition is aromatic ring can be condensed on the Z26, R25 represents alkyl, aryl or heterocyclic group, Q3 represents it is that the represented compound of molecular formula (IV '-1) generates the necessary group of methine, L67 and L68 all represent a methine separately, p18 represents 0 or 1, if Z26 generally, R25, Q3, each has L67 and L68 a substituting group that makes the represented methine of molecular formula (IV '-1) form the dye of positive ion and (also is, each is not with anion substituent), M8 represents to be used for the negative ion of balancing charge, and m8 represents to be used to neutralize necessary from 0 to 10 the number of branch charge of the electron.

Dyestuff IV ' a is included in the represented methine dyes of following molecular formula (IV '-2) (anionic dye).More particularly, have the dyestuff of the many cyclic condensations structure that comprises that three or more rings are formed corresponding to dyestuff IV ' a by the nitrogen heterocyclic ring that Z27 generated.

(4) use at least a dyestuff IV ' c and at least a simultaneously by the represented methine dyes of following molecular formula (IV '-2):

Wherein Z27 represents to be used to generate the necessary atomic group of nitrogen heterocyclic ring, its precondition is aromatic ring can be condensed on the Z27, R26 represents alkyl, aryl or heterocyclic group, Q4 represents it is that the represented compound of molecular formula (IV '-2) generates the necessary group of methine, L69 and L70 all represent a methine separately, p19 represents 0 or 1, if Z27 generally, R26, Q4, each has a substituting group that makes the represented methine of molecular formula (IV '-2) generate anionic dye L69 and L70, M9 represents to be used for the kation of balancing charge, and m9 represents to be used to neutralize necessary from 0 to 10 the number of branch charge of the electron.

Dyestuff IV ' c is included in the methine dyes (dye of positive ion) by top molecular formula (IV '-1) representative.More particularly, have the dyestuff of the many cyclic condensations structure that comprises that three or more rings are formed corresponding to dyestuff IV ' c by the nitrogen heterocyclic ring that Z26 generated.

When being used in combination represented methine dyes of molecular formula (IV '-1) and dyestuff IV ' a, R24 and R25 be the alkyl, aryl or the heteroaromatic group that replace of aromatic group (aryl or heteroaromatic group) one of at least preferably.

In a more preferred embodiment, R24 and R25 are alkyl, aryl or the heteroaromatic groups that is replaced by aromatic group (aryl or heteroaromatic group).

When being used in combination dyestuff IV ' c and during by the represented methine dyes of molecular formula (IV '-2), R24 and R26 be the alkyl, aryl or the heteroaromatic group that replace of aromatic group (aryl or heteroaromatic group) one of at least preferably.

In a more preferred embodiment, R24 and R26 are alkyl, aryl or the heteroaromatic groups that is replaced by aromatic group (aryl or heteroaromatic group).

Compound in the molecular formula (IV '-1) more preferably can be represented with following molecular formula (IV '-3):

L71 wherein, L72, L73, L74, L75, L76, all represent methine separately with L77, p20 and p21 all represent 0 or 1 separately, and n13 represents 0,1,2,3 or 4, Z28 or Z29 all represent a kind of be used to generate 5 or 6 necessary atomic groups of nitrogen heterocyclic ring separately, and its precondition is aromatic ring can be condensed on Z28 or the Z29, and R27 or R28 all represent an alkyl separately, aryl or aromatic heterocycle group, its precondition is R27 generally, R28, Z28, Z29, L71, L72 and L73 are not with anion substituent for every kind, are yet, each is all with the substituting group that is used to generate the dye of positive ion, and equivalent in meaning in M8 and m8 and the molecular formula (IV '-1).

Compound in the molecular formula (IV '-2) more preferably can be represented with following molecular formula (IV '-4):

L78 wherein, L79, L80, L81, L82, L83, all represent a methine separately with L84, p22 and p23 all represent 0 or 1 separately, and n14 represents 0,1,2,3 or 4, Z30 or Z31 all represent a kind of be used to generate 5 or 6 necessary atomic groups of nitrogen heterocyclic ring separately, and its precondition is aromatic ring can be contracted to contain on Z30 or the Z31, R29 or R30 all represent an alkyl separately, aryl or aromatic heterocycle group are that R29 and R30 respectively are with an anion substituent as its precondition, and equivalent in meaning in M9 and m9 and the molecular formula (IV '-2).

Represented when independent use molecular formula (IV '-3), and when being the included methine dyes of dyestuff IV ' c, at least one among R27 and the R28 be the alkyl, aryl or the aromatic heterocycle group that replace of aromatic group (aryl or aromatic heterocycle group) preferably.

In a more preferred embodiment, R27 and R28 are alkyl, aryl or the aromatic heterocycle groups that aromatic group (aryl or aromatic heterocycle group) replaces.

When be used in combination molecular formula (IV '-3) represented and for included methine dyes and the molecular formula (IV '-4) of dyestuff IV ' c represented, and when being the included methine dyes of dyestuff IV ' a, R27, at least one alkyl, aryl or aromatic heterocycle group of replacing of aromatic group (aryl or aromatic heterocycle group) preferably among R28 R29 and the R28.

In a more preferred embodiment, R27 has at least two to be the alkyl that aromatic group (aryl or aromatic heterocycle group) replaces, aryl or aromatic heterocycle group among R28 R29 and the R28; In further preferred embodiment, R27 has at least three to be the alkyl that aromatic group (aryl or aromatic heterocycle group) replaces, aryl or aromatic heterocycle group among R28 R29 and the R28; In particularly preferred embodiments, R27 at least, R28, among R29 and the R28 is alkyl, aryl or the aromatic heterocycle group that aromatic group (aryl or aromatic heterocycle group) replaces all.

(5) use the represented spectral sensitizer (having the many cyclic condensations structure that comprises three rings) of following molecular formula:

Wherein, Y1 and Y2 all represent O or S separately, and Za and Zb all represent to generate the necessary atomic group of phenyl ring separately, and numerical value (4 in the molecular formula, 5,6 and 7) shown the bonding position of phenyl ring, phenyl ring is bonded to (4,5), on any one position in (5,6) and (6,7).R24's in Ra and Rb and the molecular formula (IV ') is equivalent in meaning, and La, Lb and Lc all represent a methine separately, and equivalent in meaning with L73, and n represents 0,1 or 2, and M10 and m10 be equivalent in meaning with M7 and m7 respectively.

(i) in the preferred embodiment of molecular formula (V '), n is 1, and La and Lc respectively are the methine of non-replacement, and Lb contains the methine (preferably methyl or ethyl) that the alkyl of 1 to 5 carbon atom replaces.

(ii) in (i), the phenyl ring by Za and Zb generate more preferably is bonded on (4,5) or (5,6) position.In this case, Y1 and Y2 especially preferably are 0.

(iii) in (ii), Ra and Rb are alkyl, aryl or the aromatic heterocycle groups that aromatic group replaces.

(iv) in (iii), substituent selection will make spectral sensitizer generate the dye of positive ion or anionic dye generally.

(v) the dye of positive ion of the represented spectral sensitizer of molecular formula (V ') and the anionic dye that belongs to the represented spectral sensitizer of molecular formula preferably use simultaneously in addition.

In the present invention, the dye of positive ion refers to not contain the dyestuff of anion substituent, and anionic dye refers to contain the dyestuff of anion substituent.

Related anion substituent is the substituting group that has negative charge among the present invention, and this substituting group be can stable dispersion under neutrality or weak basic condition atomic group, particularly contain the substituting group of hydrogen atom.The example comprises sulfo group (SO ₃ ^-), sulfate (OSO ₃ ^-), carboxyl (CO ₂ ^-), phosphate (PO ₃ ^-); alkyl sulfonyl-amino formoxyl alkyl (for example; methyl sulphonyl carbamyl ylmethyl); acyl amino formoxyl alkyl (for example; acetyl-amino formoxyl methyl); acyl group sulfamoyl alkyl (for example, acetyl amine sulfonyl methyl) and alkyl sulphonyl sulfamic alkyl (for example, methyl sulphonyl sulfamic methyl).

In many cases, using the photosensitive material (obtaining by absorb chromophore on one deck or more multi-layered silver halide particle) of silver halide particle to show a wide spectral sensitivity as mentioned above distributes.Inventor of the present invention finds, the dyestuff of the ground floor and the second layer and subsequent layer had by the J-sensitivity that (for example, J-assembles) cause of associating can improve this problem.

Describe employed molecular formula among the present invention (IV ') below in detail, (IV '-1), (IV '-2), (IV '-3) and (IV '-4) represented compound.

According to molecular formula (IV '), Q in (IV '-1) and (IV '-2), the structure of Q3 and Q4 can generate any methine dyes.Its preferred embodiment comprises cyanine dyes, portion's cyanine dyes, if rhodacyanine dye, oxonol dye, three nuclear portions cyanines combustion dyestuff, four nuclear portion cyanine dyes, pole-changing dyestuff, styryl color, hemicyanine dye, chain cyanine dyes and half oxonol dyes.In these dyestuffs, cyanine dyes more preferably, portion's cyanine dyes, if rhodacyanine dye, further cyanine dyes (wherein electric charge can be a positive charge, negative charge and betaine) more preferably.These dyestuffs (F.M.Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds, John Wiley ﹠amp; Sons, NewYork, Lodon (1964), and D.M.Sturmer, Heterocyclic Compounds-Special Topics In Hetero-Cyclic Chemistry, Chap.18, Sec.14, pp.482-515, John Wiley ﹠amp; Sons, New York, London (1977)) in have a detailed description.

For portion's cyanine dyes with around the painting dyestuff, at USP 5,340, the molecular formula (XII) described in the 694 21-22 pages or leaves and (XIII) is preferred.

When generating cyanine dyes by Q, molecular formula ( IV ') can represent with following resonance molecular formula:

At Q, the number of the methine among Q3 or the Q4 is preferably 0 to 7, and more preferably 0 to 5, further more preferably 3.Here, as long as Q, Q3 or Q4 generate above-mentioned dyestuff (cyanine dyes for example, portion's cyanine dyes, if rhodacyanine dye, three nuclear portions cyanines combustion dyestuff, pole-changing dyestuff, hemicyanine dye, styryl color), and the number of methine can be 0 (for example, simple portion cyanines).Methine is preferably replaced by generating the necessary substituting group of methine dyes (for example, heterocyclic group, alkyl, aryl).Substituting group is preferably heterocyclic group, alkyl or aryl, more preferably heterocyclic group.

Aromatic group comprises the aromatic group (for example, 4-dimethylaminophenyl, 4-methoxyphenyl, phenyl, 4-dimethylamino naphthyl) of replacement or non-replacement.

The preferred embodiment of aliphatic group comprises alkoxy carbonyl (for example, ethoxy carbonyl) and acyl group (for example, acetyl group).Other example comprises above-mentioned with the represented substituting group of V.In those examples; preferably, for example, the amino of replacement or non-replacement (for example; amino; dimethylamino), cyano group, alkoxy carbonyl are (for example; ethoxy carbonyl); replace or the alkyl sulphonyl (for example, methyl sulphonyl) of non-replacement and the acyl group (for example, acetyl group) of replacement or non-replacement.

Molecular formula ( IV ') in, Z24 represents to generate 5 yuan or the required atomic group of 6 member heterocyclic ring containing nitrogens.The nitrogen heterocyclic ring that forms by Z24 can with the aromatic ring condensation.This nitrogenous heterocyclic example comprises thiazoline ring, thiazole ring, oxazoline ring, oxazole ring, the selenazoline ring, the selenazoles ring, 3, the 3-dialkyl group-the 3H-pyrrole ring is (for example, 3,3-dimethyl-3H-pyrroles), imidazoline ring, imidazole ring, the 2-pyridine ring, 4-pyridine ring, imidazo [4,5-b] quinoxaline ring, oxadiazoles ring, thiadiazoles ring, tetrazole ring, pyrimidine ring, piperazine and pyrazine ring.In these nitrogen heterocyclic rings, thiazole ring preferably, oxazole ring, selenazoles ring, 3,3-dialkyl group-3H-pyrrole ring, imidazole ring and 2-pyridine ring, more preferably thiazole ring, oxazole ring, imidazole ring and 2-pyridine ring.

Suppose that at nitrogenous heterocyclic substituting group be V, the substituting group of V representative is not particularly limited, yet the example comprises that halogen atom (for example; chlorine, bromine, iodine; fluorine), sulfydryl, cyano group; carboxyl, phosphate, sulfo group; hydroxyl contains 1 to 10, and preferred 2 to 8; the more preferably carbamyl of 2 to 5 carbon atoms (for example, methylamino formoxyl, ethylamino formoxyl; morpholino carbonyl), contains 0 to 10, preferred 2 to 8; the more preferably sulfamoyl of 2 to 5 carbon atoms (for example methyl sulfamoyl, ethyl sulfamoyl, piperidino sulfonyl); nitro contains 1 to 20, and preferred 1 to 10; the more preferably alkoxy of 1 to 8 carbon atom (for example, methoxyl, ethoxy; the 2-methoxyethoxy, the 2-phenyl ethoxy), contain 6 to 20; preferred 6 to 12, more preferably aryloxy group (for example, the phenoxy group of 6 to 10 carbon atoms; right-methylphenoxy, right-the chloro phenoxy group, naphthoxy); contain 1 to 20, preferred 2 to 12, more preferably the acyl group of 2 to 8 carbon atoms (for example; acetyl group, benzoyl, three chloro acetyl group); contain 1 to 20, preferred 2 to 12, more preferably the acyloxy of 2 to 8 carbon atoms (for example; acetoxyl group, benzoyloxy), contain 1 to 20; preferred 2 to 12; more preferably the acylamino-of 2 to 8 carbon atoms (for example acetylamino) contains 1 to 20, and preferred 1 to 10; the more preferably sulfonyl of 1 to 8 carbon atom (mesyl for example; ethylsulfonyl, benzenesulfonyl), contain 1 to 20; preferred 1 to 10; the more preferably sulfinyl of 1 to 8 carbon atom (for example, methanesulfinyl, second sulfinyl; the phenylsulfinyl base); contain 1 to 20, preferred 1 to 10, more preferably the sulfonamido of 1 to 8 carbon atom (for example; methanesulfonamido; the second sulfonamido, benzenesulfonamido-), amino; contain 1 to 20; preferred 1 to 12, more preferably substituted-amino (for example, the methylamino of 1 to 8 carbon atom; dimethylamino; dibenzyl amino, anilino-, diphenylamino); contain 0 to 15; preferred 3 to 10, the more preferably ammonium of 3 to 6 carbon atoms (for example trimethyl ammonium, triethyl ammonium); contain 0 to 15; preferred 1 to 10, more preferably the diazanyl of 1 to 6 carbon atom (for example front three diazanyl) contains 1 to 15; preferred 1 to 10; the more preferably urea groups of 1 to 6 carbon atom (for example urea groups, N, N-dimethyl urea groups); contain 1 to 15; preferred 1 to 10, more preferably the imino group of 1 to 6 carbon atom (for example succinimide base) contains 1 to 20; preferred 1 to 12; the more preferably alkylthio group of 1 to 8 carbon atom (for example, methyl mercapto, ethylmercapto group; the rosickyite base); contain 6 to 20, preferred 6 to 12, more preferably the arylthio of 6 to 10 carbon atoms (for example; thiophenyl; right-the methylbenzene sulfenyl, right-the chlorobenzene sulfenyl, 2-pyridine sulfenyl; the naphthalene sulfenyl) contains 2 to 20; preferred 2 to 12, more preferably alkoxy carbonyl group (for example, the methoxycarbonyl group of 2 to 8 carbon atoms; carbethoxyl group; the 2-benzyloxycarbonyl group) contain 6 to 20, preferred 6 to 12, the more preferably aryloxy carbonyl of 6 to 10 carbon atoms (for example phenyloxycarbonyl); contain 1 to 18; preferred 1 to 10, more preferably non-substituted alkyl (for example, the methyl of 1 to 5 carbon atom; ethyl; propyl group, butyl), contain 1 to 18; preferred 1 to 10; the more preferably substituted alkyl of 1 to 5 carbon atom (for example, methylol, trifluoromethyl; benzyl; carboxyethyl, ethoxycarbonylmethyl group, acetylamino methyl); contain 2 to 18; preferred 3 to 10, more preferably 3 to 5 carbon atoms, and the substituted alkyl that contains a unsaturated alkyl is (for example; vinyl; ethinyl, 1-cyclohexenyl group, benzylidyne; benzal); contain 6 to 20, preferred 6 to 15, more preferably the replacement of 6 to 10 carbon atoms or non-substituted aryl are (for example; phenyl; naphthyl, right-carboxy phenyl, right-nitrobenzophenone; right-tolyl); contain 1 to 20, preferred 2 to 10, more preferably the replacement of 4 to 6 carbon atoms or non-substituted heterocycle group are (for example; pyridine radicals; the 5-picolyl, thienyl, furyl; morpholino, tetrahydrofurfuryl).Above-mentioned every kind of group can be just like a phenyl ring or the structure that naphthalene nucleus is such in the condensation thereon.In addition, these substituting groups each can further replace with V.

In these substituting groups, alkyl preferably, aryl, alkoxy, halogen atom and their phenyl ring condensation product, more preferably methyl, phenyl, methoxyl, chlorine atom, bromine atoms, iodine atom and their phenyl ring condensation product.

Z25 represents a formation fat or aromatic cycle compound is necessary and formation contains three or more the rings necessary atomic group of many cyclic condensations structure of (comprising the nitrogen heterocyclic ring that forms by Z24).The example of the ring texture that forms by Z25 comprise have dicyclo or bigger many cyclic condensations ring structure non-replacement alicyclic structure (for example, decahydronaphthalenes), have dicyclo or bigger many cyclic condensations ring structure replacement alicyclic structure (substituent example comprise above-mentioned as substituting group V example and those substituting groups of describing), the non-substituted aroma ring texture that has dicyclo or a bigger many cyclic condensations ring structure (for example, pentalene, indenes, naphthalene, azulenes, anthracene, luxuriant and rich with fragrance), have dicyclo or bigger many cyclic condensations ring structure the substituted aroma ring texture (substituent example comprise above-mentioned as substituting group V example and those substituting groups of describing), the non-substituted heterocycle structure that has dicyclo or a bigger many cyclic condensations ring structure (for example, quinolizine, purine, naphthylene), have dicyclo or bigger many cyclic condensations ring structure the substituted heterocycle structure (substituent example comprise above-mentioned as substituting group V example and those substituting groups of describing), by two or more cycloaliphatic ring structures, aromatic ring structure and heterocycle condensation obtain has structure (for example, the coumarone of dicyclo or bigger many cyclic condensations ring structure, benzothiophene, indoles, oxathiin, quinoline, thiazine, benzothiazine, benzo oxathiin, azophenlyene, indoline, the benzo morpholine, chromene encircles penta pyrans, two benzo-thiophenes, benzoxazine, coumarone, dibenzothiophene, carbazole, benzodihydropyran, cumarin, xanthenes, thianthrene), said structure can replace with a substituting group V.

In the ring texture that forms by Z25, preferably have non-substituted aroma ring texture (for example, the pentalene of dicyclo or bigger many cyclic condensations ring structure, indenes, naphthalene, anthracene, luxuriant and rich with fragrance), have the substituted aroma ring texture of dicyclo or bigger many cyclic condensations ring structure, by two or more cycloaliphatic ring structures, aromatic ring structure and heterocycle structure condensation obtain has structure (for example, the coumarone of dicyclo or bigger many cyclic condensations ring structure, benzothiophene, indoles, oxathiin, quinoline, thiazine, benzothiazine, the benzo oxathiin, azophenlyene, indoline, the benzo morpholine, chromene encircles penta pyrans, two benzo-thiophenes, benzoxazine, coumarone, dibenzothiophene, carbazole, benzodihydropyran, cumarin, xanthenes, thianthrene; The substitution product that comprises them).More preferably by three or more cycloaliphatic ring structures, aromatic ring structure and heterocycle structure condensation obtain has structure (for example, anthracene, the phenanthrene of one three ring or bigger many cyclic condensations ring structure, dibenzofurans, dibenzothiophene, carbazole, the benzo oxathiin, xanthenes, thianthrene; The substitution product that comprises them).Further more preferably anthracene, dibenzofurans, dibenzothiophene and carbazole.

In molecular formula (IV '-1), (IV '-2), in (IV '-3) and (IV '-4), as long as aromatic ring can be condensed to above them, Z26 then, Z27, Z28, Z29, each expression of Z30 and Z31 forms the required atomic group of nitrogen heterocyclic ring.The example of aromatic ring comprises phenyl ring, 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, 1-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.

Nitrogen heterocyclic ring can further replace with an above-mentioned substituting group V.At Z26, Z27, Z28, Z29, the substituting group on Z30 or the Z31 is aryl preferably, aromatic heterocycle or aromatic rings condensation product.

L65 represents a methine independently of one another to L84.L65 can have substituting group to the represented methine of L84, and substituent example comprises and contains 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), contains 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 (for example, chlorine, bromine, iodine, fluorine), contain 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 amino (for example, the methylamino of 4 to 10 carbon atoms, N, the N-dimethylamino, N-methyl-N-phenylamino, 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), contain 6 to 20, preferred 6 to 12, more preferably the arylthio of 6 to 10 carbon atoms (for example, thiophenyl, right-the methylbenzene sulfenyl).Can become ring maybe can form an auxochrome with another methine.

L65 is to L72, and L76 is to L79, and L83 preferably is non-replacement methine to L84 separately.

P17, p18, p19, p20, p21, each expression 0 or 1 of p22 and p23 more preferably represents 0.

R24, R25, R26, R27, R28, each expression of R29 and R30 alkyl, aryl or a heterocyclic group.Their instantiation comprises and contains 1 to 18; preferred 1 to 7; 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); contain 1 to 18; preferred 1 to 7, more preferably the substituted alkyl of 1 to 4 carbon atom is (for example, with above-mentioned substituting group V; preferably aralkyl (for example; benzyl, the 2-phenethyl), the alkyl of replacement); unsaturated alkyl (for example; allyl), hydroxyalkyl (for example 2-hydroxyethyl, 3-hydroxypropyl); carboxyalkyl (for example; the 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 is (for example; the ethoxy carbonyl methyl; 2-benzyloxycarbonyl ethyl), aryloxycarbonyl alkyl (for example, 3-phenyloxycarbonyl propyl group); the acyloxy alkyl (for example; 2-acetoxyl group ethyl), acyl group alkyl (for example 2-acetyl ethyl), the carbamyl alkyl is (for example; 2-morpholino carbonyl ethyl); sulfamoyl alkyl (for example N, N-dimethylamino sulfonyl methyl), sulfoalkyl is (for example; the 2-sulfoethyl; the 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; the sulfato alkyl (for example; 2-sulfato-ethyl, 3-sulfato propyl group, 4-sulfato butyl); the heterocyclic substituted alkyl (for example; 2-(pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkyl sulfonyl-amino formoxyl alkyl (for example mesyl carbamyl ylmethyl); contain 6 to 20; preferred 6 to 10, more preferably non-substituted aryl (for example, the phenyl of 6 to 8 carbon atoms; the 1-naphthyl); contain 6 to 20, preferred 6 to 10, more preferably the substituted aryl of 6 to 8 carbon atoms (for example; with above-mentioned V substituting group; especially, right-methoxyphenyl, right-aminomethyl phenyl; to the chloro-phenyl; the aryl that replaces), contain 1 to 20, preferred 3 to 10; more preferably the non-substituted heterocycle group of 4 to 8 carbon atoms (for example; the 2-furyl, 2-thienyl, 2-pyridine radicals; the 3-pyrazolyl; the 3-isoxazolyl, 3-isothiazolyl, 2-imidazole radicals; the 2-oxazolyl; the 2-thiazolyl, 2-pyridazinyl, 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).

In molecular formula (IV '-1) and (IV '-3), preferred, R25, alkyl with at least one expression aromatic group (aryl or aromatic heterocycle group) replacement among R27 and the R28, aryl or aromatic heterocycle group, and preferred R25 and R27 and R28 neither are with anion substituent.Substituent example comprises substituting group V.At this moment, the dyestuff in molecular formula (IV '-1) or (IV '-3) must form the dye of positive ion.

The preferred embodiment of aryl substituted alkyl for example 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-, between-, right-halogenated phenoxy) ethyl, 2-(adjacent-, between-, right-the methoxyl phenoxy group) ethyl) and aryloxycarbonyl alkyl (for example, 3-phenyloxycarbonyl propyl group, 2-(1-naphthoxy carbonyl) ethyl).The preferred embodiment of aromatic heterocycle substituted alkyl comprises 2-(2-pyridine radicals) ethyl, 2-(4-pyridine radicals) ethyl, 2-(2-furyl) ethyl, 2-(2-thienyl) ethyl and 2-(2-pyridine radicals methoxyl) ethyl.The preferred embodiment of aryl comprises-1-methoxyphenyl, phenyl, naphthyl and diphenyl.The preferred embodiment of aromatic heterocycle group comprises the 2-thienyl, 4-chloro-2-thienyl, 2-pyridine radicals and 3-pyrazolyl.

In these groups, the alkyl and replacement or the non-substituted aryl that replace of aromatic group (aryl or aromatic heterocycle group) more preferably.

In molecular formula (IV '-2) and (IV '-4), preferred, R26, alkyl with at least one expression aromatic group (aryl or aromatic heterocycle group) replacement among R29 and the R30, aryl or aromatic heterocycle group, and preferred R26 and R29 and R30 both have an anion substituent.Substituent example comprises substituting group V.At this moment, the dyestuff in molecular formula (IV '-2) or (IV '-4) must form anionic dye.

The preferred embodiment of alkyl group comprises and contains 1 to 15; preferred 1 to 10 carbon atom and sulfo group; the alkyl group of phosphate or carboxyl substituted (for example, sulphur methyl, sulfoethyl; 2; 2-two fluoro-2-carboxy ethyls, 2-phosphoric acid ethyl), sulfo group; the unsaturated alkyl of phosphate or carboxyl substituted (for example; 3-sulfo group-2-propenyl), sulfo group, the alkoxyalkyl of phosphate or carboxyl substituted is (for example; 2-sulphur methoxy ethyl); sulfo group, the alkoxy carbonyl alkyl of phosphate or carboxyl substituted (for example, sulphur ethoxy carbonyl ethyl; 2-sulphur benzyloxycarbonyl ethyl); sulfo group, acyloxy alkyl of phosphate or carboxyl substituted (for example, 2-phosphoric acid acetoxyl group ethyl) and sulfo group; the acyl alkyl of phosphate or carboxyl substituted (for example, 2-sulphur acetyl group ethyl).The preferred embodiment of the alkyl that aryl replaces comprises 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 examples of the alkyl that aromatic heterocycle group replaces comprises sulfo group, the alkyl that the aromatic heterocycle group of phosphate or carboxyl substituted replaces (for example, 3-(2-pyridine radicals)-3-sulfopropyl, 3-(2-furyl)-3-sulfopropyl, 2-(2-thienyl)-2-sulfopropyl).

The preferred embodiment of aryl comprises by sulfo group, the aryl of phosphate or carboxyl substituted (for example, 4-sulfophenyl, 4-sulphur naphthyl).The preferred embodiment of aromatic heterocycle group comprises sulfo group, 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, sulfo group more preferably, the aralkyl of phosphate or carboxyl substituted, sulfo group, the aryloxy alkyl of phosphate or carboxyl substituted, further 2-sulphur benzyl more preferably, 4-sulphur benzyl, 4-sulphur phenethyl, 3-phenyl-3-sulfopropyl, 4-phenyl-4-sulphur butyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulphur butyl, 2-(4 '-sulfo group-4-diphenyl) ethyl, 4-phosphoric acid benzyl, 3-sulfo group-2-propenyl and 2-(4-sulphur benzyl) ethyl, 2-sulphur benzyl most preferably, 4-sulphur benzyl, 4-sulphur phenethyl, 3-phenyl-3-sulfopropyl and 4-phenyl-4-sulphur butyl.

N13 and n14 all represent 0,1,2,3 or 4 separately, preferably represent 0,1,2 or 3, more preferably represent 0,1 or 2, further more preferably represent 0 or 1.Each is 2 or when bigger, methine will repeat as n13 and n14, but that these methines do not need is identical.

P17, p18, p19, p20, p21, p22 and p23 all represent 0 or 1 separately, preferably represent 0.

M7, each is included in M8 and M9 in the molecular formula, like this in order that in being necessary and during the ionic charge of dyestuff, show kation or anionic existence.Cationic instantiation comprises inorganic cation, for example hydrogen ion (H ⁺), alkali metal ion (for example, sodion, potassium ion, lithium ion) and alkaline-earth metal ions (for example, calcium ion), and organic cation, for example ammonium ion (ammonium ion, tetraalkyl ammonium ion, pyridinium ion, ethylpyridine 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.Also, 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.

M7, m8 and m9 all represent to be used for the required number of balancing charge number separately, and when forming inner salt, its value is 0.

The instantiation of the dye of positive ion in the molecular formula (IV ' c) and (IV '-1) (IV '-3) and (V ') below will be told about, yet the present invention never is only limited to this.

General formula (IV ' a), (IV '-2), (IV '-4) and (V ')In the specific examples of the anionic dye that comprises be presented below, yet the present invention never is so limited.

Dyestuff among the present invention can be according to F.M Harmer, Heterocyclic Compounds-Cvanine 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 Company Inc. New York (1977) and (quote with in order to describe specific example) described above patent 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.

For being used in combination dyestuff, can use any in the cyanine dyes of being everlasting the nuclear as basic heteronucleus.That is, the example of such nuclear comprises: pyrrolin nuclear, malicious azoles quinoline nuclear, thiazoline nuclear, pyrrole nucleus, azoles nuclear, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazolium nuclear and pyridine nucleus; By certain fat nuclear or aromatic hydrocarbon ring are fused to the nuclear that obtains in above-mentioned each nuclear (for example indolenine nuclear, benzene indole nucleus, indole nucleus, benzindole nuclear, aphthoxazoles nuclear, benzothiazole nucleus, aphthothiazoles nuclear, naphthalene selenazole nuclear, benzene imidazole nucleus and quinoline nuclei).These are examined each and all can be substituted on carbon atom.

Can be used for portion's cyanine dyes and composite part cyanine dyes as a kind of 5 yuan or 6 yuan of heterocycles with ketone structure, for example pyrazoline nuclear, thiohydantoin are examined, 2-sulfo-oxazolidine-2,4-diketone nuclear, thiazolidine-2,4-diketone nuclear, rhodanine nuclear, thiobarbituric acid nuclear and 2-sulfo-selenazoline-2,4-diketone nuclear also can use.

For example, can use Research DisclosureNo.17643, page 23, compound of describing among the Item IV (in November, 1978) and the compound of describing in the document that it is quoted.

The particular compound of using (dyestuff) is as follows:

A:5,5 '-two chloro-3,3 '-diethyl thiophene cyanines bromide

B:5,5 '-two chloro-3,3 '-two (4-sulphur butyl)-thiophene cyanines sodium salt

C:5-methoxyl-4,5-benzo-3,3 '-two (3-sulfopropyl)-thiophene cyanines sodium salts

D:5,5 '-two chloro-3,3 '-diethyl selenide cyanines iodide

E:5,5 '-two chloro-9-ethyls-3,3 '-two (3-sulfopropyl) thiophene carbonyl cyanines pyridiniujm

F: dehydration-5,5 '-two chloro-9-ethyl-3-(4-sulphur butyl)-3 '-ethyl oxyhydroxide

G:1,1-diethyl-2,2 '-cyanines bromide

H:1,1-amyl group-2,2 '-cyanines perchloric acid

I:9-methyl-3,3 '-two (4-sulphur butyl)-thiophene carbonyl cyanines pyridiniujms

J:5,5 '-diphenyl 9-ethyl-3,3 '-two (2-sulfoethyl) oxa-carbonyl cyanines sodium salt

K:5-chlorine 5 '-phenyl 9-ethyl-3-(3-sulfopropyl)-3 '-(2-sulfoethyl) oxa-carbonyl cyanines sodium salt

L:5,5 '-two chloro-9-ethyls-3,3 '-two (3-sulfopropyl) oxa-carbonyl cyanines sodium salt

M:5,5 '-two chloro-, 6,6 '-two chloro-1,1 '-diethyl 3,3 '-two (3-sulfopropyl) imidazoles carbonyl cyanines sodium salt

N:5,5 '-diphenyl-9-ethyl-3,3 '-two (3-sulfopropyl) thiophene carbonyl cyanines sodium salt

Be used for sensitizing dye of the present invention by directly sensitizing dye being disperseed to join in the silver halide photographic emulsions of the present invention at emulsion, also can be with it at a kind of solvent such as water, methyl alcohol, ethanol, propyl alcohol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxyl-1-propyl alcohol, 3-methoxyl-1-butanols, 1-methoxyl-2-propyl alcohol, acetonitrile, tetrahydrofuran and N, the dissolving back adds in the emulsion in N '-dimethyl formamide or their mixed solvent.

In addition, also can use following method, as USP 3,469, a kind of method of describing in 987: dyestuff is dissolved in a kind of volatile organic solvent, solution is dispersed in water or the hydrophilic colloid, dispersed system is added in the middle of the emulsion again; A kind of method described in JP-B-24185 (term " JP-B " refers to " having examined open Jap.P. " herein): a kind of non-water-soluble dyestuff is dispersed in a kind of water-soluble solvent, and dissolving dye not adds this dispersed system in the emulsion then; As JP-B-44-23389, JP-B-44-27555, the method described in the JP-B-57-22091: dyestuff is dissolved in the acid, adds the solution that obtains in the emulsion or produce a kind of aqueous solution, and allow acid or alkali exist simultaneously, again solution is added in the emulsion; As USP3,822,135 and 4,006, a kind of method described in 025: by allowing surfactant exist simultaneously, produce a kind of aqueous solution or colloidal dispersion system, then this solution or dispersed system are added in the emulsion; A kind of method described in JP-A-53-102733 and JP-A-105141: directly dyestuff is disperseed in hydrophilic colloid, then this dispersed system is added in the emulsion; A kind of method described in JP-A-51-74624: move red compound dissolution dyestuff with a kind of can the generation, then this solution is added in the emulsion.

For dissolving dye, also can use ultrasound wave.

The using method and the preferred embodiment of the dyestuff of expression are described below among molecular formula among the present invention (IV '), (IV '-1) to (IV '-4), (V '), (IVc ') and (IVa ').

In the present invention, when using the anionic dye and the dye of positive ion simultaneously, the anionic dye and the dye of positive ion the two preferably account for adding the sensitizing dye total amount 30% or more than.

And preferred, a kind of in the dye of positive ion and the anionic dye adds with 80% or more amount corresponding to saturated coverage, and the sensitizer total amount that also can add adds corresponding to 160% or more amount of saturated coverage.

Dyestuff can be pre-mixed those two kinds of dyestuffs the back adding, yet the dye of positive ion and anionic dye preferably separately add.In a preferred embodiment, add the dye of positive ion earlier, in a preferred embodiment, kation adds with 80% or more amount corresponding to saturated coverage, and then adding anionic dye, in another preferred embodiment, the kation addition corresponding to saturated coverage 80% or more, anionic dye adds with 50% amount corresponding to saturated coverage.

When separately adding dyestuff, the dyestuff that the back adds in the gelatin dry film, preferably have 0.5 or more, more preferably have 0.8 or more fluorescent yield.

Dyestuff can be in the process of preparation emulsion adding whenever.And dyestuff can add under any temperature, however when adding dyestuff the emulsion temperature preferably at 10 to 75 ℃, more preferably at 30 to 65 ℃.

For the photographic emulsion that sensitization mechanism takes place at this, 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 composite bed absorbing 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 (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 (hkl) 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.

Be used for sensitizing dye absorption the plain film shape silver halide particle in the above that the preferred the present invention of silver emulsion of the present invention reports with high surface/volume ratio.The particle radius-thickness ratio is 2 or above (being preferably 100 or following), and is preferred 5 to 80, more preferably 8 to 80, and plain film shape grain thickness is preferably less than 0.2 μ m, more preferably less than 0.1 μ m, again more preferably less than 0.07 μ m.In order to prepare plain film shape particle, adopt following technology with such radius-thickness ratio and film thickness.

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 has description at JP-A-9-80660 among JP-A-80656 and the USP 5,298,388.

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.

Silver emulsion will carry out chemical sensitization before use usually.Chemical sensitization is undertaken by being used alone or in combination chalcogen sensitizing (for example sulphur sensitizing, selenium sensitizing, tellurium sensitizing), noble metal sensitizing (as golden sensitizing) and reduction sensitization.

In the present invention, silver emulsion preferably carries out selenium sensitizing at least, more specifically, preferably only carry out selenium sensitizing or combination and carry out selenium sensitizing and another chalcogen sensitizing and/or noble metal sensitizing (particularly golden sensitizing), the more preferably combination of selenium element sensitizing and noble metal sensitizing.

In selenium sensitizing, a kind of active selenium element compound is as sensitizer.The labile selenium element compound has description in JP-B-43-13489, JP-B-44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341 and JP-A-5-40324.The example of selenium sensitizer comprises colloidal metal selenium, selenourea class (N for example; N-dimethyl selenourea, trifluoromethyl carbonyl-trimethyl selenourea, acetyl group-trimethyl selenourea), selenium substituted acid amide class (as selenium substituted acid amide, N, N-diethylbenzene selenium substituted acid amide), phosphine selenide class (as triphenyl selenizing phosphine, pentafluorophenyl group-triphenyl selenizing phosphine), selenium phosphoric acid salt (as three-right-tolyl selenium phosphate, three-just-butyl selenium phosphate), selenium ketone (as the seleno benzophenone), isocyanates, selenium carboxylic acids, selenium ester and diacyl selenide.In addition, metastable selenium element compound such as selenous acid, seleno isocyanic acid potassium, selenazoles and selenide (in JP-B-46-4553 and JP-B-52-34492 description being arranged) also can be used as the selenium sensitizer.

In sulphur sensitizing, a kind of active sulphur compound is as sensitizer.Active sulphur compound is at P.Glafleides, Chemie et Physique Photographique, 5 ^ThEd., Paul Montel (1987) and Research Disclosure, Vol.307 has description among the NO.30715.The example of sulphur sensitizer comprises thiosulfates (as hypo), Thiourea is (as rhenocure CA, the triethyl thiocarbamide, N-ethyl-N '-(4-methyl-2-thiazolyl) thiocarbamide, the ethyloic trimethyl thiourea), thioamide analog (as the thioacetic acid esteramides), rich tannin class is (as the rich tannin of diethyl, 5-benzal-N-ethyl-rich tannin), phosphine sulfide-based (as the trimethylbenzene phosphine sulfide), the thiohydantoin class, 4-oxo-oxazolidine-2-thioketones class, dimerization is sulfide-based (as dimorpholinyl disulfide, cystine, connect six sulfo-alkane-thioketones), sulfhydryl compound class (as cysteine), many thionic acids salt and elementary sulfur.Active gelatin also can be used as the sulphur sensitizer.

In tellurium sensitizing, a kind of active tellurium element compound is as sensitizer.Active tellurium element compound at Canadian Patent 800,958, BrP 1,295,462 and 1,396,696, JP-A-4-204640, comprise among JP-A-4-271341, JP-A-4-333043 and the JP-A-5-303157 that description is arranged.The example of tellurium sensitizer comprises: the tellurium ureas is (as tetramethyl tellurium urea, N, N '-dimethyl vinyl tellurium urea, N, N '-diphenylacetylene tellurium urea), phosphine telluride class is (as butyl diisopropyl tellurium phosphine, tributyl tellurium phosphine, three butoxy tellurium phosphines, ethoxy-diphenyl tellurium phosphine), (2) tellurium diacrylamine class is (as two telluriumizations two (diphenylformamide), two (the N-phenyl-N-methyl-carbamyl amine of two telluriumizations, telluriumization two (ethoxy hydroxyl)), different tellurium cyanic acid salt, the telluro amide-type, tellurium oxyhydroxide class, telluro ester class (as butyl hexyl telluro ester), telluroketone class (as the tellurium acetophenone), colloid tellurium class, (2) telluride and other telluriumization and thing are (as tellurium potassium, Pentathionic Acid tellurium sodium salt).

In noble metal sensitizing, noble metal is used as sensitizer as the salt of gold, platinum, palladium and iridium.Precious metal salt is at P.Glafleides, Chemie et Physique Photographique, 5th ed, Paul Montel (1987) and Research Disclosure Vol.307 have description among the No.307105.In these documents, preferred golden sensitizing.As mentioned above, the present invention is effective especially in the embodiment of using golden sensitizing.

Photographic Science and Engineering, Vol.19322 (1975) and Journal of Imaging ScienceSet forth the solution that contains potassium cyanide (KCN) among the Vol.3228 (1988) and can remove gold the sensitizing ring from emulsion grain.Delivered document according to these, absorbed on the silver halide particle, gold atom or gold ion separate out as cyano complex by cryanide ion, therefore golden sensitizing is suppressed.According to the present invention, when the generation of cyano group was subjected to stoping, the effect of golden sensitizer could be brought into play fully.

The example of gold sensitizer comprises gold chloride, potassium chloroaurate, golden potassium rhodanide, aurosulfo and Auric selenide.Also can use at USP 264,2361,5,049 gold compound of describing in 484 and 5,049,485.

In reduction sensitization, a kind of reductibility compound is as sensitizer, and the reductibility compound is at P.Glafleides, Chemie et Physique Photographique, 5 ^ThEd., Paul Montel (1987) and Research DisclosureVol.307 has description among the No.307105.The example of reductibility sensitizer comprises amino imino methane sulfinic acid class (as thiourea dioxide), borane compound class (as the dimethylamino borine), hydrazine compound class (as hydrazine, right-matulane), polyamine compounds class (as diethylenetriamine, triethylene tetramine), stannous chloride, silane compound class, reductones (as ascorbic acid), sulphite, aldehyde compound and hydrogen.Reduction sensitization also can carry out under high pH value or superfluous silver ion (so-called silver-colored slaking) condition.Reduction sensitization is preferably used when silver halide particle forms.

The consumption of sensitizer is usually according to silver halide kind and Chemical Sensitization and decide.

Chalcogen sensitizer consumption is that every mole of silver halide is with 10 ^-8To 10 ^-2Mol is preferably 10 ^-7To 5 * 10 ^-3Mol.Noble metal sensitizer consumption is preferably every mole of silver halide with 10 ^-7To 10 ^-2Mol.

The condition of chemical sensitization is not particularly limited.PAg is generally 6 to 10, is preferably 7 to 10.PH is preferably 4 to 10.Temperature is preferably 40 to 95 ℃, more preferably 45 to 85 ℃.

Can utilize JP-A-10-239789 63 hurdles 36 row to 65 hurdles, 2 row about the preparation method's grade that is used for photographic emulsion of the present invention.

In addition, about adjuvant such as color colour coupler, it is a kind of adjuvant that adds sensitive photographic material, the photosensitive material type that the present invention uses, and processing of photosensitive material or the like can utilize among the JP-A-10-239789 65 hurdles, 3 row to 73 hurdles, 13 row.

By with reference to each example, will describe the present invention in more detail below, but the present invention should not regard the restriction that is subjected to it as.

Embodiment 1

The preparation of silver bromide octahedral build emulsion (emulsion A) and silver bromide plane emulsion (emulsion B and emulsion C):

NH with 1000ml water, 25g deionization bone collagen gelatin, 15ml 50% ₄NO ₃The ammonia spirit of aqueous solution and 7.5ml 25% adds in the reactor.The solution constant temperature that finally obtains at 50 ℃, is fully stirred, in more than 50 minutes, add the silver nitrate aqueous solution of 750ml 1N and the kbr aqueous solution of 1mol/l simultaneously.In the middle of course of reaction, silver-colored electromotive force is constant in-40mv.The silver bromide grain that obtains is octahedral build and the equivalent sphere diameter with 0.846 ± 0.036 μ m.With the cooling of the emulsion that obtains like this,, it is precipitated cleaning, desalting after the multipolymer that wherein adds as the isobutylene of set accelerator and maleic acid sodium salt.Subsequently, to wherein adding 95g deionization bone collagen gelatin and 430ml water, the solution that finally obtains is transferred to 6.5 at 50 ℃ with pH value, and PAg is transferred to 8.3, again to wherein adding potassium thiocyanate, gold chloride and thiosulfite so that photo sensitivity to be provided, 55 ℃ with this emulsion slaking 50 minutes then.The emulsion that obtains is labeled as emulsion A.

In 1.2 premium on currency, be 15000 or following low molecular weight gelatine dissolving with the mean molecular weight of the potassium bromide of 6.4g and 6.2g, 30 ℃ of constant temperature, add 8.1ml16 by two injection methods this moment in the time more than 10 seconds with the solution that finally obtains.4% silver nitrate aqueous solution and the kbr aqueous solution of 7.2ml23.5%.Subsequently, add 11.7% water soluble gelatine solution again, be warmed up to 75 ℃ after, with the solution slaking that obtains 40 minutes.Then at constant silver-colored electromotive force in-20mv, in more than 10 minutes time, add the silver nitrate aqueous solution of 370ml 32.2% and 20% kbr aqueous solution.After the physics slaking 1 minute, cool the temperature to 35 ℃.In this way, obtaining the averaging projection district is 2.32 μ m, and thickness is 0.09 μ m, and diameter variation coefficient is single silver bromide plain film shape emulsion that disperses of 15.1%.After this, remove soluble salt by short retrogradation analysis method.When during at 40 ℃, adding the 45.6g gelatin at constant temperature, 10ml concentration is the sodium hydrate aqueous solution of 1mol/l, the phenoxetol of 167ml water and 1.66ml355, and PAg value and pH value are adjusted to 8.3 and 6.20 respectively.To wherein adding potassium thiocyanate, gold chloride and sodium thiosulfite so that photo sensitivity to be provided.55 ℃ with this emulsion slaking 50 minutes then.The emulsion that obtains is labeled as emulsion B.In addition, be labeled as emulsion C by utilizing potassium thiocyanate, gold chloride, pentafluorophenyl group-diphenyl phosphine selenide and sodium thiosulfite to replace potassium thiocyanate, gold chloride and sodium thiosulfate to carry out the emulsion that chemical sensitization makes.Think that it is 80 that dyestuff occupies the zone ², the saturated coverage of the individual layer of emulsion A and B is respectively 5.4 * 10 ^-4Mol/mol-Ag and 1.42 * 10 ^-3Mol/mol-Ag.

In each emulsion that obtains like this, during at 50 ℃, add first kind of dyestuff as shown in table 1 at emulsion constant temperature, then every kind of emulsion was stirred 30 minutes.Add second kind and the third dyestuff then continuously, every kind of emulsion was stirred 30 minutes at 50 ℃.

Table 1

	Emulsion	First kind of dyestuff addition (mol/mol Ag)	Second kind of dyestuff addition (mol/mol Ag)	The third dyestuff addition (mol/mol Ag)
					Comparative example 1	B	I-52 (1.56×10 -3)	II-63 (3.12×10 -3)
Comparative example 2	B	I-52 (1.56×10 -3)	II-38 (3.12×10 -3)
					Comparative example 3	B	I-52 (1.56×10 -3)	I-52 (1.56×10 -3)	II-63 (1.56×10 -3)
Invention 1	B	I-52 (1.56×10 -3)	I-35 (1.56×10 -3)	II-38 (1.56×10 -3)
					Invention 2	C	I-52 (1.56×10 -3)	I-35 (1.56×10 -3)	II-38 (156×10 -3)
Invention 3	A	I-52 (5.94×10 -3)	I-35 (5.94×10 -4)	II-38 (5.94×10 -4)

The dyestuff uptake is determined as follows.Each liquid emulsion that obtains is carried out centrifuging, and therefore precipitating 10 minutes under the 1000rpm rotating speed is with the sediment freeze-drying.In the sediment of 0.05g, add hyposulfurous acid sodium water solution and the methyl alcohol of 25ml 25%, get 50ml solution,, quantitatively calculate the density of dyestuff the solution that obtains high-speed liquid chromatography analysis.

The optical absorption intensity of per unit area is determined as follows.With the coating thinly on slide glass of every kind of emulsion obtaining, the microspectrophotometer MSP65 that produces with Karl Zwiss K.K company measures the transmitted spectrum of various particles and reflectance spectrum with definite absorption spectrum by following method.For transmitted spectrum, make reference with the non-existent zone of particle, the reference of reflectance spectrum is to obtain by measuring the known siloxane carbonide of reflectance.Measured zone is the circular holes of diameter 1 μ m.Adjusting the position to allow hole part not after the cambered surface of overlapping particle, at 14000cm ^-1(714nm) to 28000cm ^-1(357nm) wave number region measurement transmitted spectrum and reflectance spectrum.Absorption spectrum determines that from absorption coefficient A A is 1-T (transmittance)-R (reflectance).The absorption coefficient A ' that utilization obtains by deducting the silver halide uptake, and general-log (1-A ') to wave number (cm ^-1) integration, the value that will obtain reduces by half again, as the optical absorption intensity of per unit area.Limit of integration from 14000 to 28000cm ^-1At this moment, light source uses tungsten lamp, and light source voltage is 8 volts.For the destruction that will cause dyestuff owing to the irradiation of light reduces to minimum, in primary face, use monochromator, wavelength distance and slit width are fixed on 2nm and 2.5nm.

For the emulsion determining the absorption spectrum of emulsion, utilize wherein not add dyestuff in contrast, according to of the infinite scattered reflection degree conversion of Kubelka-Munk equation, the absorption spectrum of dyestuff is only arranged with finished product emulsion.

The spectral sensitivity of coating film is that identical such spectrum exposure instrument will produce in the exposure wavelength district by using a kind of adjustable so that photon number of each wavelength+the necessary exposure intensity measuring of 0.2 Fog density.

In Fig. 1 and Fig. 2, what " the present invention " represented is the absorption spectrum and the spectral sensitivity distribution of invention 1, and what " comparative example 3 " represented is the absorption spectrum and the spectral sensitivity distribution of comparative example 3.

A kind of gelatin hardener and a kind of coating additive are added in each emulsion that obtains, each emulsion all is coated on the cellulose acetate film carrier that has the gelatin protective seam simultaneously, obtain 3.0g-Ag/m ²Silver-colored coating weight.The film that obtains exposed 1 second down at tungsten lamp (colour temperature: 285 ℃) by a continuous wedge filter.By using the Fuji Gelatin Filter SC-50 (by FujiPhoto Film Co., Ltd. makes) to stimulate the dyestuff side, be radiated at 500nm on the sample or following light and be absorbed as color filter.The sample of each exposure developed 10 minutes at 20 ℃ with following surface development agent MAA-1.

Mitouer 2.5g

L-ascorbic acid 10.0g

Nabox (Fuji Photo Film Co., Ltd. produces) 35.0g

Potassium bromide 1g

Add water and reach 1l

PH 9.8

Measure the film that develops with Fuji Automatic Densitometer and put into optical density.Sensitivity is the inverse that obtains the necessary light intensity of optical density of photographic fog+0.2, and is that 100 base value is represented by setting when first kind of dyestuff of adding sensitivity.

The results are shown in Table 2.

Table 2

	Uptake (1) (10 -3mol/mol-Ag)	Absorb the number of plies	Optical absorption intensity (2)	Absorption intensity (80%, 50%Amax) (3)	The spectral sensitivity width (80%, 50%Smax)	Subtract blue sensitivity (4)	Particle aggregation
								Comparative example 1	2.54	1.79	151(149)	86，133	42，130	128	×
Comparative example 2	2.35	1.65	139(140)	87，132	45，134	123	×
								Comparative example 3	3.34	2.35	193(195)	80，125	57，125	180	×
Invention 1	3.21	2.26	192(192)	24，93	42，95	202	○
								Invention 2	3.22	2.27	193(195)	24，93	42，95	208	○
Invention 3	1.15	2.13	(180)	25，94	43，96	196	○

(1) absorbs the total amount of each dyestuff.

(2) the micro-spectral method is determined optical absorption intensity.Data are that formula is converted to by being benchmark with every kind of amount of dye in the bracket.

(3) after the conversion of the scattered reflection light of emulsion being dived by the Kubelka-Munk equation, the value that from spectrum, obtains.

(4) supposition sensitivity when only adding first kind of dyestuff is 100 and the sensitivity that obtains.

The absorption spectrum of the emulsion of preparation is listed among Fig. 1 in comparative example 3 and invention.As from table 2 and seen in fig. 2, according to the present invention, sensitizing dye can be absorbed in the J-aggregation that forms on the particle surface in the composite bed, so optical absorption intensity can increase in a narrow wavelength coverage.And, having the such absorption intensity and the silver emulsion of wavelength characteristic by use, the photosensitive silve halide material that obtains only has than high sensitivity in the target wavelength district, the colorrendering quality of good color separated and height.

In the absorption of composite bed in order to obtain such wavelength characteristic, the second layer or backward the dyestuff of each layer must form the J-aggregation, but also find to obtain the effect that particle aggregation reduces by realizing such a kind of absorbing state.Think this situation can be because the second layer or backward in each layer the formation of the J-aggregation of dyestuff lip-deep particle is interacted weaken.This result is the ten minutes unwanted results.

Embodiment 2

Prepared a kind of pure silver halide plain film shape grain emulsion in the mode identical with emulsion D among the embodiment 2 among the JP-A-8-227117.The surface area of particle is 5.15 * 10 ²m ²/ mol-Ag is when the dyestuff occupied area is regarded 80 as ²The time, the saturated coverage of individual layer is 1.07 * 10 ^-3Mol/mol-Ag.Replace sensitizer dyestuff 2 and 3, add 1.1 * 10 at 56 ℃ ^-3The sensitizer I-6 of mol/mol-Ag, solution stirring adds 6.0 * 10 after 30 minutes again ^-4The sensitizer I-6 and 6.0 * 10 of mol/mol-Ag ^-4The sensitizer II-7 of mol/mol-Ag.The solution that finally obtains continues to stir 20 minutes, carries out chemical sensitization as the emulsion D in the example among the JP-A-8-227117 2 in the same way then.The emulsion that obtains is labeled as emulsion 2A (contrast).Replace sensitizer dyestuff 2 and 3, add 1.1 * 10 at 56 ℃ ^-3The sensitizer I-6 of mol/mol-Ag, solution stirring adds 6.0 * 10 after 30 minutes again ^-4The sensitizer I-4 and 6.0 * 10 of mol/mol-Ag ^-4The sensitizer II-4 of mol/mol-Ag.The solution that finally obtains continues to stir 20 minutes, carries out chemical sensitization as the emulsion D in the example among the JP-A-8-227117 2 in the same way then.The emulsion that obtains is labeled as emulsion 2B (contrast).And in emulsion 2B, do not add I-4 and II-4 makes a kind of emulsion, be labeled as emulsion 2C (contrast).

The coating sample is prepared in the identical mode of sample F among the embodiment 3 among the preparation JP-A-8-227118.Use emulsion 2A to replace the emulsion F of the example coating sample F in JP-A-8-227117, the sample marking that obtains is sample 2A, and similarly the sample that replaces emulsion F to obtain with emulsion 2B or emulsion 2C is labeled as sample 2B and sample 2C respectively.

The dyestuff uptake absorbs the number of plies and optical absorption intensity, uses as measuring in the same method described in the example 1.And the absorption spectrum of every kind of emulsion and spectral sensitivity distribution, use as measuring in the same method described in the example 1.

In order to detect the sensitivity of every kind of coating sample, each coating sample uses 1/100 second (Fuji PhotoFilm Co. of the FW-Type of Fuji sensitometer exposure by a neutral wedge and a blue filter, Ltd. make), carry out Fuji Photo Film CN16 processing then, relatively photographic property.

Sensitivity be with the density that photographic fog+0.2 is provided the inverse of essential exposure, the sensitivity that is expressed as with sample 2C is the relative value of benchmark.

The results are shown in down in the tabulation 3.

Table 3

	Uptake (1) (10 -3mol/mol-Ag)	Absorb the number of plies	Optical absorption intensity	The light absorption width (80%, 50%Amax)	The spectral sensitivity width (80%, 50%Smax)	Absorption spectrum maximum wavelength (nm)	Subtract blue sensitivity (4)	Particle aggregation
									Sample 2C (comparative example)	0.99	0.93	51	18，83	23，88	471	100	○
Sample 2A (comparative example)	1.78	1.66	88	45，127	53，132	438	145	×
									Sample 2B (comparative example)	1.86	1.74	90	26，90	35，95	473	164	○

According to the present invention, have the high sensitivity photosensitive material of desirable absorption and desirable sensitivity waveform, can obtain by the method that adds dyestuff.

Embodiment 3

The method for preparing a kind of silver emulsion is described below.

By the following method preparation 7 kinds of silver emulsion particles [emulsion A-1 and emulsion B are to G] that prepare silver halide particle.

The preparation of emulsion A-1 (octahedral build internal latent image type is directly just as emulsion):

In the kbr aqueous solution gelatin that contains 0.05M of 1000ml, add 1g 3,6-two thiophenes-1, the 8-ethohexadiol, 0.034mg lead acetate and 60g calcium content are 100ppm or following deionized gelatin, 0.4M silver nitrate aqueous solution and 0.4M kbr aqueous solution, two injection method temperature constant of passing through control are controlled the adding speed of kbr aqueous solution at 75 ℃ in this method simultaneously, so that PBr 1.60, and the 300ml nitrate aqueous solution adds in more than 40 minutes time.

After adding, make the silver bromide crystal (hereinafter referred to as " slug particle ") that average particle size particle size (equivalent spheroid diameter) is about the octahedral build of 0.7 μ m and particle size homogenizing.

The slug particle that obtains adopts following container and prescription to carry out chemical sensitization.

1 developing tank

One has domed bottom, is made by metal, and the surface is the developing tank of 120 μ m with the polytetrafluorethylecoatings coatings thickness of the fluorine resin material FEP coating that E.I.Du Pont Company produces.

2 stirring vanes

There is the spiral seamless integral blade of polytetrafluorethylecoatings coatings on a kind of surface by the metal manufacturing.

3 prescriptions

Zhi Bei octahedral build adds the sodium thiosulfite of 3ml by dissolving 1mg in 1000ml water, the aqueous solution that 90mg gold potassium chloride and 1.2g potassium bromide make directly just as in the emulsion upward.The solution that finally obtains heats 80 minutes to carry out the chemical sensitization processing at 75 ℃.The potassium bromide that in the emulsion solution of such sensitizing, adds 0.15M.So far similarly, prepare the kbr aqueous solution that adds 0.9M liquor argenti nitratis ophthalmicus and 0.9M in the system to nuclear particle, and the two newborn injecting method temperature constant of passing through to control is at 75 ℃, the adding speed of control kbr aqueous solution in this method, so that PBr is 1.30, and the 670ml silver nitrate aqueous solution added in the clock time more than 70 minutes.

The emulsion that finally obtains cleans by common flucculation process water, upward in Zhi Bei the gelatin, add 2-phenoxetol and right-methyl hydroxybenzoate, obtain the octahedra silver bromide crystal that average particle size particle size (equivalent spheroid diameter) is about 1.4 μ m and particle size homogenizing.(hereinafter be referred to as and be " interior latent image type " nuclear/shell particle).

In this " internal latent image type " nuclear/shell emulsion, add 3ml by the aqueous solution that dissolving 100mg sodium thiosulfite and 40mg sodium tetraborate in 1000ml water make, add 14mg poly-(N-vinyl pyrrolidone) again.The emulsion that finally obtains slaking under 60 ℃ of heating conditions then to the potassium bromide that wherein adds 0.005M, therefore makes a kind of octahedral build internal latent image type directly just as emulsion.

Emulsion B is to the preparation (octahedral build internal latent image type is directly just as agent) of G

Octahedral build latent image type with mean grain size as shown in table 4 (equivalent spheroid diameter) and particle size homogenizing is directly just as silver emulsion, each changes the difference joining day of silver nitrate aqueous solution and kbr aqueous solution in the time of can passing through preparation emulsion A-1, and the chemicals quality of further change adding makes emulsion B.

Table 4

The emulsion title	Average particle size particle size, μ m
		B	1.20
C	0.93
		D	1.20
E	0.94
		F	0.74
G	0.66

Utilize emulsion A-1 and B to G prepare a kind of have following shown in the contrast photo-sensitive cell (sample 101) of structure.Sensitizing dye adds when the chemical sensitization of shell finishes, dye type, and discrete form adds temperature and addition and lists in the table 5.

The structure of contrast photo-sensitive cell 101

The 22nd layer of protective seam

Adjuvant	Coating weight (g/m 2)
		Matting agent (1)	0.15
Gelatin	0.25
		Surfactant (1)	5.3×10 -3
Surfactant (2)	4.1×10 -3
		Surfactant (3)	3.9×10 -3
Adjuvant (1)	8.0×10 -3
		Adjuvant (5)	0.009

The 21st layer of UV-absorbing layer

Adjuvant	Coating weight (g/m 2)
		UV-absorbing layer (1)	0.09
UV-absorbing layer (2)	0.05
		UV-absorbing layer (3)	0.01
Adjuvant (2)	0.17
		Surfactant (3)	0.013
Surfactant (4)	0.019
		Adjuvant (1)	8.0×10 -3
Adjuvant (5)	0.023
		Rigidizer (1)	0.050
Rigidizer (2)	0.017
		Gelatin	0.52

The 20th layer of blue layer of sense (high sensitivity)

Adjuvant	Coating weight (g/m 2)
		Interior latent image type is directly just as emulsion: A-1	0.38 as silver
Nucleator (1)	2.9×10 -6
		Adjuvant (3)	4.0×10 -3
Adjuvant (4)	0.013
		Adjuvant (5)	3.8×10 -3
Adjuvant (1)	9.0×10 -3
		Surfactant (5)	9.0×10 -3
Gelatin	0.42

The 19th layer of blue layer of sense (low sensitivity)

Adjuvant	Coating weight (g/m 2)
		Interior latent image type is directly just as emulsion: B	0.07 as silver
Interior latent image type is directly just as emulsion: C	0.01 as silver
		Nucleator (1)	2.5×10 -6
Adjuvant (3)	0.022
		Adjuvant (5)	9.0×10 -3
Adjuvant (1)	0.013
		Surfactant (5)	9.0×10 -3
Gelatin	0.35

The 18th layer of white light reflection layer

Adjuvant	Coating weight (g/m 2)
		Titania	0.30
Adjuvant (1)	9.0×10 -3
		Surfactant (1)	7.2×10 -5
Adjuvant (5)	0.011
		Adjuvant (8)	2.8×10 -3
Gelatin	0.37

The 17th layer of yellow uitramarine layer

Adjuvant	Coating weight (g/m 2)
		Weld discharges compound	0.62
High boiling organic solvent (1)	0.27
		Adjuvant (6)	0.18
Adjuvant (7)	0.09
		Surfactant (4)	0.062
Surfactant (5)	0.030
		Adjuvant (9)	0.031
Adjuvant (1)	6.0×10 -3
		Gelatin	0.87

The 16th layer of middle layer

Adjuvant	Coating weight (g/m 2)
		Adjuvant (10)	0.013
Surfactant (1)	4.0×10 -4
		Adjuvant (1)	7.0×10 -3
Gelatin	0.42

The 15th layer of colour mixture suppresses layer

Adjuvant	Coating weight (g/m 2)
		Adjuvant (11)	0.47
High boiling organic solvent (2)	0.23
		Polymethylmethacrylate	0.81
Surfactant (5)	0.019
		Adjuvant (1)	2.0×10 -3
Adjuvant (12)	0.61
		Gelatin	0.81

The 14th layer of green layer (high sensitivity)

Adjuvant	Coating weight (g/m 2)
		Interior latent image type is directly just as emulsion: A-1	0.69 as silver

Nucleator (1)	2.2×10 -6
		Adjuvant (3)	0.12
Adjuvant (5)	0.014
		Adjuvant (1)	3.0×10 -3
Adjuvant (2)	0.15
		High boiling organic solvent (2)	0.07
Surfactant (5)	0.06
		Gelatin	0.97

The 13rd layer of green layer (low sensitivity)

Adjuvant	Coating weight (g/m 2)
		Interior latent image type is directly just as emulsion: D	0.11 as silver
Interior latent image type is directly just as emulsion: E	0.08 as silver
		Nucleator (1)	2.7×10 -6
Adjuvant (3)	0.011
		Adjuvant (4)	0.033
Adjuvant (5)	1.5×10 -3
		Adjuvant (1)	0.010
Surfactant (5)	0.024
		Gelatin	0.26

The 12nd layer of middle layer

Adjuvant	Coating weight (g/m 2)
		Adjuvant (1)	0.014
Surfactant (1)	0.038
		Surfactant (3)	4.0×10 -3
Adjuvant (5)	0.014
		Gelatin	0.33

11th layer magenta material layer

Adjuvant	Coating weight (g/m 2)
		Rosaniline dyes discharges compound (1)	0.56

High boiling organic solvent (1)	0.18
		Adjuvant (13)	9.3×10 -4
Adjuvant (5)	0.02
		Surfactant (4)	0.04
Adjuvant (14)	0.02
		Adjuvant (1)	7.0×10 -3
Gelatin	0.45

The 10th layer of middle layer

Adjuvant	Coating weight (g/m 2)
		Adjuvant (10)	0.014
Surfactant (1)	3.0×10 -4
		Adjuvant (1)	9.0×10 -3
Gelatin	0.36

The 9th layer of colour mixture suppresses layer

Adjuvant	Coating weight (g/m 2)
		Adjuvant (11)	0.38
High boiling organic solvent (2)	0.19
		Polymethylmethacrylate	0.66
Surfactant (5)	0.016
		Adjuvant (1)	2.0×10 -3
Adjuvant (12)	0.49
		Gelatin	0.65

The 8th layer of sense red beds (high sensitivity)

Adjuvant	Coating weight (g/m 2)
		Interior latent image type is directly just as emulsion: A-1	0.33 as silver
Nucleator (1)	6.1×10 -6
		Adjuvant (3)	0.04
Adjuvant (5)	0.01
		Adjuvant (1)	1.0×10 -3

Adjuvant (2)	0.08
		High boiling organic solvent (2)	0.04
Surfactant (5)	0.02
		Gelatin	0.33

The 7th layer of sense red beds (low sensitivity)

Adjuvant	Coating weight (g/m 2)
		Interior latent image type is directly just as emulsion: F	0.10 as silver
Interior latent image type is directly just as emulsion: G	0.11 as silver
		Nucleator (1)	2.5×10 -5
Adjuvant (3)	0.047
		Adjuvant (5)	0.016
Adjuvant (1)	8.0×10 -3
		Surfactant (5)	0.02
Gelatin	0.57

The 6th layer of white light reflection layer

Adjuvant	Coating weight (g/m 2)
		Titania	1.87
Adjuvant (1)	7.0×10 -3
		Surfactant (1)	4.0×10 -4
Adjuvant (5)	0.02
		Adjuvant (8)	0.015
Gelatin	0.73

The 5th layer of cyan material layer

Adjuvant	Coating weight (g/m 2)
		Cyan dye discharges compound (1)	0.25
Cyan dye discharges compound (2)	0.14
		High boiling organic solvent (1)	0.05
Adjuvant (3)	0.06
		Adjuvant (5)	0.01

Surfactant (4)	0.05
		Adjuvant (9)	0.05
Adjuvant (1)	4.0×10 -3
		Rigidizer (3)	0.014
Gelatin	0.40

The 4th layer of light shielding layer

Adjuvant	Coating weight (g/m 2)
		Carbon black	1.50
Surfactant (1)	0.08
		Adjuvant (1)	0.06
Adjuvant (5)	0.06
		Adjuvant (12)	0.15
Gelatin	1.43

The 3rd layer of middle layer

Adjuvant	Coating weight (g/m 2)
		Surfactant (1)	6.0×10 -3
Adjuvant (1)	9.0×10 -3
		Adjuvant (5)	0.013
Gelatin	0.29

The 2nd layer of white light reflection layer

Adjuvant	Coating weight (g/m 2)
		Titania	19.8
Adjuvant (15)	0.378
		Adjuvant (16)	0.094
Surfactant (6)	0.019
		Adjuvant (8)	0.16
Rigidizer (1)	0.02
		Rigidizer (2)	0.007
Gelatin	2.45

The 1st layer image receiving layer

Adjuvant	Coating weight (g/m 2)
		Polymeric mordant stain (1)	2.22
Adjuvant (17)	0.26
		Surfactant (7)	0.04
Adjuvant (5)	0.11
		Rigidizer (1)	0.03
Rigidizer (2)	0.01
		Gelatin	3.25

Support (containing titania) to stop photoconduction and the thick ethylene glycol terephthalate of 90 μ m that scribbles primer coating.

Backing layer warpage key-course

Adjuvant	Coating weight (g/m 2)
		Ultraviolet light absorber (4)	0.40
Ultraviolet light absorber (5)	0.10
		Diacetyl cellulose (degree of acetylation: 51%)	4.20
Adjuvant (18)	0.25
		Barium stearate	0.11
Rigidizer (4)	0.50

Table 5

Sensitizing dye content in every kilogram of emulsion

Level number	The emulsion title	The sensitizing dye type	The dyestuff discrete form	The adding temperature (℃)	Amount of dye (g/kg emulsion)
						20	A-1	(9) (8)	The aqueous solution aqueous solution	70	9.38×10 -2 1.19×10 -1
19	B	(9) (8	The aqueous solution aqueous solution	60	6.50×10 -2 1.47×10 -1
						19	C	(9) (8	The aqueous solution aqueous solution	60	7.31×10 -2 1.66×10 -1
14	A-1	(7) (4) (6)	Gelatin dispersion gelatin dispersion water/organic solvent dispersion	60	1.18×10 -1 2.94×10 -3 9.23×10 -2
						13	D	(7) (4) (6)	Gelatin dispersion gelatin dispersion water/organic solvent dispersion	40	6.49×10 -2 1.62×10 -3 4.85×10 -2
13	E	(7) (4) (6)	Gelatin dispersion gelatin dispersion water/organic solvent dispersion	40	7.34×10 -2 1.83×10 -3 5.69×10 -2
						8	A-1	(5) (4) (3) (2) (1)	Aqueous solution gelatin dispersion gelatin dispersion gelatin dispersion gelatin dispersion	60	3.10×10 -2 2.26×10 -2 2.26×10 -2 2.79×10 -3 9.20×10 -2
7	F	(5) (4) (3) (2) (1)	Aqueous solution gelatin dispersion gelatin dispersion gelatin dispersion gelatin dispersion	60	1.63×10 -2 1.34×10 -2 1.34×10 -2 1.91×10 -3 6.32×10 -2
						7	G	(5) (4) (3) (2) (1)	Aqueous solution gelatin dispersion gelatin dispersion gelatin dispersion gelatin dispersion	50	1.17×10 -2 8.90×10 -3 8.90×10 -3 1.32×10 -3 4.37×10 -2

Weld discharges compound (1)

Rosaniline dyes discharges compound (1)

Cyan dye discharges compound (1)

Cyan dye discharges compound (1)

Adjuvant (1)

Adjuvant (2)

Adjuvant (3)

Adjuvant (4)

Adjuvant (5)

Adjuvant (6)

Adjuvant (7)

Adjuvant (8)

Carboxymethyl cellulose

Adjuvant (9)

Polyvinyl alcohol (PVA) (PVA-220E)

The degree of polymerization: about 2,00, saponification rate: 88%

Adjuvant (10)

Adjuvant (11)

Adjuvant (12)

Adjuvant (13)

Adjuvant (14)

Adjuvant (15)

Adjuvant (16)

Adjuvant (17)

Adjuvant (18)

Matting agent (17)

Spherical latex (the sub-size of mean grain size: 3 μ m) of polymethylmethacrylate

Surfactant (1)

Surfactant (2)

Surfactant (3)

(n＝about 12.6)

Surfactant (4)

Surfactant (5)

Surfactant (6)

Surfactant (7)

Ultraviolet light absorber (1)

Ultraviolet light absorber (2)

Ultraviolet light absorber (3)

High boiling organic solvent (1)

High boiling organic solvent (2)

Ultraviolet light absorber (4)

Ultraviolet light absorber (5)

Rigidizer (1)

CH ₂＝CHSO ₂CH ₂CONH(CH ₂) ₂NHCOCH ₂SO ₂CH＝CH ₂

Rigidizer (2)

CH ₂＝CHSO ₂CH ₂CONH(CH ₂) ₃NHCOCH ₂SO ₂CH＝CH ₂

Rigidizer (3)

Rigidizer (4)

Nucleator (1)

Polymeric mordant stain (1)

Press shown in the table 6 add the ground floor dyestuff replace adding dyestuff (7), (4) and (6) to the 14 layer emulsion A-1 after, by dyestuff (first kind of dyestuff and second kind of dyestuff) is added on the second layer and subsequently layer in the photo-sensitive cell that makes emulsion A-2 to A-4 and will use these emulsions to obtain be appointed as sample 102 to 104 respectively.

Table 6

Test piece number (Test pc No.)	The emulsion title	Dyestuff in ground floor (addition)	Dyestuff in the second layer
					First kind of dyestuff (addition)	Second kind of dyestuff (addition)
			101	A-1			(7)(1.18×10 -1) (4)(2.94×10 -3) (6)(9.23×10 -2)	Do not have	Do not have
102	A-2	(11)(2.13×10 -1)			(11)(2.13×10 -1)	(12)(2.13×10 -1)
			103	A-3			(10)(2.13×10 -1)	IV′c-25(2.13×10 -1)	IV′a-31(2.13×10 -1)
104	A-4	(10)(2.13×10 -1)			IV′c-31(4.26×10 -1)	Do not have

(addition of dyestuff: g (dyestuff)/1kg (emulsion))

The consumption that each sample in the his-and-hers watches 6 absorbs the dyestuff in the emulsion grain of per unit area into uses above-mentioned method to measure and each value and the individual layer saturated absorption of gained compared.In sample 102,103 and 104, confirm dyestuff absorb into two-layer or more multi-layered in, yet in sample 101, dyestuff absorbs in one deck.

Protective seam is by following described method preparation.

Each layer be at a kind of prevention dyestuff that contains photoconduction subsequently, and it will be coated with down on the polyethylene terephthalate of gelatin and form.

(a) contain 10.4g/m ²Mean molecular weight is 50000 acrylic acid/just-butylacrylic acid ester copolymer (80/120 (mol%)) and 0.1g/m ²1, the neutral line of two (2, the 3-the glycidoxy)-butane of 4-;

(b) one deck contains 4.3g/m ²Degree of acetylation be 55% cellulose acetate and 0.2g/m ²Methyl vinyl ether/copolymer-maleic anhydride (50/50 (mol%)) methyl half ether layer and

(c) contain 0.3g/m ²Mean molecular weight is 25000 n-butyl propylene methyl esters/2-hydroxy ethyl methacrylate/acrylic copolymer (66.1/28.4/5.5 (wt%)) and 0.8g/m ²Mean molecular weight is the neutral timing layer of Jia Jibingxisuanyizhi/methacrylic acid 2-hydroxyl ethyl ester/acrylic copolymer (66.1/28.4/5.5 (wt%)) of 40000.It is the GREEN A-G that produces of NipponKayaku K.K and a kind of potpourri of 3: 1 as a kind of compound shown in following that the photoconduction that uses stops dyestuff.

Photoconduction stops dyestuff

The alkaline development composition is by following described method preparation.

The developing solution that 0.8g is had following component is filled in the container that can break under certain pressure.

Water 695g

1-is right-tolyl-4-methylol-4-methyl-3-pyrazolidine-1-ketone 7.00g

1-phenyl-4-methylol-4-methyl-3-pyrazolidine-1-ketone 9.85g

Sulfinic acid polymkeric substance 2.10g

5-methylbenzotrazole 2.50g

Zinc nitrate hexahydrate 0.60g

Potassium sulfite 1-90g

Anhydrous nitric acid aluminium 0.60g

Methylcellulose sodium salt 56.0g contracts

Potassium hydroxide 55.0g

Carbon black 160g

Anionic surfactant (1) 8.60g

Anionic surfactant (2) 0.03g

Alkyl-modified PVA (Kuraray production) 0.06g

Cationic polymer 1.05g

The sulfinic acid polymkeric substance

Anionic surfactant (1)

Anionic surfactant (2)

Alkyl-modified PVA

Cationic polymer

These photo-sensitive cells (sample 101 to 104) all will expose from the emulsion layer side by a continuous wedge in a homenergic exposure instrument, are superimposed upon then on the protective seam that makes above.Between two kinds of materials, will and use the compressing tablet pulley to obtain the thickness of 62 μ m by above-mentioned process solutions development.Flushing is carried out at 25 ℃, measures transfering density with color densitometer after 10 minutes.

Sample and a certain energy spectrum sensitivity spectrogram that obtains are compared, and the result is compared to traditional composite bed system (sample 102), and sample of the present invention (sample 103 and 104) shows as steeper spectral sensitivity spectrum and distributes.

Respectively, each photo-sensitive cell (sample 101 to 104) is exposed by a grey continuous wedge from the emulsion layer side, overlap then on the protective seam of above-mentioned preparation.Above-mentioned rinse solution is developed between two kinds of materials by using the compressing tablet pulley to obtain the thickness of 62 μ m.Exposure was carried out 1/100 second, and the illuminance of control exposure simultaneously is to obtain a continuous exposure.Processing is carried out at 25 ℃, measures transfering density with color densitometer after 10 minutes.Horizontal ordinate is represented the logarithm of exposure then, and ordinate is represented every kind of color density, and mapping obtains a characteristic curve.The color density that the unexposed area obtains is as maximal density, and the color density in the zone that exposure enough obtains greatly is as minimum density.As the mid point sensitivity, density is that 0.3 sensitivity that obtains is as basic sensitivity the sensitivity of the middle granularity between maximal density and minimum density.The sensitivity of sample 101 is decided to be 100, obtains that the results are shown in Table 7.

Table 7

The sample sequence number	Maximal density	Minimum density	Average sensitivity	The basis sensitivity	Remarks
						101	2.30	0.16	100	100	Contrast
102	2.28	0.17	233	220	Contrast
						103	2.30	0.18	258	233	Invention
104	2.27	0.16	253	241	Invention

As can be seen from Table 7, sample 103 of the present invention and 104, mid point sensitivity and basic sensitivity all improve, and the spectral sensitization spectrum is steeper.

By using described photographic emulsion and photosensitive material, can obtain having the high photosensitive material of high sensitivity of desired absorption and desired sensitivity waveform.

Although described the present invention in detail with reference to specific embodiment.For the one skilled in the art, clearly, the various variations that can make in spirit of the present invention and scope and improvement are not got rid of.

Claims (12)

1, a kind of silver halide photographic emulsions, it contains a kind of silver halide particle, this silver halide particle is adsorbed with at least a spectral sensitizing dye of J-aggregate form in the above with one or more layers, the spectral sensitizing dye of this J-aggregate form is a cyanine dyes, portion's cyanine dyes, three nuclear portion cyanine dyes, four nuclear portion cyanine dyes or if rhodacyanine dye, this silver halide particle has less than the spectral absorption maximum wavelength of 500nm and 60 or bigger photon absorbing intensity, or have 500nm or longer spectral absorption maximum wavelength and 100 or bigger photon absorbing intensity, the maximal value of wherein setting the spectral absorption of the described emulsion that is caused by sensitizing dye is Amax, the distance that then shows the minimal wave length of 80%Amax and show between the long wavelength of 80%Amax is 20nm or longer, shows the minimal wave length of 50%Amax and the distance that shows between the long wavelength of 50%Amax is 120nm or shorter.

2, silver halide photographic emulsions as claimed in claim 1, the maximal value of wherein setting the spectral sensitivity of the described emulsion that is caused by sensitizing dye is Smax, the distance that then shows the minimal wave length of 80%Smax and show between the long wavelength of 80%Smax is 20nm or longer, shows the minimal wave length of 50%Smax and the distance that shows between the long wavelength of 50%Smax is 120nm or shorter.

3, silver halide photographic emulsions as claimed in claim 1, the long wavelength who wherein shows spectral absorption and be 50%Amax at 460nm to 510nm, 560nm zone to 610nm, 640nm to 730nm.

4, silver halide photographic emulsions as claimed in claim 2, the long wavelength who wherein shows spectral sensitivity and be 50%Smax at 460nm to 510nm, 560nm zone to 610nm, 640nm to 730nm.

5, as claim 1,2,3 or 4 described silver halide photographic emulsions, wherein said silver emulsion contains the dyestuff with at least one aryl.

6, as the described silver halide photographic emulsions of one of claim 1 to 4, wherein sensitizing dye is adsorbed onto on the silver halide particle with composite bed, wherein the second sensitizing dye layer has different structures with the first sensitizing dye layer, and the second sensitizing dye layer contains the dye of positive ion and anionic dye.

7, as the described silver halide photographic emulsions of one of claim 1 to 4, it contains a kind of sensitizing dye with basic nuclear of three or more cyclic condensations formation.

8, as the described silver halide photographic emulsions of one of claim 1 to 4, wherein the spectral absorption maximum wavelength is 60 or bigger less than 500nm, photon absorbing intensity, or the spectral absorption maximum wavelength be 500nm or longer, photon absorbing intensity be 100 or bigger silver halide particle be that radius-thickness ratio is 2 or bigger plain film shape particle.

9, as the described silver halide photographic emulsions of one of claim 1 to 4, wherein the spectral absorption maximum wavelength is 60 or bigger less than 500nm, photon absorbing intensity, or the spectral absorption maximum wavelength is 500nm or longer, photon absorbing intensity be 100 or bigger silver halide particle through selenium sensitizing.

10, a kind of silver halide photographic sensitive material that contains at least a silver halide photographic emulsions, it contains the described silver halide photographic emulsions of one of with good grounds claim 1 to 9.

11, a kind of silver halide photographic sensitive material, it comprises at least a silver halide emulsion layer, this emulsion layer contains silver halide particle, and this silver halide particle is adsorbed with the spectral sensitizing dye of the following molecular formula of at least a usefulness (the IV ') expression of J-aggregate form in the above with one or more layers

Wherein, Z24 represents forming 5 yuan or the necessary atomic radical of 6 member heterocyclic ring containing nitrogens, Z25 represents forming the necessary aryl of many cyclic condensations structure that contains 3 yuan or more rings of nitrogen heterocyclic ring that a kind of Z24 of comprising of aliphatic ring or aromatic ring and formation forms, Q represents to make molecular formula (the IV ') compound of expression to form the group of methine dyes, R24 represents alkyl, aryl or heterocyclic group, L65 and L66 all represent methine dyes, p17 represents 0 or 1, M7 represents the gegenion of balancing charge, m7 representative in and the necessary number of electric charge in the molecule, it is the number between 0 to 10;

12, silver halide photographic sensitive material as claimed in claim 11, wherein in molecular formula (IV '), Z25 represents forming a kind of necessary aryl of many cyclic condensations structure that contains four or more rings that comprises the nitrogen heterocyclic ring that formed by Z24.