JPS59148053A - Method for spectrally sensitizing photosensitive emulsion - Google Patents

Abstract

PURPOSE:To provide satisfactory solubility and spectral sensitivity to a photosensitive emulsion by spectrally sensitizing the emulsion with a specified sensitizing dye. CONSTITUTION:A spectrally sensitizing dye represented by the formula is dissolved in n-propanol, the soln. is dispersed in an aqueous liq., and the dispersion is added to a photosensitive emulsion. The soln. may be directly added to the emulsion. In the formula, each of R and R1 is alkyl or substituted alkyl; each of Z and Z1 is a group of atoms required to form a ring such as benzothiazole, naphthothiazole, benzoselenazole, benzoxazole or quinoline; Q is a group of atoms required to form a ring such as pyrazolone, indanedione, 5(4H)-isoxazolone, 2,4-chromandione, 4,6-(1H,5H)pyrimidinedione, barbituric acid, 1,3-dioxane- 4,6-dione, 3,5-pyrazolinedione, rhodanine or hydantoin; A is O or S, and each of n, d and m is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for spectrally sensitizing photographic emulsions necessary for the production of photographic light-sensitive materials.
In particular, it relates to an improved spectral sensitization method for effectively adding horapolar spectral sensitizing dyes to emulsions.

In the step e of subjecting one material to spectral sensitization, the photosensitive elements dispersed in the center of the photographic light-sensitive emulsion, such as silver halide microcrystals, zinc oxide, cadmium oxide, titanium oxide microcrystals, etc., are treated with appropriate dyes. The purpose is to dye by adding -. In particular, many efforts have been made regarding methods of spectral sensitization on silver halide emulsions. Depending on how the sensitizing dye is added to the silver halide emulsion and the conditions under which it is added, the quality of Kj absorption on the surface of the halide microcrystals varies significantly, and this affects photographic effects, such as fogging and photosensitivity. , spectral sensitivity distribution, desensitization effect, sensitivity stability, etc.
Gives a dog-like cedar sound.

This thing/ri G, D, ni, Mies (M,ee
s) 'tj,ri'he'l'heory of
the phatographic process (
1-2 published by Macmillan Publishing Co., Ltd.
Negative, from page 4130! 00 jj. The important condition for maintaining a high I/D ratio and providing a stable spectral sensitizing effect is the spectral sensitizing dye added.
The molecules, 7 molecules, stably reach and adsorb to the absorbent sites of the photosensitive silver halide crystals without excessive interaction with the binder, and without agglomerating or precipitating themselves in the binder. That's true.

In general, photography jA spectrally sensitized color is photosensitive by bath decomposition! Lh
Methanol, ethanol, methyl cellosolve, etc. are well known as organic M agents that can form free Ktr5 in water when adding UV VC. In particular, many spectral sensitizing dyes represented by cyanine dyes, merocyanine dyes, heminanine dyes, styryl dyes, etc. are very well soluble in organic solvents such as methanol, ethanol, and methyl cellosolve, so they are widely used. This is what we are doing.

By the way, even though the subject of the present invention has a strong color scheme, when bathing in methanol, ethanol, methyl cellosol, etc., the entire photosensitive 411L emulsion was prepared using these j41 attack + warning BUs. Spectrally sensitized gold can be used.

However, the dye of general formula (i) is not sensitive to these organic solvents, as are spectral sensitizing dyes such as cyanine dyes.
Does not dissolve well. Therefore, a large amount of valent solvent must be used, which reduces the surface activity of coexisting coating aids, coagulates the binder, and, in the case of color photosensitive materials, reduces the surface activity of coexisting coating aids, and in the case of color photosensitive materials, other photographic substances that coexist. Additives (such as couplers) may be solidified. This makes high-speed coating, for example, coating at lθ0 or more per 7 minutes, extremely difficult.

In addition, if the organic solvent used is not evaporated by the drying process and remains on the photosensitive material, photographic properties (such as sharpness) may deteriorate,
Reducing low-F in film properties (e.g. film strength) 7
This poses a practical problem.

Therefore, the purpose of this paper is to develop the spectroscopy of the general formula (I) of a photosensitive emulsion that solves the above-mentioned problems. ii) provides a spectral sensitization method using a sensitizing dye.

The above purpose was to dissolve a photographic spectral sensitizing dye shown in Ichisho Nisan, which will be described later, in n-propanol, and add the solution to an aqueous solution (water-bearing colloid aqueous solution) of 6≦. dispersed,
By adding this dispersion to a light-sensitive emulsion or directly adding the solution to a light-sensitive emulsion,
Light-sensitive emulsions can now be spectrally sensitized.

For the dye of general formula (i), the solubility of the dye is not as high as that of n-proaminol, but the solubility of 1,3-propanediol and 2-propanediol is the lung point at voltage e. Or respectively, zi4+! Since the temperature is 15°C and 30°C, when they are dissolved in them and added to a photosensitive emulsion for coating, those baths are not evaporated during the line transfer process and are exposed to light. This causes a decrease in the sharpness of the photosensitive material and a decrease in the film strength of the photosensitive material.These circumstances result in a large loss for the photographic material. .

- It was not possible to sufficiently dissolve the dye of general formula <D with propatool.

On the other hand, when the n-propanol of the present invention was used as a solvent for the dye of general formula (1), specific and fully satisfactory results were obtained in terms of #dissolubility, spectral sensitization sensitivity, and boiling point. . In particular, it is surprising that among propatools, only n-propatool dissolves the dye of general formula (I) of the present invention very well.

General formula (i) 111-2-1- Here, l't and R1 may be the same or different, and an alkyl group (preferably carbon number / ~I
) X7C", 16-substituted alkyl group (preferably vjl
;,'b: number of carbon atoms/~10. e, -J94 groups include halogen atom, hydroxyl group, alkoxy group, aryl group, dialkylamino group, alkoxycarbonyl group, (
, acyloxy group, cyan group, acyl group), and Z and Zl may be the same or both, and benzothiazole salt, naphthothiazole 'Ei
b benzothornazole ring, nandoselenazole ring,
The six atomic groups necessary to form the benzoj-xazole ring, naphthoquinol ring, and quinoline ring (including halogen atoms, alkoxy groups, alkoxycarbonyl groups, alkyl groups, acyl groups, acyloxy groups, hydroxyl groups, It may be substituted with a trifluoromethyl group, a cyanide group, a sulfamoyl group, or a carbamoyl group.
? When the substituent has a returning atom, it is preferable that the number of carbon atoms is /J%. ) is Table 2) C, Q is pyranolone cedar, indandione nucleus, 5(4N()-isooki''!7-
Zoron bales! , 4t-noromandione nucleus, , ,!
Knee (Zl (, jIl) pyrimidinedione nucleus, barbile i'l;'? bale, '-f obarbitur f bed comfort,
/, 3-dimexane-hiro, 6-dione nucleus, 31 j-pyrazolidinedione nucleus, 311-nut L-2, /-b
) Biran-/, 3(,21-1)-jimann nucleus, j(
4tI■) - Inoxacillone nucleus, logenin, hydantoin nucleus, Naohita ``tontoin nucleus, /, 3-cyclobutanedione nucleus is formed.
, N) 1 (by replacing 1 with 5 IFs) L
It's okay to stay. ) τ, A is an acidic atom, and the parent is a sulfur atom.

In the 11X formula (I), R and R1 are particularly preferably an alkyl group or an alkyl group having an alkoxy group, and Q is a barbylic acid group, a 2-thiobarbituric acid nucleus, an indandione nucleus, ! .

A nonmetallic atomic group necessary to form a t-chromandione nucleus is preferable, and a nonmetallic atomic group necessary to form a barbylic acid group is particularly preferable.

″Also, at least one of Z and Z□ is a nonmetallic atomic group necessary to form a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring, a naphthoxazole ring, a benzoselenazole ring, or a naphthoselenazole ring. (It may be substituted with a halogen atom, an alkoxy group, an alkoxycarbonyl group, an alkyl group, an acyl group, an acyloxy group, a hydroxyl group, a trifluoromethyl group, a cyan group, a sulfamoyl group, or a carbamoyl group).

``il't knee, n, d, and m each / is good.

Next, typical examples of the sensitizing dye of general formula (I) used in the present invention are shown below.

-1 ■-2 ■-3 I-j- -4 -7 ■-ta■-/ / Knee/2 -0 02F■5 ■-/3 ■-/≠ ■-/, f J-/ Otsu\N (02FI5)2 ■-77 ■-/Ta0゛su3 The spectral sensitizing dye of general formula (I) used in the present invention is a known one, and is disclosed in US Patent No. 3. Good t,y.

No. 1 Akira ms, No. 2170'l l 7/J No. Elf
1, No. 2, 73, RI A4 can be easily synthesized based on the method described in the specification.

'l: The dye of general formula (i) is preferably l1n-propatool/00 mlK vs. O2θ7~t),
It can be used after being dissolved to a degree of 2 Va.

As for the amount of the spectral sensitizing dye of general formula (I) used in the present invention, a commonly used spectral sensitizing amount is applied. Specifically, per mole of silver halide /×7θ ~/×10
Molar amounts are preferred.

A 61-color sensitization method can be used in combination with the spectral sensitization method according to the present invention. For example, ordinary cyanine dye # can also be used as a supersensitizer.

In the present invention, the color of general formula (I) X'rn-11J/
When dissolving in ξnol, it is more preferable to use an organic acid or a 4fA-free acid in combination. In this case, as the acid, preferably used is an acid that dissolves in water or is freely miscible with water. Specific examples of acids include organic acids (aliphatic acids, aromatic acids) and inorganic acids, including those with a sulfo group, those with a carboxyl group, those with an enolic hydroxyl group, and those with an enolic hydroxyl group. These include those that are mixed with funds. Among them, methanesulfone rs, ethanesulfone fermentation, J-propanesur; 1ζ acid, trifluoroj
Particularly preferred are those that are liquid at room temperature, such as methanesulfonic acid, isethion aZ<, 2-sulfoethyl alcohol); formic acid, acetic acid, propionic acid: sulfuric acid. Benzene sulfonic acid, halbenzenedisulfonic acid, nomiladruene sulfonic acid, naphthalene-α-sulfonic acid; barbylic acid,
thiobarbic acid; methionic acid (mecundisulfonr)
%4); Anhydro-no-methyl-j, Mage Polyrolu/, J-di(J-sulfozolovir)penzimitazole-human Doxide, Anhydro-no-methyl-yo-chloro-/, 3-di(3-sulfopropyl)penz For those that are solid at room temperature such as imidazole hydroxide, the amount of acid used is 30% (by volume) based on n-propatool.
It can be used by mixing up to a certain amount.

Specifically, Japanese Patent Publication No. 37-), Publication No. 20g2, J7 of the same
−． 2.2θri No. 1 Publication, j7-. It is described in 220-ri No. 2 Publication etc.

In the present invention, when dissolving/dispersing the dye, it is preferable to use all the surfactants together.

For example, anionic interface 1 agent (U.S.A.)
ri, 19/, same i;”!-?+gu/J-, Aguku, same number, wo.

, 2) 0.1≠7, etc.), cationic surfactants, nonionic surfactants (e.g., US ft, 3r ” ” + /
/-/, ≠/3, same 3rd. /33. and//2 etc.) may be used.

As a surfactant used in combination with 11-propatol, there is a surfactant described in Japanese Patent Publication No. 4L Hirotori No. 5.
Those having groups such as 3, -0SO, -(Σ,)0 are preferable, and specific examples include the following.

') C17H33-C00CH2CH2S(J3N&
3) C5H, 100C-CH-803NaI C51 (□□ooc-c++□ 4t>c, 7n33-co-N-C112CI-1
2SO3NaCI-J 3 s) C8H, 70SO3Na CH3 r) Saponin In the present invention, dissolution of the dye is achieved by stirring, heating stirring, or preferably ultrasonic stirring. Degradable dyes can also be dissolved at low temperatures.

Dispersion may be effected by mechanical high-speed stirring, or ultrasonic stirring, or a combination of both. It is also possible to add a compound '+/)) which improves dispersibility during dispersion.

The hydrophilic colloid used during dispersion may be the same as that used in photographic emulsions (preferably those having a hydrophilic group (sulfo group or carboxy group), such as gelatin, are used). Depending on the type of dye, it is also possible to disperse the dye in water without using a hydrophilic colloid during dispersion. The color patch dispersion thus obtained can be added to the photographic light-sensitive milk 31 substantially immediately after dispersion. It can also be used by dispersing it into a hydrophilic colloid and storing it for a long time (for example, λ weeks).

During dispersion, the colored light dispersion can also be neutralized with a base.

Bases that can be used during dispersion are not particularly sensitive, such as sodium hydroxide, potassium hydroxide, sodium carbonate, diethylamine, triethylamine, etc.
It is possible to effectively neutralize the acid used in the present invention,
And given)','4i1. ．． It does not have a negative effect on the agent.
11-40 The photosensitive emulsion used is a photosensitive emulsion such as photosensitive silver halide, titanium oxide, or titanium oxide. A water-retaining colloid containing microcrystals such as zinc or cadmium sulfide may be used. Preferably, a gelatin silver halide emulsion is used, and the silver halide may be any of silver iodobromide, silver bromide, silver chlorobromide, silver chloride, silver iodochlorobromide, and the like. In addition, chemical ripening that can be carried out as required is reduction sensitization/i%, sulfur) lI sensitization, and sensitization of blue metals (these sensitization methods are often referred to in this field). There may be b pieces in 101 ways such as combinations. Regardless of the degree or method, it is a mountain and a river.

The present light beam J may be overused in light-sensitive emulsions with spectral equalization for M.

In addition to gelatin, hydrocolloids used in photographic emulsions include aldimine, agar, gum arabic, and algin.
Hydrophilic polymers such as acylated gelatin (for example, acylated gelatin, carbonated gelatin 2ζ'), polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polystyrene sulfone 7ζ It has no harmful effects on photosensitive halogen compounds such as cellulose compounds (monomi, hydroxyethylcellulone, carboxydimethylcellulose, texturin, etc.) and water-soluble starch. Goods trade can also be used.

The photographic emulsion spectrally sensitized according to the present invention contains commonly used additives such as stabilizers, capri inhibitors, sensitizing materials, hardeners, coloring agents, coating/111 auxiliaries, It is possible to add and coexist a development precursor, an ijJ plastic agent, a polymer other than centin, and the like. The spectrally sensitized complete milk Al) according to the present invention can be used for supporting materials such as cellulose derivative film, polyethylene terephthalate film, baryta paper, paper, resin laminate paper, synthetic paper,
It is applied to glass plates, Bujisnak film, metal plates, etc.

The photosensitive emulsion of the present invention can be used in a wide variety of photosensitive materials. The emulsions used are not only emulsions for black sun-sensitive materials, but also emulsions for color positives, and emulsions for color and ξ-.
Emulsions for color/Funo J, emulsions for color reversal (sometimes containing cazolar, and emulsions that do not require a stand), emulsions for photographic light-sensitive materials (e.g. lith film), polarization tube display Emulsions used in photosensitive materials for X-ray recording (especially materials for direct and indirect photography using screens), colloid transfer process
process) (e.g. U.S. Patent No. λ, 7/l, 0
The emulsions used in the silver salt diffusion transfer process (described in 3F),
on transfer proc-ess) (for example, U.S. Patent No. 2.lj2,0/lI, U.S. Patent No. Emulsions used in color diffusion transfer processes (as described in U.S. Pat.
．． ♂/7, same 3rd. /6! , 667, 5A, 2, Y
I3, AOt, 3rd degree, 2!3, 9/3. Same 3rd
, 2.27, 3-3'0. 3.227.33/,
Same 3rd. λ,! 7.3j), same No. 3. ≠/, t, A4Z
4t, same 3rd. ≠ / J-, 7th, same No. 3. ≠/j,
Emulsions used in A41 [described in etc.], dyes, etc.
Transfer process (1m1Jibition)
transfer process) (described in U.S. Pat.
iatory of color Photog
r-aplyJ (American Photogr.
aphic PublishersCo-/ri+p, especially Chapter 2j) + rBri jishJourn
al of PhotographyJvolo
///, p.

301-30Apr, 7, /! ;'A
Emulsions used for printing and
Materials that record out images (e.g., U.S. Pat. No. 2,3
tri.

≠Geta, Belgian Patent No. 70'i', 2! ! Emulsions used in
direct print image) photosensitive materials (for example, U.S. Patent No. 3.θ33,1,1.2;
Emulsions used in photosensitive materials for heat development (for example, U.S. Pat. 3./'
I-za, /2.2, British Patent No. 1. //θ,otit,
Emulsions that are not used for physical development (for example, those listed in WJ Octopus 0..277, WJ Octopus 0..277, WJ Octopus 0..277, WJ Octopus 0..277, etc.) Emulsion used, emulsion for surface positive (for example, U.S. Patent No. 2+
Hiro 77.873. 2nd, 5tti, ≠ 7), 3rd.
．． 3t7,771. Same 3rd. jθ/, 30 ri, same 3rd,
30/, 3. /θ, same No. J, j Oj.

070, same y, 3. s3/, ryo, same No. 3,60/,
jOjf, same gJ, 3, 601, 30t, same No. 3゜101.307, same J J lj O/ * J /-
2. No. 3! 10.34#, UK%ifF! ! / ,
/rg, 7//, same 1st, /I l,
7/2, same No. 1, /II,.

713, etc.).

The silver halide in the photographic emulsion used in the present invention (which may be either solid-sized grains or fine grains) can be produced by conventional methods, such as single-jet method, double-jet method, or a combination thereof. For example, methods for preparing silver emulsions are described by Trrvelli and Sm1th.
The Photographic Journal month vo
1.7ri, pp, 330-331 (/ri3ri) C,
Written by E, K, He4aes The 'l'heo
ryof Photo-graphic Processes
sJMac Mjllan; and Glafk+, is
4 rPhotograph Chemistry
lvol, I pp, j, 2 7~! ,i
A, Fauntain Press has N mountain 1.1d.

Example/ The solubility of the dye Nee 2 in n-propertool and other solvents shown in Table 1 was tested in Test 1.#j*'f
'R'/ fiKi 1,7j・//' As is clear from Table 1, the test results using n-propertools were higher than the holopolar dyes of the present invention ( It can be seen that the solubility for C is specifically high.

Also, when used in combination with acid or surfactant (Kata!, 3)
The solubility is further improved significantly. Therefore, it can be seen that the amount of organic solvent used is specifically high.

Example λ The above dye 1-J was tested in bath solution 1 with n-propanol and other solvents shown in Table 2.As is clear from Table λ, Test A using n-propanol was conducted. / is 1
Holopolar of the present invention compared to methanol etc.
It can be seen that the solubility for the dyes is specifically high.

In addition, when acid or surfactant 7+lJ is used in combination (77
b), 3) Solubility is significantly improved. Therefore, it can be seen that the amount of organic solvent used is temporarily high.

Example 3 The dye 1-10 was tested for bath solubility in n-bronoζ°nol and other solvents shown in Table 3 for 7 hours, and the results are shown in Table 3.

Table 3 As is clear from Table 3, the test PA using n-propertool was 7'l'l' more soluble for the polypolar dye of the present invention than methanol etc. in boiling. It can be seen that this is uniquely high. Therefore, it can be seen that the use of an organic solvent t1- is uniquely difficult.

Example Hiro For the above dye i-//, n-propertool and Part V
Testing the solubility in other solvents shown in the table As is clear from the table, the testing company using n-bronoξnol was
It can be seen that the solubility of the holobocy dye of the present invention is specifically better than that of methanol etc. in Examples 3 to 3j.

Moreover, when an acid is used in combination, (A, -2) dissolution J1 (is further significantly improved. Therefore, it can be seen that the amount of organic solvent used is specifically high.

Example! Silver iodobromide gelatin emulsion (7 moles of iodine, gelatin (solid) / AgN0'3: 3 (weight ratio); 0゜! 3 moles dust / h-y\L it"J) below ( a)
and the above dye 1- by method (b) for comparison.
．． Spectral sensitization was performed using 2.

(a) Prepare the following two types of dye solutions and add the above emulsion l.
Next, add the dye 1-2 solution and the dye hole bath solution to the song and mix.7j.

dye solution ( Here, the following dye A was used.

(b) The following 12 types of color solution were prepared, and the dye Knee 2 solution and the dye A solution were added to the above emulsion/nuri in this order and mixed.

Dye Solution It should be noted that Dye 1-2 was dissolved in methanol to a nearly perfect degree.

The emulsions spectrally sensitized in (a) and (b) above were each coated on a cellulose triacetate film base, and after drying, they were simultaneously coated with a Luxten filter 5it using daylight color (equivalent to J4toOK) of 6Ko Lux. (Yellow filter for minus blue sensitivity foot measurement) Excretion and light exposure 17
30 seconds), and then developed for 2 minutes at 2O'C with a developing solution of my own prescription. Next, it was stopped, fixed, washed with water, and then dried. This was measured using a P-type density analyzer manufactured by Fuji Photo Film Co., Ltd. to obtain the negative full sensitivity and fog value. The basic point of optical density at which sensitivity was determined was [Cub+)+0.10]. The obtained results are listed in Table 7 as illusory values.

Composition of developer As is clear from Table 1, the method of the present invention has high sensitivity. T 10 as photosensitive element instead of halogenated steel
2. Zn Ok was used, and instead of gelatin, cellulose ether phthalate, borihinyl alcohol, and -:1tCIri acrylamide were used as hydrocolloids.
The specific viscosity is 0. ．． Even when a mixture of polyacrylamide, shavings, etc. with 2j~/,j was used, results as high as 1J were obtained.

Claims (1)

[Claims] A photographic spectral sensitizing dye represented by the following general formula (I) is
- Dissolve in propatool, add and disperse the solution in an aqueous liquid, and form this dispersion? : A spectral sensitization method for photographic light-sensitive emulsions characterized by adding the solution to the light-sensitive emulsion or directly adding the solution to the light-sensitive emulsion. General formula (I), -Zl-1 to Q- =C nee (CH=CI-1) m-□-N-R1 where R
and f (□ represents an alkyl group or a substituted alkyl group, which may be the same or different, and Z and Zl
may be the same or different, respectively; a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring,
It represents a group of nonmetallic atoms necessary to form a naphthoselenazole ring, a penzoxazole ring, a naphthoxazole ring, and a quinoline ring, and Q is a pyrazolone nucleus, an indanedione nucleus, a j(≠H)-isoxacilone nucleus, and λ. ≠-chromandione nucleus, ≠, &-(/H,jH)pyrimidinedione nucleus, barbylic acid nucleus, 2-thiopahuturic acid nucleus, /, 3-dioxane-≠. t-dione nucleus, 3. Terpyrazolidinedione nucleus, 3H-
naphtho (j, /-b] pyran-/, 3()H)
-dione nucleus, j(≠H)-isoxacillone nucleus, rhodanine nucleus, hydantoin nucleus, thiohydantoin nucleus, /, 3
- A group of nonmetallic atoms necessary to form a cyclobutanedione nucleus is present, A represents an acid atom or a sulfur atom, and n
, d and m each represent 2.