JPH03150558A - Direct positive silver halide photographic printing paper - Google Patents

Abstract

PURPOSE:To obtain a direct positive silver halide photographic sensitive material processable in the lightroom and superior in whiteness by incorporating a specified compound and a bluing oil-soluble dye. CONSTITUTION:At least one of direct positive silver halide emulsion layers is fogged in advance, and contains the compound having a lambdamax of 350 - 600 nm, such as pyraxoine dyes and pyrazolooxonole dyes, and the bluing oil-soluble dye, such as anthraquinone type dyes and azo type dyes, thus permitting the obtained photographic direct positive printing paper to be processed in the ightroom and superior in whiteness.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a direct positive type silver halide photographic photographic paper that has been covered in advance, and moreover, to a silver halide photographic paper that can be handled in an environment that can be called a bright room. Regarding photographic paper.

(Prior art) In recent years, in the field of printing and plate making, in order to save labor, streamline the work environment, and improve the working environment, there has been active development of photosensitive materials that allow film-making, which was traditionally done in a dark room, to be carried out in a bright room. .

Examples of light-sensitive materials that can be handled in a bright room include those that have spectral sensitivity to light sources rich in ultraviolet light, such as ultra-high-pressure mercury lamps, mercury lamps, metal halide lamps, xenon lamps, and halogen lamps.

This includes direct-positive photographic paper for so-called proofing, but it has the disadvantage of producing a more yellowish tone compared to negative photographic paper, and the development of direct-positive photographic paper with good whiteness has been difficult. It was strongly desired.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a direct positive silver halide photographic light-sensitive material that can be handled in a bright room and has excellent whiteness.

A direct positive type silver halide photographic paper having at least one layer consisting of a silver halide emulsion, characterized in that it contains a compound having a λmax in the range of 350 to 600 nm and a bluish oil-soluble dye. Achieved by paper.

There is no particular restriction on the chemical structure of the compound having λmax in the range of 350 nm to 600 nm.
U.S. Pat. No. 2.27', /I.

/ / / 7g, pyrazolone oxonol dye described in U.S. Patent No. 2. Tata A, diarylazo dyes described in Ir7, U.S. Patent No. 3. ≠23. λ07, 3.31
'l,≠r7, styryl dyes and butadienyl dyes, US Patent No. 2. ! , 27,5g No. 3, merocyanine dye, material, U.S. Patent No. 3゜4t gutter,! No. 77, No. 3.1! rλ, -Zag No. 3, 7/1, 1172
Merocyanine dyes and oxonol dyes described in US Patent No. 3,77B.

Enamine hemyoxonol dyes described in AJ/No. /77.4
', No. 77, Tokukai Showa G-G Yu/3θ issue, same getter? F
lr20, same≠tar//Hirohiro 2θ, US Patent No. 1.
! 33. ≠No. 7.2, No. 3. /Hiroshi? .

No. 117, same No. 3. /77.071 No. 3゜Cog 7
, No. 127, No. 3. ! Hiro 0.117, Hiro 3.67
Yo, 704L, 3.1 evening 3. The dye described in No. 0'j is used.

More specific examples of dyes that can be used in the present invention include dyes represented by the following general formulas (1) to (IV).

General formula l R1 1 (2 1 formation) General formula m .

Q is pyrazolone, barbylic acid, thiobarbylic acid, inoxacilone, 3-oxythionaphthene/
Represents the atomic group necessary to form 23-indandione. R is a substituted or unsubstituted alkyl group, R11R2,
R3 and R4 are hydrogen atoms, alkoxy groups, dialkylamino groups, or sulfone groups R5 hydrogen atoms are halogen atoms, M is hydrogen atoms, sodium atoms or potassium atoms, X is an anion, m + n 1 and R3 are 1 represents λ. However, when m is /, an inner salt is formed. ] - Formation ■ RIO 9 One format ■ [In the formula, Y is an alkyl group, or a carboxyl group 6 r R7r RB + Rg l 11ti.

, R11 R12 13 R14 , R15 , R16 and R17 represent a hydrogen atom, an alkyl group, a hydroxyl group, an amino group, an acylamino carboxyl group or a sulfone group. However, R
□2 and R□3 may be bonded to each other to form a benzene ring. ] Among the dyes of types CI) to (V), dyes with acidic groups (sulfone group, carboxyl group, etc.) are preferred.

A specific example is shown below.

dye-l Dye-1 Dye-3 Dye-G Dye-6 Dye-7 O3H dye-g Dye-ta 1 Dye-10 Dye-/1 α 2 Dye-12 Dye-73 dye ／　≠ Dye-/j dye-/ Dye-/7 5 03Na dye ／♂ Dye-/li Dye-20 6 Dye −λ/ Dye-, 2λ Dye-23 dye 4 03Na SO, Na Two or more of these dyes can also be used in combination.

The dyes of the invention are used in amounts necessary to enable bright room handling. The specific amount of dye used can vary depending on the amount of desensitizer (for example, water-soluble rhodium salt) used, so it is difficult to set a uniform amount, but it is generally 10-3 g/bo...
A preferred amount can be found in the range of Ig/n, especially 10-3 g/n (~0.5 g/rd).

In addition, the blue tinting of the present invention refers to using a blue dye alone or a red dye, as a means to adjust the hue of photographic paper after processing.
This method uses two or more kinds of green dyes, blue dyes, etc. in combination to adjust the absorption characteristics of photographic paper after processing. As such dyes, Japanese Patent Application Laid-open Nos. 60154251 and 55-93150
The dyes described in No. In addition, oil-soluble refers to functional dyes that are water-insoluble and dissolve in organic solvents such as benzene, chloroform, ethyl acetate, acetone, methanol, and dibutyl tuclate. Dyes are a typical example.

Next, typical examples of oil-soluble dyes used in the present invention will be shown.

D-]0 2 3 C3 7 14 5 6 7-9 The oil-soluble dye used in the present invention can be added to the photographic layer by the same method as conventionally used for oil-soluble couplers, that is, by adding the oil-soluble dye to the photographic layer. is dissolved in a high boiling point solvent that is substantially insoluble in water, along with a low boiling point solvent if necessary, mixed with an aqueous gelatin solution containing a surfactant, and then mixed with an emulsifying device such as a colloid mill, a homogenizer, and an ultrasonic dispersion device. A suitable method is to emulsify and disperse it and then add it to the photographic layer.

High boiling point solvents used in this case include carboxylic acid esters, phosphoric acid esters, carboxylic acid amides, ethers, substituted hydrocarbons, etc. Specifically, di-n-butylfuraric acid ester , diisooctyl fucorate, dimethoxyethylfucorate, di-n-butyl adipate, diisooctyl azeate, tri-n-butyl citrate, butyl laurate, di-n- Sebacate, tricresyl phosphate, tri-n-butyl phosphate, tri-isooctyl phosphate, N, N-diethyl caprylic acid amide, N, N-dimethyl palmitic acid amide, n-butyl-pentadecyl phenyl ether, ethyl -2. Examples include 4-tert-butylphenyl ether, succinic acid ester, maleic acid ester, chlorinated paraffin, etc., and these can be used alone or in combination of two or more. Examples of low-boiling solvents include ethyl acetate, butyl acetate, cyclohexane, propylene carbonate, methanol sec-butyl alcohol, tetrahydrofuran, dimethylformamide, benzene, chloroform, acetone, methyl ethyl ketone, diethyl sulfoxide, methyl cellosolve, etc. One or more of these can be used as needed. Further, as the surfactant, anionic surfactants, nonionic surfactants, and combinations thereof can be used, such as alkylbenzene sulfonates, sulfosuccinate salts, saponins, and the like. Examples of gelatin include alkaline method gelatin, acid method gelatin, and modified gelatin (for example, Japanese Patent Publication No. 3B-48
No. 54, No. 40-12237, U.S. Special Kitsuki 2,5
25,753, etc.) can be used alone or in combination, and if necessary, a natural or synthetic binder (eg, polyvinyl alcohol, polyvinylpyrrolidone, etc.) can also be used.

The oil-soluble dye used in the present invention can be emulsified and dispersed in a melted state only in a low boiling point solvent, or it can be dispersed by a dispersion method using a polymer latex solution and then added to the photographic layer. It is also possible to do so. In addition, in the above emulsification and dispersion process, oil-soluble dyes may be dispersed alone or used as emulsions and dispersed among photographic additives such as couplers, ultraviolet absorbers, antioxidants, stain inhibitors, and optical brighteners. It may be emulsified and dispersed together with other substances.

The oil-soluble dye according to the present invention may be added to any layer in the photographic layer, and has the same effect for improving the whiteness of the white background.

The amount of oil-soluble dye added is usually preferably 0.05 mg or more and 5II1 g or less.

The silver halide emulsion used in the present invention may be produced by any of the acidic method, neutral method, or ammonia method, and the silver halide may be silver bromide, silver chloride, or silver chlorobromide. , silver iodobromide, silver chlorobromoiodide, and the like.

Further, the silver halide grains used in the present invention have a good grain diameter of 0.0/-.lambda. microns, but it is preferable to use grains with an average grain diameter of 0.102-7 microns.

Further, the particle size frequency distribution may be wide or narrow, but a narrower one is preferable. In particular, 0% of the total number of particles falls within a particle size range of ±1.10%, preferably ±20% of the average particle size.
So-called monodispersed emulsions containing preferably r% of emulsion are preferred. Further, the silver halide grains may have a single crystal habit or a mixture of various crystal habits, but a single crystal habit is preferable.

The direct positive silver halide used in the present invention is an inorganic desensitizer (i.e., noble metal atoms contained in silver halide grains, etc.)
and an organic desensitizer that adsorbs on the silver halide surface, either singly or in combination.

In order to incorporate the inorganic desensitizer used in the present invention into silver halide grains, a water-soluble noble metal compound such as iridium,
Chlorides of group R metals of the periodic law, such as rhodium, are added at 10-7 to 10-2 mol per mol of silver halide, preferably! I,<
5 to 10'' mol of halo may be added as an aqueous solution during preparation of silver halide grains.

Examples of organic desensitizers that can be used in the present invention include dimethine cyanine dye containing a λ-(nitrosubstituted phenyl)-indole nucleus, bis-(/-alkyl-λ-phenyl)-indole-3-trimethine Cyanine dyes, cyanine dyes containing an aromatic substituted 1 indole nucleus, imidazoquinoxaline dyes, asymmetric cyanine dyes containing a carbazole nucleus, -trimethine cyanine dyes containing a monoaromatically substituted indole nucleus 1.2-3-3-) Realkyl -3H-nidroyl toll nucleus-containing mucyanine dye, complex-fused pyrimidinedione nucleus-containing cyanine dye, λ-inoxazoline! -On nucleus, λ-pyrazoline-! μ-classified merocyanine dyes with -one nuclei or complex fused pyrimidinedione nuclei, λ-allylimino (or alkylimino)-p-allyl (or alkyl)-3-
Cyanine dyes containing a thiazoline nucleus, merocyanili secondary ammonium salt dyes having a 3-arylamino or 3-lower fatty acid amide-substituted 2-pyrazoline-y-one, pyrylium, thiapyrylium, selenapyrylium salt dyes,
Cyanine dyes having a nitro-substituted λ-arylindole nucleus, bipyridinium salt dyes, cyanine dyes containing a pyrrole nucleus bonded at the 2-position carbon atom, /, 2-diaryltrimethine indole dyes, cyanine dyes containing a goupyrazole nucleus, Polymethine dyes containing an imidazole nucleus, dimethine cyanine dyes containing a λ-phenyl-substituted indole nucleus, trimethine cyanine dyes consisting of λ indole nuclei, cyanine dyes containing a /-cyanoalkyl-arylindole nucleus, one nucleus is nitro cyanine and merocyanine dyes with desensitizing substituents such as /-
Cyanine dyes containing an alkyl-λ-phenyl-substituted indole nucleus, cyanine dyes containing an /-alkoxy-1-arylindole nucleus, cyanine dyes containing an imidazo[≠, s, A]quinoxaline nucleus, cyanine dyes containing a cycloheptane triene ring, dye, indole-grafted dimethine cyanine dye, pyrazolo[/+'a) cyanine dye containing benzimidazole nucleus, pyrazolo[1,/-b] cyanine dye containing quinazolone nucleus, pyrrolo[λMF-b) containing pyridine nucleus Dimethine cyanine dyes, cyanine dyes containing a pyrrole nucleus, dyes containing a pyrrolo[λ,tb]thiazole nucleus, cyanine dyes containing an indole or indolenine nucleus containing a benzoyl or phenylsulfonyl substituent, and the like are useful.

Fog can be applied to the direct positive type silver halide used in the present invention by a conventionally known technique after removing water-soluble salts generated after the silver halide is precipitated. Fog can be imparted by using a fogging agent (reducing agent) alone or by combining the fogging agent with a gold compound or a useful metal compound that is more electrically positive than silver.

Typical fogging agents useful in making such emulsions include, for example, formalin, hydrazine, polyamines (triethylenetetramine, tetraethylamine, etc.), thiourea dioxide, tetra(hydroxymethyl)phosphonium chloride, and amine borane hydrogen. Examples of useful metal compounds that are still more electrically positive than silver include boron compounds, stannous chloride, tin(II) chloride, etc., and include gold, rhodium, platinum, palladium, iridium, etc. Soluble salts such as potassium chloroaurate, chloroauric acid, palladium ammonium chloride,
Included are sodium iridium chloride and the like.

A fogging agent is generally used as a fogging agent per mole of silver halide.
It is used in the range of 1.10 to 0x10%.

Typical gold compounds include chloroauric acid, sodium chloroaurate, sulfur compounds, selenium compounds, etc., and generally have a concentration of 1.0x10-6 to 0x10 per mole of silver halide.
It is preferable to contain it in a molar range.

The degree of fogging of the prefogged direct positive silver halide emulsions used in the present invention can be varied over a wide range. The degree of fogging is determined by the silver halide composition and grain size of the silver halide emulsion used, as well as the type and concentration of the fogging agent used, as is well known to art technicians.
It is related to the pH, pAg, temperature and time of the emulsion at the time of imparting fog.

The direct positive silver halide photographic light-sensitive material of the present invention includes a selenium compound as described in JP-A No. 1988-19020, a halogen-free photoactive compound as described in JP-A-60-19020, and a nitro-substituted solarization promoters such as pentsindazoles and nitro-substituted pentsindazoles, and sensitizing dyes such as dimethine trimethine cyanine dyes, halogen-substituted hydroxyphthalein dyes, phenazine dyes, cyanine dyes containing benzothiazo-/hebenzoselenazole nuclei, Cyanine dyes containing a naphthoxazole nucleus, triphenylmethane dyes, cyanine dyes containing an indolenine nucleus, cyanine dyes containing a λ-pyridine-rhodani/nucleus, cyanine dyes containing a thiazole nucleus, asymmetric cyanine, quinoline, meso-substituted High sensitivity can be provided by containing substances such as at least seven sensitizing dyes selected from cyanine dyes, cyanine dyes containing rhodanine nuclei, and polymethine dyes having three nuclei.

The direct positive silver halide photographic material of the present invention may contain various other commonly used photographic additives. As stabilizers, for example, triazoles, azaindenes, Daiko benzothiazolium compounds, mercapto compounds, or cadmium, cobalt, nickel,
Water-soluble inorganic salts such as manganese, gold, thallium, and zinc may also be contained. Also, as a hardening agent, for example, formalin,
Aldehydes such as glyoxal and mucochloric acid, S-
Triazines, epoxies, aziridines, vinyl sulfonic acids, etc. Also coating aids such as saponin, sodium polyalkylene sulfonate, lauryl or oleyl monoether of polyethylene glycol, amylated alkyl taurine, fluorine-containing compounds, etc. For example, polyalkylene oxide and its derivatives may be contained as the material. Furthermore, it is also possible to contain a color coupler. In addition, a whitening agent, an ultraviolet absorber, a preservative, a matting agent, an antistatic agent, etc. can also be contained as necessary.

In the present invention, it is preferable to use a fluorescent whitening agent to improve whiteness.

As water-soluble brighteners, compounds described in Japanese Patent Publication No. 48-30495 are used; as water-insoluble brighteners, compounds described in Japanese Patent Publication No. 60-198
Oil or latex dispersions of the compounds described in No. 54251 or titanium oxide are advantageously used.

The support used in the present invention may be paper, baryta coated paper, paper coated with an α-olefin polymer such as polyethylene, or the like. These supports may further contain titanium oxide, dyes, etc. in order to increase the whiteness.

Preferably, a water-impermeable reflective support is used.

The developing agent used in the development of the silver halide photographic material according to the present invention includes, for example, those described in "The Celery of the Photographic Process" by E. K. Meese, T. H. James. 3rd edition, pages 278-381 (1966), the organic or inorganic developer and development aid may be used alone or in combination.

Preferably, hydroquinones such as ferrous oxalate, hydroxylamine, N-hydroxymorpholine, hydroquinone, hydroquinone monosulfonate, chlorohydroquinone, t-butylhydroquinone, catechol, resorcinol, pyrogallol, amitol, phenidone, 4- pyrazolidones such as hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone; Such as phenylenediamines, ascorbic acid, etc. More preferably, metol alone, a combination of phenidone and metol,
Combinations of metol and hydroquinone, combinations of phenidone, metol and L-butylhydroquinone, combinations of phenidone and ascorbic acid, combinations of phenidone and baraminophenol, etc., but even more diverse combinations have been used to achieve almost the same good results. Obtainable.

The above-described developing agent to be contained in the developer of the silver halide photographic light-sensitive material used in the present invention may be used in a usual amount, and generally in an amount of I x 10-' to 1 mol/1N of developer. .

In addition, the developing solution for the silver halide photographic light-sensitive material used in the present invention contains the above-mentioned developing agent and preservatives such as sulfite and hydroxylamine, as well as caustic alkali, alkali carbonate, and boron, which are used in general black and white developing solutions. pH adjustment and buffer functions such as acids and alkalis, amines, etc., inorganic development inhibitors such as bromkali, penzimidazole, penztriazole, and nitroindazole shown in British Patent No. 1376600, etc. It is optional to add organic development inhibitors such as.

(Examples) The present invention will be explained in more detail with reference to Examples below, but the embodiments of the present invention are not limited thereto.

(Example 1) <Preparation of emulsion layer coating solution> An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution at 60°C in the presence of rhodium ammonium chloride.
Add at the same time with stirring until the average particle size is 0.17μ
A silver bromide cubic monodisperse emulsion was prepared. This was washed with water and desalted using a normal sedimentation method, and then the pH was adjusted to 7.0, and the p and Ag were adjusted to 7.5.
Add 0 mg of thiourea dioxide and incubate at 60 °C for 70 min.
It was heated for a minute to impart fog nuclei to the silver halide grain surfaces. A stabilizer was added to this pre-fogged direct positive emulsion.
), lN11COC1I□SO□CII=CI+□)n
=2.3 and phenoxyethanol was added as a preservative.

<Preparation of bluish dye emulsion> 2 g of Exemplary Compound D-8 was added to 10 g of Talesyl Phosphate.
0 d dissolved in 50 ml of ethyl acetate was mixed at about 60°C with a 12% aqueous gelatin solution 800 containing 7 g of dodecylbenzenesulfonic acid in solid content, and stirred vigorously using a homogenizer to prepare an emulsifier dispersion.

<Preparation of subbing layer> The following fluorescent brightener <a> was 2o0mg/rIf, gelatin was 1.5g/rrr (compound (b) was 20mg/rIf).
ryr) In addition, the following bluish dye emulsion and dye are listed below.
A coating solution was prepared so that the amount added was 1.

0 <2''> (b) Preparation of protective layer> Gelatin was 1.5 g/nf, polyethyl acrylate l-
The solid content of the dispersion is 0. 3g/rtr, particle size 3μ
m amorphous SiO. Matting agent 40mg/rr? A coating liquid containing a fluorine-based surfactant C311 sodium fulhenzenesulfonate represented by the following structural formula as a coating aid.

An emulsion layer is placed on top of the undercoat layer, and a protective layer is placed on top of the undercoat layer. Polyethylene laminate 1 to paper (containing 15 wL% titanium white in the surface laminate layer) with a thickness of 150 μm is coated on a support in an amount of 1 g/nf of silver. Sample No.
, 1 to 7 were prepared.

Evaluation of brightness> The sample obtained in this way was
After exposure with a 607-type printer, a fixing solution with the following composition (Fixer Ll'-308 manufactured by Fuji Photo Film Co., Ltd.) was used, and using a Fuji Photo Film Co., Ltd. FC360F (development was carried out at 38°C 20''). ) processed.

Developer composition><Evaluation of safelight safety> An unexposed sample was left for 4 minutes under a 4001 ux light intensity of a UV-cut fluorescent lamp, and the blackening density (when subjected to the above treatment) was expressed.

The results obtained are shown in Table-1.

It is understood that Samples 3 to 7, which are embodiments of the present invention, exhibit good performance in terms of brightness and safelight safety.

Claims (1)

[Claims] In photographic paper having at least one layer consisting of a prefogged direct positive silver halide emulsion, λmax
direct positive type silver halide photographic paper, characterized in that it contains a compound having a wavelength in the range of 350 to 600 nm and a bluish oil-soluble dye.