JPS63201647A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the sweating phenomenon of the titled material due to a lipophilic additive by incorporating the lipophilic additive for photography which is dispersed with a lipophilic surfactant without using a high boiling point org. solvent, in the hydrophilic colloidal layer of the titled material. CONSTITUTION:The titled material contains said additive which is dispersed with the lipophilic surfactant without using the high boiling point org. solvent in at least one layer of the hydrophilic colloidal layers. The lipophilic surfactant used for dispersing said additive in the hydrophilic colloidal layer without using the high boiling point org. solvent, is composed of an anionic surfactant having one of an aliphatic hydrocarbon group contg. at least 15 carbon atoms or having at least two aliphatic hydrocarbon groups contg. at least 17 total carbon atoms. Thus, the sweating phenomenon of the titled material due to said additive is improved.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically to a silver halide photographic material having improved perspiration properties using an oleophilic m-additive for photography.
This invention relates to silver oxide photographic materials.

[Invention'I! Scenery]

Generally, in photosensitive materials, cyan, magenta, and yellow foggers are contained in the hydrophilic colloid layer to form dye images. these turnips 2
A water-insoluble organic group (for example, a long-chain alkyl group) called a ballast group is introduced into - to prevent diffusion that causes color mixing. Therefore, in order to disperse the coupler in the hydrophilic colloid layer, it is necessary to dissolve the coupler in a water-insoluble high-boiling organic solvent to make a uniform solution, then dissolve it in a low-boiling organic solvent and disperse it using a surfactant. However, this method requires high boiling temperature and
There is a drawback that a so-called "sweating" phenomenon occurs in which simultaneously dispersed lipophilic additives such as alpha organic solvents and couplers ooze out onto the surface of the photosensitive material.

This problem has been addressed by methods such as reducing the amount of high-boiling, ζ organic solvents used, but reducing the amount used deteriorates dispersion stability and can lead to troubles such as coupler precipitation in the hydrophilic colloid layer. There was a limit to the number of deaths.

In addition, Japanese Patent Publication No. 59-33904 discloses a technique for dispersing a specific cyan coupler using only a surfactant with a boiling point of 102°C or less without using a high-boiling point organic solvent, but the dispersion stability is insufficient and cannot be put to practical use. Furthermore, JP-A-61-193144 describes that dispersion can be achieved using petroleum sulfonate alone. However, petroleum sulfonate contains non-sulfonated mineral oil and essentially uses a high-boiling point organic solvent, making it impossible to prevent sweating.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a color photographic material free from the sweating phenomenon caused by lipophilic additives.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic light-sensitive material in which at least one hydrophilic colloid layer contains a lipophilic photographic additive dispersed using a lipophilic surfactant without using a high boiling point organic solvent. achieved by.

The present invention will be explained in more detail below.

In the present invention, the lipophilic surfactant used to disperse the lipophilic photographic additive into the hydrophilic colloid layer without using a high-boiling organic solvent is a single aliphatic surfactant having at least 15 carbon atoms. Anionic surfactants having either hydrocarbon groups or 8 at least two aliphatic hydrocarbon groups having a total of at least 17 carbon atoms.

Examples of anionic surfactants preferably used as a dispersant according to the present invention include those represented by the following general formulas (1) to [■].

General formula (1) In the formula, R represents a hydrogen atom or a methyl group, R1 and R2 each represent a hydrogen atom or an alkyl group or alkenyl group having 1 to 40 carbon atoms, and the number of carbon atoms of R2 and R2 is The total is 17 or more. W is -C00N, 5O
yH or 10PO(014)2, and M represents a hydrogen atom or a cation. a represents 0 or 1, - is R
When R is a hydrogen atom, it represents an integer of 0 to 10, when R is a methyl group, it represents an integer of 0 to 50, and n represents an integer of O to 4.

General formula (II) U K In the formula, R5 represents a furkyl group or an alkenyl group having 15 to 40 carbon atoms, and b represents 0* or 1.

R, W, -, n and a are R1W in general formula (1)
It has the same meaning as %, n and a, respectively.

General formula (II) In the formula, R4 and VRs each represent an alkyl group having 1 to 40 carbon atoms, and the total number of carbon atoms of R4 and R is 17
The above 1M has the same meaning as M in general formula (1).

General formula [■] R, -^-(B)n'X In the formula, R6 and R1 each represent an alkyl group or an alkenyl group having 1 to 40 carbon atoms, and R6 and 502MCl1□000- represents a trivalent group as shown, B represents a fullkylene group, oxyethylene group, or oxypropylene group having 1 to 10 carbon atoms, and X represents 1000
M, -SO,M, -〇SO,M, -01'0(ON)2
0M represents the general formula (1
) is synonymous with M in ).

(V) No, 5-CIICOOR.

CH, C0OR.

In the formula, R8 and R1 each represent an alkyl group having 6 to 40 carbon atoms WL, and the total number of carbon atoms of R6 and R1 is 1.
6M, which is 7 or more, has the same meaning as M in general formula (1).

General formula (VI) where Ro. , R11 and R12 each represent a hydrogen atom or an alkyl group having 3 to 30 carbon atoms Wt, and the total number of carbon atoms of R1゜, RIl and RI2 is 17 or more. 0M has the same meaning as M in general formula (1). be.

General formula [■] R + zX In the formula, R13 represents an organic group having an alkyl group or alkenyl group having 15 to 60 carbon atoms including a branch having 4 or more carbon atoms, and X has the same meaning as X in general formula [■] It is.

General formula [■] Rl 4- X In the formula, R8 is at least one -OR+s or 10C
OR, an organic group having an alkyl group having 4 to 30 carbon atoms or an alkenyl group having a substituent of 5 (having 1 carbon atom)
7 or more), RI5 represents an alkyl group, alkenyl group, alkaryl group or alkenylaryl group having 1 to 30 carbon atoms, and X has the same meaning as X in the general formula [■].

Among the surfactants represented by general formulas [13 to [■], (1
), (II], l'), (V), [■] and [■] are preferred, and (1), (■), [■], [■] and [■] are particularly preferred.

Specific examples of the lipophilic anionic surfactants represented by (1) to [■] above (hereinafter referred to as the active agent of the present invention) used in the present invention are shown below, but the present invention is not limited thereto.

It-I C1tH*5OsO-NaIf-2C
, Mountain, 0 (C11□C1120),. 11-3 in S03
Cl-)13i0(CHzCHO)+0(CH
2) 4S03NILU 4 CIJzsOPO
(ONa)zIt -5Cl 5HsscOO(CHz
CHzO)isOiNaN-I CJI+5CO
N(CH2)zsOJaC,H,FIV-2C,,I2. C0NCl1. C) C, H, to I2COO.

■3 Ce111tsO□NcJlzcH2sO
JaCl1lH21 C.H.? N-8Cl 2H25sOJc11zc00 (CI2
C00C)-CHtCH2SOJaC-HI? N-9CsH+tNCHzO3OJa C1□Ls V-I CLCOOC+21hsNa0
J -CHCooCI $H3)V -2CH2C00
C. +121 Na0=S CHCOOC+oHi+■-I
C,H,,Cll0SO,NaCIHI? ■-2C+J2sCHCH*5OJa C, H,.

■-3C, □H23CHCH2SO, C, H,.

Ca1ls　　　　　CHA OC, I+,.

■-4C,H,, Cl1CII2SO, 0COCJL
In the present invention, the lipophilic photographic additives that can be dispersed using the dispersant are those used in the production of photographic materials such as black-and-white photographic materials and color photosensitive materials. , dyes such as lipophilic couplers, ultraviolet absorbers, antioxidants, optical brighteners, anti-capri agents, anti-stain agents, filter dyes, anti-halase dyes, and hardeners to achieve photographic performance. Necessary additives may be mentioned.

Various types of typical lipophilic dye image-forming couplers are used, and examples of lipophilic couplers are listed below.

(yellow dye-forming coupler) C, 511,.

rσ (Magenta dye-forming coupler) M-11 C.I.

(Cyan dye-forming coupler) CJ* C.I. (Mask-forming colored coupler) C! (Development inhibitor releasing DIR coupler) N-3 Next, typical examples of lipophilic ultraviolet absorbers are listed.

Representative examples of lipophilic antioxidants include the following.

O-1 H O ■ O-2 H C.I.

Specific examples of representative fluorescent brighteners (BL) and dyes (F) are shown below.

0I: aH F-3 In the present invention, the amount of the activator of the present invention required to disperse the lipophilic photographic additive varies depending on the type of the photographic additive and the activator, but for example, in the case of a coupler. , 0.1~
It is used in a range of 1% by weight.

Among the lipophilic photographic additives dispersed by the activator of the present invention, preferred are dye-forming couplers and ultraviolet Ig absorbers, with dye-forming couplers having a virazoa azole skeleton being particularly preferred.

Next, a typical method for dispersing a lipophilic photographic additive into a hydrophilic colloidal binder using the activator of the present invention will be described. First, the lipophilic photographic additive is mixed with a low boiling point organic solvent,
For example, it is dissolved in ethyl acetate, methanol, ethanol, etc. To disperse the lipophilic photographic additive thus dissolved in the hydrophilic colloid, the activating agent of the present invention can be dispersed in accordance with conventional methods, for example, using a mixer, a printer, a colloid mill, an ultrasonic wave, etc. Dispersed into hydrophilic colloid using a disperser. II. As the aqueous colloid, all those commonly used as binders for photography can be used.

The dispersion of the present invention is mixed with a hydrophilic colloid binder or a silver halide photographic emulsion to prepare a photographic coating solution by a method similar to a conventionally known dispersion method.

The activator of the present invention is used in the materials of auxiliary layers such as protective layers, interlayers, filter layers, anti-halation layers, pack layers, subbing layers, etc., in addition to the silver halide photographic emulsion layer. It ends with the fact that it can be used for.

When a color photographic material is used as a photographic material, the activator of the present invention can be used in a blue-sensitive emulsion layer, a green-sensitive emulsion layer,
It is used in the constituent layers of color photographic materials, such as each red-sensitive emulsion layer, a yellow filter layer, and various intermediate layers.

〔Effect of the invention〕

In a photographic material containing a lipophilic photographic additive dispersed in a hydrophilic colloid layer using the lipophilic anionic surfactant according to the present invention, the sweating phenomenon is significantly reduced.

〔Example〕

The present invention will be further explained below with reference to Examples, but it is not difficult to carry out the present invention! ! Mr. i is not limited to this.

Example 1 A multilayer color photographic material was prepared by sequentially forming layers having the compositions shown below on a thoria-7tylcellulose film support from the support side.

The coupler and the ultraviolet absorber were dispersed and changed using the surfactants shown in Table 1 (Samples 1 to 14).

1st N: Antihalation layer (IIC) Gelatin layer containing black colloidal silver.

Gelatin 2.2 g/m2 #S2S2 Interlayer (IL) Gelatin layer containing an emulsified dispersion of 2.5-not-t-octylhydroquinone.

Gelatin 1.2g/m2 3rd layer; low-sensitivity red-sensitive silver halide emulsion layer (RL), average grain size (r), 0.30μ, monodisperse emulsion (emulsion) consisting of 8gBrl containing 16mol% of 8g I) --- Silver coating ju1.8g/s+'' Sensitizing dye I -------- 6 x 10-5 moles of sensitizing dye for 1 mole of silver -
---1 mole of silver: 1. OX 10-'Morsian coupler (C-6) 0.06 mol per mol of silver Colored cyan coupler (L-7)---0.003 mol per mol of silver DIR compound (N -5) ------- 0.0015 mol per mol of silver DIR compound (N -6) ------- 0.002 mol per mol of silver Gelatin 1.411/II" 4th layer; High-sensitivity red-sensitive silver halide emulsion layer (RH) Monodispersed emulsion (emulsion n) consisting of 8 gBrl containing 7.0 mol% of average grain size (r) of 0.5 μg (emulsion n)---Silver coating j11. 3g/m2 Sensitizing dye I ------- 3 X to-'mol sensitizing dye n per mole of silver
------- 1.0 per mole of silver. OX 10-% Morcian coupler (C-6) -------0.0 per mole of silver
2 mol colored cyan coupler (L-7)---0.0015 mol per 1 mol of silver DIl+Compound (N-6)---O,001 mol per mol of silver 1.0 g of gelatin /m” 5th layer; Intermediate layer (IL) Same as the 2nd layer, gelatin layer.

Gelatin 1. Og/So2 No. 6M; Low sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion-1----One coating silver 11.5g/So2 sensitizing dye m
------- 2.5X 10-' mole sensitizing dye ff per mole of silver
-------- 1,2X 10-' mole magenta coupler per mole of silver (M -to) --------0.05 mole colored magenta coupler per mole of silver (L-8) ---0.009 mol DIR compound (N -5) for 1 mol of silver --- 0.0010 mol DIR compound (N -7) for 1 mol of silver ------ Silver o, ooao mole gelatin per 1 mole 2.0 g/m2 7th layer: Highly sensitive green-sensitive silver halide emulsion layer (NiH) Emulsion-n--- Silver amount per coating 1.4 g 7 m' Sensitization dye m
------- 1,5X 10-' mol sensitizing dye N per mol silver
------- 1.0 per mole of silver. OX 10-' mole magenta coupler (M-10) -------0 per mole of silver
．． 020 mol Colored magenta coupler (L-8)---0.002 mol per mol of silver DIR compound (N-7)---0.0010 mol per mol of silver 1.8 g of gelatin / Peng 2 8th layer; Yellow filter layer (VC) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of an antioxidant (^o-1).

Gelatin 1.5g/-2 9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL) average grain size (r) 0.48μ theory, Δg containing 8g16 mol%
Monodisperse emulsion consisting of B+4 (emulsion [[[) --- Silver coating j10.9 g/s' Sensitizing dye V -------- 1.3X 10" mole yellow coupler (Y - 6) --------0.00 per mole of silver.
29M gelatin 1.9g/m' 10th layer; high! A degree blue-sensitive emulsion layer (BH) average grain size (r
) Monodispersed emulsion (emulsion IV) consisting of 0.8 μ ring, 8 g 115 mol % of BrI (emulsion IV) --- Silver coating fi 0.5 g/s2 Sensitizing dye V -------- 1 per mole of silver ．． OX 10-' mole Yellow coupler (Y-6) --------0 per mole of silver
．． 08 mol DIR compound (N-6) -------0.0015 mol gelatin per 1 mol silver 1.6 g/m" 11th layer; 1st retention IN (Pro-1) Silver iodobromide ( 3
Gelatin layer containing g11 mol%, average particle size (r) 0.07μ-)-m-silver coating amount 0.5g/So2 ultraviolet absorbers U-7 and U-9.

Gelatin 1.2 g/m" 12th M; 2nd Preservation II (PTO-2) Polymethyl methacrylate particles (average particle size 1.5 microns) Ethyl methacrylate dimethyl methacrylate dinotacrylic acid copolymer particles (average particle size 2.5μ-) CJ+ 7SO,NC)+2COONIL
Long/m'C,H.

and a gelatin layer containing a formalin scavenger ()IS-1).

Gelatin 1.2g/2 bites In addition to the above composition, each layer contains a gelatin hardening agent (H-
1), polyethyl acrylate latex, and a surfactant were added.

Further, a back layer having the following composition was provided on the opposite side of the support from the milk M layer.

Back side 1 @ 1 layer Stearic acid 20-g Diacetyl cellulose 10 mg Back side 2nd layer Stearin l1lj 10 mg Diacetyl cellulose 50 mg Silica matting agent (average particle size 3 μ-) 50 mg The compounds contained in each layer of the photographic light-sensitive material are as follows: It is as follows.

Sensitizing dye 1; Anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; Anhydro 9-ethyl-3,3'-di (
3-sulfoprovir) -4,5,4',5'-nobenzothiacarpocyanine hydroxide 13-sensitizing dye m: 7-hydro5,5'-Schiff,nyl-9-
Ethyl-3,3'-no(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye■; anhydro9-ethyl-3,3'-no(
3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide mt color xv; anhydro 3,3'-di(3-sulfopropyl)-4,5-benzo-5,5' -Dimethoxythiacyanine hydroxide Each of the samples thus prepared was stored for one week at 30° C. and 80% RH to prepare forced deterioration samples.

Thereafter, each sample was placed horizontally, a 1% aqueous solution of sodium hydroxide was added dropwise, and the contact angle was measured using a contact angle measuring device (Goniometer Model G-1 manufactured by Elma). Blank sample (
If the contact angle value increases compared to Sample 7), which is not subjected to forced deterioration, it is considered that sweating is occurring.

Further, each sample was exposed to a wedge of white light, and then subjected to the following development treatment, and the sensitivity and capri were measured.

The sensitivity was expressed as the reciprocal of the exposure amount giving a density of 1J+o, 5, and was expressed as a relative sensitivity with the blank sensitivity as 100.

The results are also shown in Table-1.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline, sulfate 4,75° anhydrous sodium sulfite 4,25° human aquinylamine, 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to make 11.

[Bleach solution]

Ethylenenoaminetetraacetic acid iron heptammonium salt
100g Ethylene-7minetetraacetic acid a2 ammonium salt
to,og heptammonium chloride 150.0g glacial acetic acid
Add 10.0 liters of water and 1
1 and then use ammonia water to adjust the pH to 6.0 to 11! i!
do.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.56 Sodium metasulfite 2.3g Add water to make 11, and adjust to pl+6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5 pieces! Konigutsukusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5m1*-i Ning-g/#! Oil-based additive 1゜1 Comparative compound-1 Petroleum sulfonate (compound described in JP-A-61-193144) Nishiki comparative compound-2 (compound described in JP-A-59-33904) 1 Sample in which sweating was visually observed 12.13 was dispersed by adding tricresyl phosphate (high boiling point organic solution v&) 3 (1*g) in addition to the comparative compound.

As is clear from Table 1, the samples (1 to 11) in which the lipophilic additive was dispersed only with the active agent of the present invention and contained in the hydrophilic colloid layer, even when stored under high humidity. On the contrary, samples using known comparison compounds (12, 13 and V
14), a sweating phenomenon was observed, as well as deterioration of photographic performance such as a decrease in sensitivity and an increase in capri.

Example 2 Color photographic paper was prepared by sequentially coating the following layers on a paper support whose surface was coated with polyethylene containing anatase titanium oxide as a white pigment. The coupler and the dispersant for the ultraviolet absorber were changed as shown in Table 2 (Samples 15 to 22).

1st M: Gelatin sublayer gelatin 1.0 g/Ugly 2 ft52M: Blue-sensitive silver halide emulsion layer ^, emulsion consisting of ΔgBrcl containing 5 mol% CI---coated silver jl
o, 3 g/haze 2 Sensitizing dye Vl ------- 3 X 10-' moles per mole of silver Yellow coupler (Y -8) -------0.
3 mol antioxidant (80-1) ------5067m"
Gelatin 1.2 g/plow 2 3rd layer; middle layer 90-1 ・----10 g/plow 2 Gelatin 0
．． 7g/m'' 4th layer; emulsion consisting of 8gBrc1 containing 115 mol% gc to the green-sensitive silver halide emulsion layer -
---Coated silver NO, 4 g/a'' Sensitizing dye ■----- 3 x 10-' moles per mole of silver Magenta coupler (M-11) ------0 per mole of silver .1 mole 80-1---40-g/-2 Gelatin 1.25g/2 5th layer; Intermediate layer ultraviolet absorber (U3)---10mg/-
m2 6th M; red-sensitive silver halide emulsion layer consisting of 8gBrc1 containing 8gC115 mol% -
11 coated silver R0.4g7m" Sensitizing dye ■-1--.- 3 x 10-mol cyan coupler (C-6) for 1 mole of silver -------0 for 1 mole of silver .1 mol 80-1------40mg/m2 Gelatin 1.411/II2 7th layer; Intermediate layer ultraviolet absorber (U-7) --------1o Sog/Mackerel 2^0 1 ------- 10mg/s" Gelatin 1.0g/s+2 8th R1; Protective layer Gelatin layer containing gelatin hardener (H-1) Gelatin 0.5g/m" The sensitive dyes are as follows.

Sensitizing dye ■; anhydro 5,5'-nochloro 3.3'
-no(3-sulfopropyl)thylrh carbocyanine hydroxide sensitized color 1 Sensitive dye ■; Anhydro-2-(2-((3-1(3-
Ethyl-2-(3H)-benzothiazolylidene)methyl l-5,5'-nomethylcyclohesenylidene)methyl]benzothiazolium]ethanesulfonate Samples 15 to 22 were subjected to forced degradation in the same manner as in Example 1. After that, the contact angle was measured, and the following development treatment was performed to evaluate the photographic performance. Note that sample 18 before forced deterioration was used as a blank. The results are shown in Table-2.

Processing process (38℃) Color development 3 minutes 30 seconds Bleach constant 11
Wash with water for 11 minutes and 30 seconds and dry for 3 minutes and 30 seconds.
The composition of the treatment liquid in each 1-minute treatment step is as follows.

[Color developer]

4-7mi/-3-methyl-N-ethyl-N-(β-notanesulfone-7midoethyl) 7niline sulfate 4,0°Hydroxylamine sulfate 2.0g Potassium carbonate 25,0°Sodium chloride-0 , 1g Sodium Bromide 0.2g Anhydrous Sodium Sulfite 2.0g Bennol Alcohol 10.0ml Polyethylene Glycol (Average Degree of Polymerization 400) 3.0ml Whitex (Fluorescent Whitening Agent, Sumitomo Chemical Co., Ltd.) 50%
Aqueous solution: Add 2.0 liters of water to bring the solution to 11, and adjust the pH to 10.0 using sodium hydroxide.

[Bleach-fix solution]

Ethylenenoaminetetraacetic acid iron ammonium salt
so,og Ammonium thiosulfate 100.0゜ Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water and make 11
and adjust the DH to 7.0 using sulfuric acid.

Table 2 *1 g of oily additive (g/a) Comparative compounds 1 and I/2 are the same as those in Example 1 Sample 20. Sample No. 21 was dispersed by adding 15 g of triflecul phosphate in addition to the comparative compound.

Table 2 shows that even in color photographic paper, the samples according to the present invention suppressed the sweating phenomenon and exhibited stable photographic performance.

Applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment ,f′,“ May 10, 1986

Claims (1)

[Claims] A silver halide photographic light-sensitive material, wherein at least one hydrophilic colloid layer contains a lipophilic photographic additive dispersed using a lipophilic surfactant without using a high-boiling point organic solvent.