JPS62115151A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the contamination of a developing soln. and a roller by incorporating latex having hydrophilic groups fixed on the surface and a nonionic surfactant into at least one of antistatic layers. CONSTITUTION:Latex having hydrophilic groups fixed on the surface and a nonionic surfactant are incorporated into at least one of antistatic layers. The latex is obtd. by converting latex into protective colloid with a polymer having hydrophilic groups or by allowing a compound having a hydrophilic group to take part in a latex forming reaction so that the compound is distributed on the surfaces of latex particles. The hydrophilic groups contribute toward stabilizing the latex. Any of synthetic and natural water soluble polymers may be used as the polymer having hydrophilic groups. Since the latex having hydrophilic groups fixed on the surface is used in combination with the nonionic surfactant, satisfactory antistatic properties are provided and the contamination of a roller is remarkably improved without exerting unfavorable influence on the photographic characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material that relies on good antistatic properties.

[Background of the invention m] Silver halide photographic exposure 1ll (hereinafter referred to as photographic exposure 1.!l)
Call it E. ) generally consists of an electrically insulating support (1) and a photographic constituent layer (1) 11, so there is no contact between the inside of the culm and the surface of the material used in the production of photographic light-sensitive materials. M; Mo 1 dormitory or! III+ By removing tJt, electrostatic charge is often stored (tl).

This accumulated electrostatic charge causes many problems, but the most serious problem is that the electrostatic charge accumulated in the developing process is discharged. When photographic film is exposed to light and subjected to processing, dot-like stub marks or dendritic or feather-like streaks occur. i 1fff becomes significantly obsolete.For example, if it is specified as a medical or industrial X-ray film, it will lead to a very dangerous judgment.This phenomenon becomes obvious only after development and is very troublesome. This is one of the major problems (6).In addition, these accumulated electrostatic charges can cause secondary failures such as dust adhesion to the film surface and uneven coating. b 4iru.

Such electrostatic charges are often accumulated during the production and use of the above-mentioned photographic light-sensitive materials. This occurs due to separation of the support surface and emulsion surface during the process. In addition, in finished products, separation of the base surface and emulsion surface occurs when the photographic film is wound and changed, or between mechanical parts or fluorescent intensifying screens in automatic photographing machines for X-ray film. Occurs due to contact separation, etc. It can also occur due to contact with other packaging materials.

The photosensitive material r induced by the accumulation of such electrostatic charges
The static marks of No. 1 become more noticeable as the sensitivity of photographic materials increases and the processing speed increases.

Particularly in recent years, as photographic materials have become more sensitive and more machines are subjected to harsh handling such as high-speed coating, high-speed removal, and high-speed automatic development processing, layer static marks are more likely to occur. It has become.

In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic photosensitive material O'1. However, the antistatic agents that can be used for photographic photosensitive materials cannot be the antistatic agents that are generally used in other molecules I, and are subject to various restrictions specific to photographic photosensitive materials. In other words, Zj: T, '; Performance requirements include not giving negative impressions (71), not accelerating the fatigue of the photographic photosensitive processing solution, not contaminating the conveyance roller, and not reducing the adhesive strength between the constituent layers of the photographic photosensitive material rN1. However, the application of antistatic agents to photographic materials is subject to numerous restrictions.

One way to eliminate these problems caused by static electricity is to increase the electrical conductivity of the photosensitive surface so that the static charges can be dissipated in a short time before the accumulated charges are released. It is.

Therefore, methods have been considered to improve the conductivity of the support and various coated surface layers of photographic photosensitive material R1, and various hygroscopic substances and water-soluble Attempts have been made to use surfactants such as poly7-.

Among these, surfactants with antistatic ability are small in size, and are described in US Patent No. 3, for example. (No. 182, 123, 3, 20
No. 1,251, 3.519.5 (i1?i, 3.519.5).
[i25.695, West German Patent No. 1,552,40
No. 8, No. 1,597,472, JP-A-49-8582
No. 6, No. 53-129623, No. 54-1592
No. 23, No. 48-19213, Special Publication No. 46-3931
No. 2, No. 49-11567, No. 51-46755,
Anionic, betaine and cationic surfactants described in JP-A No. 55-14417, etc., or JP-A-52
-80023, West German Patent No. 1,422.809, West German Patent No. 1,422,818, Australian Patent No.
Nonionic surfactants are known, such as those described in No. 4.441/1959.

However, these materials exhibit specificity due to differences in film support type and photographic composition, giving good results for certain film supports and photographic emulsions and other photographic components, but not for other different film supports. The body and photographic constituent elements may not be at all good at preventing static electricity, or even if the antistatic property fQ is excellent, it may have a negative impact on photographic properties such as sensitivity, fog, graininess, and sitopness of the photographic emulsion. It has been extremely difficult to apply these materials to photographic photosensitive applications because they cause staining, contamination of the processing solution, and roller sludge.

In addition, antistatic technology using a nonionic interfacial talking agent is
It is closely related to the liniment used together.

However, although progress has certainly been made in terms of anti-static performance, the contamination of the developing processing solution and the contamination of the transport roller have not been reduced at all, which can lead to serious film failure. What is the cause?

For example, the ethylene oxide addition polymer of phenol-formalin composite described in Japanese Patent Publication No. 51-9G10 has been described as having excellent anti-static properties when used with various coating agents. However, the method of the patent does not solve problems caused by contamination during the development process.

In other words, the roller stains, which are thought to be caused by dry deposits on the transport rollers, are extremely bad and cause problems in terms of density unevenness in the film.

Also, JP-A-53-29715, 1Fil Go-7
G 741 YJ describes a photographic light-sensitive material containing a specific anionic surfactant and a polyoxyethylene nonionic surfactant, but as with the previous patent, there is a risk of contamination of the developing processing solution and contamination of the transport roller. No improvement in film failure can be obtained.

It is known that a fluorine-containing surfactant is used as another means of improving antistatic performance. This method utilizes the negative chargeability of fluorine groups to reduce the power generation performance of the film, thereby reducing the occurrence of static marks. For example, British Patent No. 1.259.398, U.S. Patent No. Re-29,255, U.S. Patent No. 4.013,696, Equity Uri No. 48-43130, and JP-A-11-4B-5.
No. 2,223, No. 50-16525, No. 52-127
No. 974, No. 54-48520, No. 55-25077
For example, the number etc.

Furthermore, Japanese Patent Application Laid-Open Nos. 60-76742 and 60-80849 disclose techniques in which a fluorine-containing compound and a nonionic surfactant are used in combination.

However, although improvements in charging performance can be seen in some cases by following these methods, there are various problems encountered in the processing process.
In other words, the problem of density unevenness caused by contamination of the transport roller caused by contamination of the processing solution has not yet been sufficiently resolved.

[Object of the Invention] The first object of the present invention (311, current!) To provide a photographic photosensitive material RL that does not cause contamination of cQ processing liquids or rollers, etc., and has antistatic properties. It is in the fact that

The second Lf l+'v c of the present invention is good without giving any bad shadow ν5 to the special bamboo which desensitizes etc. '<1: Lightning protection 1
1- To provide photographic materials with excellent properties.

[Structure 1 of the Invention The object of the present invention is to provide a photographic film 114 having at least one antistatic layer on a support L, and to provide a silver halide photographic photosensitive layer 1'+1 with the above-mentioned At least one layer of the antistatic layer contains a latex and a nonionic surfactant on which hydrophilicity is fixed.

[Specific Structure of the Invention] In the present invention, a hydrophilic group is fixed in the margin below the surface of latex, which means a state in which the latex is made into a protective colloid by a polymer having a hydrophilic group, or a hydrophilic group. This refers to a state in which a compound having a group participates in the latex formation reaction and is placed on the surface of the latex particle, and both contribute to the stabilization of the latex.

The state in which latex is converted into a protective colloid by a polymer having a hydrophilic group is a state in which the polymer having a hydrophilic group is strongly adsorbed and immobilized on the surface of the latex. In addition, the state in which a compound having a hydrophilic group participates in the latex formation reaction and is placed on the latex particle surface refers to a state in which a compound having a hydrophilic group (e.g., a polymer having a hydrophilic group, a hydrophilic compound in the molecular structure) There are polymers that have both ethylenic groups and ethylenic double bonds, and compounds that have hydrophilic groups and groups that are easily chain-transferred by radicals during the formation of molecules (M4), etc.) that participate in the latex formation reaction, and these compounds A part of the particles is covalently bonded to the latex and fixed on the surface of the latex particles.

Polymers having hydrophilic groups include 1.11 synthetic water-soluble polymers and natural water-soluble polymers, both of which can be preferably used in the present invention. Among these, synthetic water-soluble polymers include those having, for example, nonionic groups, anionic groups, and nonionic 3'A and anionic groups in their molecular structures.

Examples of the nonionic group include an ether group, an ethylene oxide group, and a hydroxyl group, and examples of the anionic group include a sulfonic acid group or its JR, a carboxylic acid group or its salt, phosphorus ML1 or its salt,
etc. can be mentioned. Natural water-soluble polymers include those having, for example, nonionic groups, anionic groups, and nonionic and anionic groups in their molecular structures.

Polymers with hydrophilic groups include synthetic water-soluble polymers and natural water i8 (!l polymers), in which case b stands for the anionic group, and b stands for the nonionic group and the anion 11 group. It can be preferably used.In the present invention, a polymer having a hydrophilic group is defined as
It is sufficient to dissolve 0.05g or more in 100g of purified water.
Preferably it is 0.1 g or more.

Examples of synthetic water-soluble polymers include those containing 10 to 100 mol% of repeating units represented by the following general formula ['] in one polymer molecule.

General formula [P] ■ In the formula, R1 is a hydrogen atom or an alkyl group, preferably having 1 to 7 carbon atoms! I's alkyl group (including those having substituents; for example, methyl group, ethyl group, propyl group, butyl group, etc.), halogen atom (for example, chlorine atom) or -C
82C00M, I- is -CONH-1-NH
C0-1-COO-1-0C0-1-CO- or 10-, and J is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those with the right substituents).

For example, methylene group, ethylene group, propylene group, trimethylene group, butylene L! , hexylene group, etc.), arylene group (also includes an exchangeable group).

For example, phenylene group), or -CG H2C, H20) Y rho-6CI-12
→7[=(m is an integer from 0 to 40, n is an integer from 0 to 4, 10M, -NH2, -803M, -0-P-OM.

! 0M -CR2, does not represent a hydrogen atom or R3, but this 0M
-305M is most preferred. M represents a hydrogen atom or a cation, R2 represents an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), and R3, R4, R5, R6, R7 and R8 are represents an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc.), X represents an anion, and p and q each represent O or Represents 1.

Next, specific examples of the synthetic water-soluble polymer of general formula [P] will be given.

Margin below SP-1 number average molecular weight Mn P-2 P-3 P-4 P-5 5P-6 SP-7 P-8 CH3 ■ P-10 CH3 ■ P-11 P-12 SP-14 P-15 ! 5 SP 17 CH.

■ 5P-1,8 P-19 P-20 9,000 G S　P　-21 P-22 P-23 P-24 P-25 5P-26 SP-27 P-28 SP-29CH.

"P-30 P-31 o3Na 163.000 P-32 P-33 P-34 P-36 SP-37So 50 -fcH2-'CH÷
7,3000OH CH'= Musical accompaniment 5P-38,1060 (CH2-CJ-2,,700■ OOH CI+.

5P-396040 (CI(2-C→-4,800C0
0CHZCH2SO0Na CH.

5P-47 The synthetic water-soluble polymer of the present invention can be easily synthesized by various methods such as solution polymerization, bulk polymerization, and suspension polymerization.

For example, in solution polymerization, a mixture of monomers at an appropriate concentration (usually 40% by weight or less, preferably 10 to 25% by weight M% based on the solvent) in an appropriate solvent (e.g., ethanol, methanol, water, etc.) is generally used. a polymerization initiator (e.g.
benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at an appropriate temperature (e.g. 40°C).
The copolymerization reaction is carried out by heating to 120°C to 120°C, preferably 50 to 100°C. The reaction mixture is then poured into a medium that does not dissolve the water-soluble polymer produced.
The unreacted mixture is separated off by settling the product and then drying it. The molecular weight of the water-soluble polymer of the present invention is i, ooo to 1. Goo, 000° is preferably 2,000 to 200,000.

The molecular weight of the water-soluble polymer of the present invention is expressed in number average molecular weight (♀), and was measured in terms of standard polystyrene using Gel Vermeation Chromatography-HLC-802A manufactured by Toyo Soda.

Synthesis Example 1 (Exemplary Compound 5P-18) 3-Sulfobobyl acrylate potassium salt 50 (]
(00,22 mol, 4./l'-azobis(4-cyanovalein u) 3.00 and greasy water 200,
Three units of Q were placed in a flask, and the mixture was reacted at 80°C for 8 hours. After the reaction is completed, the reaction solution is poured into a large amount of acetic acid solution while stirring vigorously to precipitate the reaction product. Next, the precipitate was filtered, washed with acetone, and dried in air at 60°C to obtain polymer 5P-18 of the present invention. The yield was 45 g (90% of the theoretical yield), and the number average molecular weight was 4,300 Mn.

Synthesis Example 2 (Exemplary Compound 5P-21> Styrene 52 (+ (0.50 mol), Acrylic Acid 3
6 (1 (0,50 mol), /1./I'-azobis(4
- 5.0 g of Ciatsuvalein M) and 500 g of greasy ethanol were placed in a third flask, and the mixture was subjected to an IFJ reaction at 8 o'clock under reflux. After the reaction is complete, pour into a large amount of acetone while stirring vigorously, and proceed to Synthesis Example 1.
Polymer 5P-21 of the present invention was obtained by the same treatment as above. The yield S was 80 (+ (91% of the theoretical yield)), and the number average molecular weight Mn = 2,600.

Synthesis Example 3 (Exemplary Compound 5P-42) Hydroxyethyl methacrylate 520 (0.40 mol), sodium 2-acrylamido-2-methylpropanesulfonate 137 (] (00.60 mol, 4.4'
- 5.0 g of azobis (4-cyatubarein M), and
Degassed water-ethanol-80/20Vχ solution 500-
Three of these were placed in a flask, and the mixture was reacted at 80° C. for 10 hours. After the reaction was completed, the reaction solution was poured into a large amount of acetone while stirring vigorously to precipitate the reaction product.

Then, the precipitate was filtered, washed with acetone, and dried in air at 60°C to obtain polymer 5P-42 of the present invention. Yield is 1
Number average molecular weight Mn = 80g (95% of theoretical yield)
It was 5,300.

Natural water-soluble polymers are described in detail in the Comprehensive Technical Information Collection of Water-Soluble Polymer Water-Dispersible Resins (Management Development Center Publishing Department), but include lignin, starch, pullulan, cellulose, alginic acid, dextran, dextran, and guar gum. , gum arabic, glycogen, laminaran,
Lignin, nigeran, etc., and their derivatives 7:l
L, yes.

Further, as derivatives of natural water-soluble polymers, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carbo4nidial4:renated, alkylphosphorylated derivatives, and 3B thereof are particularly preferable.

In the present invention, two or more natural water-soluble polymers may be used in combination.

In addition, among natural water-soluble polymers, glucose polymers and their derivatives are 1) T-like, glucose polymers,
Among these, Fl powder, glycogen, cellulose, lignin, dextran, nigeran, etc. are preferable, and des:1-lan and its derivatives are particularly preferable.

Dextran is a polymer of α-1, 6X', and 7-conjugated D-glucose, and is generally produced by culturing dextran-producing bacteria in the presence of sugars.
Dextran sucrase isolated from the culture solution of dextran-producing bacteria such as Nostoc and Mesenteroides can be obtained by reacting with saccharides. In addition, these native dextran can be lowered to a desired molecular weight by a partial decomposition polymerization method using an acid or alkaline enzyme, and a product having an intrinsic viscosity in the range of 0.03 to 2.5 can be obtained.

In addition, dextran modified products include dextran sulfate ester and its salts in which the @ acid group exists in the dextran molecule as an ester bond, carboxyalkyl dextran in which the carboxyalkyl group exists in the dextran molecule as an ether bond, and carboxyalkyldextran hM'H esters in which a sulfate group is present in an ester bond and a carboxyalkyl group in an ether bond, and salts thereof; dextran phosphate esters in which a phosphate group is present in a dextran molecule in an ester bond, and salts thereof. , hydroxyalkyldextran in which a hydroxyalkyl group is added to the dextran molecule.

The use of these dextrans in silver halide 9 page photosensitive 14 II is disclosed in Japanese Patent Publication No. 35-11989, U.S. Patent No. 3,762,924, and Japanese Patent Publication No. 12820-1973
No. 45-18418, No. 45-40144),
4 (I-31192), these dextrans are incorporated directly into a silver halide emulsion or a gelatin layer to improve the covering power of a developed silver image and to improve the coverage of the developed silver image. Improves density and contrast.

Of these dextrans and their derivatives! The II manufacturing method is described in detail in these special features.

Among these dextrans and their modified products, particularly preferable are anioleic j
Among them, dextran sulfate, carboxyalkyl de-4-nistran sulfate, and dextran phosphate are the most preferred.

These dextran-producing bacteria can be synthesized by using the aforementioned dextran as a raw material and reacting it with a sulfating agent such as chlorsulfonic acid in the presence of a hydrochloric acidic organic solvent such as pyridine or formamide to obtain dextran 51 ester.

Furthermore, 0) carboxyalkyl such as lecarboxylic acid Quitran sulfate is obtained.

Furthermore, carboxyalkyldextran can be obtained by using dextran as a raw material and reacting it with a carboxyalkylating agent such as monochlorocarboxylic acid in an alkaline environment. Furthermore, if this is reacted with a sulfurizing agent such as chlorosulfonic acid in the presence of a basic solvent such as pyridine or formamide, the carboxyl 1117128
921M ester can be obtained. If this is reacted with oxides of alkali metals such as sodium and potassium, oxides or hydroxides of alkaline earth metals such as calcium and magnesium, ammonia, etc., the resulting salts of dextran sulfate and carboxyalkyl sulfate, respectively. is obtained.

Dextran has three hydroxyl groups that can be substituted per anhydroglucose unit, so 1! [! In terms of H, the maximum degree of substitution is IM up to 3! The ester group and the carboxyalkyl group can be substituted, but the reaction conditions can be selected and any substitution can be made within the range of a degree of substitution of 3 or less.
It can be manufactured to a certain degree.

However, the sum of the degrees of substitution of the sulfate ester group and the carboxyalkyl group cannot exceed 3.

The carboxyalkyldextran boxyalkyldextran sulfate ester produced in this manner can be produced by varying the intrinsic viscosity of the raw material dextran and by various combinations of the degree of substitution of the sulfate ester of the 1-acid and the degree of substitution of the carboxy-4-dialkyl ester. It is possible to manufacture similar products.

As for polymers having a hydrophilic group and an ethylenic double bond in the molecular structure, it is desirable that the polymer has a compound represented by the following general formula [VI] [Vt] or [■1] as a main component. J Nijii.

Here, examples of the hydrophilic group include the same ones as those mentioned for the polymers that refer to the hydrophilic group.

General formula [Vi[] [wherein R1 is 21i!] The organic group of li, Ml, represents a hydrogen atom or a monovalent cation, nl represents 30 to 95 mol%, and R2 represents 70 to 5 mol%. General formula [W] C8 2 COOH3 M2, Ms. M4 and M5 each represent a hydrogen atom or a monovalent cabone, R3 represents 30-95'U nyl%, nl represents 70-0 mol%, and R5 represents 70-0 mol%. However, nq+n5 is 70 to 5 mol%. ] General formula [■] R'a [wherein R'a is a hydrogen atom or an alkyl group, M6,
My, Ms and M9 each represent a hydrogen atom or a monovalent cabone, R6 is 30 to 70 mol%, R7
represents 5 to 50 mol%, and R8 represents 70 to 5 mol%. However, n7+n6 is 70 to 30 mol%. 1 Next, to specifically explain the general formulas [VI], [■1 and [■], the divalent organic group represented by R1 is ethylene, 1-herimethylene, tetramethylene, hequinamethylene, propenylene, and 3.

Divalent residues of aliphatic hydrocarbons such as 6-thioxaoctane-1,8-diyl, 2,2-dimethyltrimethylene, propylene, 1,4-cyclohexylene, or 1,2-dichloroethylene, 2 -Halogen atoms, cyano groups, alkyloxy groups, aryloxy groups, etc., such as chlorotrimethylene, 2-bromotrimethylene, 1-cyanomethylethylene, 1-chloromethylethylene, 1-methoxymethylethylene, 1-phenoxyethylene, etc. or 1,4-phenylene, 1,3-
Divalent residues of aromatic hydrocarbons such as t-rylene, 2-chloro-1,4-phenylene, 2-cyano-1,4-7-enylene, 2-methoxy-1,5-phenylene or halogen atoms, cyano or 1.1'-(1,4
-phenylene) dimethyl, 2,2'-(2-chloro-1
, 4-phenylene) diethyl, 2,2'-(2-cyano-1,4-phenylene) diethyl, etc., or an aryl group substituted with a halogen atom, a cyano group, etc. Examples include divalent residues of aliphatic hydrocarbons.

Ml, M2, M3. M, 13 and M5 represent a hydrogen atom, a monovalent cation of an alkali metal such as lithium, sodium to lithium, or potassium, or an ammonium cation. As a polymer having a hydrophilic group and an ethylenic double bond in its molecular structure, a compound represented by the general formula [VI] is preferable.

Next, typical examples of the polymer of the present invention will be exemplified below, but the invention is not limited thereto.

” lower margin (however, nt: n2 = 50 mol%: 50 mol coefficient, number average molecular weight (Mn) = approximately 10.000) 70 mol%
, Mn = approximately 6,000) 5 molar ratio, Mn = approximately 20,000) (However, ro: n2 = 75 molch: 25 molar ratio, Myt
- about 20,000) (ru: n2 = 50 moles Ll): 50 moles, M
n-about 25,000) D-7 (However, old: n2 = 30 mol% near 0 mol ratio, My1 =
Approximately 1=,000) M)-1=15,000) ■ CH2C0NHCH2CH25O3Na (however, nl:
n2=: 50 mol%: 50 mol ratio, M+1 - about 2,00
0) Cl42CUONa CH2CONHC[2CI-T2 S 03 Na (however, nI: nl: )13==8Q mol%: 10 mol%=10 mol%, Mre=about 6,000) CH2C
0NCH2C) (2sO3NaCH3 (however, nl:nz=95mol%=5molti, Mh-
Approximately 3,000) :! ,9 C011,lHCH2CH2S O3N a (however, n
I: n2=50 moyb%: 50 mo, +L-%,
Mn = approximately 10,000) CH3 (However, nl: nl: ns = 50 mol%: 4
5 mol%: 5 mol%, R4n-about 15,000) Synthesis of these polymersッ, IJ, JP-A-55-502
It is described in No. 40.

Examples of the hydrophilic group of a compound having a group in which a hydrophilic group and a radical are easily chain-transferred in the structure of the molecule 1i4 include polymers having a hydrophilic group similar to those of '111be/, :'t, +'. It will be done.

Furthermore, a group in which a radical is likely to undergo chain transfer refers to a group in which an active point is likely to transfer, such as a polymerization initiator radical generated during polymerization of a polymerizable unsaturated compound or a vehicle coalescence growing chain radical, and is preferable. I can do better. However, in the above groups, 1 is a hydrogen atom or an alkylnyl group, RTL is a hydrogen atom, an alkyl group, or a carbonyl group, and X is a hydrogen atom or a halogen atom.

The fact that these groups are easily chain-transferable is shown in "Copolymerization-2-", Polymer Science Society of Japan, Published November 1976, 381.
It is written on the page. And among these groups -3H
1-NHR', -10H2Br are more preferred, -
8H is most preferred.

Groups that are susceptible to chain transfer may have a negative value of the hydrophilic parameter π. In this case, it is preferable that the group that is susceptible to chain transfer and the hydrophilic group are not the same. Further, the number of hydrophilic groups may be at least 1 per molecule, preferably 1 to 4 per molecule, and more preferably 1 to 2 per molecule. When the number of hydrophilic groups is two or more in one molecule, the hydrophilic groups may or may not be the same.

In addition, the number of groups that are easily chain-transferred in one molecule should be at least 1, preferably 1 to 3, and 1 to 2.
More preferably.

Preferably, the compound having at least one hydrophilic group and one group in each molecule that is susceptible to chain transfer of radicals is represented by the general formula [T].

General formula [T] (A-), J→8)1 However, in the general formula [K], Δ is a hydrophilic group, and the details are as described above. B is a group in which radicals are easily chain-transferred, and the details are as mentioned above. m is an integer of 1 or more, preferably 1 to 4, more preferably 1.
It is 2.口 is an integer of 1 or more, preferably 1 to 3
, more preferably 1. J is eight and B jfi J
Anything is acceptable as long as it is chemically bonded via substitution 3. S
Alkyl groups, including those with the right J, buy 19! Examples include a phenylene group including those having a substituent group, a heterocyclic group including a substituent group, and a group in which four of these are combined.

As a specific example of a compound having 11 hydrophilic groups and a group that is easily linked with a radical in its molecular structure, for example, the following compound T-
1 to Compound T-113.

Below margins A, 3 T-], ]HOOC! -CH:! -S.E.T.
-2HOOG-CH2-CH2-8HT-11HO-C
Hl 7,0H7GH2-NH-Co-0xin-19El
■ 0■ T-12HOOC-CHt-NI4-Co-OT]2
-8R"r-1< (HOCzT(4)2N-b-
CIiz-3T4 T-15)%N-02H(-S
HT-20I (000-CH-CHz -8HH2SH 7-28 CH.

Tsu T (OCIC-0-OH, -3H NH□ +-31C6H5T-22 HOO -C-5H) 1000-C, H4-502-C
JI,-C! H2-5HrBH5 -35 Karasu03F-(Oi-12), -5HT-36C
H3-〇-C1(,-5H-d-39Hooc-cI(!
-c■-su T-4[I N201S-(CH
), -8H6H5 T-41Na01S- (01%% -31-I T-42
Na03S-(CH2)4-8l(Ll(.

7-4 g C! -1,.

HOoo-C)i, -C-37,1 CH3 0H.

S　OsN’Hz HC) 0(': N?-i.

)100C T-74EOOC-(cat)4-CH-8HUS-C
H, -CH2 C,H,OH c,Hg I(
IC,H.

C□H3 T-97B rCHl C;! J2 C0OHT 98
B r (OH2)30NT-99CH1rCH
2) tcHBrcOOHl -400'Br(C;
H2)5C;0OHT”101 Br(C) (2 people O
HT-102Br(GHz)tocclOHT-103
ct'cH, co book, T-104CI (CH2
) 40HT-10507 (CHz%0OOH ding-106
CICHt (GHz') zooOHT-107c/rO
H, ), cooHT-1080,s, c*12NHcH
, CFI20H (, H-cH2 OOH v-nz Hs +cEχCH, c-exhaust SO-IH■-1
12 H8-CHxCHx ()-8on H-
, 113C1 (.

HOOC-C-CH,BH CH.

The following margins These compounds (1) to (113) are all known compounds, and some of them are added to the developer as a dark coloring and sludge generation prevention agent as described in JP-A-54-133331. is used.

In the present invention, methods for fixing a polymer having a hydrophilic group on the surface of latex include adding it to the polymerization system as a dispersant before polymerization when producing latex by emulsion polymerization, and producing latex without a dispersant. There is a way to add it afterwards. In the method of adding before polymerization, graft polymerization occurs on the added polymer having a hydrophilic group, which is incorporated into the latex particles and fixed, with the end of the polymer having a hydrophilic group exposed on the surface of the latex particle. Become. In addition, in the method of adding after polymerization, when the polymer having a hydrophilic group is added to the latex, it is heated and stirred at 60° C. or higher for 1 hour, followed by cooling and use. Then, the polymer having hydrophilic groups, which was merely mixed, is strongly adsorbed to the latex surface and becomes immobilized.

This can be seen from the fact that when the viscosity of the system is measured, the viscosity decreases after heating and cooling, resulting in a decrease in the amount of polymers having hydrophilic groups with M separation. In the present invention, it is more preferable to add it before polymerization.

The latex of the present invention can be easily produced by various methods. For example, there are the emulsion method, the method of redispersing the 4-dimensional polymer by solution polymerization, bowl polymerization, etc., but the emulsion polymerization method is preferred.

In the emulsion polymerization method, water is used as a dispersion medium, and the ratio of 10 to 5
Using 0% by weight of monomer, 0.05 to 5% by weight of polymerization U1 initiator to the monomer, and 0.1 to 20% by weight of a water-soluble polymer, the temperature is about 30 to 100°C, preferably 60 to 60°C. 90
It is obtained by polymerization under stirring at ℃ for 3 to 8 hours. The concentration of hexamer, the amount of initiator, the reaction temperature, time, etc. can be varied widely and easily.

The polymer having a hydrophilic group used in the latex of the present invention is preferably used in an amount of 0.1 to 20% by weight, J: more preferably 1 to 15% by weight, based on the monomer ω.

In the present invention, as a method for fixing a polymer having a hydrophilic group and an ethylenic double bond in its molecular structure to the surface of latex, when producing latex by emulsion polymerization, it is added as a dispersant to the polymerization system before polymerization. There is a way to add it.

In this case, the added polymer having a hydrophilic group and an ethylenic double bond in its molecular structure undergoes graft polymerization and is incorporated into the latex particles. It is considered that the terminal end of the polymer having the above properties is exposed on the surface of the latex particle.

In the emulsion polymerization method, water is used as a dispersion medium, and the ratio of 10 to 5
Using 0% by weight of monomer, 0.05 to 5% by weight of polymerization initiator, and 0.1 to 20% by weight of a polymer having a hydrophilic group and an ethylenic double bond in the molecular structure. , about 30-100'C1 preferably 60-90'C
It is obtained by polymerizing under stirring for 3 to 8R.

Monomer concentration, initiator amount, reaction temperature, time, etc. can be varied widely and easily.

The polymer having a hydrophilic group and an ethylenic divalent bond in its molecular structure used in the latex of the present invention is preferably used in an amount of 0.1 to 20% by weight relative to the monomers. is 1 to 15% by weight.

In the present invention, as a method for fixing a compound having a hydrophilic group and a group to which radicals can easily chain transfer to the surface of latex, J
There is a method of polymerizing a polymerizable unsaturated compound in the presence of a compound. By this method, a polymerizable unsaturated compound is bonded to the radical and a compound having a group that is easily chain-transferred via a group that is easily chain-transferred, thereby obtaining a polymer in which a hydrophilic group is introduced into the molecule.

Compounds having a hydrophilic group, J: and a group to which radicals can easily undergo chain transfer in one molecule are used alone or in combination of two or more, and the blend m is the vinyl 7mer 1 that forms the latex.
o, oooi to 0.5% by weight is preferred, and J: more preferably 0.001 to 0.2% by weight based on the weight of 0.00 parts.

A surfactant is normally used as a dispersant during latex production, but it is preferable not to use it in the present invention. When used, dispersion stability often deteriorates.

Examples of the initiator include water-soluble peroxides (e.g., potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (e.g., 2,2'-azobis-(2-amizip-O-pan)-hydrochloride, etc.), etc. be able to.

Examples of the ethylenic monomer compounds forming the latex of the present invention include acrylic esters, methacrylic esters, vinyl esters, olefins, styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric acid diesters,
Acrylamides, allyl compounds, vinyl ethers,
1F selected from vinyl ketones, heterocyclic compounds, glycidyl esters, unsaturated nitriles, and polyfunctional upper 1 various unsaturated acids! Alternatively, a heptamer compound in which two or more strains are combined can be mentioned.

More specifically, these monomer compounds are as follows:
Examples of acrylic esters include methyl acrylate,
■Dellacryl 1~, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate 1~,
Isobutyl acrylate, 5ec-butyl acrylate-1
~, tart-butyl acrylate, amyl acrylate
h, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, terL-A quartz acrylate-1-, 2-chloroethyl acrylate-1, 2-
Propyl methacrylate, 4-chlorobutyl acrylate, cyanethyl acrylate-1-12-acetoxyedyl acrylate, dimethylaminoedyl acrylate,
Benzyl acrylate 1-, methoxybenzyl acrylate
1-, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate-1-, tetrahydrofurfuryl methacrylate, phenyl acrylate-1-12-hydroxyethyl acrylate-1-, 5-hydroxybempuru Acryle-1-, 2.2-dimethyl-, 3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2 -(2-methoxyethoxy)ethyl acrylate,
2-(2-butoxyethoxy)ethyl acrylate, ω
Examples include -methoxypolyethylene glycol acrylate (additional mole number n=9), 1-bromo-2-methoxyethyl acrylate, 1°1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate,
amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-
Phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminomethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate,
Naphthyl methacrylate, 2-hydro 4-nidiethyl methacrylate, 4-hydro 4-sibdel methacrylate,
Triethylene glycol monomethacrylate-1~, dipropylene glycol monomethacrylate-i~, 2-medoxyethyl methacrylate-1~, 3-methoxybutyl methacrylate, 2-acetyl methacrylate, 2-
Acetoacetyl=Siedyl methacrylate, 2-1-xynyl methacrylate, 2-1so-propo4
-Sibdel methacrylate, 2-butoxyethyl)V methacrylate 1-12-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethyl) 1-4- c) Ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n=6), allyl methacrylate, dimethylaminoethyl methacrylate methyl chloride salt, and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salidylate, etc. can be mentioned.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3-dimethylbutadiene, and the like.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, and more! Examples include helifluoromethylstyrene and vinylbenzoic acid methyl ester.

Examples of crotonate esters include butyl crotonate, hexyl chlorate, and the like.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methyl-oxyethyl acrylamide, dimethylaminoethyl acrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethyl acrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.: Methacrylamides, e.g., methacrylamide, methylmethacrylamide , ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, ter
t-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N-(2-acetoacetoxyethyl) methacrylamide, etc. Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc. Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl Vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, xyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N - Niglycidyl esters such as vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc., such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, methacrylateryl, etc.; Polyfunctional monomers, such as divinylbenzene , methylene bisacrylamide, ethylene glycol dimethacrylate, etc.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates such as monomethyl itaconate, monoethyl itaconate, mozupdel itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, etc. Niditoraconic acid such as monoethyl maleate, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.
Methacryloyloxyalkylsulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido- 2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid , niacryloxyalkyl phosphates such as 2-methacrylamido-2-methylbutanesulfonic acid,
For example, acryloyloxyethyl bosphate, 3-
Acryloyloxypropyl-2-phosphate etc.:
Methacryloxyalkyl phosphates, e.g.
Methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.: Examples include sodium 3-7 lyloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (eg, Na, Ni, etc.) or ammonium ions. Furthermore, as other monomer compounds, rice 1 mI & permission No. 3.459.7
No. 90, No. 3,438,708, No. 3,554,
No. 987, No. 4,215,195, No. 4,247
, No. 673, Japanese Patent Application Publication No. 57-205735, and the like can be used. Examples of such crosslinking monomers include 1;1, specifically N-(2-acetoacetoxyethyl)acrylamide, N-(2-(2-7cetoacetoxyethoxy)
(ethyl) acrylamide, etc.

Among these monomer compounds, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used.

Next, an example of synthesis of the latex of the present invention will be given.

Iohtai White Synthesis Example 1 Distilled water 360i1 degassed with N2 gas in 11 Kolben
2 and synthetic water-soluble poly'? (Sl]-8) 4.5
g and raise the temperature to 80°C. Immediately add 0.271 J of am[ium persulfate] dissolved in 5 volumes of distilled water, and dropwise add a mixture of 1-90 ethyl acrylate (l) over about 1 hour. After the addition is complete, stir roughly for 4 hours. After the reaction, the unreacted monomers are recovered by steam distillation for 1 hour, cooled to room temperature, and the desired latex L-(1
) is 10. Number average molecule ffiMrl with particle size 0.2μ
= 850,000.

Synthesis Example 2 Distilled water 3601f degassed with N2 gas in 11 Kolben
Add i and synthetic water-soluble polymer (1)-1) 4.5 () and raise the temperature to 80°C. To this, quickly add 0.27 (l) of ammonium persulfate dissolved in distilled water,
Thereto, 1 to 90 g of ethyl acrylate was added dropwise over about 1 hour, and after the dropwise addition was completed, the mixture was stirred for an additional 4 hours to react. After the reaction is complete,
Steam distillation was carried out for 1 hour to collect unreacted upper sludge, and the mixture was cooled to room temperature to obtain the desired latex L-(2). Particle size 0.1 μ and number average molecule fftMn == 700,00
It was 0.

Synthesis Example 3 Distilled water 36 (h1
Add 2.30% of dextran sulfate and 2.30% of dextran sulfate and heat to 80℃. To this, 0.27 Q of ammonium persulfate dissolved in distilled water was quickly added, and a mixture of 41 sugrene, 49 g of butyl acrylate, and 0.9 (J) of acrylic acid was added dropwise thereto over about 1 hour, and the mixture was further stirred for 4 hours. After the reaction is completed, steam distillation is performed for 1 hour to recover unreacted monomers, and the mixture is cooled to room temperature to obtain the desired latex L-(8). Particle size is 0.25μ, number average molecular weight is 1yln = 660, It was 000.

Synthesis Example 4 360 d of distilled water degassed with N2 gas in one kolben
and raise the temperature to 80℃. To this, 0.27 (l) of ammonium persulfate dissolved in 5'vQ of distilled water was quickly added, and 50% of butyl acrylate-1-400 and styrene were added thereto.
(The mixture of I was added dropwise over about 1 hour, and after the completion of the addition, the mixture was stirred for 4 hours to allow the reaction to proceed. After the completion of the reaction, steam distillation was performed for 1 hour to recover unreacted t-sumer.

Dissolve the synthetic water there while keeping it at 80℃! [polymer(
After adding 5 g of D-1) and stirring for 2 hours, the mixture was cooled to room temperature to obtain the desired latex 1-(15).

Number average intermolecular Mn = 600,000 with particle size 0.3μ
Met.

In addition, the number average molecular weight was determined using Gel Permeation Chlor 1-Graph I L C-802A manufactured by Toyo Soda Co., Ltd. in terms of standard polystyrene, and the particle size was determined using Coulter N4 manufactured by Coulter Co., Ltd. It was measured.

Synthesis Example 5 In the same manner as Synthesis Example 1, instead of the synthetic water-soluble polymer, a compound lower-3 having a hydrophilic group and a group to which radicals can easily undergo chain transfer was used.
9 was synthesized with latex (12) by adding 0.03 (l). Number average intermolecular Mn = 80,000, average particle size was 0.
It was 2 μm.

As a result of various studies, the present inventors have found that by using a latex nonionic surfactant (Jl) having a hydrophilic group fixed to the surface according to the present invention, it has good antistatic properties and photographic properties. It has been found that roller contamination is significantly improved without having any adverse effect on the product.

Next, the nonionic surfactant used in combination with the latex according to the present invention having a hydrophilic group fixed to its surface will be explained.

Nonionic surfactants preferably used in the present invention include the following general formulas [N-I], [N-n] and [N-
II].

The following is a blank general formula [Rie] 3L, -A + Cll2CJI, O→oJl General formula [West ■] General formula [g-] A In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, alkenyl represents a group or an aryl group, and each of these groups includes those having a substituent. R1 is preferably an alkyl group or alkenyl group having 4 to 24 carbon atoms,
Aryl group, particularly preferably hexyl group, dodecyl group, isostearyl group, oleyl group, t-butylphenyl group, 2,4-di-t-butylphenyl group, 2,4-
Di-t-pendelphenyl group, p-dodecylphenyl group, m-pentadecaffenyl group, t-octylphenyl 1
．． 2.4-dinonylphenyl group, ocdylnanodyl group, etc.

A is 10-1-S-1-COO-1-OCO-1-N-
Rlol-CO-N-Rlo or an alkyl group including a substituent. ). R2, R3, R7
and R9 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, or a carbamoyllamoyl group;
Also included are those having a t substituent. R l-, , l'5
and Rotma alkyl group, aryl 1, (, al-1:
1, aryloxy group, halogen II;
(or represents a sulfamoyl group, and each of these groups includes those having a substituent.

R6 and R8 are preferably an alkyl group having 1 to 20 carbon atoms, a phenyl group, a 7-aryl group such as p-chlorophenyl group, -OR+5 (where 1te15 is an alkyl group having 1 to 20 carbon atoms=1, or represents an aryl group, and these groups include those containing substituents (the same shall apply hereinafter), halogen atoms such as chlorine atoms and bromine atoms, -C O R Acyl group represented by 15, -N R 16C O R +
5 (here, R 16 is a hydrogen atom or a carbon number of 1 to 20
The alkyl group is shown below. The same applies below. ), and a sulfonamide group represented by -NR+sSO2[+s. Among these, R6 and R8 are more preferably an alkyl group or a halogen atom, and most preferably a tertiary alkyl group such as a t-butyl group, a t-amyl group, or a thi-Oucdel group.

R2, Ra, R7 and R9 are preferably hydrogen atoms or the groups listed above as preferred R6 and R8. Among these, R7 and R9 are particularly preferably hydrogen atoms.

R4 and R5 represent a hydrogen atom, an alkyl group or an aryl group, and these groups include those having substituents. Particularly preferred as R4 and R5 are hydrogen atoms,
These include alkyl groups having 1 to 8 carbon atoms, 7-nyl J4, furyl groups, and the like.

R4, R5, R6, R7, and R8 and R9 may be linked to each other to form a ring, for example, a Schif[]hexyl ring.

Furthermore, in the general formula [N-II J], the substituent on the 1-nyl ring is left-right asymmetrical.

nl, R2, R3 nl is a number from 2 to 50, particularly preferably from 5 to 3017), because of the average added mole of ethylene oxylide.R3 and 04 may be the same or different. J Koi.

m is an integer from 2 to 50.

These compounds are described, for example, in U.S. Pat. No. 2,982,651.
No. 3, 428. 45 (No. i, 3, 457,
No. 07C, No. 3, 454, 625, No. 3, 55
No. 2,972, No. 3,655, 387, Japanese Patent Publication No. 51-9610, Japanese Patent Publication No. 53-29715 No. 54-
No. 89626, Patent Application No. 85764, Patent Application No. 1983
-9o9o9q, "New Surfactant" by Hiroshi Horiguchi (Sankyo Publishing, 1915), etc.

Next, specific examples of nonionic surfactants preferably used in the present invention will be shown.

Compound example below margin N-1 HO+CH2CF20+2H HO+CH2CH2O+1oH CI7H33C00+CHz CH20+t5HC8H
170+CH2CH2O+7H C12H250+CH2CH2O+1oHC16H33
0+CH2CH2O+12Ha +1) = 15 a + b = 20 C12H25S)+CH2CH20+H6HC+2H2
sO+CHCHzO+3(CH2CH20+15HCH
3 CH2CH20+ CH2CH20+1□HN -25
C, J-T9 0+CI71.2 Cl-120 sir, , HN-2
8 N-29 -3O CI2H25Cl2H25 CsH+7-t CsH+7-t -4O N-44 C6H11-t Ustllll-L In the present invention, the latex according to the present invention on which the hydrophilic group is fixed on the surface is a nonionic surfactant. The antistatic layer of the present invention includes a subbing layer, an intermediate layer, and a surface protective layer on the same side as the silver halide emulsion layer. , an overcoat back layer on the side opposite to the silver halide emulsion layer, etc. Among these, surface layers such as a surface protective layer, an overcoat layer, and a back layer are particularly preferred.

The amount of nonionic surfactant used in the present invention varies depending on the form, type, coating method, etc. of the photographic material used, but is generally 0.1 to 1,000 per 112 parts of the photographic material.
J: 0 mg, particularly preferably 0.5 to 200 mg.

Nonion f1 of the present invention. It is also possible to use another antistatic agent in the surfactant-containing layer or other layers, and by doing so, a more preferable antistatic effect can be obtained.

The latex according to the present invention on which a hydrophilic group is fixed can be added to the antistatic layer as it is or after being dispersed in water. The amount of the latex added is 10 to 100 parts by weight of the binder of the antistatic layer added.
It is preferable to add 60 parts by weight.

As a binder for the antistatic layer, gelatin or a gelatin derivative may be used in combination with the latex according to the present invention on which a hydrophilic group is fixed on the surface.

In addition to lime-treated gelatin, gelatin
of the society of science
Photography of Japan (Bull, 5o
c1Sci, Phot, Japan,) No. 1
Oxygen-treated gelatin such as that described on page 6.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin derivatives include gelatin and various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds. The product obtained by reacting is used. Specific examples thereof include U.S. Patent No. 2,614,928, No. 3, U.S. Pat.
British Patent No. 861,414, British Patent No. 1.033.189,
1, 005, No. 784, Equity N7112-268
It is described in No. 45 etc.

The silver halide emulsion of the present invention includes any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

Furthermore, silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and the surface layer of the grain. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle.

The silver halide grains used in the silver halide emulsion of the present invention may have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or irregular crystal shapes such as spherical or plate shapes. It may also have a crystalline form.

In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5 μm or less, particularly preferably 3 μm or less.

The silver halide emulsion of the present invention may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion of the present invention may be a combination of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. I5, sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization using gold or other negative metal compounds, etc. can be used alone or in combination.

Further, a color light-sensitive material may be prepared by containing a dye-forming coupler in the silver halide emulsion layer.

[Example 1 of the Invention The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (1) Preparation of sample A silver halide emulsion layer having the following composition was coated on an undercoated polyethylene terephthalate film support having a thickness of 180 μm, and a protective layer having the following composition was further coated on top of it. and dried to prepare a black and white silver halide photosensitive material. The nonionic surfactant and latex of the present invention or a comparative latex were added to the protective layer.

(Emulsion layer) Thickness: 5μ Composition Gelatin 2.5g/m2 Silver iodobromide (silver iodide 1.5 mol%) 5 (1/TI'1
-Phenyl-5-mercaptotetrazole 25m (1/12(
Protective layer) Thickness: Approximately 1μ Composition and coating amount Gelatin Q, 9 (1/1112
2.6-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mo/n2 Latex of the present invention or latex for comparison o, gg Finonionic surfactant 40 mg/m2 Expressed in weight%.

(2) Method for determining antistatic ability: Antistatic ability was determined by measuring surface resistivity and static mark generation. 0 surface resistivity is measured using a brass electrode (with electrode spacing of 0.14 cm and length of 10 cm).
The part in contact with the test piece is made of stainless steel), and the 1-minute value is measured using a insulation meter TR8651 manufactured by Takeda Tanukiken. ■Static mark generation test is performed by placing an unexposed photosensitive material on a rubber sheet with the nonionic surfactant-containing surface facing downward.
J: It's a method to generate static marks by pressing with a rubber roller and then peeling off.

The surface resistivity was measured at 25° C. and 25% R1-1, and the static mark generation test was conducted at 25° C. and 25% RH. Note that the humidity of the test piece of sample r1 was controlled under the above conditions for 24 hours.

In order to evaluate the degree of static mark generation, each sample was developed at 20° C. for 5 minutes using a developer having the following composition.

Developer composition N-methyl-〇-aminofuconol 1iA acid m 40
Anhydrous sodium sulfite 60 p Hydroquinone 10 Q Sodium carbonate (monohydrate) 53 g Potassium bromide 25 (] Add water to make 11.

The evaluation of static marks was based on the following 5-level criteria.

A: No static marks were observed.

A small number of B star deck marks appear.

C. Many block marks occur.

D. Star deck marks occur significantly.

E: Static marks appear on the entire surface.

(3) Photographic sensitivity test method: The sample was exposed to tungsten lamp light, developed with a developer having the following composition (35° C., 30 seconds), fixed, and washed with water to examine its photographic properties.

Developer composition drying up,
Sodium p-tetrapolyphosphate 2.0g Anhydrous sodium sulfite 509 Hydroquinone 10g Sodium carbonate (
1 water J! ! 2) 40Q1-phenyl-3
-Pyrazolidone 0.39 Potassium Bromide
2.0 () Add water and mix
1000 cm
It was cut into 17.1cm x 17.1cm square pieces. After uniform exposure so that the optical density after development becomes 1.0, automatic development processing is carried out using a silicone conveyance roller and three baths: a developing bath, a fixing bath, and a washing bath. ), 50 sheets were continuously developed and published. Wash the squeeze roller thoroughly and dry it! /= The appearance of streak-like density unevenness at the tip of the 51st sample was examined.

The degree of roller contamination was evaluated according to the following four-level criteria.

A: No density unevenness was observed.

B: Slight unevenness occurs.

C: Considerable density unevenness occurs.

D= Significant unevenness in Han score occurs.

The results are shown in Tables 1 and 2.

Try the margin G below! 31 No. 12 latex is latex L-(1
Same as 2).

The latex of sample No. 15 is latex L-(15)
Same as .

Comparative latex Δ Described in Japanese Patent Publication No. 45-5331 EA: Ethyl acrylic 1 no 1 BA nibdel acrylate St: Styrene AA Niacrylic acid VAc: Vinyl acetate VClce: Vinyl 1] As is clear from Ride Table 1 and Table 2. Comparative samples Nos. 19, 10, 20J3 and 21 containing the nonionic surfactant of the present invention and the comparative latex had significantly inferior sensitivity 11! ! Comparative samples Nos. 11 and 22, which contained the latex of the present invention but did not contain a nonionic surfactant, had significantly poor antistatic ability and large roller stains. In contrast, the sample of the present invention containing both the nonionic surfactant of the present invention and the latex of the present invention lowers the surface resistivity without adversely affecting the sensitivity, improves the antistatic ability to reduce static marks, and improves the antistatic ability of the roller. It can be seen that contamination can be improved.

Claims (1)

[Claims] A silver halide photographic light-sensitive material comprising a photographic constituent layer having at least one antistatic layer provided on a support,
A silver halide photographic material, wherein at least one layer of the antistatic layer contains a latex having a hydrophilic group fixed to the surface and a nonionic surfactant.