JPH077185B2 - Method for producing silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material), and more particularly to a method for producing a light-sensitive material using a latex polymer.

(Prior Art) In general, a light-sensitive material is formed by coating at least one photosensitive emulsion layer on a support and, if necessary, coating a photographic structure layer such as an undercoat layer, an intermediate layer, an antihalation layer and a protective layer. is doing. Various latex polymers have been used in these layers.

Latex polymers used in light-sensitive materials are described in, for example, "Research Disclosure" No. 7, 19551.
As described in Section (1980), improved dimensional stability,
Improved adhesion, added flexibility, improved scratch resistance, improved water resistance,
Such as film physical property improving agent, development accelerator, antistatic agent, mordant, matting agent, etc., and also hydrophobicity of couplers, pigments, development terminators, antifoggants, UV absorbers, sensitizing dyes, etc. There are a wide variety of applications, including dispersion of substances, that is, use as a loadable latex.

Like other hydrophilic colloid layers, a coating layer made of a latex polymer that constitutes a light-sensitive material is required to be applied uniformly and at high speed without coating failure such as cissing when manufacturing a light-sensitive material. The largest cause of coating failure such as cissing is coarse particles mixed in the coating liquid layer. Therefore, a step of removing coarse particles through a filter with a coating solution composed of a latex polymer is required before the production of a light-sensitive material.

(Problems to be Solved by the Invention) However, even if a latex polymer from which coarse particles have been removed through a filter after latex polymer synthesis is prepared, a coating solution containing the latex polymer is prepared after storage for several weeks to several months. Therefore, when passing the liquid delivery piping system, the filter placed inside the liquid delivery piping system is clogged and the liquid delivery load increases significantly, and finally the liquid delivery becomes impossible, or the pump from the pump Frequently, stable manufacturing problems such as fluctuations in the liquid feeding pressure and loss of control of the liquid feeding amount occurred. Due to such a problem, it has been unavoidable to carry out the treatment by a manufacturing cost disadvantageous method such as shortening the shelf life of the latex polymer and downsizing the scale of the latex polymer production.

The above problem becomes noticeable as the amount of hydrophilic component contained in the latex polymer increases, so that the hydrophilic unit is immobilized on the latex polymer particles by copolymerizing a crosslinkable monomer to improve hydrophilicity. This is a particularly serious problem in a latex polymer having a high hydrophilic component content that prevents the elution of units.

The technique for making a water-soluble polymer resistant to diffusion is one of the important means for putting the water-soluble polymer into practical use in applications such as an antistatic agent, a pH lowering agent, and a mordant (dye fixing agent). These techniques are disclosed in JP-A-54-109831, JP-A-61-296352, and JP-A-61-296352.
62740 (hereinafter anionic crosslinked latex), JP-A-51
-73440, 54-1398, 54-74430, 54-124726,
54-145529, 54-155835, 55-22766, 55-3317
2, 59-219745, JP-B-59-31697, 59-33899, U.S. Patent Nos. 3958995, 4312940, 43966698 (hereinafter, cationic cross-linked polymer), and recently disclosed. The importance is increasing.

The crosslinked latex polymer having a large hydrophilic component content represented by the general formula [V], which will be described later, causes a significant pressure increase particularly in the filtration filter portion during the above liquid feeding, which is a serious problem in the stable production of a light-sensitive material. There has been an urgent need to develop a technique for using a hydrophilic polymer crosslinked latex.

The present inventors considered that the clogging of the filtration filter after long-term storage of the latex polymer was caused by the instability of the latex particles, and studied various dispersion stabilizers, etc., but the effect was not sufficient.

However, in addition to the above, the inventors have found that the presence of an antibacterial substance in the latex polymer composition solves the above-mentioned problems, and has reached the present invention. A method of adding an antibacterial substance to a latex polymer is disclosed in JP-A-60-152538, but these antibacterial substances have an adverse effect on photographic characteristics such as sensitivity, fog, graininess and sharpness of the light-sensitive material. It could not be used in a silver halide photographic light-sensitive material.

(Object of the Invention) A first object of the present invention is to provide a method for producing a photosensitive material containing a latex polymer composition which does not cause coating failure such as cissing.

A second object of the present invention is to provide a method for producing a light-sensitive material containing a latex polymer composition which does not increase the filtration pressure at the time of filter filtration even if it is stored for a long period of time.

A third object of the present invention is to provide a method for producing a light-sensitive material containing a latex polymer composition which is useful for a silver halide light-sensitive material and does not adversely affect photographic characteristics.

(Means for Solving the Problems) The object of the present invention is to provide a photosensitive material containing a latex polymer composition, represented by the following general formulas [I], [II] and [II].
At least one of compounds represented by I] or [IV]
It is achieved by a method for producing a silver halide photographic material, which is characterized in that it is produced using a coating solution prepared by adding at least one latex polymer composition containing a seed.

General formula [I] In the formula, R ₁ represents a lower alkylene group, and the alkylene group may be linear or branched. X is a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, -COR ₂ , Represents —SO ₃ M, R ₂ represents a hydrogen atom, —OM, a lower alkyl group, an aryl group, an aralkyl group, a lower alkoxy group, an aryoloxy group, an aralkyloxy group, Represents

R ₃ and R ₄ are each a hydrogen atom, a lower alkyl group, an aryl group,
Aralkyl group, --COR ₇ , --SO ₂ R ₇ , which may be the same or different from each other, R ₅ and R ₆ each represent a hydrogen atom, a lower alkyl group, an aryl group or an aralkyl group. , Which may be the same or different from each other, R ₇ represents a lower alkyl group, an aryl group or an aralkyl group, and M represents a hydrogen atom, an alkali metal atom or an atom necessary for forming a monovalent cation. Represents a group, m represents 0 or 1 and n represents 0 or an integer from 1 to 5.

General formula (II) In the formula, R ₈ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, The stands, R _9, R ₁₀ are each a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an arylthio group,
It represents an alkylsulfoxy group or an alkylsulfonyl group, and R ₉ and R ₁₀ may combine with each other to form an aromatic ring.

R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.

When R ₈ is an alkyl group, it may be linear, branched or cyclic. When R ₉ and R ₁₀ are alkyl groups, they may be cyclic.

General formula (III) In the formula, R ₁₃ represents a hydrogen atom, a lower alkyl group or a hydroxymethyl group, and R ₁₄ represents a hydrogen atom or a lower alkyl group.

General formula (IV) R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₀ each represent a hydrogen atom or a lower alkyl group.

The latex polymer of the present invention is not particularly limited, but at least one of the compounds represented by the general formulas [I], [II], [III] and [IV] in the latex polymer represented by the following general formula [V] is particularly preferable. The effect of including is great.

General formula [V] In the formula, R ₂₁ represents a hydrogen atom or an alkyl group, and L ₂₁
Represents a divalent, trivalent or tetravalent linking group. Y represents a hydrophilic functional group. i is 0 or 1 and j is 1, 2 or 3
Is.

A is a repeating unit containing a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups, and B
Is a repeating unit containing a monomer having a copolymerizable ethylenically unsaturated group.

x is 30 to 90 mole percent, y is 1 to 50 mole percent, and z is 0 to 80 mole percent.

The compound of the present invention will be described in more detail.

In the general formula [I], R ₁ represents a lower alkylene group (eg ethylene group, propylene group, methylethylene group, etc.), and an alkylene group having 1 to 6 carbon atoms is particularly preferable.

X is a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), nitro group, hydroxy group, cyano group, lower alkyl group (eg, methyl group, ethyl group, iso-propyl group, tert-butyl group, etc.),- COR ₂ , Represents —SO ₃ M, R ₂ represents a hydrogen atom, —OM, a lower alkyl group (eg, methyl group, n-butyl group, tert-octyl group, etc.), an aryl group (eg, phenyl group, 4-chlorophenyl group, 3-) Nitriphenyl group etc.), aralkyl group (eg benzyl group, p-iso-propylbenzyl group, o-methylbenzyl group etc.), lower alkoxy group (eg methoxy group, n
-Butoxy group, 2-methoxyethoxy group, etc.), aryloxy group (eg, phenoxy group, naphthoxy group, 4-
Nitrophenyloxy group), aralkyloxy group (eg benzyloxy group, p-chlorobenzyloxy group, etc.), Represents

R ₃ and R ₄ are each a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, 2-ethylhexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, 2-methoxyphenyl group, 3-acetamidophenyl group). Etc.), an aralkyl group (for example, a benzyl group, an o-chlorobenzyl group, etc.), —COR ₇ , and —SO ₂ R ₇ , which may be the same or different from each other, and R ₅ and ₆ are each Hydrogen atom, lower alkyl group (eg, methyl group, iso-propyl group, 2-cyanoethyl group, etc.), aryl group (eg, phenyl group, 4
-Ethoxycarbonylphenyl group, 3-nitrophenyl group, etc.) and aralkyl group (for example, benzyl group, p-chlorobenzyl group, etc.), which may be the same or different, and R ₇ is a lower alkyl group ( For example, ethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, etc., aryl group (eg, phenyl group, naphthyl group, 4
-Sulfophenyl group, 4-carboxyphenyl group, etc.)
M represents a hydrogen atom, an alkali metal atom (eg, sodium, potassium, etc.) and an atomic group necessary for forming a monovalent cation (eg, ammonium cation, phosphonium cation, etc.), and m represents 0 or 1. n represents 0 or an integer from 1 to 5.

The lower alkyl group and lower alkoxy group represented by the above general formula [I] preferably have 1 to 8 carbon atoms. Next, typical specific examples of the compound represented by the general formula [I] (hereinafter referred to as compound I) are shown, but the compound of the general formula [I] of the present invention is not limited thereto.

(Exemplified compound) Most of these exemplified compounds are commercially available as reagents and can be easily obtained, or can be easily synthesized by existing synthetic methods. For example J.Am.Che
A part of the compound of m = 1 can be easily synthesized by the method described in m.Soc., Vol. 41, p. 669 (1919).

In the general formula [II], R ₈ is a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, tert-butyl group, n-octadecyl group,
2-hydroxyethyl group, 2-carboxyethyl group, 2
-Cyanoethyl group, sulfobutyl group, N, N-dimethylaminoethyl group, etc.), substituted or unsubstituted cyclic alkyl group (eg, cyclohexyl group, 3-methylcyclohexyl group, 2-oxocyclopentyl group, etc.), substituted or unsubstituted Alkenyl group (eg, allyl group, methylallyl group, etc.), substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxybenzyl group, o-chlorobenzyl group, p-iso-propylbenzyl group, etc.), substituted or unsubstituted Aryl groups (eg, phenyl group, naphthyl group, o-methylphenyl group, m-nitrophenyl group, 3,
4-dichlorophenyl group), heterocyclic group (2-imidazolyl group, 2-furyl group, 2-thiazolyl group, 2-pyridyl group, etc.), R ₉ and R ₁₀ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, chloromethyl group, 2-hydroxyethyl group, tert-butyl group, n-
Octyl group), substituted or unsubstituted cyclic alkyl group (eg cyclohexyl group, 2-oxocyclopentyl group etc.), substituted or unsubstituted aryl group (eg phenyl group, 2-methylphenyl group, 3,4-dichlorophenyl group) , Naphthyl group, 4-nitrophenyl group, 4-aminophenyl group, 3-acetamidophenyl group, etc.), cyano group, heterocyclic group (for example, 2-imidazolyl group, 2-thiazolyl group, 2-pyridyl group, etc.), Substituted or unsubstituted alkylthio group (eg, methylthio group, 2-cyanoethylthio group, 2-ethoxycarbonylthio group, etc.), substituted or unsubstituted arylthio group (eg, phenylthio group, 2-carboxyphenylthio group, p-methoxyphenyl) Thio groups), substituted or unsubstituted alkyl sulfoxy groups (eg methyl groups). Sulfoxy group, a 2-hydroxyethyl sulfoxide group), a substituted or unsubstituted alkylsulfonyl group (e.g., methylsulfonyl group, an aromatic ring of 2-bromo-like ethylsulfonyl group) represents R ₂ and R ₃ are mutually bonded to (For example, a benzene ring, a naphthalene ring, etc.) may be formed.

R ₄ and R ₅ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, iso-propyl group, 2-
Cyanoethyl group, 2-n-butoxycarbonylethyl group, 2-cyanoethyl group, etc.), substituted or unsubstituted aryl group (for example, phenyl group, naphthyl group, 2-methoxyphenyl group, m-nitrophenyl group, 3,5- And a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, p-iso-propylbenzyl group, o-chlorobenzyl group, m-methoxybenzyl group, etc.).

Next, typical examples of the compound represented by the general formula [II] (hereinafter referred to as compound II) are shown below, but the compound II of the invention is not limited thereto.

(Exemplified compound) Some of the above compounds are commercially available and can be easily obtained, and can be synthesized according to the synthetic method described in French Patent 1,555,416.

In the general formula [III], R ₁₃ is a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, isopropyl group, etc.),
It represents a hydroxymethyl group, and R ₁₄ represents a hydrogen atom or a lower alkyl group (eg, methyl group, n-butyl group, isoamyl group, etc.). The lower alkyl group preferably has 1 to 5 carbon atoms, particularly 1 carbon atom.

And a compound represented by the following general formula [III] (hereinafter referred to as compound I
(Referred to as II), the compound II of the present invention
I is not limited to these.

(Exemplified compound) Some of these compounds are commercially available from Sanai Oil Co., Ltd. Moreover, it can be synthesized with reference to the following documents.

(1) Henry Recueil des travaux chiniques des Rays
-Bas 16 251 (2) Mass.chemisches Zentralbatt 1899 I 179 (3) E.Schmidt.Berichte der Deutchen Chemischen G
esellschaft. 52 397 (4) E.Schmidt.ibid 55 317 (5) Henry Chemiches Zentralblatt. 1897 II 338 Synthesis of this III-I literature (1), (2) to (3), the synthesis of III-2 (2), III-3 should be synthesized according to literature (5), and III-4 should be synthesized according to literature (2).

In formula [IV], R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₀ are each a hydrogen atom, a lower alkyl group (for example, a methyl group,
Ethyl group, isopropyl group, etc.). The lower alkyl group preferably has 1 to 5 carbon atoms.

Next, typical specific examples of the compound represented by the general formula [IV] (hereinafter referred to as compound IV) are shown below.
The IV is not limited to these.

(Exemplified compound) The addition amount of the compounds [I], [II], [III], and [IV] is appropriately in the range of 1 to 100,000 ppm, preferably 100 to 10,000 ppm, based on the latex polymer composition.

Any one of the compounds [I], [II], [III] and [IV] of the present invention may be used alone, or two or more arbitrary compounds may be selected and used in combination. Absent.

The compounds [I], [II], [III] and [IV] of the present invention may be added as they are, but they are dissolved in water or an organic solvent such as methanol, ethanol, isopropyl alcohol, acetone, ethylene and ethrene glycol. Alternatively, it may be added as a solution to the latex polymer.

Alternatively, it may be dissolved in a high boiling point solvent, a low boiling point solvent, or a mixed solvent of both, and then emulsified and dispersed in the presence of a surfactant and added to the latex polymer.

It goes without saying that even if a latex polymer containing the compounds [I] to [IV] is used in a light-sensitive material, it does not adversely affect the photographic performance.

Next, the latex polymer having a high effect according to the present invention will be described in detail below.

The latex polymer desirable in the present invention preferably has a monomer represented by the following general formulas (M-I) to (M-XVII) as a repeating unit.

R in the formula₃₁Represents a hydrogen atom, a carboxyl group or a salt thereof.
Then R₃₂Is a hydrogen atom, alkyl group, substituted alkyl group, halogen
R atom, cyano group, R₃₃Is a hydrogen atom, alkyl group, substituted alkyl group, aryl
A ren group or a substituted arylene group, R₃₄, R₃₅Can be the same or different and
Child, alkyl group, substituted alkyl group, carboxyl group or
Its salt, -COOR₃₃Group (R₃₃Synonymous with the above), halogen source
Child, hydroxyl group or salt thereof, cyano group, carbamoyl group
Represents, k represents 0, 1, 2 l represents 0, 1, 2 R₃₆, R₃₇Can be the same or different and
Child, alkyl group, substituted alkyl group, phenyl group, substituted group
Represents a phenyl group, R₃₈Is an alkyl group, substituted alkyl group, phenyl group, substituted
Represents a phenyl group, R₃₉Represents an alkyl group or a substituted alkyl group, R₄₀,
R₄₁, R₄₂, R₄₃The same or different, hydrogen source
Child, alkyl group, substituted alkyl group, halogen atom, shear
R represents₄₄Represents a hydrogen atom, an alkyl group or a halogen atom, and R₄₅Represents an alkenyl group, R₄₆Represents a hydrogen atom, an alkyl group, or a substituted alkyl group.
Then R₄₇Represents an alkyl group or a substituted alkyl group, R₄₈Represents a hydrogen atom, an alkyl group or an alkenyl group, R₄₉, R₅₀Can be the same or different and can be hydrogen atom,
Represents a kill group, R₅₁Is an alkylene group, a substituted alkylene group, CH_{2 a}0CH_{2 b}0_cCH_{2 d}(A, b,
c and d represent 0 or 1, respectively, and L₁₁Is a -COO-phenylene group,(R₃₆Represents the same as above), q represents 0 or 1, and when q = 0, R_{twenty one}—N may form a pyridine ring, and R₅₂, R₅₃, R₅₄May be the same or different
Often represents an alkyl group or a substituted alkyl group, R₅₅ A
Stands for Nion, R₅₆Represents a hydrogen atom, an alkyl group, or a substituted alkyl group.
Then L₁₁, L₁₂Can be the same or different -COO-,(R₃₆Is synonymous with the above) -O-, -S-, -OOC-, -CO
Represents a phenylene group, r represents 0 or 1, L₁₃Is -COO-,(R₃₆Represents the same as above), -OOC-, R₅₇Represents a hydrogen atom, an alkyl group, or a substituted alkyl group.
, T represents 3 or 4, and C₅₈Is a carbon atom,Or represents a heterocycle L₁₄Is -OOC-, -CO-,(R₃₆Is synonymous with the above),(R₃₆Represents the same as above), and L₁₅Is −CO−R₄₇(R₄₇Is as defined above), (-COOR₄₇(R₄₇
Is as defined above), a cyano group,(R₃₆Is the same as above), -SO₂-R₄₇(R₄₇Is synonymous with the above)
Represents R₅₉Is a hydrogen atom, -CO-R₄₇(R₄₇Is synonymous with the above
Then L₁₆Is(R₄₆Is synonymous with the above)(R₃₆Represents the same as above), and L₁₇Represents an oxygen atom or a nitrogen atom,₆₀ Represents an alkylene group or a triazole ring, A represents a halogen atom or an amino group, and R represents₆₀Thoria
In the case of a sol ring, A represents a plurality of halogen atoms
Good.

R ₆₁ and R ₆₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a hydroxyl group and a salt thereof, an amino group, a carboxy group and a salt thereof, or a cyano group, and Z is a carbon atom bonded to N. Represents a component forming a plurality of rings of the numbers 3 to 13.

Specific examples of the monomer represented by the general formula (MI) include those shown in the following table.

Specific examples of the monomer represented by the general formula (M-II) include the following.

Specific examples of the monomer represented by the general formula (M-III) include the following.

Specific examples of the monomer represented by the general formula (M-IV) include the following.

The following are mentioned as a specific example of general formula (MV).

The following to be mentioned as specific examples of the _{MO-57 CH 2 = CH-} OCH 3 MO-58 CH 2 = CH-OC 4 H 9 (n) the formula (M-IV).

MO-59 CH ₂ = CH-S-CH ₂ CH ₂ CH ₂ SCH ₃ MO-60 CH ₂ = CH-S-CH ₂ SCH ₃ Specific examples of general formula (M-VII) include the following. .

MO-61 CH ₂ = CHCN MO-63 ClCH = CCl ₂ Specific examples of the general formula (M-VIII) include the following.

MO−64 CH ₂ = CH CH = CH ₂ The following are specific examples of (M-IX).

MO-67 CH ₂ = CHCOCH ₃ Specific examples of (MX) include the following.

The following are specific examples of (M-XI).

Specific examples of (M-XII) include the following.

MO-78 CH ₂ = CH-COO-CH ₂ CH = CH ₂ The following to be mentioned as specific examples of the _{MO-80 CH 2 = CHOCH 2} CH 2 OCH = CH 2 (M-XIII).

Specific examples of (M-XIV) include the following.

The following are specific examples of (M-XV).

The following are specific examples of (M-XVI).

Specific examples of (M-XVII) include the following.

Specific examples of (M-XVIII) include the following.

In the present invention, general formulas [I], [II], [III] and [I
The effect of incorporating one of the compounds represented by the formula V] is particularly remarkable in the latex polymer represented by the following general formula [V].

General formula [V] In the formula, R ₂₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group, L represents a divalent, trivalent or tetravalent linking group, and Y represents a hydrophilic functional group. i is 0 or 1,
j is 1, 2 or 3. x is 30 to 90 mole percent,
y is 1 to 50 mole percent and z is 0 to 80 mole percent.

R ₂₁ is preferably a hydrogen atom, a lower alkyl group is a methyl group, an ethyl group, and a substituted alkyl group is a carboxymethyl group.

As L, -COO-, (R ₃₆ represents the same as those shown in M-III above.) An arylene group, a phenylene group, a naphthylene group and the like) are preferable.

The hydrophilic functional group represented by Y is preferably a carboxyl group, a sulfo group, a phosphoric acid group, a salt compound thereof, an ammonium group, a cyano group and the like.

As an example of the crosslinkable monomer containing at least two or more copolymerizable ethylenically unsaturated groups represented by A, those represented by the above-mentioned monomer compound examples M-XII and M-XIII are preferable. Examples include MO-75-84.

The copolymerizable ethylenically unsaturated monomer represented by B can be arbitrarily selected from the above-mentioned monomer compound examples. In addition, in order to have more complex functions, A,
Both B may each include two or more types of monomer units.

Next, representative specific examples containing the latex polymer represented by the general formula [V] are shown below, but the latex polymer of the present invention is not limited thereto.

(Exemplified compound) These latex polymers can be synthesized by the following method.

When the compounds of the general formulas MI to M-XVII are insoluble in water, they can be synthesized by a usual emulsion polymerization method. For the method, see Takayuki Otsu and Masayoshi Kinoshita, “Experimental Method for Polymer Synthesis”.
(Chemical coterie) etc. can be performed according to the method described in the textbook. (The fact that the compounds represented by MI to M-XVII are "insoluble" means that 5 g or more does not dissolve in 100 g of water.) Further, the monomers represented by M-I to XVII If is soluble in water, a solution of the monomer in heated water (when the monomers do not dissolve in each other, use an auxiliary solvent such as water, alcohol, acetone, etc.) and a polymerization initiator are added at the same time. Can be synthesized. In this case, the polymerization temperature may be 50 to 100 ° C, but it is preferable to carry out the polymerization temperature at 80 to 100 ° C to obtain a polymer dispersion.

An example of actually synthesizing a typical latex polymer is shown below.

The representative synthetic examples of latex polymers are shown below.

Synthesis Example 1 Synthesis Example of PL-2 A three-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was added with 1.5 g of 72% sodium dodecylbenzenesulfonate methanol solution as an emulsifier and 1300 ml of distilled water, and a nitrogen stream. Below, the mixture was heated and stirred at an internal temperature of 95 to 97 ° C. Acrylic acid 120g (1.67mol), ethylene glycol dimethacrylate 80g (0.40mol) monomer mixture and an aqueous solution of potassium persulfate 14.0g (0.05mol) dissolved in 400ml distilled water were added dropwise over 150 minutes at the same time to emulsify Polymerized. After the dropping was completed, the polymerization was further performed at an internal temperature of 95 to 97 ° C for 90 minutes. After cooling to about 80 ℃, 53.3g (1.33mol) of sodium hydroxide was added to distilled water 20
After dissolving in 0 ml, the mixture was added and neutralized. After cooling to room temperature, the sandy aggregate was filtered off, and the aqueous dispersion of the crosslinked polymer example 1 was obtained.
2170 g (solid content concentration 11.3 wt%) was obtained. Viscosity is 7cp (25
℃), pH was 6.3.

Synthesis Example 2 Synthesis of PL-6 (i) Synthesis of quaternary amine monomer (N-o-vinylbenzyloxybenzyl N, N, N-trihexyl ammonium chloride) 1 In a three-necked flask, o-chloromethylphenoxymethylstyrene 68.4 g (0.26 mol), 6-0.5 g (0.22 mol) of tri-n-hexylamine, 0.5 g of nitrobenzene as a polymerization inhibitor, and 400 ml of acetonitrile were added, and the mixture was heated under reflux for 7 hours with stirring.

After cooling to room temperature, this solution was washed several times with 500 ml of n-hexane to remove unreacted o-chloromethylphenoxymethylstyrene. Concentrate the precipitated crystals into ethyl acetate 30
Recrystallization from 0 ml gave 75.3 g of white crystals of the desired quaternary ammonium monomer (yield 63.7%). (Ii) Polymer dispersion (synthesis of PL-6) As a surfactant in a 300 ml three-necked flask. (= 40, manufactured by Nippon Emulsion Co., Ltd.) 0.8 g, the quaternary amine monomer 15.8 g (0.03 mol), divinylbenzene
2.6 g (0.02 mol) and 130 ml of distilled water were added and the mixture was heated with stirring at 60 ° C. Here, 2,2′-azobis (2
-Amidinopropane) hydrochloride (0.15 g) dissolved in degassed distilled water (10 ml) was added, and the mixture was heated and stirred at 60 ° C for further 5 hours. After cooling to room temperature, it was filtered to obtain latex polymer PL-6.

Synthesis Example 3 Synthesis method of PL-16 0.428 kg of sodium lauryl sulfate and 80.0 kg of distilled water were added to a 100 l SUS reaction vessel and dissolved by stirring, and then 13.95 kg of methyl methacrylate and 0.60 k of N-methylolacrylamide.
g, 80% acrylic acid 0.563 kg, and ferrous chloride 0.96 g were added, and the mixture was heated so that the internal temperature was 60 ° C. while degassing with nitrogen gas.

To this, 40.95 g of potassium persulfate dissolved in 2.0 l of distilled water and a solution of 15.76 g of sodium hydrogen sulfite dissolved in 0.114 l of 2N aqueous ammonia were simultaneously added. After a further 2 hours, the same materials as described above were added and heating was continued for 3 hours.

Then, the mixture was cooled to room temperature and filtered through a 200 mesh pyrene net to obtain 99.66 kg (yield 99.8%) of bluish milky latex polymer PL-16.

The filter for filtering the latex polymer is not particularly limited, but a pole filter, a membrane filter or the like having pores of about 3 to 10 μm, which is usually used for removing dust, is suitable. Representative filters include Epocell 3 manufactured by Nippon Pall Co., Membrane Filter SS manufactured by MILLIPORE, and Fuji Micro Filter Pre-filter FP Cartridge FPC-3P manufactured by Fuji Film.

The light-sensitive material in which the latex polymer composition of the present invention is used will be described in more detail below.

The silver halide emulsion of the light-sensitive material used in the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride. For example, in the case of performing rapid processing or low replenishment processing of color paper, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and the silver chloride content is 80 to 100. The case of mol% is especially preferable. In addition, high sensitivity is required, and at the time of manufacturing,
During storage and / or when it is necessary to suppress fog during processing to a particularly low level, a silver chlorobromide emulsion or a silver bromide emulsion containing 50 mol% or more of silver bromide (3 mol% or less of silver iodide) May be contained), and more preferably 70 mol% or more. Silver iodobromide and silver chloroiodobromide are preferable for the color light-sensitive material for photographing, and the silver iodide content is preferably 3 to 15%.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention is represented by the grain diameter (in the case of spherical grains or grains close to spheres) and the ridge length in the case of cubic grains, which is the average based on the projected area. Is expressed in terms of yen) is preferably 2 μm or less and 0.1 μm or more, and more preferably 1.5 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably 15 It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a rhodohedron, and a tetradecahedron, or may have a coexisting form thereof. It may have an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms.

Further, tabular grains may be used, and particularly, the value of length / thickness ratio is 5
~ 8 or more than 8 tabular grains are 50% of the total projected area of grains.
Emulsions occupying at least% may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is "Research Disclosure", Volume 170, No.17643.
It can be prepared using the method described in Sections (I, II, III) (December 1978).

The emulsion used in the present invention is usually one that has undergone physical ripening, scientific ripening and spectral sensitization. Additives used in such a process are described in "Research Disclosure" Vol. 176, No. 17643 (December 1978) and No. 187.
Volume, No. 18716 (November, 1979), the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations described in the table below are shown.

Examples of the photographic light-sensitive material used include various color and black-and-white light-sensitive materials.

For example, color negative film for photography (general purpose, movie etc.), color reversal film (for slide, movie etc., and sometimes without coupler), color photographic paper, color positive film (movie etc.), Color reversal printing paper, photothermographic material (for details, see US Pat.
626, JP-A-60-133449, JP-A-59-218443, JP-A-6
No. 1-238056), color light-sensitive materials using the silver dye bleaching method, photographic light-sensitive materials for plate making (lith film, scanner film, etc.), X-ray photographic light-sensitive materials (direct / indirect medical, industrial, etc.), photography Black and white negative film, black and white photographic paper, micro photosensitive material (for COM, micro film etc.), color diffusion transfer photosensitive material (DTR), silver salt diffusion transfer photosensitive material, printout photosensitive material and the like.

When applied to color light-sensitive materials, various couplers can be used.

Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or multi-ring ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in "Research Disclosure (RD)" No. 17643 (19).
December 1978) Item VII-D and ibid. No. 18717 (November 1979)
Are described in the patents cited in.

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9.
No. 28, No. 3,933,501 and No. 4,022,620, etc., an oxygen atom-releasing yellow coupler or Japanese Examined Patent Publication No. 55-10739, U.S. Pat. Nos. 4,401,752, 4,326,024
Issue, "Research Disclosure" No.18053 (1979
April), British Patent No. 1,425,020, West German Application Publication No. 2,2
Representative examples thereof include nitrogen atom-releasing yellow couplers described in No. 19,917, No. 2,261,361, No. 2,329,587 and No. 2,433,812. α-pivaloyl acetanilide coupler is a fast coloring dye,
Particularly, the light fastness is excellent, while the α-benzoylacetanilide type coupler can obtain a high color density.

Examples of the magenta coupler that can be used in the present invention include oil-protected type isazozolone type or cyanoacetyl type couplers, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamine group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat.No. 3,725,067, Research Disclosure No. 24220 (1984 June) Piazolotetrazoles and Research Disclosure N
O.24230 (June 1984) described in piazolopyrazoles. The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable in view of less yellow sub-absorption of the coloring dye and light fastness, and European Patent No. 119,8
The pyrazolo [1,5-b] [1,2-4] triazole described in No. 60 is particularly preferable.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,826 and the like. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan coupler, U.S. Pat.
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication No. 3,329,729 and 2,5-diacylamino-substituted phenol couplers and U.S. Pat. Third 3,446,622
No. 4, No. 4,333,999, No. 4, 451, 559 and No. 4,4
Nos. 27,767 and the like, phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the 5-type couplers described in JP-A-61-179438.
Examples include amide-1-naphthol couplers.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more of the same photosensitive layers in order to satisfy the properties required for the photosensitive material, and the same compound can be used in two or more different layers. It can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Also, the process of latex dispersion method,
An example of an effect, latex for impregnation is described in US Pat.
No. 9,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

The photographic light-sensitive material used in the present invention is applied to a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or a rigid support such as glass. For details on the support and coating method, see "Research Disclosure" Vol. 176, No. 17643XV (P.2).
7) It is described in Section XVI (P.28) (December 1978 issue).

The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

There is no particular limitation on the developing method of the silver halide photographic light-sensitive material. For example, "Research Disclosure"
Any of known methods and known processing solutions as described in Volume 176, pp. 28-30 can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. Treatment temperatures are usually chosen between 18 ° C and 50 ° C, but may be below 18 ° C or above 50 ° C.

Conventional methods can be applied to form a dye image.

For example, the negative-positive method (eg, “Journal of the Socie
ty of Motion Picture and Television Engineers "No. 61
Vol. (1953), pp. 667-701); developed with a developer containing a black-and-white developing agent to produce a negative silver image, then at least one uniform exposure or other suitable fog treatment. And a color reversal method for obtaining a positive dye image by subsequent color development; a silver dye bleaching method in which a photographic emulsion layer containing the dye is exposed and then developed to form a silver image, and the dye is bleached using the black and white catalyst as a catalyst. Are used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4
-Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4 -Amino-N-ethyl-N-
β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

LFA Mason's Photographic Processing Che
mistry (Focal Press, 1966), pages 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364, JP-A-48-6493.
Those described in No. 3 and the like may be used.

Color developers also include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides,
A development inhibitor such as iodide and an organic antifoggant or an antifoggant can be contained. If necessary, a water softener, a preservative such as hydroxylamine,
Organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competing couplers, fogging agents such as sodium polon hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid chelating agents, antioxidants It may also contain agents.

The photographic emulsion layer of the color developer is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), covallo (III), chromium (IV) and copper (II), peracids, quinones, nitroso compounds and the like.

For example, ferricyanide, dichromate, iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamine-
Aminopolycarboxylic acids such as 2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates and nitrosophenol can be used. Of these, potassium ferricyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium ammonium (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

As the fixing solution, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers) and application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set. Of these, the relationship between the number of flush tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and Television Engineers (Journal).
of the Society of Motion Picture and Television En
gineers) ”, Volume 64, pp. 248-253 (May 1955 issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 2-6, particularly preferably 2-4.

The developing solution used for black-and-white photographic processing may contain a known developing agent. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-
Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p
-Aminophenol and the like can be used alone or in combination. Generally, other known preservatives are used in the developer.
Contains alkaline agents, pH buffers, antifoggants, etc., and further contains dissolution aids, color tones, development accelerators, surfactants, defoamers, water softeners, hardeners, viscosity imparting agents, etc., if necessary. May be included.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. What is "lith type" development processing? For the photographic reproduction of line development, or the photographic reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as the developing agent and the development process is carried out under a low sulfite ion concentration. It is a development process that makes the process contagious. (For details, see Mason "Photographic Processing.
Chemistry "(1966) pp. 163-165. Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 As a latex polymer, the exemplified compounds PL-2 and PL-
Select 3, PL-4, PL-5, PL-6, PL-12, PL-16,
When the compounds represented by the general formulas [I], [II], [III] and [IV] are aged without addition and the exemplified compounds I-1, II-2, III-1 and IV-1 of the present invention Was added immediately after synthesizing the polymer latex, and then the increase in filtration pressure was compared with the case of aging.

[Evaluation of increase in filtration pressure]

FIG. 1 is a diagram for explaining the basic configuration of a filtration pressure measuring device. In Fig. 1, each polymer latex 2
Is placed in the polymer latex storage container 1, and a filter 5 (having a filter pressure sensor) is provided by means of a liquid feed pump and a liquid feed pipe 3.
To the polymer latex receiver 9. The increase (Δp) in filtration pressure at that time was detected as an electric signal (filtration pressure amplifier 6, recorder 7, wiring 8) and evaluated.

Increase of filtration pressure Δp is 25 ml of polymer latex transfer rate
It was evaluated by the filtration pressure through a filter (manufactured by Kokusai Densoku Co., Ltd.) equipped with a filter (manufactured by Nippon Pall Co., Ltd., Epocell 3, average pore diameter 3 μm) per minute.

ΔP = P ₁ −P ₀ P ₁ ; filtration pressure (0.5 kg / c) when polymer latex 0.5 l was sent
m ² ) P ₀ ; Filtration pressure (kg / cm ² ) immediately after sending the polymer latex When ΔP = 0.2 kg / cm ² is exceeded, serious trouble occurs in the production of the photographic material.

[Latex polymer storage conditions over time]

It was stored in a sealed polyethylene container at a temperature of 20 to 25 ° C. under light exclusion for 1 month and 6 months.

[Raising filtration pressure of latex polymer composition over time]

Table 1 summarizes the rise in filtration pressure over time for various latex polymer compositions.

From the results shown in Table 1, after the synthesis, very general storage conditions (20 ~
Even at 25 ° C.), the filtration pressure rises even during storage for 1 month, and the unstable production of the photosensitive material makes it impossible to stably produce a photosensitive latex polymer. It will be apparent that the storage stability of the latex polymer is remarkably improved by adding at least one of [IV].

Although details of the cause of the latex polymer storage stability improving effect are not clear, Reference Examples 1, 2 and 3 regarding causes of the latex polymer filtration pressure increase are shown below.

Reference Example 1 Table 2 shows PL-2 among the latex polymers of Example 1.
Changes in particle size of 5, 12, and 16 were investigated immediately after synthesis and under the storage conditions.

The particle size of the latex polymer was measured using Coulter N4 (Nikkaki Co., Ltd.). It can be seen that each latex shows almost no change before and after filtration and regardless of addition of the additive (II). No change in particle size due to storage time is observed.

As described above, it is suggested that the cause of deterioration of filtration pressure over time depending on latex polymer is not due to agglomeration of latex particles, but due to some cause that cannot be detected by the above-mentioned particle size measuring method.

Reference Example 2 The latex polymer PL-2 represented by the general formula [V] is used as the latex polymer, and the general formulas [I] and [I
I), [III], one of the representative compounds of the present invention shown below selected from the compounds represented by [IV] is stored over time with and without addition immediately after latex synthesis, respectively, filtration pressure rise and The state of microbial propagation of the latex polymer at that time was examined.

[Measurement / evaluation method of filtration pressure rise]

 The same procedure as in Example 1 was performed.

[Latex polymer storage conditions]

 Save as in Example 1.

[Evaluation method of microbial reproduction state]

The presence / absence of microorganisms is determined by the simple medium Hajikart Y for food hygiene management that is imported and sold by Daiichi Pure Chemicals Co., Ltd.
& F (for quantifying microorganisms other than bacteria) and Easycult TT
C (for bacteria) was used, the test latex polymer was applied to this simple medium, and then the number was determined by the number of colonies on the medium after storage in a 35 ° C. thermostat for 3 days.

Even if one or more colonies were confirmed, it was judged that there was microbiological growth (positive ... (+) mark).

The sample in which no colony was confirmed was determined to have no microbiological growth (negative ... (-) mark).

The results are shown in Table 3.

Reference Example 3 (Forced Experiment) As the latex polymer, the same cross-linked acrylic acid latex PL-2 as used in Example 1 was used. Compound Example I-1 of the present invention was added to one group of samples in an amount of 0.3% by weight based on the latex liquid, and the other group was left unadded. For forced testing, microorganisms isolated from crosslinked acrylic acid latex were added to all samples immediately after synthesis.

The filtration pressure rise was measured in the same manner as in Example 1 and is shown in Table 4.
As is clear from Table 4, in the sample to which the compound I-1 was added, the filtration pressure did not increase at all and the proliferation of the microorganism was not observed in the sample 6 months after the addition of the microorganism. On the other hand, in the sample without the compound of the present invention, the filtration pressure was increased even after one month, and the microorganisms were actively propagated.

The effect of compound I-1 on the increase in filtration pressure during latex storage is also clear from the above reference examples.

The measurement was carried out in the same manner as in Example 1, but with latex PL-2 alone, the filtration pressure of latex increased with time,
In the latex sample to which one of the compounds [I] to [IV] of the present invention was added, the filtration pressure did not increase even after 6 months, and the effect of improving storage stability was recognized.

Further, according to the results of the microorganism check conducted in parallel, molds and bacteria were inevitably detected in the samples whose filtration pressure increased with time.

It was also confirmed that the compounds [I] to [IV] were dependent on the amount added. When I = 1, 0.3% by weight based on the latex solution, I
For -11, it was found that the addition of 0.05% by weight could almost completely suppress the rise in filtration pressure.

(Effects of the Invention) The present invention is useful for a photographic light-sensitive material which does not cause coating failure such as cissing and does not increase in filtration pressure during filter filtration even after long-term storage and is stable and excellent in production suitability. The latex polymer composition is now ready for delivery.

[Brief description of drawings]

FIG. 1 is a diagram illustrating an example of a filtration pressure measuring device used in the present invention. The numbers in the figure indicate the following. 1 ... Polymer latex storage container 2 ... Polymer latex 3 ... Liquid feeding pipe 4 ... Liquid feeding pump 5 ... Filtration device 6 ... Filtration pressure amplification device 7 ... Recorder 8 ... Wiring (for electrical signal) 9 …… Polymer latex receptor

Claims (2)

[Claims] 1. At least one silver halide photographic light-sensitive material.
The layer is formed by the following general formula [I], [II], [III] or [I]
[V] A method for producing a silver halide photographic material, which comprises using a coating solution prepared by adding at least one latex polymer composition containing at least one compound represented by the formula [V]. General formula [I] In the formula, R ₁ represents a lower alkylene group, X represents a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, —COR ₂ , Represents —SO ₃ M, R ₂ represents a hydrogen atom, —OM, a lower alkyl group, an aryl group, an aralkyl group, a lower alkoxy group, an aryloxy group, an aralkyloxy group, Represents R ₃ and R ₄ are each a hydrogen atom, a lower alkyl group, an aryl group,
Aralkyl group, --COR ₇ , --SO ₂ R ₇ , which may be the same or different from each other, R ₅ and R ₆ each represent a hydrogen atom, a lower alkyl group, an aryl group or an aralkyl group. , Which may be the same or different from each other, R ₇ represents a lower alkyl group, an aryl group or an aralkyl group, and M represents a hydrogen atom, an alkali metal atom or an atom necessary for forming a monovalent cation. Represents a group, m represents 0 or 1 and n represents 0 or an integer from 1 to 5. General formula (II) In the formula, R ₈ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, The stands, R _9, R ₁₀ are each a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an arylthio group,
It represents an alkylsulfoxy group or an alkylsulfonyl group, and R ₉ and R ₁₀ may combine with each other to form an aromatic ring. R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. When R ₈ is an alkyl group, it may be linear, branched or cyclic. When R ₉ and R ₁₀ are alkyl groups, they may be cyclic. General formula (III) In the formula, R ₁₃ represents a hydrogen atom, a lower alkyl group or a hydroxymethyl group, and R ₁₄ represents a hydrogen atom or a lower alkyl group. General formula (IV) R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₀ each represent a hydrogen atom or a lower alkyl group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the latex polymer of the latex polymer composition is represented by the following general formula [V]. General formula [V] In the formula, R ₂₁ represents a hydrogen atom or an alkyl group, and L ₂₁
Represents a divalent, trivalent or tetravalent continuous group. Y represents a hydrophilic functional group. i is 0 or 1, and j is 1, 2 or 3. A is a repeating unit containing a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups, and B
Is a repeating unit containing a monomer having a copolymerizable ethylenically unsaturated group. x is 30 to 90 mole percent, y is 1 to 50 mole percent, and z is 0 to 80 mole percent.