JP2003231708A - Method for producing copolymer fine particle and sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing copolymer fine particles which are easy to produce, and to handle and cause only a small amount of precipitation in a dispersing solution, and to provide a sheet having a hydrophilic binder layer containing the copolymer fine particles, which causes no adhesion upon piling under high humidity and causes no peeling-off on handling under any of dry and wet conditions. <P>SOLUTION: The copolymer fine particles are prepared by suspension polymerization of a mixture containing 0.5-4 mass% of an ethylenic unsaturated monomer having a carboxylic group, 0-20 mass% of an ethylenic unsaturated monomer having a nonionic hydrophilic group and 76-98.5 mass% of a hydrophobic ethylenic unsaturated monomer in the presence of a maleic acid copolymer in a an aqueous medium, followed by addition of a water soluble polymerization initiator. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing copolymer fine particles and a sheet-like material obtained by coating the copolymer fine particles on a support.

[0002]

2. Description of the Related Art It is common practice to prepare a sheet-like material by providing layers for various purposes on the surface of a support such as a plastic film, a glass plate, a synthetic paper or a paper.
For example, various types of binders are used as supports for the purpose of improving mechanical properties such as slipperiness, and imparting functionality such as image formation and receiving and holding pixels (ink, pigment, dye, etc.). Layered on top.

This functional layer is provided by applying a coating liquid containing a binder, but in recent years, in consideration of environmental costs, those using an organic solvent as the coating liquid have been rapidly reduced, Aqueous coating liquids are being used.

Therefore, it is necessary to use a water-soluble polymer or a water-dispersed polymer (for example, latex) as the binder in the coating liquid, but the functional layer formed by these water-based coating liquids is an organic solvent-based coating liquid. It is more likely to contain water than the applied one, and for example, when the sheet-shaped materials are superposed in a high-humidity atmosphere, the problem that the sheet-shaped materials adhere to each other easily occurs.

As a method for preventing such adhesion, particles (matting agent) having a diameter larger than the thickness of the binder have been incorporated.

For example, in the case of silver halide photographic light-sensitive materials, such matting agents include inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide and calcium carbonate, polymethylmethacrylate, polystyrene and ethylcellulose acetate propionate. In many cases, fine particles of an organic substance such as

However, although the use of such a matting agent is effective in preventing adhesion, the matting agent may come off during handling of the sheet-shaped material, and the equipment handling the sheet-shaped material may become dirty.
When the sheet-shaped material and the exfoliated matting agent come into contact with each other, the surface of the sheet-like material is scratched, marks of the matting agent are exfoliated, or when the sheet-shaped material is handled in a wet state, it exfoliates due to swelling of the binder. There was a problem that the quality of the sheet-shaped material deteriorated, such as rust.

Further, the matting agent used for the purpose of preventing the adhesion of the sheet-like material requires a diameter larger than the thickness of the binder, so that it significantly precipitates depending on the size of the particle size, and a recovery step after polymerization. There was a problem with redispersibility during storage of the dispersion liquid or during production of the sheet material.

Various means have been taken to prevent sedimentation, but one of them, which is a method of polymerizing in the presence of gelatin, is that gelation may occur during polymerization depending on the type of the monomer. The types of monomers that can be produced were limited.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing copolymer fine particles (matting agent) which has a small amount of sedimentation in a dispersion liquid and is easy to produce and handle. Another object of the present invention is to provide a sheet-like material having a hydrophilic binder layer containing copolymer fine particles (matting agent) which does not adhere due to the overlapping of the sheet-like materials and does not come off during dry handling or wet handling. .

[0011]

The above objects of the present invention have been achieved by the following constitutions.

1. 0.5 to 4% by mass of ethylenically unsaturated monomer having a carboxylic acid group and 0 to 20% by mass of ethylenically unsaturated monomer having a nonionic hydrophilic group, and hydrophobic ethylenically unsaturated monomer A method for producing fine copolymer particles, which comprises adding a water-soluble polymerization initiator after suspension-polymerizing a mixture of the body 76 to 98.5 mass% in the presence of a maleic acid-based copolymer in an aqueous medium.

2. 0.5 to 4% by mass of ethylenically unsaturated monomer having a carboxylic acid group and 0 to 20% by mass of ethylenically unsaturated monomer having a nonionic hydrophilic group, and hydrophobic ethylenically unsaturated monomer Preparation of copolymer fine particles, characterized in that a water-soluble polymerization initiator and gelatin are added after suspension polymerization of a mixture of the body 76 to 98.5 mass% in the presence of a maleic acid copolymer in an aqueous medium. Method.

3. A sheet-like material comprising at least one hydrophilic binder layer and a layer containing the copolymer fine particles produced by the production method described in 1 above on a support.

4. A sheet-like material, comprising at least one hydrophilic binder layer on a support and a layer containing the copolymer fine particles produced by the production method described in 2 above.

The present invention will be described in more detail. Specific examples of the ethylenically unsaturated monomer having a carboxylic acid group include (meth) acrylic acid, itaconic acid and maleic acid. In the carboxylic acid group-containing monomer, at least one of the carboxylic acid groups in the carboxylic acid group-containing monomer may be a salt with an alkali metal or an alkaline earth metal.

Specific examples of the ethylenically unsaturated monomer having a nonionic hydrophilic group according to the present invention are shown below, and any of them is preferably used.

For example, 2-hydroxyethyl acrylate, polyethylene glycol monoacrylate (polymerization degree of polyethylene glycol: 2 to 20), 2-hydroxy-propyl acrylate, poly (2-methylethylene glycol) monoacrylate (poly (2-methyl Polymerization degree of ethylene glycol: 2 to 20), 2,3-dihydroxypropyl acrylate, 2-N-pyrrolidone ethyl acrylate, 2-hydroxyethyl acrylate, polyethylene glycol monomethacrylate (polymerization degree of polyethylene glycol: 2 to 20), Polymerization degree of 2-hydroxy-propyl methacrylate, poly (2-methylethylene glycol): (2-20), 2,3-dihydroxypropyl methacrylate, 2-N-pyrrolidone ethyl methacrylate DOO, N- vinylpyrrolidone, N-
Vinyl oxazolidone, acrylamide, N-2-hydroxyethyl acrylamide, N, N-diethanol acrylamide, N- (2- (polyethylene glycol)
Ethyl) acrylamide (polyethylene glycol polymerization degree: 2 to 20), N, N- (2,2 '-(polyethylene glycol) diethyl) acrylamide (polyethylene glycol polymerization degree: 2 to 20), N-methyl acrylamide, N -Ethyl acrylamide, N-propyl acrylamide, methacryl acrylamide, N-2-hydroxyethyl methacrylamide, N, N-diethanol methacrylamide, N- (2- (polyethylene glycol) ethyl) methacrylamide (degree of polymerization of polyethylene glycol: 2 To 20), N, N- (2,2 '-(polyethylene glycol) diethyl) methacrylamide (degree of polymerization of polyethylene glycol: 2 to 20), N-
Methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, p-hydroxymethyl styrene, p- (2-hydroxyethyl) styrene, p- (2-hydroxyethyloxycarbonyl) styrene, p- (polyethylene glycoloxy) Carbonyl) styrene (Polyethylene glycol polymerization degree: 2
20), p-((polyethylene glycol) oxymethyl) styrene (polyethylene glycol polymerization degree: 2
20) and the like, but the present invention is not limited thereto.

The hydrophobic ethylenically unsaturated monomer is not particularly limited, but examples thereof include acrylic acid esters such as methyl acrylate, ethyl acrylate,
(N-, i-) propyl acrylate, (i-, s-,
t-) butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, myristyl acrylate, lauryl acrylate, stearyl acrylate, phenyl acrylate, cresyl acrylate, benzyl acrylate. , Phenethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, 2-naphthyl acrylate, etc .; as methacrylic acid esters, methyl methacrylate, ethyl methacrylate, i-propyl methacrylate, (i-,
s-, t-) Butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, myristyl methacrylate, lauryl methacrylate, stearyl methacrylate, phenyl methacrylate, cresyl methacrylate. , Benzyl methacrylate, phenethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, 2-naphthyl methacrylate, etc .; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, vinyl caproate, benzoate. Vinyl acrylate; Butyl acrylamide, t- as acrylamides Tyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, β-cyanoethyl acrylamide, diacetone acrylamide, etc .; Methacrylamides such as propyl methacrylamide, butyl methacrylamide, t-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, etc .; styrene as styrene, Methyl styrene, dime Rustyrene, trimethylenestyrene, ethylstyrene, i-propylstyrene, chlorostyrene, methoxystyrene, acetoxystyrene, chlorostyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene; acrylonitrile as other monomer, Examples thereof include vinylidene chloride and phenyl vinyl ketone.

Further, a crosslinkable ethylenically unsaturated monomer may be used, for example, hydroquinone diacrylate, hydroquinone dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol. Dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, 1,
4-butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol triacrylate,
Glycerol tridimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1
-Trishydroxymethylethane triacrylate,
1,1,1-Trishydroxymethylethane dimethacrylate, 1,1,1-Trishydroxymethylethane trimethacrylate, 1,1,1-Trishydroxymethylpropane diacrylate, 1,1,1-Trishydroxymethylpropane trimethacrylate Methacrylate, triallyl cyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, divinylbenzene and the like can be mentioned. Moreover, you may combine the said monomer in multiple types.

The suspension polymerization in the present invention can be carried out by a general suspension polymerization method in which a monomer in which an initiator is dissolved is dispersed in an aqueous medium or is polymerized while being dispersed.

In the suspension polymerization of the present invention, the amount of the maleic acid copolymer used is 0.1 to 25 in the aqueous suspension.
It is preferably in the range of mass%.

The maleic acid-based copolymer is a copolymer obtained from a compound copolymerizable with maleic acid.
In the present invention, examples of the copolymer with maleic acid include styrene, isobutylene, diisobutylene, ethylene, methyl vinyl ether, acrylonitrile, propylene, butadiene and vinyl acetate. Of these, styrene, ethylene and isobutylene are preferable. Most preferred is styrene. The molecular weight is preferably 20,000 to 100,000, particularly preferably 30,000 to 70,000. The degree of esterification is 2
0 to 50% is preferable, and 35 to 50% is particularly preferable.

In the suspension polymerization in the present invention, a surfactant may be used as a dispersant for the monomer. For example,
Sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl (phenyl) ether sulfate,
Anionic surfactants such as sodium dialkyl sulfosuccinate, polyoxyethylene alkyl (phenyl)
Nonionic surfactant such as ether, sodium salt of (meth) acrylic acid polyoxyethylene sulfate,
Sodium alkyl allyl sulfosuccinate, anionic polymerizable surfactant such as glycerin allyl nonylphenyl polyoxyethylene sulfate ammonium ether, nonionic polymerizable such as polyoxyethylene alkylbenzene (meth) acrylate, glycerin allyl nonyl phenyl polyethylene glycol ether Examples thereof include surfactants.

The oil-soluble polymerization initiator used in the suspension polymerization of the present invention is preferably monomer-soluble.
Generally used ones such as organic solvent-soluble peroxides and azobis compounds can be used.

For example, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), lauryl peroxide, benzoyl peroxide and the like can be mentioned. Further, a chain transfer agent may be added to the monomer as needed.

In the present invention, it is necessary to add the water-soluble polymerization initiator to the aqueous medium after the polymer particles are formed.

As the water-soluble polymerization initiator used in the present invention, persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2, 2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane]
Examples thereof include azo initiators such as dihydrochloride. These may be used alone or in combination of two or more, and persulfate is particularly preferable.

The amount of the water-soluble polymerization initiator added is preferably in the range of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the granular vinyl polymer.

Other suspension stabilizers include anionic fine particle suspension stabilizers (silica, clay, talc, etc.), anionic, cationic and nonionic surfactants ((sulfonated)).
Alkylaryl polyethers, polyhydric alcohol ethylene glycol ethers, carboxyalkyl-substituted polyglycol ethers and esters, sodium salts of condensation products of naphthalenesulfonic acid and formaldehyde,
(Glycidol polyether phosphoric acid ester, higher alcohol sulfuric acid ester, fatty acid ester derivative of sulfosuccinic acid, α-sulfo lower alkyl ester of fatty acid and sulfuric acid ester product of glycidol polyether, etc.)
Can be used.

The polymerization conditions for obtaining the copolymer fine particles of the present invention are preferably a reaction temperature of 50 to 90 ° C, more preferably 55 to 85 ° C. The stirring may be carried out for 10 to 120 minutes when the monomer is dispersed and heating for 1 to 10 hours.

The glass transition temperature (Tg) of the copolymer fine particles of the present invention can be appropriately selected depending on the application, but is preferably 40 ° C. or higher, more preferably 70 ° C. or higher.

The average particle size of the copolymer fine particles of the present invention can be appropriately selected depending on the application, but the diameter is preferably not less than the thickness of the hydrophilic binder layer, more preferably 1.5 to 4 times.

Examples of the hydrophilic binder of the hydrophilic binder layer preferably used in the present invention include a hydrophilic protective colloid and an aqueous dispersion of a resin. Gelatin is preferably used as the binder of the hydrophilic colloid layer, but other hydrophilic colloids can be used together.

For example, gelatin derivatives, graft polymers of gelatin with other polymers; proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, sodium alginate, cellulose sulfate, dextrin, dextran. , Sugar derivatives such as dextran sulfate; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Can be used. As the gelatin, besides lime-processed gelatin, acid-processed gelatin may be used in combination, and further, a hydrolyzed product of gelatin or an enzymatically decomposed product of gelatin may be used.

The sheet material of the present invention is characterized in that a hydrophilic binder layer is provided on a support. Examples of the support include polyethylene terephthalate (PE
T), polyethylene naphthalate (PEN), plastic films such as triacetyl cellulose (TAC),
Papers such as polyethylene (PE), coated paper, coated paper,
Examples thereof include glass.

The use of the sheet material is not particularly limited, and examples thereof include silver halide photographic light-sensitive materials, thermal transfer recording materials, printing plate materials, ink jet recording materials and the like. In particular, it is preferably used for silver halide photographic light-sensitive materials.

[0038]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

<Manufacturing Method of Copolymer Fine Particles (Matting Agent)> MA-1 10 g of hydroxyethyl methacrylate, 4 g of methacrylic acid, 70 g of methyl methacrylate and 16 g of styrene were mixed, and 4 g of lauryl peroxide as a polymerization initiator was added to the mixed monomer. Dissolve. On the other hand, water 400
5 g of a copolymer of methyl vinyl ether and maleic anhydride and 0.6 g of sodium dioctylsulfosuccinate.
g is dissolved, the above-mentioned monomer and polymerization initiator are added to the solution while stirring, and the solution is dispersed at 2500 rpm for 30 minutes. This suspension was placed in a 1 liter round bottom flask and heated at 60 ° C. for 5 hours while slowly stirring, and then it was visually confirmed that polymer particles were formed, and 0.5 g of ammonium persulfate was added to the suspension. After heating for an hour, the resulting polymer particle dispersion was designated as MA-1. The arithmetic particle size measured by Multisizer was 6.8 μm.

MA-2 5 g of hydroxyethyl methacrylate, acrylic acid 2
g, 77 g of methyl methacrylate and 16 g of styrene are mixed, and 4 g of lauryl peroxide, a polymerization initiator, is dissolved in this mixed monomer. On the other hand, 400g of water
In addition, 4 g of a copolymer of methyl vinyl ether and maleic anhydride and sodium dodecylbenzenesulfonate 0.2
g is dissolved, the above-mentioned monomer and polymerization initiator are added while stirring the solution, and the mixture is dispersed at 2000 rpm for 60 minutes. This suspension was placed in a 1 liter round bottom flask and heated at 60 ° C. for 5 hours while slowly stirring, and then it was visually confirmed that polymer particles were formed, and 0.5 g of ammonium persulfate was added to the suspension. After heating for an hour, the resulting polymer particle dispersion was designated as MA-2. The arithmetic particle size measured by Multisizer was 8.0 μm.

MA-3 10 g of hydroxyethyl methacrylate, 4 g of methacrylic acid and 86 g of methyl methacrylate are mixed, and 4 g of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) is dissolved in this mixed monomer. . On the other hand, in 400 g of water, 1 g of a copolymer of methyl vinyl ether and maleic anhydride and 0.6 g of sodium dioctylsulfosuccinate were dissolved and placed in a 1 liter round bottom flask, and the monomer and the polymerization initiator were stirred while stirring the solution. Is added and dispersed at 2500 rpm at 60 ° C.
After heating, the dispersion was stopped after 2 hours from the start of heating, and after standing still for 3 hours, the formation of polymer particles was visually confirmed, 0.5 g of sodium persulfate was added, and heating was continued for 10 hours. After that, the generated polymer particle dispersion is added to M
It was set to A-3. The arithmetic particle size measured by Multisizer was 7.6 μm.

MA-4 hydroxyethyl methacrylate 1 g, acrylic acid 2
g, mixed with 97 g of methyl methacrylate monomer,
4 g of a polymerization initiator, lauryl peroxide, is dissolved in this mixed monomer. On the other hand, 4 g of a copolymer of methyl vinyl ether and maleic anhydride and 0.2 g of sodium dodecylbenzenesulfonate were dissolved in 400 g of water, and the above-mentioned monomer and polymerization initiator were added while stirring the solution, and the mixture was added at 30 rpm at 2500 rpm. Disperse for minutes. This suspension was placed in a 1 liter round bottom flask and heated at 60 ° C. for 5 hours while slowly stirring, and then it was visually confirmed that polymer particles were formed, and 50 g of a 5% gelatin solution which had been swollen and dissolved in advance was added. 0.5 g of ammonium persulfate was added, and after heating for further 10 hours, the resulting polymer particle dispersion was designated as MA-4. The arithmetic particle size measured by Multisizer was 8.2 μm.

<Method for producing comparative copolymer fine particles (matting agent)> MA-11 10 g of hydroxyethyl methacrylate, 4 g of methacrylic acid, 70 g of methyl methacrylate, and 16 g of styrene were mixed, and 4 g of lauryl peroxide as a polymerization initiator was mixed with the mixed monomer. Dissolve. On the other hand, water 400
5 g of a copolymer of methyl vinyl ether and maleic anhydride and 0.6 g of sodium dioctylsulfosuccinate.
g is dissolved, the above-mentioned monomer and polymerization initiator are added while stirring the solution, and the mixture is dispersed at 2000 rpm for 30 minutes. This suspension was placed in a 1-liter round bottom flask and heated at 60 ° C. for 15 hours with slow stirring, and the resulting polymer particle dispersion was designated as MA-11. The arithmetic particle size measured by Multisizer was 6.9 μm.

MA-12 A mixture of 10 g of hydroxyethyl methacrylate, 74 g of methyl methacrylate and 16 g of styrene was added,
4 g of a polymerization initiator, lauryl peroxide, is dissolved in this mixed monomer. On the other hand, in 400 g of water, 5 g of a copolymer of methyl vinyl ether and maleic anhydride and 0.6 g of sodium dioctylsulfosuccinate were dissolved, and the monomer and the polymerization initiator were added while stirring the solution,
Disperse at 2000 rpm for 30 minutes. Place this suspension in a 1 liter round bottom flask and mix with gentle stirring to 60
After heating at 0 ° C. for 5 hours, 50 g of a 5% gelatin solution swollen and dissolved in advance was added, and after heating for 10 hours, the resulting polymer particle dispersion was designated as MA-12. The arithmetic particle size measured by Multisizer was 7.6 μm.

MA-13: A mixture of 10 g of hydroxyethyl methacrylate, 4 g of methacrylic acid, 70 g of methyl methacrylate and 16 g of styrene, and 4 g of lauryl peroxide as a polymerization initiator is dissolved in the mixed monomer. On the other hand, water 400
In 3 g, 3 g of gelatin was swollen and dissolved, and 0.6 g of sodium dioctylsulfosuccinate was further dissolved. While stirring the solution, the monomer and the polymerization initiator were added, and 2
Disperse for 30 minutes at 000 rpm. Add this suspension to a 1 liter round bottom flask and slowly stir at 60 ° C.
When heated at, gelation occurred. No polymer particle dispersion of MA-13 was obtained.

The following silver halide photographic light-sensitive material (sheet-like material) is prepared using the copolymer fine particles shown in Table 1.

<Preparation of Emulsion Em-1> An emulsion Em-1 comprising tabular silver iodobromide grains was prepared as follows.

(A-1 Solution) Ocein gelatin 24.2 g Water 9657 ml 10% methanol solution of surfactant (EO-1) 1.20 ml Potassium bromide 10.8 g 10% nitric acid 160 ml EO-1: HO (CH _{2 CH 2 O) n [CH} (CH 3) CH 2 O] 17 (CH 2 CH 2 O) m H (n + m = 5~7) (B-1 solution) 2.5 mol / L aqueous silver nitrate solution 2825ml (C -1 liquid) potassium bromide 841 g with water 2825 ml (D-1 liquid) ossein gelatin 121 g water 2040 ml 10% methanol solution of surfactant (EO-1) 5.70 ml (E-1 liquid) 1.75 mol / L potassium bromide aqueous solution Using the mixing stirrer described in JP-B-58-58288, 475.0 ml each of solution B-1 and solution C-1 was added to solution A-1 at 35 ° C. The mixing method was added at 2.0 minutes and subjected to nucleation.

After the addition of solutions B-1 and C-1 was completed, 60
The temperature of the A-1 solution was raised to 60 ° C over a period of time, the whole amount of the D-1 solution was added, the pH was adjusted to 5.5 with a 3% aqueous solution of potassium hydroxide, and the B-1 solution and the C-1 solution were again prepared. 5 each
It was added for 42 minutes at an addition rate of 5.4 ml / min. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +8 mV and +30 mV using the E-1 solution.

After the addition was completed, the pH was adjusted to 6.0 with a 3% aqueous solution of potassium hydroxide and immediately desalted and washed with water to obtain a seed emulsion. Observation of this seed emulsion with an electron microscope revealed that 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0: 2.0.
The hexagonal tabular grains had an average thickness of 0.090 μm and an average equivalent circle diameter of 0.510 μm.

The resulting seed emulsion was heated to 53 ° C., and 450 mg of spectral sensitizing dye (SD-1) and spectral sensitizing dye (SD-2) were added.
After adding 8 mg as a solid fine particle dispersion, an aqueous solution containing 60 mg of stabilizer (ST-1), 15 mg of adenine, 50 mg of ammonium thiocyanate, 2.5 mg of chloroauric acid and 5.0 mg of sodium thiosulfate, silver iodide. A dispersion liquid containing 5 mg of a fine grain emulsion (average particle diameter of 0.05 μm) and 6.0 mg of a selenium sensitizer (Se-1) was added, and the mixture was aged for a total of 2 hours and 30 minutes. ST-1 at the end of aging
750 mg was added.

A solid fine particle dispersion of the spectral sensitizing dye was obtained by adding the dye to water at 27 ° C. and stirring with a high-speed stirrer (dissolver) at 3500 rpm for 30 to 120 minutes. Moreover, the dispersion liquid of Se-1 contains 120 g of Se-1 in 5%.
Add to 30 kg of ethyl acetate at 0 ° C. and stir to completely dissolve it, while dissolving 3.8 kg of gelatin in 38 kg of pure water, add 93 g of a 25% aqueous solution of sodium dodecylbenzenesulfonate, and add The two liquids were mixed and dispersed with a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. and a dispersing blade peripheral speed of 40 m / sec for 30 minutes, and then the pressure was rapidly reduced to a residual ethyl acetate concentration of 0.3 mass. Ethyl acetate was removed with stirring until the content became less than 50%, and the mixture was diluted with pure water to obtain 80 kg.

SD-1: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl)
Oxacarbocyanine sodium salt SD-2: anhydro-5,5'-di (butoxycarbonyl) -1,1'-diethyl-3,3'-di (4-sulfobutyl) benzimidazolocarbocyanine sodium Salt ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene Se-1: triphenylphosphine selenide <Preparation of emulsion Em-2> Using emulsion Em-1 as a seed emulsion,
Emulsion Em consisting of tabular silver iodobromide grains using the following solution
-2 was prepared.

[0054]   (A-2 solution)   Oscein gelatin 19.04g   2.00 ml of 10% methanol solution of surfactant (EO-1)   Potassium iodide 7.00 g   Em-1 equivalent to 1.55 mol   Make up to 2800 ml with water   (B-2 solution)   Potassium bromide 1493g   Make up to 3585 ml with water   (C-2 solution)   Silver nitrate 2131g   Make up to 3585 ml with water   (D-2 liquid)   3% gelatin and silver iodide grains (average grain size 0.05 μm)     Fine particle emulsion consisting of (*) equivalent to 0.028 mol   * 5.0 mass% gelatin aqueous solution 6.64 containing 0.06 mol of potassium iodide An aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide per liter. 2 liters of each solution was added over 10 minutes. The pH during the formation of fine particles is nitric acid. It was used at 2.0 and the temperature was controlled at 40 ° C. After forming particles, aqueous sodium carbonate solution Was used to adjust the pH to 6.0.

Liquid A-2 was vigorously stirred in the reaction vessel while keeping it at 55 ° C., and half of liquid B-2 and liquid C-2 were added by the simultaneous mixing method over 35 minutes. During this period, the pH was kept at 5.8. The pH was adjusted to 8.8 with a 1% aqueous potassium hydroxide solution, and the B-2 solution, C-2 solution and D-2 solution were added to D-
The two liquids were added by the double-mix method until the liquids disappeared. The pH was adjusted to 6.0 with a 0.3% aqueous solution of citric acid, and the B-2 solution and the C-2 solution were used.
The remaining amount of the liquid was added by the simultaneous mixing method over 25 minutes. During this period, pAg was kept at 8.9. The addition rates of the B-2 solution and the C-2 solution were changed in a function-like manner according to the critical growth rate to suppress the generation of small particles and the polydispersion due to Ostwald ripening.

After completion of the addition, desalting, washing with water and redispersion were carried out in the same manner as Em-1. After redispersion, the pH was 5.80 at 40 ° C.
The pAg was adjusted to 8.2.

When the obtained silver halide emulsion was observed by an electron microscope, the average equivalent circle diameter was 0.91 μm,
Average thickness of 0.23 μm, average aspect ratio of about 4.0, width of particle size distribution (standard deviation of particle size distribution / average particle size) 20.
The emulsion consisted of 5% tabular silver halide grains.

The thus obtained emulsion was heated to 47 ° C., and 5 mmol of the above silver iodide fine grain emulsion, spectral sensitizing dye (SD-1) 3
After adding 90 mg and spectral sensitizing dye (SD-2) 4 mg as a solid fine particle dispersion, adenine 10 mg, ammonium thiocyanate 50 mg, chloroauric acid 2.0 mg
And an aqueous solution containing 3.3 mg of sodium thiosulfate,
(Se-1) 4.0 mg of the dispersion liquid was added, and the total was 3 hours for 3 hours.
Aged for 0 minutes. ST-1 at 750m at the end of aging
g was added.

A silver halide photographic light-sensitive material was prepared according to the following formulation, using an emulsion prepared by mixing the prepared Em-1 and Em-2 at a mass ratio of 6: 4.

(Preparation of sheet material 1) The following formulation (per surface) was applied to both surfaces of a 175 μm thick polyethylene terephthalate film base colored blue with a concentration of 0.15.
In the order of crossover cut layer, emulsion layer, intermediate layer, and protective layer, the amount of silver per side is 1.8 g / m ² , the protective layer gelatin amount is 0.4 g / m ² , and the intermediate layer gelatin amount is 0.4 g / m ² .
m ² , emulsion layer gelatin amount 1.5 g / m ² , crossover cut layer gelatin amount 0.2 g / m ² ,
It was dried to prepare a silver halide photographic light-sensitive material 1 (sheet-shaped material 1).

The amount of each additive is the amount per 1 m ² of the light-sensitive material. First layer (crossover cut layer) Solid fine particle dispersion dye AH 180 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound I 5 mg Latex L 0.2 g Hardener H-1 5 mg Colloidal silica (average particle diameter 0.014 μm ) 10 mg Hardener H-2 2 mg Second layer (emulsion layer) Gelatin 1.5 g Silver halide emulsion 1.8 g (silver amount) Compound G 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino- s-Triazine 5 mg t-Butylcatechol 130 mg Polyvinylpyrrolidone (average molecular weight 10000) 35 mg Styrene-maleic anhydride copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylol propane 350 mg Diethylene glycol 50 mg Nitrophenyl-tri Phenyl-phosphonium chloride 20 mg Resorcin-4-ammonium sulfonate 500 mg 2-Mercaptobenzimidazole-5-sulfonate 5 mg Compound H 0.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg 1- (3-sulfophenyl) -5-mercaptotetrazole sodium 5 mg 1- (3-carboxyphenyl) -5-mercaptotetrazole 5 mg colloidal silica 0.5 g latex L 0.2 g dextran (average molecular weight 1000) 0.2 g compound P 0.2 g 2-anilino-4,6-dimercapto-s-triazine monosodium 0.2 g Third layer (intermediate layer) gelatin 0.4 g Hardener formaldehyde 10 mg Hardener H-1 5 mg Hardener bis (Vinyls Honylmethyl) ether 18 mg Latex L 0.05 g Sodium polyacrylate 10 mg Compound S-1 3 mg Compound K 5 mg Hardener H-3 1 mg Fourth layer (protective layer) Gelatin 0.4 g Copolymer fine particles (matting agent) (Table 1) Description) 50 mg hardener formaldehyde 10 mg hardener H-1 5 mg hardener bis (vinylsulfonylmethyl) ether 18 mg latex L 0.1 g polyacrylamide (average molecular weight 10000) 0.05 g sodium polyacrylate 20 mg polysiloxane SI 20 mg Compound I 12 mg Compound J 2 mg Compound S-1 7 mg Compound K 15 mg C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 50 mg Compound S-2 5 mg C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 1 mg Hardener H-3 1.5 mg

[0062]

[Chemical 1]

[0063]

[Chemical 2]

Hardener H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium hardener H-2: Hexahydro-1,3,5-triacryloyl-s-triazine compound J: p -Ethylene oxide 1 of nonylphenol
2 mol adduct compound S-1: sulfosuccinic acid (i-amyl dodecyl)
Sodium salt compound S-2: Bis (2,3,3,3) sulfosuccinate
4,4,5,5,6,6,7,7-dodecylfluoroheptyl) sodium salt As described in Table 1, the sheet-shaped material 2 was prepared in the same manner as the sheet-shaped material 1 except that the copolymer fine particle species was changed. 4, 1
1, 12 were produced.

On the emulsion layer side of the silver halide photographic light-sensitive material, the amount of gelatin in the emulsion layer and the amount of gelatin in the protective layer were adjusted so that the thickness of the portion without the copolymer fine particles was 3.8 μm.
Was manufactured.

Evaluation Method <Evaluation of Sedimentation Property> The coating solution was allowed to stand for 24 hours at 35 ° C., and evaluated by the amount of sedimentation of the copolymer fine particles.

[0067] ◎: Practical with less than 15% ◯: Practical with less than 30% X: More than 30% and not practical.

<Evaluation of Sticking> Six pieces of each silver halide photographic light-sensitive material sample were cut into a size of 3.5 cm × 10 cm, and 3 pieces were taken so as not to contact each other.
It was left for 1 day in an atmosphere of 0 ° C. and 80% RH. afterwards,
Six samples were piled up and left still under the same atmosphere for one day with a weight of 800 g being applied.

Thereafter, with the weight applied, at 23 ° C. and 50
The sample was peeled off after standing for 1 day in an atmosphere of% RH.

The state of adhesion when peeled off was evaluated on a 5-point scale.
The evaluation criteria are as follows. 5: Peel without resistance, no adhesion mark 4: Peel without resistance, but adhesion mark is less than 20% of the total area 3: Peel without resistance, but adhesion mark is 20% to 6% of the total area
Less than 0% can be seen 2: Resistance to peeling is felt, and 60% or more of adhesion area is observed 1: There is resistance to peeling, and peeling of the hydrophilic binder is recognized.

<Evaluation of Dry Stripping Property> The emulsion side surface of each silver halide photographic light-sensitive material sample was fixed on a metallic flat test table, and a felt material was stuck on the surface to a thickness of 5 mm, 1
A stainless steel plate with a square cm square bottom is contacted so that the felt surface touches the surface of each sample.
A load of 500 g was applied, and the sample was rubbed back and forth 20 times in a plane direction over a length of 5 cm.

The surface after rubbing was observed and the level of exfoliation of the copolymer fine particles was evaluated on a 5-point scale. 5: No peeling off 4: Slight peeling off 3: Clear peeling off 2: Almost peeling off 1: Complete peeling off

<Evaluation of wet peelability> After the development processing described below was performed, the evaluation was made according to the evaluation criteria described later. For the development processing, the following developing solution and fixing solution were put in an automatic processor SRX-701 (manufactured by Konica Corp.), and dry-to-dry 30
Each sample was processed in seconds mode. The replenishment amount for developing and fixing is 7 pieces per 1 sheet (25.4 cm x 30.5 cm)
It was set to be ml. (Developer formulation) Part-A hydroxide potassium 450 g potassium sulfite (50% solution) 2280 g diethylenetriamine pentaacetic acid 120 g sodium hydrogen carbonate 132 g 5-methylbenzotriazole 1.2 g 1-phenyl-5-mercaptotetrazole 0.2 g 1, 4-dihydroxybenzene 340 g Part-B glacial acetic acid 170 g triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitroindazole 0.4 g starter solution formulation (for 1 liter finish) glacial acetic acid 120 g potassium bromide 225 g Finish to 1000 ml (fixer formulation) Part-A Ammonium thiosulfate (70 mass / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Natri citrate Um 50 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B Aluminum sulphate 800 g (Preparation of developer) The developer is prepared by adding P to about 1 liter of water.
Art-A and Part-B were added at the same time, water was added while stirring and dissolving to make 10 liter, and pH was adjusted to 1 with glacial acetic acid.
It was adjusted to 0.50 and used as a developing solution. Add 20 ml of the starter solution to 1 liter of this developing solution, and p
The H was adjusted to 10.40 to obtain a working solution.

(Preparation of Fixing Solution) To prepare a fixing solution, Part-A and Part-B were simultaneously added to about 5 liters of water, and water was added while stirring and dissolving to make 18 liters, and sulfuric acid and sodium hydroxide were added. The pH was adjusted to 4.4 using the solutions as the fixer working solution and fixer replenisher.

The processing temperature was 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing, and 45 ° C. for drying.

After the development, the surface was observed, and the peeling level of the fine particles of the copolymer was evaluated on a 5-point scale. 5: No peeling off 4: Slight peeling off 3: Clear peeling off 2: Almost peeling off 1: Complete peeling off

<Transparency> The transparency of each sheet-shaped material was visually evaluated on a scale of 5 according to the following evaluation criteria.

5: Very high transparency, clear film 4: Very slightly opalescent, but not much less transparent 3: Slightly opalescent, slightly less transparent than 4: 2: Transparency Slightly bad 1: The film is milky white and has almost no transparency. Table 1 shows the above process and results.

[0079]

[Table 1]

From Table 1, when the copolymer fine particles of the present invention are used as a matting agent, there is no adhesion due to superposition of sheet-like materials in a high humidity atmosphere, and dry handling
It can be seen that a sheet-like material that does not fall off can be obtained in either case during wet handling.

[0081]

EFFECTS OF THE INVENTION The present invention provides a method for producing copolymer fine particles, which has less sedimentation in a dispersion liquid and is easy to produce and handle, and can be adhered by stacking sheet-like materials in a high-humidity atmosphere. It was possible to provide a sheet-like material having a hydrophilic binder layer containing copolymer fine particles that does not fall off during dry handling or wet handling.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J011 AA08 BA03 BA04 BA08 JA13                       PA70 PC02                 4J026 AA53 AC23 BA24 BA27 BA28                       BA29 BA30 FA03 GA06                 4J100 AB02P AB07P AB07R AC04P                       AF10P AG02P AG04P AG08P                       AJ02Q AJ08Q AJ09Q AL03P                       AL04P AL05P AL08P AL08R                       AL66P AM15P AM15R AM21R                       AQ08R AQ15R BA02P BA02R                       BA03P BA03R BA04P BA05P                       BA10P BA15R BA31P BA40P                       BB01P BB03P BC04P BC43P                       BC49P BC54P BC68R BC80R                       CA05 EA09 FA21

Claims (4)

[Claims] 1. 0.5 to 4% by mass of an ethylenically unsaturated monomer having a carboxylic acid group and 0 to 20% by mass of an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylene. A copolymer characterized by adding a water-soluble polymerization initiator after suspension polymerization of a mixture of 76 to 98.5% by mass of a water-unsaturated monomer in an aqueous medium in the presence of a maleic acid copolymer. Method for producing fine particles. 2. 0.5 to 4% by mass of an ethylenically unsaturated monomer having a carboxylic acid group and 0 to 20% by mass of an ethylenically unsaturated monomer having a nonionic hydrophilic group and a hydrophobic ethylene. Characterized in that a water-soluble polymerization initiator and gelatin are added after suspension polymerization of a mixture of 76 to 98.5% by mass of a polyunsaturated monomer in the presence of a maleic acid copolymer in an aqueous medium. A method for producing fine particles of a copolymer. 3. A sheet-like material comprising at least one hydrophilic binder layer and a layer containing the copolymer fine particles produced by the production method according to claim 1 on a support. 4. A sheet-like material comprising a support and at least one hydrophilic binder layer and a layer containing the copolymer fine particles produced by the production method according to claim 2.