JP2001026605A - Active methylene-containing polymer latex, its production, and sheet material coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active methylene contg. polymer latex giving little remaining monomer and coagulated substance which shows stability during polymerization and improved stability over time, and its production method, and a sheet material having excellent transparency, coating properties, film strength, and film adhesion, when it is applied on a support. SOLUTION: In the production method of an active methylene group-contg. polymer latex by polymerizing in an aq. solution contg. a hydrophilic polymer, the method satisfies the following polymn. conditions, (1) the active methylene contg. monomer is 10-50 wt.% of the total used monomer, (2) concn. of solid component is 15-35 wt.% of the total weight, (3) a polymerization initiator is 0.15-0.45 mol% of the total used monomer, (4) polymerization temp. is 30-85 deg.C, (5) polymerization time is 3-6 hr. (6) required stirring power is 0.2-1.0 W/m3, and (7) viscosity of the finished latex is 8-30 cP(centi Poise).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer latex containing an active methylene group, a polymer latex containing an active methylene group, and a sheet material coated with the same on a support. In particular, it relates to a sheet material useful for an image recording material.

[0002]

2. Description of the Related Art Active methylene group-containing polymers can be used in various fields such as adhesives, coating agents, and binders for sheet materials because of their specific reactivity (for example, JP-A-8-104829, Id 8-2836
No. 27, No. 9-310042 and No. 7-286130
No.).

[0003] In image recording materials, generally gelatin is often used as a binder. However, by partially replacing the latex obtained by polymerizing a monomer having an active methylene group in the presence of a hydrophilic polymer with gelatin, the pressure resistance performance is improved. It is known that sensitivity is improved. Examples of using an active methylene group-containing polymer in a silver halide photographic light-sensitive material are described in JP-A-7-239523 and JP-A-7-239523.
Nos. 137060 and 8-304946.

However, a latex obtained by polymerizing a monomer having an active methylene group in the presence of a hydrophilic polymer synthesized by a conventional method has a high viscosity, is inferior in stability at the time of polymerization, has a large amount of residual monomer, and has an agglutination. It was difficult to obtain a polymer having desired properties due to poor stability over time. As a result, when the composition is applied to a support as a sheet material, the applicability is unsatisfactory, and the film strength and adhesiveness of the object to be applied cannot be sufficiently obtained, and many points to be improved remain. .

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an active methylene group-containing polymer latex having low viscosity, stable polymerization, little residual monomers and aggregates, and improved stability over time. I will provide a. It is still another object of the present invention to provide a sheet material having excellent coatability, adhesiveness and film strength when applied to a support using the same.

[0006]

The present invention has the following constitution.

(1) In a method for producing an active methylene group-containing polymer latex, which is polymerized in an aqueous solution containing a hydrophilic polymer, a monomer having an active methylene group is used in an amount of 10 to 50% by weight based on all monomers used. The solid concentration is 15 to 35 based on the weight.
% By weight The polymerization initiator of the oxidizing agent was added in an amount of 0.1% based on all the monomers used.
15 to 0.45 mol% Polymerization temperature: 30 to 85 ° C. Polymerization time: 3 to 6 hours Stirring required power: 0.2 to 1.0 W / m ³ Finished latex has a viscosity of 8 to 30 cP (centipoise). A method for producing an active methylene group-containing polymer latex, wherein the polymerization is carried out under conditions satisfying all of the following.

(2) The method for producing an active methylene group-containing latex according to (1), wherein the hydrophilic polymer has a monomer unit selected from isoprenesulfonic acid and a salt thereof.

(3) An active methylene-containing polymer latex produced by the method described in (1) or (2).

(4) A sheet material, characterized in that a coating solution containing the active methylene group-containing polymer latex according to (3) is applied on a support and then dried.

The present invention will be described in detail.

The constitution (1) of the present invention is a method for stably polymerizing a polymer latex containing an active methylene group in an aqueous solution containing a hydrophilic polymer. This is a method for obtaining a latex having excellent aging stability.

When a monomer having an active methylene group is emulsion-polymerized in an aqueous solution containing a hydrophilic polymer, the active methylene group has a high reactivity, and the resulting polymer latex having an active methylene group has a high viscosity. Stability over time after polymerization was poor, and it was often difficult to exhibit the characteristic of bending angle. In particular, the coating process was difficult due to the high viscosity, so that it was difficult to use in applications such as coating of a sheet material. The present invention, as a result of careful examination of the synthesis method, can solve those problems by satisfying all the following conditions,
It has been found that the present invention can be applied to a wide range of applications.

That is, in an aqueous solution containing a hydrophilic polymer, a monomer having an active methylene group is 10 to 50% by weight based on all monomers used, and a solid content concentration is 15 to 35% by weight based on the total weight. The polymerization initiator of the oxidizing agent is added in an amount of 0.1 to all the monomers used.
15-0.45 mol% Polymerization temperature 30-85 ° C, Polymerization time 3-6 hours Stirring power required 0.2-1.0 W / m ³ Finished latex has a viscosity of 8-30 cP (centipoise). By satisfying all these conditions, stable emulsion polymerization can be performed, and a stable emulsion polymer can be obtained.

First, the monomer having an active methylene group used in the present invention will be described.

In the active methylene group, a CH ₂ group sandwiched between an X group represented by XCH ₂ Y and a Y group has a reaction activity. Here, X or Y is sandwiched adjacent to a strong electron-withdrawing group such as CO (carbonyl group), COO (carboxyl group), CN (cyano group), SO ₂ (sulfonyl group), and NO ₂ (nitro group). Methylene group. Therefore, the methylene group is very chemically active and, conversely, unstable,
When polymerizing using a monomer having an active methylene group, it is easy to aggregate, or it is difficult to participate in the polymerization,
It is unstable. Thus, the present inventors have found a method for stably polymerizing a polymer latex having an active methylene group having excellent properties as a polymer by satisfying the above conditions.

Specific examples of the monomer having an active methylene group useful in the present invention are shown below.

[0018]

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[0019]

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In the present invention, the amount of the monomer having an active methylene group is preferably 10 to 50% by weight, based on the total monomers used in the polymer latex having an active methylene group, so that the polymerization is not hindered, and the activity in the application stage is low. The reactivity of the methylene group is also sufficient. Preferably 15 to
35% by weight.

The monomer to be copolymerized with the monomer having an active methylene group useful in the present invention includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, (n-, i-, s-) propyl acrylate, (N-, i-, s-) propyl methacrylate, (n-, i-, s-, t-) butyl acrylate, (n-, i-, s-, t-) butyl methacrylate, amyl acrylate, amyl methacrylate ,
Neopentyl acrylate, neopentyl methacrylate, hexyl acrylate, hexyl methacrylate,
Octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-
Acrylates or methacrylates such as ethylhexyl acrylate, 2-ethylhexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, propyl acrylamide, butyl acrylamide,
Acrylamides such as N, N-dibutylacrylamide, cyclohexylacrylamide, phenylacrylamide, benzylacrylamide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and vinyl valerate, methyl vinyl ketone, ethyl vinyl ketone And styrenes such as styrene, α-methylstyrene, p-hydroxystyrene and p-chloromethylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride, butadiene, isoprene, chloroprene and the like.

Next, the hydrophilic polymer used in the polymerization of the present invention will be described.

The hydrophilic polymer may be a synthetic polymer, a semi-synthetic polymer, or a natural polymer as long as it is a hydrophilic and water-soluble polymer. For example, as synthetic polymers, polyvinyl alcohol (which may be completely saponified, intermediate saponified, or partially saponified), sulfonic acid-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, isoprenesulfonic acid and / or a salt thereof Homopolymer or copolymer of styrene sulfonate, homopolymer or copolymer of maleic anhydride and / or its ring-opened product or salt thereof, homopolymer of acrylic acid and / or salt thereof Or copolymer, methacrylic acid and / or salt thereof homopolymer or copolymer, sulfopropylacrylamide and / or homopolymer or copolymer, acrylamide homopolymer or copolymer, vinylpyrrolidone homopolymer Or copolymer, vinyl imidazo Homopolymers thereof or copolymers thereof, etc., methyl cellulose as a semi-synthetic polymers, cellulose,
Examples of natural products such as hydroxyethylcellulose, salts of carboxymethylcellulose, carboxymethyl starch and the like include alginic acid or its salts, gelatin, casein and the like. Among these, in the present invention, a homopolymer or copolymer of isoprenesulfonic acid and / or a salt thereof is preferable (configuration (2)). The copolymerization partner with isoprenesulfonic acid is the same as the copolymerization partner of the active methylene-containing monomer.

Examples of the isoprenesulfonic acid polymer useful in the present invention include the following.

[0025]

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[0026]

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[0027]

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[0028]

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In the emulsion polymerization of the present invention, a surfactant as a dispersant may be used in addition to the hydrophilic polymer. The use of a surfactant is more stable and preferable.

Examples of the surfactant include alkyl benzene sulfonates such as sodium dodecylbenzenesulfonate and ammonium pentadecylbenzenesulfonate; alkyl sulfates such as sodium lauryl sulfate and sodium tetradecyl sulfate; and sodium dioctyl sulfosuccinate. Anionic surfactants such as carboxylate salts such as sulfosuccinate, sodium laurate and sodium stearate; 2,4-dinonylphenyl polyethylene oxide (polymerization degree 4 to 20); polyethylene oxide (polymerization degree 10 to 100) And other nonionic surfactants. The amount of the surfactant to be used is preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total monomers used.

The polymerization initiators usable in the present invention include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, 4,4'-azobis-4-cyanovaleic amide, and 2,2 ' -Azobis (2-methylamidooxime) dihydrochloride and the like. In the emulsion polymerization, redox polymerization is also preferably used, and as a polymerization initiator used in the polymerization, redox-based hydrogen peroxide-ferrous salt, persulfate-acidic sodium sulfite, cumene hydroperoxide-ferrous salt is used. And benzoyl peroxide-dimethylaniline.

In the polymerization system of the present invention, the concentration of the polymerization initiator is preferably 0.15 to 0.45 mol% based on all monomers used. The concentration of the polymerization initiator is related to the magnitude of the molecular weight (or degree of polymerization) of the finished polymer. When the addition amount is small, the molecular weight increases but the residual monomer amount increases, and when the addition amount is large, the molecular weight decreases. This leads to a decrease in film strength when formed into a film. This range of the present invention is the most suitable quantitative range for the present invention.

The solid content concentration is related to the total amount of monomers charged. To stably polymerize the polymer latex of the present invention, the solid content concentration including the water-soluble polymer (based on the total amount of the finished latex) is 15 to 35. By controlling the amount by weight, a stable latex can be obtained. If the solid content is too low, it is uneconomical,
If it is too large, the stability may be slightly inferior.

The polymerization temperature and the polymerization time are adjusted so that the polymerization temperature is 30 to
By performing the polymerization at a temperature of 85 ° C. for a polymerization time of 3 to 6 hours, a stable latex can be produced, and stability over time after polymerization can be imparted. If the polymerization temperature is too high or the polymerization time is too long, the latex particles may aggregate, the active methylene group may change, and the polymerization bath atmosphere may be changed with an inert gas such as nitrogen gas during polymerization. It is important to completely replace the air.

The stirring conditions during the polymerization are also important factors. In the present invention, the method of stirring is not particularly limited, but the shape of the stirring blade is preferably a Faudler blade, an anchor blade, a max blend blade, a full zone blade, or a loop blade, and a blade selected from these may be combined.

It has been found that the stability of the emulsion polymerization in the present invention greatly depends on the specifications of the stirrer.

That is, there is a relationship between the net stirring power required and the liquid volume, and it is important that the following equation be in the range of 0.2 to 1.0 W / m ³ . The power required for stirring per unit internal volume is calculated by the following equation.

Pv = P / V = (NP × ρ × n ³ × d ⁵ ) / V Here, Pv: power required for stirring per unit internal volume (W / m ³ ) P: power required for stirring (W) V : Liquid volume (m ³ ) NP: Number of power, fixed value of stirring blade, empirical value is adopted ρ: Liquid density (kg / m ³ ) n: Number of rotations (1 / sec) d: Stirring blade diameter (m ) For NP, for example, for the Faudler wing and the anchor wing, 1.
5, a value such as 2.5 for a combination of a max blend blade and a full zone blade, and 1.0 for a loop blade and an anchor blade, and these are used.

As another method for obtaining the required net stirring power per unit internal volume, there is a method using an ammeter of a motor of a stirrer for a polymerization vessel. The stirrer is turned in advance when the polymerization vessel is empty, the rotational load of the transmission or reduction gear and the stirrer itself is known by an ammeter, and the effective voltage is subtracted from the ammeter reading at the time of polymerization reaction. , And dividing by the liquid volume.

In the present invention, it is also important to adjust the viscosity of the finished latex to 8 to 30 cP, and within this range, a latex having good aging stability can be obtained. The viscosity of the present invention employs a value of 25 ° C. with an E-type viscometer. The dimension of this viscosity is cP (centipoise).

The constitution (3) of the present invention is a polymer latex containing an active methylene group polymerized in the constitution (1) or (2), and the constitution (4) is a polymer latex containing the active methylene group of the constitution (3). It is a sheet material used and processed into a support.

The sheet material coated with the active methylene group-containing polymer latex of the present invention can be coated with various image forming layers to obtain a silver halide photographic material, a silver halide photographic material for thermal development. It is useful for producing image forming materials such as ink jet recording materials, printing plate materials, and magnetic recording media.

Further, the active methylene group-containing polymer latex of the present invention may be used in combination with the subbing layer, silver halide emulsion layer, intermediate layer, antihalation layer, protective layer, back layer, antistatic layer, and heat sensitive layer of the image recording layer. It can be used as a recording layer, a magnetic recording layer, an inkjet image receiving layer, a printing plate adhesive layer, a printing plate photosensitive layer, a printing plate protective layer, and the like.

Examples of the support for the image recording material include a plastic film support, a paper support, a plastic film or sheet laminate paper support, and an aluminum support.

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

[0046]

Example 1 [Polymerization Example 1 (LL-1)] Distilled water was added to a 1500-liter reactor equipped with a stirrer, a thermometer, a dropping pump, a nitrogen inlet tube, and a reflux condenser, and nitrogen gas was added. It was heated until the internal temperature reached 80 ° C. while introducing and deoxidizing. As a dispersant,
22.5 kg of hydrophilic polymer P-10 and 0.45 kg of sodium dodecylbenzenesulfonate were added, and 3.39 kg of ammonium persulfate was further added as a polymerization initiator.
Was added, and 247.5 kg of styrene, 22.5 kg of n-butyl acrylate, 90 kg of glycidyl methacrylate and 90 kg of M-1 were added dropwise using a dropping pump over about 90 minutes. After the completion of the dropwise addition, the reaction was continued for 4 hours. After cooling to room temperature, 2%
The pH was adjusted to 4.0 using NaOH to obtain the desired active methylene group-containing polymer latex (LL-1).

[Polymerization Example 2 (L-1)]
A thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser equipped with a stirrer (wing diameter 5 cm) were attached to the head flask, 345 ml of distilled water was introduced, the air was replaced with nitrogen gas, and the internal temperature was reduced. The temperature was raised to 80 ° C. The stirrer was rotated, and the required stirring power was 0.00011 W, the required stirring power per unit volume was 0.22 W / m ³ , and the number of revolutions was 6.1667 times / second. 7.5 g of the hydrophilic polymer (P-10) and 0.15 g of sodium dodecylbenzenesulfonate were added and dissolved, and 1.13 g of ammonium persulfate was further added to keep the temperature at 80 ° C. 82.5 g of styrene from the dropping funnel,
7.5 g of n-butyl acrylate, 30 g of glycidyl methacrylate and an active methylene group-containing monomer (M-
1) 30 g of the mixture was added dropwise over 90 minutes. During that time, the temperature rising by polymerization heat is controlled and kept at 80 ° C,
After the polymerization was continued for 4 hours after the completion of the dropping, the temperature was lowered to room temperature.
After cooling, the pH was adjusted to 4 using a 2% aqueous sodium hydroxide solution.
0 to prepare a polymer latex (L-1).

[Polymerization Example 3 (L-2)] Using the same apparatus as in Polymerization Example 2, 345 ml of distilled water was introduced, the air was replaced with nitrogen gas, and the internal temperature was adjusted to 30 ° C. . The stirrer was rotated, and the required stirring power was 0.00011 W, the required stirring power per unit volume was 0.22 W / m ³ , and the number of revolutions was 6.1667 times / second. Hydrophilic polymer (P-8)
Was added and dissolved by adding 0.15 g of sodium dodecylbenzenesulfonate. Further, 1.13 g of ammonium persulfate and 0.78 g of sodium thiosulfate were added, and the mixture was kept at 30 ° C. 82.5 g of styrene from the dropping funnel,
7.5 g of n-butyl acrylate, 30 g of glycidyl methacrylate and an active methylene group-containing monomer (M-
2) 30 g of the mixture was added dropwise over 90 minutes. During that time, control the temperature that rises with the heat of polymerization and keep it at 30 ° C.
After the polymerization was continued for 4.5 hours after the completion of the dropwise addition, the mixture was cooled to room temperature, and the pH was adjusted to 4.0 with a 2% aqueous sodium hydroxide solution to prepare a polymer latex (L-2).

[Polymerization Example 4 (L-3)]
A thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser equipped with a stirrer (wing diameter 5 cm) were attached to the head flask, 865 ml of distilled water was introduced, the air was replaced with nitrogen gas, and the internal temperature was reduced. The temperature was raised to 80 ° C. The stirrer was rotated, and the required stirring power was 0.00011 W, the required stirring power per unit volume was 0.22 W / m ³ , and the number of revolutions was 6.1667 times / second. 7.5 g of a hydrophilic polymer (P-10), 150 g of a hydrophilic polymer having the following structure and 0.15 g of sodium dodecylbenzenesulfonate were added and dissolved, and 1.13 g of ammonium persulfate was further added to the mixture at 80 ° C. Kept. 82.5 g of styrene, 7.5 g of n-butyl acrylate, 30 glycidyl methacrylate from the dropping funnel
g and an active methylene group-containing monomer (M-1) (30 g) were added dropwise over 90 minutes. During that time, the temperature rising by the heat of polymerization was controlled and maintained at 80 ° C.
After the polymerization was continued for a period of time, the mixture was cooled to room temperature, and the pH was adjusted to 4.0 using a 2% aqueous sodium hydroxide solution.
Polymer latex (L-3) was prepared.

[Active methylene group-containing polymer latex (L-4 to 7), LL-2 and Comparative Examples (LC-1 to 1)
4) Polymerization] Polymerization was carried out in the same manner as (L-1), (L-2) or (L-3) except that the polymerization composition shown in Table 1 and the polymerization composition shown in Table 2 were changed.

Comparative Examples (LC-1, 2, 4 to 14) were the same as (L-1) or (L-3) except that the polymerization compositions and polymerization conditions shown in Tables 1 and 2 were changed. Was polymerized.

LL-2 was scaled up and polymerized in the same manner as (LL-1) except that the polymerization composition and polymerization conditions shown in Tables 1 and 2 were changed. Furthermore, (LC-3) of the comparative example was scaled up a little larger and polymerized in the same manner as described above.

[0053]

[Table 1]

Here, St: styrene, BA: n-butyl acrylate, GMA: glycidyl methacrylate,
PM: ring-opened product of sodium styrenesulfonate / maleic anhydride copolymer, DBS: sodium dodecylbenzenesulfonate, APS: ammonium persulfate, TSN
a: shows sodium thiosulfate.

[0055]

[Table 2]

With respect to the polymerized latex containing an active methylene group, the particle size, viscosity, residual monomer amount, and aggregates of the polymer particles were measured.

[Measurement Method] <Amount of Residual Monomer> 5 ml of a polymer latex sample was sampled with a whole pipette and sealed in a 20 ml vial. This was used for headspace gas chromatography (HS-
Quantitation was performed by GC).

<< HS >> Equipment: HP7694 Heating temperature: 60 ° C. Heating time: 60 minutes Loop temperature: 120 ° C. Transfer line: 130 ° C. << GC >> Equipment: HP5890 SERIES II Column: DB-624 (0.53 mmid × 30 m) Injection : 150 ° C Detector: FID, 250 ° C Mobile phase: He, 20ml Oven: 80 ° C The value measured by the above method is the amount in the gas phase at 60 ° C × 30 minutes, not the absolute value of the residual monomer in the sample. .

<Measurement of Aggregate> After polymerization, 500 g of a polymer latex sample was filtered with a 500 mesh filter having a filtration area of 7 cm ² , and the solid matter remaining on the mesh filter was dried and weighed.

<Measurement of particle size> Electrophoretic light scattering photometer EL
It was measured by S-800 (manufactured by Otsuka Electronics Co., Ltd.).

<Measurement of Viscosity> A 25 ° C.
Was used to measure the viscosity of the latex liquid.

The results of the measurement are shown in Table 4 below together with Example 2.

Example 2 Polymerization was carried out under the same polymerization conditions as in (L-1) except that the polymerization composition of the active methylene group-containing polymer latex was changed as shown in Table 3, and the active methylene group-containing polymer having a different monomer composition was used. Polymer latex (L-8-12) and comparative polymer latex (LC-15-19) were prepared.

[0064]

[Table 3]

Here, BAM: t-butylacrylamide, HEMA: 2-hydroxyethyl methacrylate,
CHMA: cyclohexyl methacrylate, NA: n-
Nonyl acrylate, MMA: methyl methacrylate,
HEA: 2-hydroxyethyl acrylate, NPM
A: neopentyl methacrylate, VPiv: vinyl pivalate, VAc: vinyl acetate, Vdc: vinylidene chloride, AA: acrylic acid, OSSA: sodium dioctyl sulfosuccinate, LS: sodium lauryl sulfate, St
A: Sodium stearyl sulfate, ABCVA: 4,4 '
-Azobis-4-cyanovaleric amide, KPS: indicates potassium persulfate.

These active methylene group-containing polymer latexes were evaluated in the same manner as in Example 1. Table 4 shows the measurement results of Examples 1 and 2.

[0067]

[Table 4]

(Results) As shown in the properties of the active methylene group-containing polymer latex polymerized by the polymerization method of the present invention, the active methylene group-containing polymer latex (LL-
1-2) and (L-1 to 12) had low viscosity, low occurrence of aggregation, good filterability, and little residual monomer. On the other hand, the active methylene group-containing polymer latex deviating from the conditions of the present invention in comparison (LC-1 to 19) had many occurrences of aggregation and poor filterability, and also had many residual monomers.

Example 3 An active methylene group-containing polymer latex polymerized in Examples 1 and 2 was mixed with an undercoat layer material of a polyester film support to form an undercoat layer coating solution. . This undercoat layer was applied onto a polyester film support to prepare a sheet material (a support with an undercoat layer). The transparency and applicability of the sheet material were examined. As one of application examples of the sheet material, a silver halide emulsion layer was coated on the sheet material to prepare a silver halide photographic light-sensitive material, and its scratch resistance, coatability, and adhesion were examined.

[Preparation of sheet material] <Support having coated undercoat layer> Biaxially stretched film thickness of 180 μm
8W / on both sides of polyethylene terephthalate film
m ² · min under corona discharge treatment, active methylene group-containing polymer latex is mixed with the latex for the undercoat layer coating solution on one side of both sides to form the undercoat layer lower layer coating solution and the undercoat layer upper layer coating solution Then, the following coating solution for the undercoat layer is applied so as to have a dry film thickness of 0.6 μm, dried at 140 ° C., and further the coating solution for the undercoat layer for the upper layer described below has a dry film thickness of 0.03 μm. And dried at 140 ° C. to produce a sheet material (sublayer coated support), and to produce Samples (S-1 to 14) and Comparative Samples (SC-1 to SC-6).

<< Coating Solution for Underlayer Underlayer >> A mixture of the following latex A and latex B (A: B = 40: 60 by weight) 188 g Surfactant A 3.0 g Active methylene group-containing polymer latex (see Table 5) (Addition of 20/100 to 40/100 based on the weight ratio of the mixture of latexes A and B described above) Distilled water was added to make up to 1000 ml to prepare an undercoat layer lower layer coating solution.

Here, latex A is styrene / butyl acrylate / glycidyl methacrylate = 20/40.
The latex B is a styrene / glycidyl methacrylate = 60/40 copolymer (solid content 30%).

<< Coating solution for upper layer of undercoat layer >> Polymer A and the active methylene group-containing polymer latex shown in Table 5 3.0 g Surfactant A 0.2 g Acetic acid 0.4 g Hardening agent A 0.3 g or more Distilled water was added to make up to 1000 ml to prepare an undercoating layer upper layer coating solution.

[0074]

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As described above, S-1 to S14 were prepared from the sheet material coated with the lower layer as shown in Table 5 below, and SC-1 to SC-6 were prepared as the comparative sample, and the viscosity of the coating solution was measured. The properties were evaluated and are shown in Table 5.

In Table 5 below, L represents the active methylene group-containing polymer latex, LA represents latex A, LB represents latex B, and LALB represents a mixture of LA and LB.

[Preparation of photographic light-sensitive material for X-ray halide] As an example of application of the sheet material of the present invention, a photographic light-sensitive silver halide material was prepared.

<< Coating of Silver Halide Emulsion Layer >><Preparation of Seed Emulsion-1><A1> Ossein Gelatin 24.2 g Distilled Water 9657 ml Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous methanol solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml <B1> 2.5N AgNO ₃ aqueous solution 2825 ml <C1> Potassium bromide 841 g Finish with water to 2825 ml <D1> 1.75 N KBr aqueous solution The following silver potential control amount 42 ° C. No. 58-58288, 58-5828
Using a mixing stirrer described in the specification of No. 9, 464.3 ml of each of the solution B1 and the solution C1 was added to the solution A1 by a simultaneous mixing method over 1.5 minutes to form nuclei.

After stopping the addition of the solution B1 and the solution C1, it took 40 minutes to raise the temperature of the solution A1 to 50 ° C., adjust the pH to 5.0 with 3% KOH, and then again The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 42 ° C. to 50 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.045 μm. It was confirmed by an electron microscope that the average particle size (circular diameter conversion) was 0.42 μm. The variation coefficient of the thickness was 42%, and the variation coefficient of the distance between twin planes was 45%.

<Preparation of Tabular Silver Bromide Emulsion> A tabular pure silver bromide emulsion was prepared using Seed Emulsion-1 and the following three kinds of solutions.

<A2> Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous methanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3669 ml with water <B2> Odor 1747g Potassium iodide Finished to 3669ml with water <C2> 2493g silver nitrate Finished to 4193ml with water Vigorously stirring solution A2 in a reaction vessel while keeping it at 50 ° C, then simultaneously mix the total amount of solution B2 and solution C2 over 100 minutes It was added by the method. During this time, the pH was kept at 9.0 with the KOH solution, and the pAg was kept at 8.6 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed functionally with respect to time so as to match the critical growth rate. That is, they were added at an appropriate addition rate so that no small particles were generated except for the seed particles that were growing, and that they did not become multicomponent due to Ostwald ripening.

After completion of the addition, the emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% (by weight) of a modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added as an aggregating polymer. Stir for 3 minutes. Thereafter, a 56% (by weight) aqueous solution of acetic acid is added to adjust the pH of the emulsion.
Was adjusted to 4.6 and stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.
1.25 l was added, and after stirring and standing, the supernatant was drained.

Subsequently, an aqueous gelatin solution and sodium carbonate 1
A 0% (by weight) aqueous solution was added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, it was found that the average grain size was 0.84 μm, the average thickness was 0.16 μm, the average aspect ratio was about 5.3, and the grain size distribution was 20%. Tabular silver halide grains were obtained. The amount of gelatin at the end of physical ripening was 15.9 g per mol of silver halide.

After the above-prepared emulsion was heated to 55 ° C., the following spectral sensitizing dye (A) 450 per mole of silver halide was used.
mg, and 45 mg of the spectral sensitizing dye (B).
100 mg of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. After 10 minutes, 3.5 mg of chloroauric acid, 10 mg of sodium thiosulfate,
100 mg of ammonium thiocyanate was added. After a further 40 minutes, 0.3 mol of the following silver iodide fine grains were added. After a further 10 minutes, 5 mg of triphenylphosphine selenide was added.
Methyl-1,3,3a, 7-tetrazaindene 500m
g, and after 5 minutes, 13 g of trimethylolpropane,
After adding 30 g of gelatin, the emulsion was rapidly cooled and the emulsion was gelled to complete the chemical sensitization.

<Preparation of fine silver iodide particles><A3> 100 g of ossein gelatin 8.5 g of KI Make up to 2000 ml with distilled water <B3> 360 g of AgNO ₃ Make 605 ml with distilled water <C3> 352 g of KI Make 605 ml with distilled water Solution A3 was added to the reaction vessel, and solution B3 and solution C3 were added at a constant rate over 30 minutes by a simultaneous mixing method while stirring at 40 ° C. The pAg during the addition is the normal pAg
It was kept at 13.5 by control means. The formed silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm. This emulsion is called a silver iodide fine grain emulsion.

Here, the spectral sensitizing dyes (A) and (B)
Has the structure of sensitizing dye (A): 5,5'-di-chloro-9-ethyl-
Anhydride of sodium 3,3'-di- (3-sulfopropyl) oxacarbocyanine Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3 '-Di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride.

<Preparation of silver halide photographic light-sensitive material> Three layers were simultaneously coated on both surfaces of the undercoated support obtained above, from the side closer to the support (dye layer) to the first layer. The following coating amount is an attached amount per one side.

[0090] (first layer: Intermediate layer 1) lime-processed inert gelatin 0.1 g / m ² filter dye F 30 mg / m ² Sodium -i- amyl -n- decyl sulfosuccinate 5.0 mg / m ² poly methacrylate Latex 70 mg / m ² (second layer: emulsion layer) The additives added to the emulsion are as follows. The amount of addition other than gelatin is indicated by the amount per mol of silver halide.

Lime-treated inert gelatin (per side) 1.25 g / m ² 1,1-dimethylol-1-bromo-1-nitromethane 70 mg polyvinylpyrrolidone (molecular weight 10,000) 0.7 g styrene-maleic anhydride copolymer 2.5g nitrophenyl - triphenylphosphonium chloride _{50mg C 4 H 9 OCH 2 CH} (OH) CH 2 N (CH 2 COOH) 2 1.0g 1- phenyl-5-mercaptotetrazole 8.5mg colloidal silica (manufactured by DuPont Ludox AM) 10 g t-butylcatechol 150 mg compound Z 1.7 g KBr 200 mg thallium nitrate 55 mg trimethylolpropane 6.5 g dextran (average molecular weight: described in Table 1) 1.2 g compound B 150 mg sodium polystyrene sulfonate (flat) Molecular weight 300,000) 1.3 g polymer latex (as the glass transition point 40 ° C.) 10 g * silver amount per one side was coated to a 1.3 g / m ^2.

(Third Layer: Protective Layer) Next, the following was prepared and applied as a protective layer coating solution. It represents the m amounts with ² per one surface below.

Lime-treated inert gelatin 0.80 g Dextran 0.15 g Polymethyl methacrylate (a matting agent having an area average particle diameter of 3.5 μm) 28 mg Silicon dioxide particles (a matting agent having an area average particle diameter of 1.2 μm) 14 mg I-2 55 mg F-16 2.6 mg II-2 2.1 mg Hardener H 0.1 g Preservative 1 mg

[0094]

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[0095]

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[Evaluation Method] <Coatability> The coating state of the undercoat layer lower layer coating solution and the lower coating layer upper layer coating solution applied thereon was reflected by a fluorescent lamp and evaluated as follows.

A: no coating unevenness is visible B: slight surface fluctuation is observed C: slight coating unevenness and streaks are observed D: slight coating unevenness and streaks are observed E: at agglomerates , Streaks are generated, and coating unevenness is considerably observed. F: Many agglomerates, many streaks and unevenness are generated.

<Measurement of transmittance of sheet material> Using a turbidity meter Model-t-2600DA manufactured by Tokyo Denshoku Co., Ltd.
The transmittance of the sheet material was measured.

<Scratch Resistance Test> A photographic light-sensitive material sample for a silver halide X-ray having a sheet material was prepared as follows.
C. and humidity of 55% RH for 24 hours, place a sapphire needle having a tip with a curvature radius of 0.15 mm on the sample at a right angle, and apply a load to the sapphire needle while moving the sample at 60 cm / min. It was gradually increased at a constant rate from 0 g to 200 g. The load when the flaw reached the sheet material surface or the polyester support was read as scratch resistance, and the numerical value was evaluated as the following rank. In addition, on the scratch line, the load was also read for those that partially reached the support after being partially dug even at 200 g or more.

A: 200 g or more B: 150 to 199 g C: 100 to 149 g D: 50 to 99 g E: 49 g or less.

<Adhesion between Sheet Material and Silver Halide Emulsion Layer> Adhesion of the prepared silver halide X-ray photographic light-sensitive material before development processing of the X-ray halogenated emulsion layer (hereinafter referred to as a film with a pre-processing film) ), The adhesiveness in the liquid during the development processing (hereinafter, referred to as a film during processing), and the adhesiveness after drying the development processing (hereinafter, referred to as a film after processing) are evaluated by the following evaluation methods. did.

A) With a film before treatment, b) With a film after treatment Samples that had been dried before development or after development were dried.
Humidity is controlled for at least 24 hours at 3 ° C. and 80% RH. Under a similar atmosphere, the razor is applied to the surface of the silver halide emulsion layer with a razor at a width of at least 30 mm and the polyester at an angle of 45 ° with respect to the surface. Scratch up to the film, 2
A 4.5 mm wide cellophane tape was pressure-bonded and rapidly peeled off almost horizontally in the direction opposite to 45 ° with respect to the surface. The area of the peeled silver halide emulsion layer was evaluated on the following five scales.

A: no peeling (0%) B: less than 5% peeling C: 5 to 20% peeling D: 21 to 50% peeling E: 51 to 100% peeling F: peeling exceeding 100%

C) With film during processing During each of the development-fixing-water washing processing, the surface of the halogenated emulsion layer of the sample was scratched with a sharp needle to reach the polyester film in a grid pattern, and the layer was wetted. Rub it hard for 10 seconds with your hands wearing rubber gloves. At this time, the area of the peeled silver halide emulsion layer is compared with the lattice area, and the peeled area is evaluated as follows.

A: No peeling (0%) B: Less than 5% peeling C: 5 to 20% peeling D: 21 to 50% peeling E: 51 to 100% peeling F: Peeling exceeding 100%.

The development-fixing process was performed according to the following formula.

[Development] In order to evaluate the presence of a film on the photographic light-sensitive material for a silver halide X-ray, the following development treatment was carried out.

(Developer Formulation) Part-A (for finishing 10 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-methylbenzotriazole 1.2 g 1- Phenyl-5-mercaptotetrazole 0.2 g 1,4-dihydroxybenzene 340 g Add water to make 5000 ml. Part-B (for finishing 10 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitro Indazole 0.4g Starter solution formulation (for 1 liter finishing) Glacial acetic acid 120g Potassium bromide 225g Add water to make up to 1000ml (Fixing solution formulation) Part-A (for 18 liter finishing) Thio Ammonium sulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B (18 liter finishing) For use) Aluminum sulfate 800g (Preparation of developer) To prepare the developer, add about 1 liter of water to P
Art-A and Part-B were added at the same time, water was added while stirring and dissolving to make up to 10 liters, and the pH was adjusted to 1 with glacial acetic acid.
It was adjusted to 0.50 and used as a developer.

20 ml of a starter solution was added per liter of the developing solution, and the pH was adjusted to 10.40 to obtain a working solution.

(Preparation of Fixing Solution) The fixing solution was prepared by simultaneously adding Part-A and Part-B to about 5 liters of water, adding water while stirring and dissolving to make up to 18 liters, and adding sulfuric acid and sodium hydroxide. The pH was adjusted to 4.4 using this solution, which was used as a fixer solution and a fixer replenisher.

The processing temperatures were 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing and 45 ° C. for drying, respectively.

[0112]

[Table 5]

(Results) The viscosity and coatability of the undercoat layer coating solution were as follows. The active methylene group-containing polymer latex prepared by the preparation method of the present invention had low viscosity and good coatability. On the other hand, those prepared by methods other than the present invention had high viscosity and were difficult to apply. In addition, it was found that the transmittance of the sheet material of these coating materials of the present invention was excellent.

Further, with respect to the presence of a film on the emulsion layer of the photographic light-sensitive material for a silver halide X-ray from these sheet materials, any of those of the present invention showed an excellent film. As described above, it was found that the active methylene group-containing polymer latex of the preparation method of the present invention has very stable properties and also exhibits excellent properties.

[0115]

The active methylene group-containing polymer latex has recently attracted attention, but it has been difficult to obtain a polymer made from its reaction activity, especially a polymer latex having both good stability and good properties. A stable product can be obtained by the preparation method, and as shown in the examples, the application can be expected.

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Claims (4)

[Claims] 1. A process for producing an active methylene group-containing polymer latex, wherein polymerization is carried out in an aqueous solution containing a hydrophilic polymer, wherein the amount of the monomer having an active methylene group is from 10 to 50% by weight based on all monomers used. On the other hand, the solid content concentration is 15 to 35% by weight.
15-0.45 mol% The polymerization temperature is 30-85 ° C. The polymerization time is 3-6 hours The power required for stirring is 0.2-1.0 W / m ^{3 The} finished latex has a viscosity of 8-30 cP (centipoise). A method for producing an active methylene group-containing polymer latex, wherein the polymerization is carried out under conditions satisfying all of the following. 2. The method for producing an active methylene group-containing polymer latex according to claim 1, wherein the hydrophilic polymer has a monomer unit selected from isoprenesulfonic acid and a salt thereof. 3. An active methylene group-containing polymer latex produced by the method according to claim 1 or 2. 4. A coating solution containing the active methylene group-containing polymer latex according to claim 3, coated on a support,
A sheet material characterized by being dried.