JPH07128786A - Polyester film provided with primer layer, photographic sensitive material using the film as supporting body, and production thereof - Google Patents

Abstract

PURPOSE:To improve adhesion property and transparency by forming a primer layer formed by using a primer coating liquid containing aq. dispersion liquid in which vinyl monomers are dispersed and polymerized. CONSTITUTION:The primer layer is formed on at least one surface of a film by using a primer coating liquid containing aq. dispersion prepared by dispersing and polymerizing vinyl monomers in a water-soluble polyester soln. The aq. dispersion obtd. by dispersing and polymerizing vinyl monomers in a water-soluble polyester soln. is obtd. by dissolving water-soluble polyester in hot water and dispersing vinyl monomers in the obtd. water-soluble polyester soln., and then effecting emulsion polymn. or suspension polymn. The primer layer is formed by applying the coating liquid containing the aq. dispersion prepared by dispersing and polymerizing vinyl monomers in a water-soluble polyester soln.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester film having improved adhesion and a photographic light-sensitive material using the polyester film.

[0002]

2. Description of the Related Art Polyester films, for example, polyethylene terephthalate or its copolymer biaxially stretched film, polyethylene naphthalate or its copolymer biaxially stretched film, and laminate films of these polyesters are transparent, Since it has excellent dimensional stability, mechanical properties, electrical properties, chemical resistance, etc., it is used in various fields as a base film for magnetic recording materials, electrical insulating materials, photographic photosensitive materials and the like.

However, when a biaxially stretched polyester film is used as a base film for magnetic recording materials, electrical insulating materials, photographic photosensitive materials, etc., the surface of the biaxially stretched polyester film is highly oriented and crystallized. However, there is a problem that the adhesiveness is poor. In particular, when a biaxially stretched polyester film is used as a base film of a photographic light-sensitive material, various photographic constituent layers are composed of hydrophilic colloid such as gelatin, so that sufficient adhesiveness cannot be obtained and thus the support There is a problem that the photographic constituent layers formed on the body are peeled off.

In order to improve the adhesion between the biaxially stretched polyester film and various photographic constituent layers containing a hydrophilic colloid, the biaxially stretched polyester film is subjected to a physical treatment such as corona discharge, ultraviolet ray treatment, plasma treatment or ultraviolet ray treatment. Treatments, flame treatments and chemical treatments such as treatments with chemicals such as alkali, amine, trichloroacetic acid and phenols are performed. However, these methods have the drawback that the adhesive strength deteriorates over time, and the working environment is contaminated by volatilization of the chemicals used, and further the treatment of chemicals after use is difficult. There was a practically disadvantageous problem of causing environmental pollution.

It is also known that an undercoat layer is provided on a support, and it is known that a styrene-butadiene type latex, a vinylidene chloride type latex or the like is applied in the process of producing a biaxially stretched polyester film. Since these undercoat layers have excellent adhesion to the support but poor adhesion to the emulsion layer, which is a photosensitive layer, a further hydrophilic colloid layer such as gelatin, an acrylic latex undercoat layer It was necessary to provide.

As a method for solving these problems, JP-A-63-34139 discloses a method of using a copolymer obtained by grafting a polyester copolymer on an acrylic resin, and JP-A-63-37937. Describes a method of using a copolymer obtained by grafting an acrylic resin on a polyester copolymer, and a method of undercoating with one layer is proposed, but the polyester copolymer and the acrylic resin are compatible with each other. Therefore, in order to obtain the graft copolymer used in these methods, an organic solvent which dissolves both is required. Further, it is possible to obtain a graft copolymer using these raw materials as an aqueous dispersion, but since the aqueous dispersion must be obtained by dispersing it after dissolving it in an organic solvent, the use of an organic solvent is essential. However, contamination of the working environment due to the use of organic solvents was unavoidable.

Further, it has been proposed to use a water-soluble polyester having an alicyclic dicarboxylic acid component as the undercoat layer. The photographic light-sensitive material using the support having these undercoat layers has good adhesiveness when the photographic light-sensitive material is processed for 90 seconds, but the photographic light-sensitive material is processed by rapid processing for 45 seconds or less. When processing is attempted, pick-off of the emulsion layer occurs, and the adhesiveness under such conditions is insufficient and there is a problem.

[0008]

The first object of the present invention is to provide a polyester film having a primer layer using a resin which can be synthesized in an aqueous system without using an organic solvent, and which has excellent adhesiveness and transparency. To provide the manufacturing method,
The second purpose is to have no adverse effect on photographic performance,
Another object of the present invention is to provide a photographic light-sensitive material in which the photographic constituent layers are firmly adhered to the support and which does not cause emulsion pick-off even in the rapid development of the photographic light-sensitive material.

[0009]

The above objects of the present invention are as follows: (1) A primer layer formed on at least one side of a primer coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester. A polyester film provided. (2) The polyester film as described in (1) above, wherein the polyester film is a biaxially stretched polyester film. (3) The water-soluble polyester has at least terephthalic acid, isophthalic acid, a dicarboxylic acid having a sulfonate, an alicyclic dicarboxylic acid as a dicarboxylic acid component, and at least ethylene glycol as a glycol component, Moreover, the ratio of terephthalic acid and isophthalic acid in the water-soluble polyester is terephthalic acid / isophthalic acid = 30/70 to 70/30 in a molar ratio, and the dicarboxylic acid having a sulfonate is used with respect to all dicarboxylic acid components. The polyester film according to the above (1) or (2), wherein the polyester film has 5 to 15 mol% and contains ethylene glycol in an amount of 50 mol% or more based on all glycol components. (4) At least one surface of the polyester film before the final crystal orientation is applied with a primer coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester, and then dried. The polyester film according to the above (1) to (3), which is obtained by subjecting the polyester film to stretching, heat treatment, and final crystal orientation. (5) The polyester film as described in (1) to (4) above, wherein a hydrophilic colloid layer is provided on the primer layer. (6) The polyester film as described in (1) to (5) above, wherein the hydrophilic colloid layer is a layer containing gelatin. (7) At least one surface of the polyester film before the final crystal orientation is applied with a primer coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester, and then dried. The method for producing a polyester film according to the above (1) to (6), characterized in that the final crystal orientation is completed by stretching, stretching and heat treatment. (8) A photographic light-sensitive material characterized in that at least one silver halide emulsion layer is provided on at least one side having a primer layer of the polyester film described in (1) to (4) above. (9) At least one surface of the polyester film before the final crystal orientation is applied with a primer coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester, and then dried. The production of the photographic light-sensitive material according to the above (8), wherein the final polyester orientation is completed by stretching, stretching and heat treatment, and at least one silver halide emulsion layer is coated on the obtained polyester film. Method. Achieved by

The present invention will be described in detail below.

First, an aqueous dispersion prepared by dispersing and polymerizing a vinyl monomer in an aqueous solution of the water-soluble polyester of the present invention will be described.

The water-soluble polyester used for preparing the above aqueous dispersion is, for example, substantially obtained by polycondensation reaction of polybasic acid or its ester-forming derivative with polyol or its ester-forming derivative. Examples include linear polymers.

Examples of the polybasic acid component of the water-soluble polyester include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid can be used, and maleic acid,
Unsaturated polybasic acids such as fumaric acid and itaconic acid and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used in small proportions.

As the polyol component, for example,
Ethylene glycol, diethylene glycol, 1,4-
Use of butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, trimethylolpropane, poly (ethylene oxide) glycol, poly (tetramethylene oxide) glycol. You can

In the present invention, the water-soluble polyester preferably has terephthalic acid and isophthalic acid as main dicarboxylic acid components, and the ratio of terephthalic acid to isophthalic acid used is 30 / molar.
It is particularly preferably 70 to 70/30 from the viewpoint of coatability on a polyester support and solubility in water. Further, it is preferable that the terephthalic acid component and the isophthalic acid component are contained in an amount of 50 to 80 mol% with respect to the total dicarboxylic acid component.

In order to impart water solubility to the polyester, a component having a hydrophilic group, for example, a component having a sulfonate, a diethylene glycol component, a polyalkylene ether glycol component, a polyether dicarboxylic acid component or the like is added to the polyester. It is an effective means to introduce it as a polymerization component. In particular, it is preferable to use a dicarboxylic acid having a sulfonate as a component having a hydrophilic group.

As the dicarboxylic acid having a sulfonic acid salt, those having a group of an alkali metal sulfonic acid salt are particularly preferable. For example, 4-sulfoisophthalic acid, 5-
Alkali metal salts such as sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5- (4-sulfophenoxy) isophthalic acid can be mentioned. 5-
Sulfoisophthalic acid sodium salt is particularly preferred. From the viewpoint of water solubility and water resistance, the dicarboxylic acid having these sulfonates is preferably used in the range of 5 to 15 mol%, particularly 6 to 10 mol% based on the total dicarboxylic acid components.

Further, in the water-soluble polyester of the present invention using terephthalic acid and isophthalic acid as main dicarboxylic acid components, it is preferable to use alicyclic dicarboxylic acid as a copolymerization component. Examples of these alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid,
1,3-Cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid and 4,4′-bicyclohexyldicarboxylic acid can be mentioned.

Furthermore, in the water-soluble polyester of the present invention using terephthalic acid and isophthalic acid as the main dicarboxylic acid components, dicarboxylic acids other than the above can be used as copolymerization components. As these dicarboxylic acids,
Examples thereof include aromatic dicarboxylic acids and linear aliphatic dicarboxylic acids. The aromatic dicarboxylic acid is preferably used within the range of 30 mol% or less of the total dicarboxylic acid component. Examples of these aromatic dicarboxylic acid components include:
Examples thereof include phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid and biphenyldicarboxylic acid. The linear aliphatic dicarboxylic acid is preferably used within the range of 15 mol% or less of the total dicarboxylic acid component. Examples of these linear aliphatic dicarboxylic acid components include adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

Examples of the glycol component of the water-soluble polyester of the present invention include ethylene glycol,
1,4-butanediol, neopentyl glycol,
1,4-cyclohexane dimethanol, diethylene glycol, triethylene glycol, polyethylene glycol may be mentioned.

When the water-soluble polyester of the present invention uses terephthalic acid and isophthalic acid as the main dicarboxylic acid component, ethylene glycol is used as the glycol component of the water-soluble polyester of the present invention in an amount of 50 mol of all glycol components. It is preferable to use one having a content of at least 100% from the viewpoint of mechanical properties and adhesiveness to the polyester support.

The water-soluble polyester of the present invention can be synthesized by using dicarboxylic acid or its ester-forming derivative and glycol or its ester-forming derivative as a starting material. Various methods can be used for the synthesis, for example, a known polyester production method of forming an initial condensate of a dicarboxylic acid and a glycol by a transesterification method or a direct esterification method and melt-polymerizing the same. be able to. More specifically, for example, transesterification reaction is performed with an ester of dicarboxylic acid, for example, dimethyl ester of dicarboxylic acid and glycol, and after distilling methanol off, the pressure is gradually reduced and polycondensation is performed under high vacuum. Method of performing, esterification reaction of dicarboxylic acid and glycol, after distilling the water produced, gradually reduced pressure, under high vacuum, a method of polycondensation,
Examples include a method in which an ester exchange reaction is performed with an ester of a dicarboxylic acid and a glycol, an esterification reaction is further performed by adding a dicarboxylic acid, and then polycondensation is performed under high vacuum.

As the transesterification catalyst and polycondensation catalyst, known ones can be used. As the transesterification catalyst, manganese acetate, calcium acetate, zinc acetate or the like can be used, and as the polycondensation catalyst, antimony trioxide or germanium oxide can be used. , Dibutyltin oxide, titanium tetrabutoxide and the like can be used. However, various conditions such as the polymerization method and the catalyst are not limited to the above examples.

In the present invention, an aqueous dispersion obtained by dispersing and polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester is, for example, an aqueous solution of a water-soluble polyester obtained by dissolving the water-soluble polyester in hot water. It can be obtained by dispersing a vinyl-based monomer in, and performing emulsion polymerization or suspension polymerization. The polymerization is preferably emulsion polymerization.

A polymerization initiator is used for the polymerization of the vinyl monomer. Examples of the polymerization initiator that can be used include ammonium persulfate, potassium persulfate, sodium persulfate, and benzoyl peroxide. Among these, ammonium persulfate is preferable.

The polymerization can be carried out without using a surfactant, but it is also possible to use a surfactant as an emulsifier for the purpose of improving the polymerization stability. In this case, general nonionic and anionic surfactants can be used.

As the vinyl-based monomer, an acrylic-based monomer such as alkyl acrylate or alkyl methacrylate (wherein the alkyl group is methyl group, ethyl group, n
-Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); 2-hydroxyethyl acrylate, 2-hydroxyethyl Hydroxy group-containing monomers such as methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-methylolacrylamide, N
-Methylol methacrylamide, N, N-dimethylol acrylamide, N-methoxymethyl acrylamide,
Amide group-containing monomers such as N-methoxymethyl methacrylamide and N-phenylacrylamide; amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate; epoxy group-containing glycidyl acrylate and glycidyl methacrylate Monomers: Monomers containing carboxyl groups such as acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) or salts thereof, and the like. Examples of monomers other than acrylic monomers include epoxy group-containing monomers such as allyl glycidyl ether; sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and their salts (sodium salt, potassium salt, ammonium salt, etc.) Or a monomer containing a salt thereof; a monomer containing a carboxyl group such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) or a salt thereof; maleic anhydride, Monomers containing acid anhydrides such as itaconic anhydride; vinyl isocyanate; allyl isocyanate; styrene; vinyl trisalkoxysilane; alkyl maleic acid monoester;
Alkyl fumaric acid monoester; acrylonitrile;
Methacrylonitrile; alkyl itaconic acid monoester; vinylidene chloride; vinyl acetate; vinyl chloride and the like.

The amount of the vinyl-based monomer used is 99/1 to (water-soluble polyester) / (vinyl-based monomer) in a weight ratio.
It is preferably in the range of 5/95, and 97/3 to 50 /
More preferably in the range of 50, 95/5 to 80 /
The range of 20 is particularly preferable.

The primer layer of the present invention can be formed, for example, by applying a coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of the above water-soluble polyester.

A necessary amount of a surfactant such as an anionic surfactant, a cationic surfactant or a nonionic surfactant can be added to the coating solution for forming the primer layer. As such a surfactant, the surface tension of the aqueous coating solution can be 40 dyne / cm ² or less,
Those capable of promoting wetting to a polyester film are preferable, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene-fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfate, alkyl sulfonate,
Examples thereof include alkyl sulfosuccinate, quaternary ammonium chloride salt, and alkyl amine hydrochloride. Further, the coating liquid for forming the primer layer includes, for example, an antistatic agent, an ultraviolet absorber, a pigment, an organic filler,
Other additives such as an inorganic filler, a lubricant, an antiblocking agent and a stabilizer can be added.

Next, the polyester film provided with the primer layer will be described.

The polyester constituting the polyester film is a linear polyester synthesized from an aromatic dibasic acid or its ester-forming derivative and a diol or its ester-forming derivative. Specific examples of such polyesters include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylene dimethylene terephthalate), and polyethylene-2,6-naphthalene dicarboxylate. These polyesters also include copolymers and blends of these polyesters with small proportions of other resins.

The polyester film may be a single-layer polyester film, a laminated polyester film thereof, or a polyester film laminated with other constituent layers.

The polyester film can be obtained by melt-extruding a linear polyester resin by a conventional method to form a film, stretching, and completing orientation crystallization.

In the present invention, the polyester film is a differential scanning calorimeter in a nitrogen stream at 10 ° C.
The value of the heat of fusion of crystal measured at a temperature rising rate of 4 / min is 4c
It is preferable that the crystal orientation is such that it exhibits al / g or more.

The primer layer of the present invention may be provided on the polyester film which has been stretched and heat-set after the film forming step of the polyester film has been completed, by a means such as coating, or during the film forming step. At the stage, the polyester film before stretching and heat setting may be provided by a means such as coating, and then the film forming step may be completed.

When a primer layer is provided on the polyester film which has been stretched and heat-set after the film-forming process is completed,
The adjusted coating solution is applied to a polyester film which is biaxially stretched and heat-set at a desired stretching ratio, and the temperature is 120 ° C to 140 ° C.
The primer layer can be formed by drying at a hot air temperature of ° C to form a continuous film on the film.

Stretching and heat setting can be carried out, for example, by longitudinally stretching a polyester film at a draw ratio of 2 to 5 times, then horizontally stretching at a draw ratio of 2 to 5 times, and heat setting.

When the primer layer is provided on the polyester film before the stretching and heat setting are completed in the middle of the film forming process, the polymer is formed into a film form when the coating solution for forming the primer layer is applied. It may be in a stage of melt extrusion to obtain an unstretched film, and the stretched film is stretched but not stretched to the final stretching ratio, for example, either in the longitudinal direction or in the transverse direction. Uniaxially stretched film that has been stretched in a longitudinal direction or a transverse direction so that oriented crystallization can be completed by further stretching in a longitudinal or transverse direction. Good.

Next, the unstretched film coated with the coating liquid for forming these primer layers or the stretched film not stretched to the final stretching ratio is dried,
It is guided to a process such as stretching and heat setting, and drawn at a desired draw ratio to complete heat setting. For example, when the coating liquid for forming the primer layer is applied at the stage of uniaxially stretching the polyester film in the longitudinal direction, the longitudinally uniaxially stretched polyester film applied is guided to a stenter, laterally stretched, and heat-fixed. During this period, the coating liquid dries to form a continuous film on the film. Drying is preferably performed before or during stretching.

Conditions for oriented crystallization of polyester film,
For example, as the conditions such as stretching and heat setting, the conditions conventionally accumulated in the art can be adopted.

In the present invention, the primer layer of the present invention is preferably provided at a stage in the middle of the film forming process.

The coating liquid for forming the primer layer of the present invention is preferably used as an aqueous coating liquid. Usually, the solid content concentration of the coating liquid for forming the primer layer is 3
It is preferably 0% by weight or less, and more preferably 10% by weight or less. Further, the coating amount is preferably 0.5 to 20 g, and more preferably 1 to 10 g in terms of coating liquid weight per 1 m ² of the film.

As the coating method, various known methods can be used. For example, a roll coating method, a gravure roll coating method, a roll brushing method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method and a curtain coating method can be used alone or in combination.

The polyester film obtained as described above is excellent in transparency, has good adhesiveness to the hydrophilic colloid layer, does not deteriorate the photographic performance of the photographic light-sensitive material, and is halogenated. It also has excellent adhesion to the silver emulsion layer.

Examples of the hydrophilic colloid forming the hydrophilic colloid layer include proteins such as gelatin, albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugars such as alginic acid and starch derivatives. Derivatives: Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and various other synthetic hydrophilic polymers such as homopolymers or copolymers The substance may be mentioned, but gelatin is preferable. Gelatin includes lime-treated gelatin, acid-treated gelatin, and Bull Society Science Photography Japan (Bull. Soc. Sci. Photo. Ja.
pan), No. 16, p. 30, page 1966 (1966), and may be a hydrolyzed product or an enzymatically decomposed product of gelatin. Also,
Further, it may be a gelatin derivative or a graft polymer of gelatin and another polymer.

The silver halide emulsion used in the photographic light-sensitive material of the present invention may be any silver halide emulsion that is commonly used, for example, a silver bromide emulsion, a silver iodobromide emulsion or a small amount. The silver iodochlorobromide emulsion containing silver chloride may be used, but the silver iodobromide emulsion is preferable from the viewpoint of obtaining high sensitivity.

Further, as the silver halide emulsion of the present invention, it is advantageous to use a silver halide emulsion having tabular silver halide grains having an aspect ratio (ratio of grain size / grain thickness) of 3 or more. Aspect ratio is preferably 3.5
Or more, and more preferably 3.5 or more and 8.0 or less.

The silver halide emulsion having these tabular silver halide grains is said to have improved spectral sensitization efficiency and improved image graininess and sharpness, and is disclosed, for example, in US Pat. No. 4,386,156. , No. 4,504,570,
4,478,929, 4,414,304, 4,411,986, 4,400,463, 4,414,306, 4,439,520, 4 , 433,048, 4,434,226, 4,413,053, 4,459,353, 4,490,458, 4,399,215 and the like. The silver halide emulsion having tabular silver halide grains can be prepared by the methods described therein.

The silver halide emulsion may be of a surface latent image type which forms a latent image on the surface of the grain or an internal latent image type which forms a latent image on the inside of the grain. It may be of a type that forms a latent image on the.

These silver halide emulsions are used, for example, in the stage of grain preparation or physical ripening, for example, cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its salt. Complex salts may be added.

Soluble salts can be removed from the silver halide emulsion by the Nudel water washing method, the flocculation sedimentation method or the like. As a preferable method for removing soluble salts, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, and a polymer flocculant described in JP-A-63-158644. A method using certain exemplified G-3, G-8 and the like can be mentioned.

To the silver halide emulsion used in the photographic light-sensitive material of the present invention, various photographic additives can be added during the physical ripening or the chemical ripening or before or after the ripening. Examples of the compound used in such a process include Research Disclosure (RD) No. 176.
43, (RD) No. 18716 and (RD) No. 3081
19 (December 1989). The types of compounds described in these three Research Disclosures (RD) and their locations are listed below.

[0054]

[Table 1] The photographic light-sensitive material of the present invention may be various photographic light-sensitive materials such as X-ray light-sensitive materials, printing light-sensitive materials, photographing light-sensitive materials and ornamental light-sensitive materials.

[0055]

EXAMPLES The present invention will be described in more detail below with reference to examples.

In the following examples, the polyester film provided with the primer layer and the photographic light-sensitive material were
The following evaluation was performed. The obtained results are shown in Table 2.

[Adhesiveness of Undercoat Layer] A coating film (primer layer) on a polyester film is cut with a razor at an angle of 45 ° with respect to the polyester film, and a cellophane adhesive tape is pressure-bonded so that the cut may be applied. Then, the cellophane pressure-sensitive adhesive tape was rapidly peeled off, the peeled area of the primer layer from the cut to the portion where the cellophane pressure-sensitive adhesive tape below was pressure-bonded was obtained, and the adhesiveness was evaluated according to the following evaluation criteria. Evaluation criteria 1. The adhesion is very weak and the primer layer peels off completely. 2. The peeled area is 50% or more and less than 100% of the portion where the cellophane adhesive tape is pressure-bonded. 3. The peeled area is 10% or more and less than 50% of the portion where the cellophane adhesive tape is pressure-bonded. 4. The adhesive strength is strong, and the peeled area is 5% or more and less than 10% of the portion where the cellophane adhesive tape is pressure bonded. 5. The adhesive strength is very strong, and the peeled area is less than 5% of the portion where the cellophane adhesive tape is pressure bonded.

[Transparency of undercoat layer] TURBIDIMETER MODEL
The haze (%) of the polyester film having a primer layer was determined using a T-2600DA turbidimeter (Tokyo Denshoku Co., Ltd.).

[Adhesiveness of Photosensitive Layer] With respect to a sample in which a silver halide emulsion layer for X-rays is provided on each primer layer of a polyester film having primer layers on both sides, a film during the development treatment (hereinafter, referred to as A wet film was attached) was evaluated by the evaluation method shown below.

During the development process (with wet film), scratches reaching the polyester film were formed in a lattice pattern with a sharp needle on the surface of the silver halide emulsion layer for X-rays on one side of the sample, and the emulsion layer was formed. While still wet, rub for 10 seconds with your hands in rubber gloves. The area of the silver halide emulsion layer for X-rays peeled at this time was compared with the lattice area, and the peeled area was evaluated according to the following evaluation criteria. Evaluation criteria 1. The adhesive strength is very weak, and the X-ray silver halide emulsion layer is completely peeled off. 2. The peeled area is 50% or more and less than 100% of the portion where the cellophane adhesive tape is pressure-bonded. 3. The peeled area is 20% or more and less than 50% of the portion where the cellophane adhesive tape is pressure-bonded. 4. The adhesive strength is strong, and the peeled area is 5% or more and less than 20% of the portion where the cellophane adhesive tape is pressure-bonded. 5. The adhesive strength is very strong, and the peeled area is less than 5% of the portion where the cellophane adhesive tape is pressure bonded. If the evaluation is 4 or more, it can be considered that there is no problem with the film attachment in practical use.

[Pickoff of Photosensitive Layer] A sample having a silver halide emulsion layer for X-rays and a protective layer provided on each primer layer of a polyester film having primer layers on both sides was exposed to light and then automatically developed. Machine SRX-5
01 (manufactured by Konica Corporation) was used to perform development processing in the 45-second processing mode. Automatic processor SRX- used here
For No. 501, the squeeze roller after fixing and washing with water was abraded in advance so that the pick-off of the photosensitive layer was easily made so that the evaluation of the pick-off of the photosensitive layer was clear. The coated sample having a size of 160 mm × 300 mm was inserted into the automatic processor in the longitudinal direction.

After the treatment, using Schaukasten in a dark room,
The pickoff was visually determined. The evaluation is as follows. 1: The emulsion layer has peeled off. 2: 50 or more emulsion pick-offs occurred and the image quality was greatly impaired. 3: There are 20 to 49 emulsion pickoffs, impairing the image quality. 4: 19 or less emulsion pick-offs occurred, but there is no practical problem. 5: The number of emulsion pick-offs was several or less.

Example (Polymerization Example of Water-Soluble Polyester) 34.02 parts by weight of dimethyl terephthalate, 25.52 parts by weight of dimethyl isophthalate, 5-sulfoisophthalic acid dimethyl sodium salt 1
2.97 parts by weight, ethylene glycol 47.85 parts by weight, 1,4-cyclohexanedimethanol 18.95 parts by weight, calcium acetate monohydrate 0.065 parts by weight, manganese acetate tetrahydrate 0.022 parts by weight, and nitrogen. 1 under airflow
After carrying out the transesterification reaction while distilling off methanol at 70 to 220 ° C., 0.04 parts by weight of trimethyl phosphate,
As a polycondensation catalyst, 0.04 parts by weight of antimony trioxide and 15.08 parts by weight of 1,4-cyclohexanedicarboxylic acid were added, and a theoretical amount of water was distilled off at a reaction temperature of 220 to 235 ° C. for esterification. . After that, the pressure in the reaction system is further reduced over about 1 hour and the temperature is raised to 280 ° C. and 1 mmH.
Polycondensation was carried out for about 1 hour at g or less to obtain a polyester copolymer (A). The intrinsic viscosity of the obtained polyester copolymer (A) was 0.35.

(Support 1) Polyester Copolymer (A)
500 g was dissolved by stirring in 3400 g of hot water at 95 ° C. for 3 hours to prepare an aqueous solution of polyester copolymer (A). In this solution, 100 g of glycidyl methacrylate
And ammonium persulfate 1. Add 0g and 5 at 80 ℃
After reacting for a time and cooling to room temperature, a coating solution was obtained.

Polyethylene terephthalate having an intrinsic viscosity of 0.65 was melt extruded from a T-die at 280 ° C. into a film, electrostatically applied, and rapidly cooled on a cooling drum at about 30 ° C. to obtain an unstretched film (thickness 1 , 000 μm) was obtained.
This unstretched film was preheated to 75 ° C., stretched 3 times in the machine direction, and then corona discharge treated on both sides of the film. Then, the coating solution was applied on both sides of the film by a wire bar coater so that the coating thickness after biaxial stretching would be 0.3 μm, and then stretched 3 times in the transverse direction at 100 ° C. and 220 ° C.
Was heat-treated to obtain a biaxially stretched polyester film (Support 1) provided with the primer layer of the present invention.

(Support 2) After both sides of the biaxially stretched polyethylene terephthalate film were subjected to corona discharge treatment,
The coating liquid used for preparing the support 1 was applied and dried to obtain a biaxially stretched polyester film (support 2) provided with the primer layer of the present invention similar to the support 1.

(Support 3) 100 g of styrene and 1 part of ammonium persulfate were added to 7300 g of the aqueous solution of the polyester copolymer (A) used for preparing the support 1. 0 g was added and the mixture was reacted at 80 ° C for 5 hours, cooled to room temperature, and the solid content was adjusted to 10
The coating liquid was obtained by adjusting the content to be wt%.

A biaxially stretched polyester film (support 3) provided with the primer layer of the present invention was prepared in the same manner as in the preparation of the support 1 except that the above coating solution was used instead of the coating solution used in the preparation of the support 1. ) Got.

(Support 4) The primer layer of the present invention was prepared in the same manner as in the preparation of the support 2 except that the coating solution used in the preparation of the support 2 was replaced with the coating solution used in the preparation of the support 3. A biaxially stretched polyester film (support 4) provided with was obtained.

(Support 5) 30 g of styrene, 30 g of butyl methacrylate, 20 g of glycidyl methacrylate, 20 g of acrylamide and 1.0 g of ammonium persulfate were added to 7300 g of the aqueous solution of the polyester copolymer (A) used for preparing the support 1. And reacted at 80 ° C. for 5 hours, cooled to room temperature and adjusted to a solid content of 10% by weight to obtain a coating liquid.

A biaxially stretched polyester film (support 5) provided with the primer layer of the present invention was prepared in the same manner as in the preparation of the support 1 except that the above-mentioned coating solution was used instead of the coating solution used in the preparation of the support 1. ) Got.

(Support 6) A primer layer was provided in the same manner as in the preparation of the support 1 except that an aqueous solution of the polyester copolymer (A) was used instead of the coating liquid used in the preparation of the support 1. An axially stretched polyester film (support 6) was obtained.

(Support 7) A support was used except that a butadiene (But) -styrene (St) (30% by weight / 70% by weight) copolymer latex was used in place of the coating solution used for preparing the support 1. A biaxially stretched polyester film (support 7) provided with a primer layer was obtained in the same manner as the preparation of the body 1.

Photographic emulsion layer <Preparation of silver halide emulsions (A), (B) and (C)>
The silver halide emulsions (A), (B), and (C) are monodisperse silver iodobromide emulsions having an average silver iodide content of 20 mol% and rounded vertices and having an average grain size. , 0.35 μm for silver halide emulsion (A), 0.40 μm for silver halide emulsion (B), and 0.65 μm for silver halide emulsion (C)
m, the coefficient of variation is 0.17 for the silver halide emulsion (A),
The silver halide emulsion (B) is 0.16, and the silver halide emulsion (C) is 0.16.

1) Preparation of seed emulsion 1 Silver iodide 2 having an average grain size of 0.2 μm by the double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0.
Monodisperse cubic grains of silver iodobromide containing mol% were prepared, and the reaction solution was brought to 40 ° C. and desalted using a demol aqueous solution and an aqueous magnesium sulfate solution. Dispersed to obtain a seed emulsion.

2) Growth from seed emulsion 1 The above seed emulsion was dispersed in a gelatin aqueous solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous ammoniacal silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were added to this solution by the double jet method. During the addition, pAg = 7.3 and pH were controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Then, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method. The pAg is kept at 9.0 and the pH is 9.0 to 8.0 until the average particle diameter reaches 95% of the target particle diameter.
Was continuously changed to. After that, pAg is set to 11.0.
Was adjusted to, and the particles were grown to a target particle size while maintaining the pH at 8.0.

Subsequently, the pH was lowered to 6.0 with acetic acid, desalting was performed using the demole aqueous solution and the magnesium sulfate aqueous solution, and then a gelatin solution was added to redisperse the silver halide emulsion (A), ( B) and (C) were prepared.

<Preparation of Silver Halide Emulsion (D)> The silver halide emulsion (D) has an average silver iodide content of 1.5 mol%, an average diameter in terms of projected area of 0.76 μm, and a coefficient of variation of It is a tabular silver iodobromide having a 0.25 and an aspect ratio of 3.6.

1) Preparation of seed emulsion 2 0.0 containing hydrogen peroxide treated gelatin kept at 30 ° C.
A 5N potassium bromide aqueous solution was vigorously stirred, and an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin was added by a double jet method. 1.5 minutes after the addition, the liquid temperature was lowered to 25 ° C over 30 minutes, and then
80 ml of ammonia water (28%) per mol of silver nitrate
Was added and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous solution of demole and an aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then an aqueous gelatin solution was added to re-disperse.

The obtained seed emulsion had an average grain size of 0.20 μm,
The spherical particles had a coefficient of variation of 0.28.

2) Growth from seed emulsion 2 The above seed emulsion was dispersed in an aqueous solution containing ossein gelatin and propyleneoxy-polyethyleneoxy-disuccinate-disodium salt vigorously stirred at 75 ° C., and potassium bromide and iodide were further added. An aqueous solution of potassium iodide and an aqueous solution of silver nitrate were added by the double jet method.

During the addition, pH = 5.8, pAg = 9.0.
Kept at. After the addition was completed, the pH was adjusted to 6.0. After further desalting at 40 ° C. using the demole aqueous solution,
An aqueous gelatin solution was added and redispersed to prepare a silver halide emulsion (D).

<Preparation of Photosensitive Silver Halide Emulsion Coating Solution>
Each of the obtained silver halide emulsions (A), (B), (C) and (D) was added with 5,5'-dichloro- at 55 ° C.
Anhydrous sodium 9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine and 5,5'-di- (butoxycarbonyl) -1, l'-diethyl-3,
Anhydrous of 3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt was added. 5,5 '
-Dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine anhydrous sodium and 5,5'-di- (butoxycarbonyl) -1, l'-diethyl-3,3 The anhydride of'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt is 20
Used in a weight ratio of 0: 1, 975 mg for silver halide emulsion (A), 600 mg for silver halide emulsion (B), and 3 for silver halide emulsion (C) per mol of silver halide.
90 mg and 500 mg to the silver halide emulsion (D).

After 10 minutes, optimum amounts of chloroauric acid and sodium thiosulfate were added.
Chemical aging by adding thorium and ammonium thiocyanate
I went. 15 minutes before the end of aging, halogenate potassium iodide
200 mg per mol of silver halide was added, and then 4-hydro
Xy-6-methyl-1,3,3a, 7-tetrazainde
3 x 10 per mol of silver halide^-2 Add a mole
It was dispersed in an aqueous solution containing 70 g of ratin.

The above-ripened silver halide emulsion (A) was used alone as emulsion A, and silver halide emulsions (B) and (C) were mixed at a weight ratio of 75:25 to form emulsion B. The silver halide emulsion (D) was used as Emulsion C as it was.

The following additives were added to each of Emulsion A, Emulsion B and Emulsion C to prepare a photosensitive silver halide emulsion coating solution. Additives are as follows, and the addition amount is shown per 1 mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 mg Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 2 - anilino-4,6-sodium dimercaptotriazine 60 mg 1,3-dihydroxybenzene-4-sulfonic acid ammonium 4g 2-mercaptobenzimidazole-5-sulfonic acid _{1.5mg C 4 H 9 OCH 2 CH} (OH) CH 2 N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg

[0089]

[Chemical 1]

(Preparation of Photographic Light-Sensitive Material Sample) Two slide hopper type coaters were used, and simultaneous coating was carried out so that the support 1
Emulsion layers and protective layers were coated on both sides of No. 7 to prepare photographic light-sensitive material samples having the combinations of support and emulsion layers shown in Table 2. The coating amount was 1.7 g / m ^{2 in} terms of silver per side of the emulsion layer and 0.99 g / m ² in terms of the amount of gelatin per side of the protective layer.

The additives used in the protective layer liquid are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

[0092]

[Chemical 2]

[0093]

[Table 2]

[0094]

[0095]

【The invention's effect】

(1) Since an aqueous dispersion obtained by dispersion-polymerizing a vinyl-based monomer in an aqueous solution of a water-soluble polyester of the present invention can be prepared without using an organic solvent, there is no danger of ignition and the working environment There is no problem above. Also, when using,
Since the primer coating liquid is water-based, the equipment can be simplified as compared with the case of using an organic solvent system. (2) An aqueous dispersion obtained by dispersion-polymerizing a vinyl-based monomer in an aqueous solution of the water-soluble polyester of the present invention exhibits excellent dispersion stability. (3) The primer layer of the present invention has excellent adhesiveness to a polyester support or a hydrophilic colloid layer such as a silver halide emulsion layer, has water resistance, and particularly exhibits excellent adhesiveness even in a developing solution. (4) The primer coating liquid containing the aqueous dispersion obtained by dispersing and polymerizing the vinyl-based monomer in the aqueous solution of the water-soluble polyester of the present invention has excellent film-forming property and thus exhibits excellent transparency.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 1/93 // C08J 5/12 CFD 9267-4F B29K 67:00 (72) Inventor Yoshihiro Wada Konica Co., Ltd. 1 Sakura-cho, Hino-shi, Tokyo (72) Inventor Hitoshi Kawamoto 4-1, Kanebocho, Hofu-shi, Yamaguchi Prefecture (72) Inventor Yoshimichi Ozawa 3-22-19, Osaki Jiyugaoka, Hofu-shi, Yamaguchi Prefecture (72) Inventor Hiroshi Naito 2265-5, Yoshijiki, Yamaguchi City, Yamaguchi Prefecture (72) Inventor Mitsuo Sato 22-23-206, Gunyashinmachi, Takatsuki City, Osaka Prefecture (72) Makoto Mohri 1-6-7 Tomobuchicho, Miyakojima-ku, Osaka City 102

Claims (9)

[Claims] 1. A polyester film comprising a primer coating formed on at least one side of a primer coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester. 2. The polyester film according to claim 1, wherein the polyester film is a biaxially stretched polyester film. 3. A water-soluble polyester having at least terephthalic acid, isophthalic acid, a dicarboxylic acid having a sulfonate, an alicyclic dicarboxylic acid as a dicarboxylic acid component, and at least ethylene glycol as a glycol component. And the ratio of terephthalic acid and isophthalic acid in the water-soluble polyester is terephthalic acid / isophthalic acid = 30/70 to 70/3 in a molar ratio.
0, 5 to 15 mol% of the dicarboxylic acid having a sulfonate with respect to the total dicarboxylic acid component, and 50 mol% or more of ethylene glycol with respect to the total glycol component. Or the polyester film according to 2. 4. A primer coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester is applied onto at least one surface of a polyester film before the final crystal orientation is performed, The polyester film according to any one of claims 1 to 3, wherein the polyester film is obtained by drying, stretching and heat treatment to complete the final crystal orientation. 5. The polyester film according to claim 1, wherein a hydrophilic colloid layer is provided on the primer layer. 6. The polyester film according to claim 1, wherein the hydrophilic colloid layer is a layer containing gelatin. 7. A primer coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester is applied to at least one surface of a polyester film before the final crystal orientation is performed, Then, drying, stretching, and heat treatment are performed to complete the final crystal orientation, and the method for producing a polyester film according to any one of claims 1 to 6. 8. A photographic light-sensitive material, wherein at least one silver halide emulsion layer is provided on at least one side having a primer layer of the polyester film according to claim 1. 9. A primer coating solution containing an aqueous dispersion obtained by dispersion-polymerizing a vinyl monomer in an aqueous solution of a water-soluble polyester is applied to at least one surface of a polyester film before the final crystal orientation is performed, 9. The photographic light-sensitive material according to claim 8, wherein the polyester film thus obtained is dried, stretched and heat-treated to complete the final crystal orientation, and at least one silver halide emulsion layer is coated on the polyester film. Production method.