JPH10291287A - Manufacture of polyester photographic substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a coated layer having a photographic sensitized layer and excellent adhesion in drying and in wetting by a method wherein a coating liquid having aqueous polyurethane and aqueous epoxy group-containing compound by a specific dry weight ratio is applied to a polyester surface, and dried. SOLUTION: A coating layer is formed on a polyester film by using coating liquid containing aqueous polyurethane and aqueous epoxy group containing compound by a specific ratio. A dry wt. ratio of aqueous polyurethane and aqueous epoxy group containing compound is 10-90 to 80/20. In the case of under 10/90 weight ratio, the formed coated layer is poor in adhesion to the polyester film being a substrate, and durability of the coated layer is deteriorated. Further, a blocking property of a completed film is also deteriorated. Besides, in the case where the weight ratio is larger than 80/20, adhesion of the obtained coated layer to a photographic sensitized layer to be topcoated becomes poor.

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 polyester-based photographic support, and more particularly, to a polyester film having an undercoat layer having excellent adhesion to a photographic photosensitive layer provided on the support. .

[0002]

2. Description of the Related Art Polyester films represented by polyethylene terephthalate and polyethylene-2,6-naphthalate are suitable as photographic supports because of their excellent mechanical strength, dimensional stability, transparency and flatness. And it is actually put to practical use.

[0003] However, the polyester film has a poor surface activity and has a disadvantage that the adhesiveness to a photographic photosensitive layer provided by overcoating a photographic emulsion mainly containing gelatin as a main component of a binder is remarkably poor. The adhesiveness with the photographic photosensitive layer as a photographic support must be exhibited not only when the finished photographic material is dry but also in a wet state during photographic processing represented by development processing. For this reason, when a polyester film is used as a support, there is often adopted a method in which a certain kind of polymer layer is provided on a film before a photographic photosensitive layer is provided to form an easily adhesive layer. Specifically, polyester copolymer, vinylidene chloride copolymer,
It is known to provide a layer of a mixture of gelatin and a hydrophilic vinyl or acrylic copolymer, a carboxy-modified polyethylene or the like. Further, the polyester film may be subjected to a pretreatment such as a corona discharge treatment before providing the polymer layer.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a polyester-based photographic support having excellent adhesion to a photographic photosensitive layer when dry and wet. Is to solve the problem.

[0005]

That is, the gist of the present invention is to provide a coating film containing an aqueous polyurethane and an aqueous epoxy group-containing compound in a dry weight ratio of 10/90 to 80/20 at least in a polyester film. The present invention relates to a method for producing a polyester photographic support, which is coated on one side and dried.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyester constituting the polyester film of the present invention refers to a polymer containing an ester group obtained by polycondensation from a dicarboxylic acid and a diol or a hydroxycarboxylic acid.

The dicarboxylic acids include terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid,
2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and as the diol,
Ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol,
Examples of the hydroxycarboxylic acid include p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.

Representative polyesters include polyethylene terephthalate (hereinafter abbreviated as PET), polyethylene-2,6-naphthalate (hereinafter abbreviated as PEN),
Examples thereof include poly-1,4-cyclohexane terephthalate. The polyester used in the present invention may be a homopolymer or a copolymer obtained by copolymerizing three or more monomers. Further, a mixture of two or more polyesters may be used. However, its mechanical strength,
PET from the viewpoint of properties required for photographic use such as thermal stability and dimensional stability, and productivity and production cost of polyester
And a homopolymer of PEN are suitably selected as the main component.

The intrinsic viscosity of the polyester used in the present invention is usually 0.45 or more, preferably 0.50 to 1.0.
0, and more preferably in the range of 0.52 to 0.90. If the intrinsic viscosity is less than 0.45, the productivity during film production may be reduced, or the mechanical strength of the film may be reduced. On the other hand, it is preferable that the intrinsic viscosity does not exceed 1.0 from the viewpoint of melt extrusion stability of the polymer.

In general, inorganic or organic particles are contained in a polyester film for the purpose of improving slipperiness, workability, and the like at the time of film production and film winding, so that the film surface is moderated. Often roughened. Particles that can be used include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite,
Molybdenum sulfide, crosslinked organic polymer particles, calcium oxalate, and the like can be given. In addition, precipitated particles generated during the polymerization of polyester are also included.

The particle size and the amount of these particles are appropriately selected depending on the type of photograph used, and depending on the application, there may be a case where the particles contain substantially no particles. In applications where a highly transparent support is required, the smaller the number of particles is, the better the particles are. The average particle size of these particles is preferably 0.005 to 5.0 μm, and more preferably 0.01 to 5.0 μm.
It is in the range of 3.0 μm. When the average particle size exceeds 5.0 μm, the film surface tends to be too rough. Further, the particles easily fall off, which may cause so-called powder dropping when using the film. Average particle size 0.005
If it is less than μm, the projections formed by the particles tend to be insufficient, and the effect of improving the slipperiness of the film is reduced.
Large amounts of particles need to be added, which can impair the mechanical properties of the film.

Further, the content of particles is
It is preferably 0 to 30% by weight, more preferably 0.01 to 20% by weight. When the amount of particles increases, the mechanical properties of the film may be impaired. In the film, two or more kinds of the above particles may be blended, or particles of the same kind but different in particle diameter may be blended. In any case, it is preferable that the average particle diameter and the total content of all the particles contained in the film satisfy the above-mentioned ranges, respectively.

In the production of polyester containing particles,
The particles may be added during the polyester synthesis reaction or may be added directly to the polyester. When it is added during the synthesis reaction, a method in which the particles are added as a slurry in which the particles are dispersed in ethylene glycol or the like at an arbitrary stage of polyester synthesis is preferable. On the other hand, when it is directly added to the polyester, it is used as dried particles or water or a compound having a boiling point of 2%.
As a slurry dispersed in an organic solvent at
A method of adding and mixing with polyester using a shaft kneading extruder is preferred. In addition, the particles to be added may be subjected to processing such as crushing, dispersion, classification, and filtration as needed.

As a method for adjusting the content of particles, a master material containing particles at a high concentration is prepared in the above-described manner, and is diluted with a material substantially free of particles during film formation. A method of adjusting the particle content is effective. In addition, as an additive other than the particles as the above-mentioned projection-forming agent, if necessary, an antistatic agent, a stabilizer, a lubricant, a crosslinking agent, a blocking agent, as long as the performance as a photographic support for the required use is not impaired. It may contain an inhibitor, an antioxidant, a colorant (dye or pigment), a light-blocking agent, an ultraviolet absorber, and the like.

The polyester film of the present invention may have a multilayer structure as long as the properties finally obtained satisfy the requirements as a photographic support. For example, it may be a co-extruded laminated film. In this case, the above description regarding the base film applies to the polyester of the outermost layer. As the polyester film of the present invention, a biaxially stretched polyester film is particularly preferably used in view of the required characteristics of the photographic support.

The method for producing a polyester film itself is as follows.
Usually, a known method can be adopted, but the stretching method is simultaneous 2
Either axial stretching or sequential biaxial stretching is performed, and particularly, sequential biaxial stretching is often performed. A more specific method for producing a polyester film is as follows. That is, the polyester raw material is supplied to an extruder, melt-extruded at a temperature equal to or higher than the melting point of the polyester, and extruded as a molten sheet from a slit die. Next, the molten sheet is quenched and solidified on a rotary cooling drum so as to have a temperature equal to or lower than the glass transition point to obtain a substantially amorphous unstretched sheet. In this case, in order to improve the flatness of the sheet, it is preferable to increase the adhesion between the sheet and the rotary cooling drum,
In the present invention, the electrostatic printing and adhesion method and / or the liquid application adhesion method are preferably employed.

The unstretched sheet thus obtained is usually stretched in the biaxial direction. Here, the longitudinal and transverse biaxial stretching is exemplified. Generally, an unstretched sheet is stretched (longitudinal stretching) in the longitudinal direction of the sheet by a group of rolls having a difference in peripheral speed.
First, the sheet is preheated and maintained at a temperature not lower than the glass transition point and not higher than the melting point. In the case of PET, this temperature is 70-150.
C., and in the case of PEN, the range of 115 to 170 C. is preferable.
Then, a total of 2 to 10 using the peripheral speed difference of the rolls
The film is stretched so as to have a double magnification. At this time, the stretching can be performed in one stage or two or more stages. Next, the film is stretched (transversely stretched) in the transverse direction, that is, in the direction perpendicular to the longitudinal direction.
That is, once the obtained uniaxially oriented film is cooled to or below the glass transition point, or without cooling, similarly, at a temperature above the glass transition point and below the melting point, specifically, PE
80 to 150 ° C for T, 120 ° C for PEN
At 180 ° C., the film is stretched 2 to 10 times while holding the end of the film with a clip.

Here, an example in the order of longitudinal stretching and transverse stretching is shown, but the order may be reversed, and each stretching may be performed by dividing it into several times. Further, division may be performed, and a part of the division may be performed alternately. For example,
A method for producing a high-strength film by a re-stretching method corresponds to this. Furthermore, biaxial stretching may be performed simultaneously. The biaxially oriented film thus obtained is usually heat-treated with elongation, limited shrinkage or lengthening within 30%. The heat treatment time is preferably in the range of 1 second to 5 minutes. At this time, a method of performing a relaxation treatment within 10%, or even within 5% after or after the heat treatment step can be also adopted particularly in order to keep the heat shrinkage in the vertical direction within a suitable range. Although the heat treatment temperature depends on the stretching conditions, it is still higher than the glass transition point and lower than the melting point.
Then, the range of 170 to 270 ° C. is preferable.

If the heat treatment is long, for example, the treatment temperature is high, or the temperature is high, the crystallization of the polyester tends to progress too much. Thermal decomposition may occur. Also, if the heat treatment is too small,
The shrinkage of the film increases. In any case, conditions are selected in which the properties of the finally obtained film meet the requirements as a photographic support.

The thickness of the obtained photographic support is appropriately selected depending on the use of each photographic material.
It is preferably in the range of 0 μm. If the thickness is less than 50 μm, the rigidity of the support tends to be insufficient,
If the thickness is more than 0 μm, the weight of the photographic material increases, and the handling tends to be poor, which is disadvantageous in terms of cost. Next, the coating layer provided on the polyester film in the present invention will be described.

The coating layer is formed by applying a coating solution on a film and then drying it. The coating may be performed after the production of the polyester film, or may be performed in the polyester film production process. The latter method is a so-called in-line coating method. In order to perform in-line coating, the coating liquid desirably satisfies several requirements, and the coating layer provided in the present invention is preferably provided by in-line coating. Such requirements include, for example, cracks in the coating layer due to stretching after coating, no white turbidity of the film thereby, good coating properties, sufficient performance even in a thin film, and an aqueous coating solution. It is necessary to satisfy such conditions.

The in-line coating referred to here is a method in which the polyester is melt-extruded, then biaxially stretched, heat-fixed, and applied at an arbitrary place from winding up. Either an unstretched sheet in a non-crystalline state, a uniaxially stretched film after being stretched in the longitudinal direction (also referred to as a longitudinal direction) (before being stretched in the transverse direction), or a biaxially stretched film before heat setting Applied to Among them, a method in which the film is applied to a polyester film stretched uniaxially in the longitudinal direction and stretched in the horizontal direction in a dried or undried state is excellent. The reason is that film formation and coating and drying can be performed at the same time, so that there is an advantage in manufacturing cost, it is possible to apply a thin film because it is stretched after coating, and heat treatment performed after coating is not achieved by other methods. It is a high temperature, and as a result, the coating film and the polyester film are strongly adhered.

It is safe to perform in-line coating,
The coating liquid is preferably aqueous based on the work environment,
The coating liquid used in the present invention essentially contains a water-based coating liquid containing an aqueous polyurethane and an aqueous epoxy group-containing compound. However, in order to improve the stability, dispersibility, coatability and the like of the coating solution, a small amount of an organic solvent can be used in combination as needed. This is the same for the aqueous polyurethane and the aqueous epoxy group-containing compound described below. Further, depending on the organic solvent contained in these raw materials, it is possible that the organic solvent is eventually contained in the coating composition.

As the organic solvent, a relatively hydrophilic one is preferably used, and specific examples thereof include aliphatic or alicyclic alcohols, glycols, esters, ethers and amide compounds. Specifically, alcohols such as methanol, ethanol, isopropanol and n-butanol; glycols such as ethylene glycol, propylene glycol and diethylene glycol; esters such as ethyl acetate and amyl acetate; ethers such as methyl cellosolve, ethyl cellosolve and n Examples of ketones include acetone, methyl ethyl ketone, etc., and other acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, etc., such as -butyl cellosolve, t-butyl cellosolve, dioxane, and tetrahydrofuran. It is. These organic solvents may be used alone or in combination of two or more as needed.

In the case where the main component of the coating liquid and each coating agent is water, the compound may be forcibly dispersed with a surfactant or the like, but a self-dispersing coating agent may be used. This is preferable from the viewpoint of dispersion stability of the coating solution. The self-dispersion type coating agent is a coating agent in which various hydrophilic groups are introduced into a compound by a chemical bond. For example, as a nonionic, a hydroxyl group, a polyether, as anionic, a sulfonic acid, a carboxylic acid, phosphoric acid and a salt thereof, and as a cationic, a hydrophilic component such as an onium salt represented by a quaternary ammonium salt. However, these chemical species can be introduced by copolymerization or grafting to form a self-dispersing coating agent.

As a method of applying a coating solution to a polyester film, for example, Yuji Harazaki, Maki Shoten, 1979
For example, a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, or any other coating apparatus as shown in “Coating System” published in the year can be used. The thickness of the finally formed coating layer is usually 0.001 to 10 μm, preferably 0.1 to 10 μm.
010 to 5 μm, more preferably 0.015 to 2 μm
It is. If the coating layer is thin, the adhesiveness to the photographic photosensitive layer expected of the coating layer may not be sufficiently exhibited. On the other hand,
If the coating layer is thick, the coating layer acts like an adhesive, and the films wound up on the rolls adhere to each other,
What is called blocking occurs. Unnecessarily increasing the thickness of the coating layer is not preferable in terms of manufacturing cost and productivity.

The term "aqueous polyurethane" as used herein means a water-soluble or water-dispersible polyurethane resin coating agent using water as a main coating medium. Examples of components constituting such a polyurethane resin include the following polyols, polyisocyanates, chain extenders, crosslinking agents, and the like. The polyester-based polyurethane, the polyether-based polyurethane, and the polycarbonate-based polyurethane in the present invention are polyester polyols, polyether polyols, and polycarbonate polyols, respectively, which are one of the main constituent polyols of the polyurethane. is there. In addition, acrylic polyols and the like are often used.

The above polyester polyols can be obtained, for example, by reacting a dicarboxylic acid and a glycol according to a conventional method. Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid, and oxybenzoic acid and the like. Carboxylic acids and their ester-forming derivatives, and the like,
Examples of glycol components include ethylene glycol,
Aliphatic glycols such as 1,4-butanediol, diethylene glycol and triethylene glycol;
Alicyclic glycols such as cyclohexanedimethanol,
Examples thereof include aromatic diols such as p-xylene diol, and polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. These polyesters have a linear structure, but can be made into a branched polyester using a trivalent or higher ester-forming component.

Examples of polyether polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. Polycarbonate polyols can be obtained, for example, by reacting a carbonate ester and a diol. Examples of carbonate esters include ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dicyclohexyl carbonate, and the like.Examples of diols include 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanediol. Cyclohexane dimethanol, 3-
Methyl-1,5-pentanediol, polyethylene glycol, polypropylene glycol, polycaprolactone diol, trimethylhexanediol, 1,4-butanediol and the like can be mentioned. Further, a polyester polycarbonate obtained by reacting a polycarbonate diol with a dicarboxylic acid or a polyester may be used.

Examples of polyisocyanates include tolylene diisocyanate, phenylene diisocyanate,
4,4'-diphenylmethane diisocyanate, 1,5
-Naphthalene diisocyanate, aromatic diisocyanate such as xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,
Aliphatic diisocyanates such as 4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate are exemplified.

The aromatic polyurethane in the present invention is:
The above-mentioned polyisocyanate component is a polyurethane in which the polyisocyanate component is aromatic. Similarly, the aliphatic polyurethane refers to a polyurethane in which the polyisocyanate component is aliphatic. When synthesizing a polyurethane, an aromatic polyisocyanate and an aliphatic polyurethane are often used in combination, but a polyurethane having two or more kinds of aromatic polyisocyanate and aliphatic polyisocyanate in one molecule can also be particularly preferably used. . Of course, two or more aromatic polyurethanes, aliphatic polyurethanes, and copolymers of the former two types may be selected and used in combination.

Examples of the chain extender or the crosslinking agent include ethylene glycol, propylene glycol, butanediol, hexanediol, diethylene glycol, trimethylolpropane, glycerin, hydrazine, ethylenediamine, diethylenetriamine, 4,4′-diaminodiphenylmethane, 4'-diaminodicyclohexylmethane, water and the like.

The polyester-based polyurethane, polyether-based polyurethane, and polycarbonate-based polyurethane in the present invention use polyester polyols, polyether polyols, and polycarbonate polyols, respectively, as one of the polyols which are the main constituent components of polyurethane. It was done. In addition, acrylic polyols and the like are often used.

The aqueous epoxy group-containing compound in the present invention is a coating agent for a compound containing an epoxy group which is water-soluble or water-dispersible using water as a main coating medium, and the compound has at least an epoxy group in the molecule. It contains one or more, preferably two or more. Examples of such an epoxy group-containing compound include glycidyl ethers such as glycols, polyethers and polyols, glycidyl esters of carboxylic acids, and glycidyl-substituted amines. Of these, glycidyl ethers are preferred. These glycidyl compounds can be easily obtained by reaction with epichlorohydrin, but the synthesis method is not limited thereto. As specific examples, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether,
Diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate,
Glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl Ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, adipic acid diglycidyl ether, orthophthalic acid diglycidyl ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, terephthalic acid glycidyl ester,
Examples include, but are not limited to, dibromoneopentyl glycol diglycidyl ether. Epoxy emulsions are also sold by various companies. For example, "Denacol E" manufactured by Nagase Kasei Kogyo Co., Ltd.
M-125 "," Denacol EX-1101 "," Denacol EX-1102 "," Denacol EX-1103 "
And the like, but are not limited thereto.

In addition, two or more of these epoxy group-containing compounds may be used in the coating solution, and it is usually natural that a mixture of a plurality of types is usually used in the course of compound synthesis. In the present invention, it is an important requirement to provide a coating layer on a polyester film using a coating solution containing the aqueous polyurethane and the aqueous epoxy group-containing compound in a specific ratio. Is a dry weight ratio (aqueous polyurethane / aqueous epoxy group-containing compound) of 10/90 to 80/2.
0, preferably 10/90 to 75/25, and more preferably 15/85 to 70/30. Weight ratio is 10 /
If it is less than 90, the provided coating layer is not excellent in adhesion to the polyester film as the support, and the water resistance of the coating layer is poor. Further, the resulting film has poor blocking properties. On the other hand, when the weight ratio is more than 80/20, the adhesiveness between the obtained coating layer and the overcoated photographic photosensitive layer deteriorates, which is not preferable.

The present invention is characterized by the use of a coating solution containing a plurality of specific compounds in a specific ratio as described above. However, as long as the gist of the present invention is not impaired, other compounds may be used as an aqueous polyurethane or an aqueous epoxy resin. An amount of not more than 40% by weight on a dry weight basis with respect to the total of the group-containing compounds may be blended. For example, inorganic or organic fine particles, wax, antistatic agent, surfactant, defoamer, coating improver, thickener, antioxidant, ultraviolet absorber, foaming for the purpose of improving blocking property and slipperiness Agents, dyes, pigments and the like.

The film before coating may be subjected to a chemical treatment or a discharge treatment in order to improve the coating properties and adhesion of the coating solution to the film. Further, for the purpose of improving the coatability, adhesiveness and the like between the polyester film of the present invention and the photographic photosensitive layer, a discharge treatment may be performed after the formation of the coating layer. In the present invention, the coating layer may be provided on one side or both sides of the polyester film, but usually a photographic photosensitive layer on one side of the support and an antistatic layer on the opposite side, a back coat layer such as an anti-curl layer Is often used as a photographic material.
Therefore, the polyester film of the present invention as a photographic support is also preferably provided with an easily adhesive coating layer on both sides.

Various photographic materials can be prepared by providing at least one photographic photosensitive layer on a photographic support produced according to the present invention. For example, a silver halide photographic emulsion layer can be provided. Such a photographic emulsion preferably uses gelatin as a main binder. As the silver halide emulsion, various usual silver halide emulsions can be arbitrarily used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye. In addition, the silver halide emulsion includes
Antifoggants, stabilizers, hardeners and the like can be added.

Examples of the hardener include aldehyde, aziridine, isoxazole, epoxy, vinyl sulfone, acryloyl, carbodiimide, triazine, polymer, and other maleimide, acetylene, and methanesulfonic acid esters. Each hardener alone or 2
More than one type can be used in combination. Plasticizers, dispersions (latex) of water-insoluble or poorly soluble synthetic polymers,
Couplers, coating aids, antistatic agents, as well as formalin scavengers, optical brighteners, matting agents, lubricants, image stabilizers, surfactants, color fog inhibitors, development accelerators, development retarders and bleach accelerators. It can also be contained.

In the photographic light-sensitive material, a protective layer, a filter layer, a back coating layer,
Auxiliary layers such as an antihalation layer, an antiirradiation layer, and an intermediate layer can be provided. Such a photographic photosensitive layer and other layers are appropriately selected depending on the photographic application to be used, and are not limited to the examples shown here.

[0041]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. The evaluation method in the examples is as follows. (1) Dry weight of coating liquid (coating agent) It was determined according to JIS K 5407-4. (2) Intrinsic viscosity of polyester [η] (dl / g) 1 g of polyester is phenol / tetrachloroethane =
Dissolved in 100 ml of a 50/50 (weight ratio) mixed solvent,
It was measured at 30 ° C. (3) Photosensitive Layer (Gelatin Layer) Adhesion 1 [Dry] A gelatin layer containing a hardening agent, a latex, a matting agent, and a yellow dye for making the evaluation result easy to understand is provided so as to have a thickness of 3 μm after drying. After sufficient hardening, 23
C. and 50% RH. Under this atmosphere, 100 square cross cuts were made at 1 mm intervals on the surface of the gelatin layer, and "Polyester Adhesive Tape No. 31" manufactured by Nitto Denko was applied thereon with care so as to prevent air bubbles. A metal roll having a load of 2 kg was reciprocated 20 times on the tape. Thereafter, the substrate polyester film side was bent at 180 ° to perform a peeling test. One end of the polyester film is connected to a 1 kg weight, and this weight is 45 c
The peeling test was performed such that peeling in the 180 ° direction started after the sample naturally dropped for a distance of m. The situation at this time was visually observed and evaluated according to the following criteria.

[0042]

[Table 1] ───────────────────────────── Evaluation status ─────────────── ◎ 良好 (Good): No peeling ○ (Normal): Peeled less than 30% △ (Somewhat bad): Peeled from 30% to less than 80% × (Poor): 80% Above peeling ───────────────────────────── The evaluation result is preferably 以上 or more, more preferably ◎. (4) Photosensitive layer (gelatin layer) adhesion 2 [when wet] After providing a gelatin layer and adjusting the humidity in the same manner as in (3) above,
A crosscut was also made. Using a felt that was immersed in water and sufficiently squeezed, it was reciprocated 30 times with a load of 500 g using Taihei Rika "rubbing tester". At this time, the remaining amount of the gelatin layer was visually observed and evaluated according to the following criteria.

[0043]

[Table 2] ───────────────────────────── Evaluation status ─────────────── ◎ (good): 100% remaining ○ (normal): 70% or more remaining Δ (slightly poor): 20% to less than 70% remaining × (bad): 20 % Remaining ───────────────────────────── The evaluation result is preferably ○ or more, and ◎ is more preferable.

The method for producing the polyester film used in the examples is described below. (Production of polyester film 1: polyethylene terephthalate film) A limiting viscosity of 0.63 polyethylene terephthalate polymerized by a conventional method is melt-extruded at 280 ° C. from a slit die onto a cooling rotary drum at 40 ° C., and an electrostatic application method is used. While quenching and solidifying, an amorphous sheet was obtained. The obtained amorphous sheet was stretched 3.5 times in the longitudinal direction at 85 ° C (longitudinal stretching), and then stretched 4.0 times in the transverse direction at 105 ° C (lateral stretching). Thereafter, heat treatment was performed at 220 ° C. to obtain a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm. (Production of Polyester Film 2: Polyethylene Naphthalate Film) Polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.63, which was polymerized and solid-phase polymerized by a conventional method, was cooled at 300 ° C. through a slit die at 40 ° C. on a cooling rotary drum. And quenched and solidified using an electrostatic application method to obtain an amorphous sheet. The obtained amorphous sheet was stretched 4.0 times in the longitudinal direction at 130 ° C. (longitudinal stretching),
Thereafter, the film was stretched 4.0 times in the horizontal direction at 135 ° C. (lateral stretching). Thereafter, heat treatment is performed at 240 ° C.
An axially stretched polyethylene naphthalate film was obtained.

Next, a method for providing a coating layer on a polyester film will be described. (Coating method) During the above polyester film manufacturing process, after the longitudinal stretching and before the transverse stretching, using a bar coater, apply the coating solutions in the following table using a bar coater so that the concentration of the coating solution is adjusted to a thickness suitable for each example. The thickness was adjusted and applied. The coating thickness in the table is that after drying and transverse stretching, that is, the thickness of the coating layer on the film after biaxial stretching heat treatment.

Next, the contents of the coating agent used in the examples will be described. (Aqueous polyurethane) Aqueous polyurethanes A1 to A6 were used. The resin is synthesized by a conventional method, neutralizing if necessary,
Dispersed in water. The composition is as follows. In addition, all of the following parts represent parts by weight.

A1: Polyester polyol (a polyester polyol comprising 664 parts of terephthalic acid, 631 parts of isophthalic acid, 472 parts of 1,4-butanediol, and 447 parts of neopentyl glycol, and adipic acid 32
1880 parts of dimethylolpropionic acid, and 1880 parts of a polyester polyol having a pendant carboxyl group) and 160 parts of tolylene diisocyanate A2: The same polyester polyol 1880 as A1 above
Aliphatic polyester polyurethane A3 consisting of 160 parts of 4,4'-dicyclohexylmethane diisocyanate in part A3: polytetramethylene glycol (molecular weight: 200
0) 31.5 parts, neopentyl glycol 17.2 parts,
Aromatic polyether polyurethane consisting of 7.8 parts of dimethylolpropionic acid, 1.5 parts of trimethylolpropane and 42.0 parts of tolylene diisocyanate A4: 31.5 parts of polyethylene glycol, 17.2 parts of neopentyl glycol, dimethylol 7.8 parts of propionic acid, 1.5 parts of trimethylolpropane, 4,4 '
Aliphatic polyether polyurethane A5 consisting of 42.0 parts of dicyclohexylmethane diisocyanate A5: polycarbonate polyol (472 parts of diethyl carbonate, 416 parts of 1,5-pentanediol,
Aromatic polycarbonate polyurethane comprising 500 parts of 1,6-hexanediol (472 parts), tolylene diisocyanate 160 parts and dimethylolpropionic acid 58.5 parts A6: 4,4'-dicyclohexyl is used instead of tolylene diisocyanate in aqueous polyurethane A5. Aliphatic polycarbonate polyurethane (aqueous epoxy group-containing compound) using methane diisocyanate Aqueous epoxy group-containing compounds B1 and B2 were used.

The contents (main components) are as follows. B1: tetraglycerol tetraglycidyl ether B2: sorbitol triglycidyl ether (aqueous acryl) polyacrylic resin compound aqueous dispersion C
1 was used.

C1: 45 mol% of methyl methacrylate,
Copolymer (melamine compound) composed of 30 mol% of n-butyl acrylate, 20 mol% of styrene, and 5 mol% of acrylic acid A melamine compound D1 was used. D1: Water-soluble melamine compounds centered on mononuclear, dinuclear, and trinuclear melamines of almost tetrafunctional methylol or methoxymethyrol melamine Examples 1 to 17 and Comparative Examples 1 to 15 Was provided with the same coating layer as described above. However,
In Table 1, PET of the polyester film refers to a polyethylene terephthalate film, and PEN refers to a polyethylene-2,6-naphthalate film. The numerical values indicating the ratio of the aqueous polyurethane and the aqueous epoxy group-containing compound in the coating layer are as follows. It means the weight ratio (% by weight) based on the dry weight of each coating agent. The thickness of the coating layer is the thickness on the finally completed film.

Comparative Examples 16 and 17 As shown in Table 1, this is an example in which no coating layer is provided.

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

According to the present invention described above, a polyester-based photographic support provided with a coating layer having good adhesiveness to a photographic photosensitive layer is provided, particularly by in-line coating in a polyester film production process. And
The industrial value of the present invention is very large.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/40 B32B 27/40 C09D 163/00 C09D 163/00 G03C 1/795 G03C 1/795

Claims (6)

[Claims] 1. An aqueous polyurethane and an aqueous epoxy group-containing compound in a dry weight ratio of 10/90 to 80/2.
A method for producing a polyester-based photographic support, which comprises applying a coating solution containing at a ratio of 0 to at least one surface of a polyester film and drying the applied solution. 2. The method for producing a polyester-based photographic support according to claim 1, wherein the aqueous polyurethane is at least one selected from polyester-based polyurethane, polyether-based polyurethane and polycarbonate-based polyurethane. 3. The method according to claim 1, wherein the polyester film is polyethylene terephthalate.
A process for producing the polyester-based photographic support described in the above. 4. The polyester film is polyethylene-
2. The composition according to claim 1, which is 2,6-naphthalate.
Or the method for producing a polyester-based photographic support according to 2. 5. The method for producing a polyester-based photographic support according to claim 1, wherein the coating is performed in a process for producing the polyester film. 6. The method for producing a polyester-based photographic support according to claim 1, wherein the coating is performed on both sides of the polyester film.