JPH05271523A - Coated polyester film substrate and its production - Google Patents

Abstract

PURPOSE:To obtain the subject substrate excellent in uniform coating properties, antistatic properties and adhesion and suitable for photography, etc., by coating the surface of a polyester film substrate with an undercoating solution containing a water- soluble copolyester, a conductive polymer and a surfactant. CONSTITUTION:The objective coated polyester film substrate is obtained by coating the surface of a polyester film substrate before completion of orientation and crystallization with an undercoating solution and subsequently completing orientation and crystallization in one or more directions. This undercoating solution contains (A) a water-soluble copolyester synthesized from dicarboxylic acid components containing terephthalic acid, isophthalic acid, a sulfonic acid salt-containing dicarboxylic acid and an alicyclic dicarboxylic acid and glycol components containing ethylene glycol in an amount of >=50mol% based on the whole glycol components, (B) a conductive polymer represented by the formula (R is H, a halogen or an alkyl; L is COO or CONH; Q is a 1 to 6C alkylene or phenylene; (a) and (b)are each 0 or 1; M is H or a cation), etc., and (C) a surfactant. In the above-mentioned dicarboxylic acid components, the molar ratio of terephthalic acid to isophthalic acid is (30/70) to (70/30) and the amount of the sulfonic acid salt-containing dicarboxylic acid is 5 to 15mol% based on the whole dicarboxylic acid components.

Description

TECHNICAL FIELD The present invention relates to a coated polyester film support excellent in coating uniformity, excellent in antistatic property and adhesiveness, and a method for producing the same.

[Prior Art] Polyester films, especially polyethylene terephthalate biaxially oriented films, are used as bases for photographic films, drawing bases, and magnetic recording tapes because of their transparency, dimensional stability, and excellent mechanical properties. It is used. In these applications, an undercoat layer is usually provided between the polyester support and the surface layer material to improve the adhesiveness between them. On the other hand, in the past, improvement of adhesion between linear polyester and metal foil, various plastics, especially hydrophilic resins such as gelatin, has been subsidized because of the advantages of work environment and explosion-proof equipment. It has been proposed to use water-soluble or water-dispersible polyester copolymers as the layer. As such an example, for example, in Japanese Examined Patent Publication No. S47-40873, for the purpose of water dissipation, 8 mol% or more of the ester-forming metal sulfonate group-containing compound with respect to the total acid component and polyethylene glycol as the total glycol component are used. However, it is easily speculated that when these are used as an undercoat layer, the water resistance of the undercoat layer, that is, the water resistance of the adhesive, is reduced. It is possible. In Japanese Patent Publication No. 56-5476, a saturated linear aliphatic dicarboxylic acid having 4 to 8 methylene groups is used for the purpose of improving adhesiveness. Not enough. Further, in JP-A-56-88454, a substantially water-insoluble water-based dispersant is used for improving the water resistance, but this is because the dispersion contains a water-soluble organic solvent. However, there are still problems with the work environment. JP-A-60-248231 is almost the same as JP-A-56-88454, except that the final aqueous dispersion does not contain an organic solvent. However, since an organic solvent is used in the process of preparing the aqueous dispersion, it is not practically preferable because the process of preparing the aqueous dispersion becomes complicated in addition to the problem of working environment.

 Further, with such a conventional technique, it is difficult to simultaneously impart excellent transparency and antistatic performance to the undercoat layer. Japanese Unexamined Patent Publication (Kokai) No. 61-164831 discloses a technique of providing an undercoat layer which is transparent, has antistatic properties, and satisfies adhesiveness. However, the polyester copolymer used is substantially water-insoluble. Since the polyester copolymer is once dissolved in a water-soluble organic solvent, it is prepared as an aqueous dispersion and used as a coating solution for the undercoat layer, so that the obtained undercoat layer has high water resistance. On the other hand, the adhesiveness with the hydrophilic colloid layer was inferior.

 In addition, since it contains a water-soluble organic solvent in order to be used as an aqueous dispersion, there are still problems in the working environment, and it is necessary to take measures such as explosion-proof of the stretching device and measures for environmental pollution. I had a problem.

 Under such circumstances, a technique for laminating a completely water-based mixed composition consisting of a polyester copolymer and a conductive polymer on a plastic film support was obtained. However, a coating film formed by applying a mixed composition of a polyester copolymer and a conductive polymer to a plastic film support and drying it lacks smoothness and uniformity. For example, vertical and yokomura. Unevenness that occurs in parallel or perpendicular to the coating direction, called twisting or chipping, and the coating liquid approaches the periphery of the coating surface and becomes thicker, or conversely it retreats and becomes thinner, resulting in uneven coating. This phenomenon becomes remarkable as the coating speed increases.

 The present inventors have found that the improvement of the smoothness of the coating film and the uniformity of the coating film can be achieved by the mixed composition of the polyester copolymer and the conductive polymer containing at least one surfactant. Found.

[Problems to be Solved by the Invention] The present invention has been made to solve the above problems, and the present inventors have found that the coating uniformity is good, and the antistatic property and the easy adhesion property are simultaneously provided. The present invention has been completed as a result of earnest research efforts in order to form the coating layer in a completely aqueous system without using an organic solvent.

 The first object of the present invention is to have excellent coatability as an aqueous solution and adhesiveness to a polyester film, as well as antistatic properties, and adhesiveness to hydrophilic colloids such as polyvinyl alcohol (PVA) and gelatin. Another object of the present invention is to provide a coated polyester film support having excellent adhesiveness even under wet conditions.

 The second purpose is to solve the problems of working environment and environmental pollution and to simplify the equipment by coating the polyester film with the coating solution for undercoat layer containing polyester resin in a completely water system. Another object of the present invention is to provide a method for producing a coated polyester film support which can be used.

 Another object is to provide a coated polyester film support for a photographic light-sensitive material, which has a silver halide emulsion layer on the coated polyester film support and has good adhesion between layers.

 Yet another object is to obtain a coated polyester film support which also exhibits good adhesion to binder-containing layers such as magnetic layers.

[Means for Solving Problems] The above object of the present invention is to apply an undercoat layer coating solution containing at least a water-soluble polyester copolymer, a conductive polymer and a surfactant to at least one surface of a polyester film. Achieved with a coated polyester film support.

 Polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film and the like can be used as the polyester film of the substrate on which the coating liquid for the undercoat layer of the present invention is applied. Among them, polyethylene film is particularly preferable. A terephthalate film is suitable.

 These polyesters may be used alone, or may be appropriately mixed as necessary and usually melt-extruded or dissolved in a solvent and cast to obtain a polyester film (base film). The substrate film used is uniaxially or biaxially stretched, if necessary.

 The water-soluble polyester copolymer used as a component of the coating solution for the undercoat layer coated on the surface of the base film can be obtained, for example, by reacting a mixed dicarboxylic acid component and a glycol component.

 The mixed dicarboxylic acid component means a dicarboxylic acid component having a sulfonate (a dicarboxylic acid having a sulfonate and / or its ester-forming derivative) as a total dicarboxylic acid component in a water-soluble polyester copolymer. It is a dicarboxylic acid component contained in an amount of 5 to 15 mol%.

 The sulfonic acid-containing dicarboxylic acid and / or its ester-forming derivative used in the present invention preferably has a sulfonic acid alkali metal salt group, such as 4-sulfoisophthalic acid and 5-sulfo. Alkali metal salts such as isophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5- [4-sulfophenoxy] isophthalic acid, or ester-forming derivatives thereof are used. , 5-Sulfoisophthalic acid sodium salt or an ester-forming derivative thereof is particularly preferable. From the viewpoint of water solubility and water resistance, it is particularly preferable that the dicarboxylic acid having a sulfonate and / or its ester-forming derivative is used in an amount of 6 to 10 mol% based on the total dicarboxylic acid component.

 Other dicarboxylic acid components include aromatic dicarboxylic acid components (aromatic dicarboxylic acids and / or ester-forming derivatives thereof), alicyclic dicarboxylic acid components (alicyclic dicarboxylic acids and / or ester-forming derivatives thereof). ), An aliphatic dicarboxylic acid component (aliphatic dicarboxylic acid and / or its ester-forming derivative), and the like.

 Examples of the aromatic dicarboxylic acid component include a terephthalic acid component (terephthalic acid and / or its ester-forming derivative), an isophthalic acid component (isophthalic acid and / or its ester-forming derivative), and the like.

 In the present invention, the aromatic dicarboxylic acid component is preferably used in the range of 50 to 80 mol% with respect to the total dicarboxylic acid component, and the terephthalic acid component and the isophthalic acid component are in a molar ratio of 30/70 to. It is particularly preferable to use it in the range of 70/30 from the viewpoints of coating property to polyester film and solubility in water.

 Specific examples of the aromatic dicarboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid and biphenyldicarboxylic acid. Alternatively, these ester-forming inductors may be mentioned.

 Examples of the alicyclic dicarboxylic acid and / or its ester-forming derivative include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. , 4,4'-bicyclohexyldicarboxylic acid or the like, or an ester-forming derivative thereof is used, but these are preferably used in an amount of 10 mol% or more based on the total viscosity of the dicarboxylic acid component from the viewpoint of the aqueous solution viscosity of the resin. Preferably, if it is too small, the above-mentioned viscosity becomes high, which may cause problems in coating properties.

 Further, in the present invention, the linear aliphatic dicarboxylic acid and / or its ester-forming derivative may be used within the range of 15 mol% or less of the total dicarboxylic acid component. Examples of such a dicarboxylic acid component include aliphatic dicarboxylic acids such as adipic acid, pimelic acid, speric acid, azelaic acid and sebacic acid, and ester-forming derivatives thereof. If the amount of the above-mentioned linear aliphatic dicarboxylic acid component is too large, not only will blocking easily occur, but also the water resistance will be poor in terms of adhesion.

 In the present invention, it is preferable to use ethylene glycol in an amount of 50 mol% or more based on the total glycol component from the viewpoint of mechanical properties of the polyester copolymer and adhesiveness with the polyester film. As the glycol component used in the present invention, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyethylene glycol or the like may be used in combination with ethylene glycol.

 As the method for polymerizing the water-soluble polyester copolymer in the present invention, various ordinary methods can be used.

For example, a method of transesterifying dimethyl ester of dicarboxylic acid and glycol, distilling out methanol, and then gradually depressurizing and performing polycondensation under high vacuum, or an esterification reaction of dicarboxylic acid and glycol. After distilling the produced water, the pressure is gradually reduced and polycondensation is carried out under high vacuum, or when dimethyl ester of dicarboxylic acid and dicarboxylic acid are used as raw materials together, dimethyl of dicarboxylic acid is used. There is a method in which an ester exchange reaction between an ester and a glycol is carried out, then a dicarboxylic acid is added to carry out an esterification reaction, and then polycondensation is carried out under high vacuum. Known transesterification catalysts such as manganese acetate, calcium acetate, zinc acetate, etc. can be used, and polycondensation catalysts such as antimony trioxide, germanium oxide, dibutyltin oxide, titanium tetrabutoxide, etc. Can be used. Further, phosphorus compounds such as trimethyl phosphate and triphenyl phosphate, and hindered phenol compounds such as Irganox 1010 may be used as the stabilizer.

However, various conditions such as the polymerization method, the catalyst and the stabilizer are not limited to the above-mentioned examples.

 The intrinsic viscosity of the water-soluble polyester copolymer used in the present invention is preferably in the range of 0.25 to 0.55 dl / g, and the particularly preferable intrinsic viscosity is 0.3 to 0.5 dl / g.

 Examples of the conductive polymer used in the present invention include polymers having at least one conductive group selected from a sulfonate, a sulfate ester group, a quaternary ammonium salt, a tertiary ammonium salt, and a carboxyl group. Particularly, a polymer having a sulfonic acid group, a carboxyl group, a sulfuric ester group or / and a salt thereof is preferable. The conductive group is required to be 5 wt% or more per polymer molecule.

 The conductive polymer may contain a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group and a vinylsulfone group.

 The number average molecular weight of the polymer may be more than 5,000, more preferably 6,000 to 100,000.

Hereinafter, examples of the conductive polymer used in the present invention will be listed, but the present invention is not limited thereto.

The amount means the number average molecular weight. ), Which is a value measured by GPC (HLC-8020 manufactured by Tosoh Corporation) expressed in terms of sodium polystyrene sulfonate.

 It is particularly preferable that the conductive polymer of the present invention has the following repeating unit.

R: hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms L: -COO-, -CONH- Q: alkylene group having 1 to 6 carbon atoms, phenylene group a, b: 0 or 1 M: hydrogen atom, Cation Preferred repeating units include, but are not limited to, the following.

 A crosslinking agent may be added to the coating solution for the undercoat layer of the present invention. Examples of the crosslinking agent used in the present invention include epoxy compounds, aziridine compounds, block isocyanate compounds, block methylol compounds, and the like, with epoxy compounds and aziridine compounds being preferred. The cross-linking agents may be mixed and used.

 The epoxy compound used in the present invention is not particularly limited as long as it is a compound having an epoxy group, but one having two or more functional epoxy groups is preferable.

 Specific examples of typical epoxy compounds are given below.

C-I sorbitol polyglycidyl ether C-II sorbitan polyglycidyl ether C-III polyglycerol polyglycidyl ether C-IV diglycerol polyglycidyl ether C-V glycerol polyglycidyl ether C-VI ethylene glycol diglycidyl ether C-VII Polyethylene glycol diglycidyl ether C-VIII Propylene glycol diglycidyl ether C-IX Polypropylene glycol diglycidyl ether Commercially available products include Denacol Series (Nagase Chemicals Co., Ltd.), Denacol EX-614B, EX-651A, EX-512, EX-521, EX-421, EX-313, EX-830, EX-841, EX-861, EX-911, EX-920 and the like can be mentioned as specific examples. It is not limited.

 Moreover, you may use together 2 or more types of epoxy compounds.

 The aziridine compound is preferably bifunctional or higher, and particularly preferably bifunctional or trifunctional with a molecular weight of 1000 or less.

 Specific examples of representative aziridi compounds are shown below, but the invention is not limited thereto.

Also, two or more aziridine compounds may be used in combination.

 The subbing layer coating liquid comprises the water-soluble polyester copolymer, the conductive polymer, and the crosslinking agent which are polyester copolymer: conductive polymer: crosslinking agent = 50 to 90% by weight: 9 to 30% by weight: 0 to 20% by weight % Is preferable.

 The surfactant used in the undercoat layer coating solution of the present invention includes the following general formulas D- [I], D- [II], D- [III], D- [IV], D- [V], D- [VI] is mentioned.

General formula D- [I] [In the formula, R ₁ represents an alkyl group having 1 to 18 carbon atoms, R ₂ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, l represents 0 or 1, and n ₁ represents 0 to 0. Represents an integer of 50, m ₁ represents an integer of 0 to 4, M ₁ represents an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a cation of a fourth ammonium salt ion. ] General formula D- [II] In the formula, R ₃ represents an alkyl group or an alkenyl group having 6 to 20 carbon atoms, l ₂ represents 0 or 1, n ₂ represents an integer of 0 to 50, and m ₂ represents 0 to 4 And M ₂ has the same meaning as M _{1 in the} general formula D- [I].

Specific examples of the anionic surfactants represented by the above general formulas D- [I] to D- [II] are shown below.

General formula D- [III] In the formula, R ₄ is an alkyl group having 6 to 20 carbon atoms. n ₃ represents an integer of 5-40.

General formula D- [IV] In the formula, R ₅ represents an alkyl group or an alkenyl group having 8 to 25 carbon atoms, and the sum of n ₄ , n ₅ and n ₆ represents an integer of 5 to 100. However, at least one of n ₄ , n ₅ , and n ₆ is 5 or more.

General formula D- [V] In the formula, the sum of n ₇ and n ₉ represents an integer of 5 to 100, and n ₈ represents an integer of 1 to 50.

General formula D- [VI] In the formula, R ₆ represents an alkyl group or an alkenyl group having 6 to 20 carbon atoms, and the sum of n ₁₀ and n ₁₁ represents an integer of 5 to 100. However, at least one of n ₁₀ and n ₁₁ is 5 or more.

Specific examples of the nonionic surfactants represented by the above general formulas D- [III] to D- [VI] are shown below.

 Representative examples of the compounds preferably used in the present invention are shown above. These are examples of the compounds included in the general formula, and the compounds used in the present invention are However, it is not limited to this. Also, these may be used in combination.

 The content of the surfactant of the present invention is preferably 0.01 to 50 g, and particularly preferably 0.05 to 10 g, per 1 kg of the undercoat layer coating solution.

 A matting agent or the like may be added to the undercoat layer coating liquid of the present invention, and a water-soluble or water-dispersible polymer other than the polyester copolymer of the present invention may be added within a range that does not impair the effects of the present invention. You may add it in.

 In addition, the coated polyester film support of the present invention is obtained by applying the undercoat layer coating solution of the present invention on at least one surface of the above polyester film before the completion of oriented crystallization, drying it, and stretching it in at least one direction. It is preferably obtained by fixing and cooling to complete the oriented crystallization.

 The undercoat layer coating solution is applied to a polyester film by a normal coating step, that is, a polyester film whose oriented crystallization has been completed is separated from the film manufacturing step and the undercoat layer coating solution is applied in a separate step. Of course, such a process requires a separate process, which is disadvantageous in terms of cost.

Therefore, from this viewpoint, the method of applying the undercoat layer coating solution in the polyester film manufacturing process is preferable. In particular, it is preferable to apply the undercoat layer coating solution to at least one surface of the polyester film at any time before the completion of oriented crystallization in the process as described above, and as an example, melt extrusion is performed in a film form from a die. An unstretched film obtained by cooling a polyester resin on a cooling drum is preheated and then vertically stretched, and then the undercoat layer coating solution of the present invention is applied, dried and further preheated and horizontally stretched, then heat set and cooled. Such a method is performed. Further, the polyester film may be subjected to surface treatment such as corona discharge or glow discharge before applying the undercoat layer coating liquid of the present invention.

 In the present invention, the polyester film before orientation crystallization is completed means an unstretched film obtained by heat-melting a polyester polymer to form a film as it is, or this unstretched film in a vertical or horizontal direction. It refers to a stretched uniaxially stretched film, and further to a vertically or horizontally biaxially stretched film, which is a biaxially stretched film before re-stretching in either one of the vertical and horizontal directions to complete the oriented crystallization.

 Both the vertical stretching and the horizontal stretching are usually carried out at a magnification of 2.0 to 5.0 times.

The concentration of the coating solution for the undercoat layer is usually 15% by weight or less, preferably 10% by weight or less. The coating amount is preferably 1 to ²⁰ g, and more preferably 5 to 15 g per 1 m ² of the film.

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

 The polyester film before the completion of the oriented crystallization applied as described above is introduced into a process such as stretching and heat setting after being dried. The coated polyester film support of the present invention in which the coating solution for the undercoat layer is coated on the polyester film support exhibits good adhesion and water resistance to hydrophilic colloids such as polyvinyl alcohol and gelatin.

 The coated polyester film support of the present invention may be provided with at least one hydrophilic colloid layer thereon to produce various films.

 For example, a photographic light-sensitive material can be prepared by providing at least one silver halide photographic emulsion layer on at least one surface of the support of the coated polyester film of the present invention. It is also possible to provide a layer containing a binder such as a magnetic layer instead of the hydrophilic colloid layer.

 Examples of the hydrophilic colloid used in the hydrophilic colloid layer include proteins such as gelatin, albumin, and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sodium alginate, and starch derivatives. Sugar derivatives: Polyvinyl alcohol, polyvinyl alcohol partial acetate, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Although hydrophilic polymer substances can be used, gelatin is preferably used. As gelatin, lime-processed gelatin, acid-processed gelatin, and Bull Society Science Photography Japan (Bull.Soc.Sci.Phot.Japan), No.16, p.30 (1966) Such oxygen-treated gelatin may be used, or a hydrolyzate or an enzyme hydrolyzate of gelatin may be used, and further, a gelatin derivative or a graft polymer of gelatin and another polymer may be used. it can.

 As the silver halide emulsion used in the silver halide emulsion layer when a photographic light-sensitive material is prepared using the coated polyester film support of the present invention, various ordinary silver halide emulsions can be optionally 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.

 Further, an antifoggant, a stabilizer, a hardener and the like can be added to the silver halide emulsion. As the binder of the emulsion, the hydrophilic colloid as mentioned above is used, but it is advantageous to use gelatin.

 For the silver halide emulsion layer and other hydrophilic colloid layers, the film strength can be increased by using a hardening agent, and such hardening agents include aldehyde type, aziridine type, isoxazole type and epoxy type hardening agents. , Vinyl sulfone-based, acryloyl-based, carbodiimide-based, triazine-based, polymer-based, other maleimide-based, acetylene-based, and methanesulfonic acid ester-based hardeners can be used alone or in combination. Also, plasticizers, dispersions of water-insoluble or sparingly soluble synthetic polymers (latex), couplers, coating aids, antistatic agents, formalin scavengers, optical brighteners, matting agents, lubricants, and image stabilizers. An agent, a surfactant, an antifoggant, a development accelerator, a development retarder, a bleaching accelerator and the like can be contained.

 In the photographic light-sensitive material, hydrophilic colloid layers other than the silver halide emulsion layer include protective layers, filter layers, back coating layers, antihalation layers, irradiation prevention layers, auxiliary layers such as intermediate layers, etc. ..

 The coated polyester film support of the present invention can be used as a support for 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.

 [Effects of the Invention] (1) The water-soluble polyester copolymer used in the present invention has no problem of environmental pollution in the work environment such as toxicity and flammability, and is more suitable than the case of using an organic solvent. Can be simplified.

(2) The polyester film support coated with the coating liquid for the undercoat layer of the present invention has excellent antistatic performance and hydrophilicity, excellent adhesion to the colloid layer, and excellent water resistance.

(3) The coating liquid for the undercoat layer used in the present invention exhibits an appropriate viscosity as an aqueous solution, and therefore exhibits a particularly excellent effect when applied to a polyester film before the completion of oriented crystallization.

(4) Since the undercoat layer coating liquid of the present invention has a low surface tension, it exerts an excellent effect in finishing a smooth and uniform surface without bleeding when applied to a polyester film.

 [Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.

 The polyester copolymer, the coating liquid for undercoat layer and the polyester film support having the undercoat layer thus obtained were measured and evaluated according to the following criteria.

(1) Intrinsic viscosity; measured at 20 ° C. in a mixed solution of phenol / 1,1,2,2-tetrachloroethane = 60/40 (weight ratio).

(2) Viscosity of undercoat layer coating solution: Each of the prepared undercoat layer coating solutions was measured at 20 ° C.

(3) Surface tension of undercoat layer coating solution: Each of the prepared undercoat layer coating solutions was measured at 20 ° C.

(4) Coating property: Each of the prepared coating liquids for the undercoat layer was coated on a uniaxially stretched polyethylene terephthalate with a wire bar at a predetermined coating film thickness.

The coating state at that time was visually evaluated. The evaluation criteria are shown below.

Evaluation of vertical and horizontal unevenness of coating When there is no unevenness Class A For weak unevenness Class B For strong unevenness Class C For coating twist failure evaluation When there is no twisting Class A For weak twisting B Class For strong twisting C (5) Adhesiveness to polyester film support: Polyethylene terephthalate having an intrinsic viscosity of 0.65 is 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. The unstretched film (thickness 1000 μm) was preheated to 75 ° C and vertically stretched (3 times), then corona discharge was applied, and the undercoat layer coating solution was applied to the surface-treated support surface and dried in a tenter. After preheating, the film was horizontally stretched (3 times) at 100 ° C., heat-set at 220 ° C., and heat-fixed to obtain a biaxially stretched polyethylene terephthalate film having a film thickness of 0.3 g / m ² (polymer conversion).

 A 45 ° cut was made with a razor on the undercoat layer surface of this polyethylene terephthalate film, a cellophane tape was pressure-bonded, and the tape was rapidly peeled off. The peeled area of the undercoat layer was evaluated on a scale of five.

(6) Adhesion to gelatin: A gelatin layer containing a hardening agent is applied on the film having the subbing layer obtained in (5), dried and hardened, and then (5) the same at 45 °. Was cut, the cellophane tape was pressure-bonded, and the tape was rapidly peeled off. The peeled area of the gelatin layer was evaluated on a scale of five.

(7) Water resistance of adhesion: Immerse the film obtained in (6) in potassium hydroxide aqueous solution of pH 10.2 for 15 seconds at 35 ° C, scratch the surface with a pen tip, and rub the area strongly. The peeled area of the gelatin layer was evaluated by 5 grades.

 The criteria of the five-step evaluation showing the adhesiveness and the water resistance of the adhesive are as follows.

 1: Adhesive strength is very weak and completely peeled off.

 2: 50% or more is peeled off.

 About 3:10 to 50% is peeled off.

 4: Adhesive strength is fairly strong and peeling is less than 10%.

 5: Adhesive strength is very strong and is not peeled at all.

 If the evaluation is 4 or more, it can be considered that the adhesiveness is practically sufficient.

(8) Surface resistivity: The surface resistivity of the film obtained in (5) was measured by using a teraohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd. under the conditions of an applied voltage of 100 V, 23 ° C. and 55% P.H.

Example 1 38.74 parts by weight of dimethyl terephthalate, 31.95 parts by weight of dimethyl isophthalate, 10.34 parts by weight of dimethyl sodium salt of 5-sulfoisophthalate, 54.48 parts by weight of ethylene glycol, 0.073 parts by weight of calcium acetate monohydrate, and tetrahydrated manganese acetate. After transesterification of 0.024 parts by weight of salt under a nitrogen stream at 170 to 220 ° C while distilling off methanol, 0.05 parts by weight of trimethyl phosphate and 0.04 parts by weight of antimony trioxide as a polycondensation catalyst and 1,4 -17.17 parts by weight of cyclohexane dicarboxylic acid was added and esterification was carried out at a reaction temperature of 220 to 235 ° C by distilling off almost the theoretical amount of water. Then, the pressure was reduced to 0.2 mmHg and the temperature was raised to 280 ° C. However, the polycondensation reaction was carried out for 2 hours.

 The water-soluble polyester copolymer (A) thus obtained was analyzed and found to have an intrinsic viscosity of 0.45 dl / g.

The water-soluble polyester copolymer was stirred in hot water at 95 ° C. for 3 hours to give a 15 wt% aqueous solution.

 Using the aqueous solution of the water-soluble polyester copolymer (A) and the conductive polymer (B-3), (A) is 80% by weight based on the total weight of (A) and (B-3). -3) is 20% by weight and the total weight of (A) and (B-3) is 8% by weight. Further, surfactant D-6 is added in an amount of 0.5 g per 1 kg of the preparation liquid. Was added to prepare an undercoat layer coating solution of the present invention.

The undercoat layer coating solution was applied to a vertically stretched polyethylene terephthalate film to prepare a biaxially stretched polyethylene terephthalate film support having a dry weight of 0.3 g / m ^{2 of} an undercoat layer. Further, a film was prepared by laminating gelatin on the film having the undercoat layer by a usual method, and the adhesive property and the like of these films were evaluated.

The evaluation is shown in Table-1.

Examples 2 to 3 An aqueous solution of the polyester copolymer (A) used in Example 1, the conductive polymer (B-3), and the following cross-linking agent (C-1) were used at the ratios shown in Table-1. A biaxially stretched polyethylene terephthalate film having an undercoat layer and a gelatin laminated film were prepared in the same manner as in Example 1.

Example 4 In Example 2, the conductive polymer was replaced with (B-3), and (B-24) was used to prepare the undercoat layer by adjusting in the same manner as in Example 1 at the ratios shown in Table 1. A biaxially stretched polyethylene terephthalate film and a gelatin laminated film were prepared.

Example 5 An undercoat layer was formed in the same manner as in Example 1 except that the conductive polymer (B-3) in Example 2 was replaced with the above (B-4) in the proportions shown in Table 1. A biaxially stretched polyethylene terephthalate film and a gelatin laminated film were prepared.

Examples 6 to 7 In Example 2, the conductive polymer was replaced with (B-3), the above (B-15) and (B-3) were used, and the crosslinking agent (C-1) was replaced with the following. A biaxially stretched polyethylene terephthalate film having an undercoat layer and a gelatin laminated film were prepared by adjusting (C-2) and (C-12) in the same manner as in Example 1.

Comparative Example 1 A biaxially stretched polyethylene terephthalate film having an undercoat layer and a gelatin laminated film were prepared in the same manner as in Example 2 except that no surfactant was added.

Comparative Examples 2 to 3 In the same manner as in Example 1 except that the polyester copolymer or the conductive polymer (B-3) in Example 1 was not added and the changes were made as shown in Table 1. A biaxially stretched polyethylene terephthalate film having an undercoat layer and a gelatin laminated film were prepared.

Example 8 On a biaxially stretched polyethylene terephthalate film having an undercoat layer obtained by applying a coating liquid for undercoat layer obtained in exactly the same manner as in Example 1 to a vertically stretched polyester film support. Then, a photosensitive layer for X-ray photography was applied on the surface by a usual method to prepare a photosensitive material sample. Coating of the obtained photosensitive material sample in a dry state before development processing (interlayer adhesion) (hereinafter referred to as film formation), wet film formation during development processing, and film formation in dry state after development processing (Hereinafter referred to as "with dry film") was measured by the following methods to evaluate the inter-layer adhesiveness. The results are shown in Table-2. Evaluation method with film (with raw film and dry film) Drying is completed before development or after development. The surface of hydrophilic photographic colloid layer of the sample reaches the support at a 45 ° angle with a razor blade. After making scratches in a grid pattern and applying adhesive tape (cellophane adhesive tape) on it, the tape is rapidly peeled off at an angle of about 45 °. At this time, the area of the photographic hydrophilic layer which would be peeled off together with the tape was compared with the area where the tape was stuck, and the evaluation was performed according to the following 5 grades.

If the evaluation is 4 or more, it is considered that the film is sufficiently strong in practical use.

(With wet film) During various development processes, the surface of the hydrophilic colloid layer for photography was scratched to reach the support with a sharp needle, and then the surface of the layer was kept wet. Rub vigorously for 10 seconds. The area of the photographic hydrophilic colloid layer, which is peeled off at this time, was compared with the lattice area, and evaluation was carried out in five levels. The evaluation criteria are the same as those for raw and dry films.

Examples 9 to 14 Photosensitive material samples were prepared in the same manner as in Example 8 except that the coating liquid for undercoat layer containing the polyester copolymer was changed as shown in Table-2. Evaluation was performed and Examples 9 to 14 were performed.

The results are shown in Table-2.

 As is clear from Table 2, the X-ray photosensitive material samples having the undercoat layer of the present invention are excellent in all of the raw film coating, the wet film coating and the dry film coating, particularly in the wet film coating. I understood it.

 This effect is obtained not only for the X-ray photographic light-sensitive material but also for various kinds of photographic light-sensitive materials (light-sensitive materials including color emulsions, emulsions for printing light-sensitive materials).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Kobayashi 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Yoshihiro Wada 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Noriyuki Tachibana 1st Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (4)

[Claims] 1. A coated polyester which is characterized in that at least one surface of a polyester film support is coated with an undercoat layer coating liquid containing at least a water-soluble polyester copolymer, a conductive polymer and a surfactant. Film support. 2. A water-soluble polyester copolymer comprising (a) terephthalic acid and / or its ester-forming derivative (terephthalic acid component) and isophthalic acid and / or its ester-forming derivative (isophthalic acid component). The molar ratio is 30/70 to 70/30, (b) the sulfonate-containing dicarboxylic acid and / or its ester-forming derivative is 5 to 15 mol% of all dicarboxylic acid components, and (c) the alicyclic group. The coated polyester film support according to claim 1, wherein the dicarboxylic acid and / or its ester-forming derivative and (d) ethylene glycol are contained in an amount of 50 mol% or more based on the total glycol components. 3. The coated polyester film support according to claim 1, wherein the conductive polymer comprises a polymer having the following repeating unit. (R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, L represents -COO- or -CONH, Q represents an alkylene group or phenylene group having 1 to 6 carbon atoms, and a And b represents an integer of 0 or 1, and M represents a hydrogen atom or cation.) 4. An undercoat layer containing at least a water-soluble polyester copolymer, a conductive polymer, and a surfactant. A coating solution is coated on at least one surface of a polyester film support before orientation crystallization is completed. Then, a method for producing a coated polyester film support, which comprises stretching at least uniaxially to further complete orientation and crystallization.