JP3041350B2 - Coated polyester film support and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a coated polyester film support which is transparent and has excellent antistatic properties and adhesiveness, and a method for producing the same.

[Prior Art] Polyester films, especially polyethylene terephthalate biaxially oriented films, have a base for photographic films, a base for drafting, and a magnetic base because of their transparency, dimensional stability, and excellent mechanical properties. It is used as a recording tape base. In these applications, the adhesion between the polyester support and the surface layer material is usually improved by providing a subbing layer between them. On the other hand, conventionally, for improving the adhesiveness between a linear polyester and a metal foil, various plastics, and particularly a hydrophilic resin such as gelatin, an undercoating layer is required because of problems in working environment and explosion-proof equipment is not required. It has been proposed to use a water-soluble or water-dispersible polyester copolymer. For example, Japanese Patent Publication No. 47-40873 discloses that an ester-forming sulfonic acid metal base-containing compound is used in an amount of 8 mol% or more based on the total acid component and polyethylene glycol is used as the total glycol component for the purpose of water dissipation. However, when these are used as an undercoat layer, it is easy to reduce the water resistance of the undercoat layer, that is, the water resistance of adhesion. It can be inferred. 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, but in this case, the water resistance of the undercoat layer is also insufficient. Not a thing. Further, in Japanese Patent Application Laid-Open No. 56-88454, a substantially water-insoluble aqueous dispersion is used to improve the water resistance. However, since the dispersion contains a water-soluble organic solvent, the process is difficult. Environmental problems remain. JP-A-60-24
No. 8231 is almost the same as the above-mentioned JP-A-56-88454, but differs mainly in that the final aqueous dispersion contains no organic solvent. However, since an organic solvent is used in the process of preparing the aqueous dispersion, the process of preparing the aqueous dispersion becomes complicated in addition to the problem of the working environment, which is not preferable in practical use.

Further, it is difficult for such a conventional technique to simultaneously impart excellent transparency and antistatic performance to the undercoat layer. JP-A-61-164831 discloses a technique for providing a subbing layer that is transparent, has antistatic properties and satisfies adhesiveness, but the polyester copolymer used is substantially water-insoluble. And, once the polyester copolymer,
After dissolving in a water-soluble organic solvent, prepared as an aqueous dispersion,
Since the obtained undercoat layer was used as a coating liquid for the undercoat layer, the resulting undercoat layer had high water resistance, but had poor adhesion to the hydrophilic colloid layer.

In addition, the use of a water-based dispersion liquid involves a water-soluble organic solvent, which leaves problems in the working environment. Further, there are various problems such as the need to take explosion-proof properties of the stretching device and environmental pollution measures. Was carrying.

Further, Japanese Patent Application Laid-Open No. 1-287142 discloses a technique for providing a polyester film excellent in alkali resistance, excellent adhesiveness with excellent water resistance, transparency and antistatic property,
In order to orient the sulfonic acid and / or salt thereof in the surface layer and obtain the desired performance, the sulfonic acid and / or salt thereof in the surface layer can be obtained only by stretching under a specific condition which is not achieved under any stretching conditions. Orientation and the desired performance can be achieved, so that the process control becomes complicated, which is not practically preferable. Further, since the stretching step is carried out in pressurized water or in the presence of pressurized steam, the operation becomes dangerous and a problem remains. Further, if the film is not stretched under such conditions, the haze value increases, and it is difficult to obtain transparency.

Japanese Patent Publication No. 1-30622 discloses a technique for obtaining a polyester film having a coating layer having good adhesion to a hydrophobic layer such as a magnetic recording material. However, such a technique is excellent in an undercoat layer. It has been difficult to simultaneously impart transparency and antistatic performance, and adhesion to a hydrophilic polymer resin to polyvinyl alcohol, gelatin, and the like.

[Problems to be Solved by the Invention] The present invention has been made to solve the above problems, and the present inventors have proposed an undercoat layer having transparency, antistatic properties, and easy adhesion at the same time, The present invention has been completed as a result of intensive research efforts to provide a completely aqueous system without using an organic solvent.

A first object of the present invention is to provide an aqueous solution having excellent applicability and adhesion to a polyester film, and having transparency and antistatic properties, and adhesion to hydrophilic colloids such as polyvinyl alcohol and gelatin. An object of the present invention is to provide a coated polyester film support having excellent adhesiveness under wet conditions.

The second object is to solve problems in working environment and environmental pollution and to simplify equipment by coating a polyester film with an undercoat layer coating solution containing a polyester resin in a completely aqueous system. It is an object of the present invention to provide a method for producing a coated polyester film support.

[Means for Solving the Problems] The object of the present invention is to provide a water-soluble polyester copolymer,
A coated polyester film support in which at least one surface of a polyester film is coated with an undercoat layer coating solution containing at least 0.05 to 10 g of a surfactant per kg of a conductive polymer undercoat layer coating solution having a number average molecular weight of 500 to 5000. Is achieved by

Polyester terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, etc. can be used as the polyester film of the substrate on which the undercoat layer coating solution of the present invention is applied, and among them, among them, Polyethylene terephthalate film is preferred.

These polyesters may be used alone, or may be appropriately mixed as needed, and a polyester film (substrate film) is usually obtained by melt extrusion or by dissolving in a solvent and casting. The base film used is uniaxially or biaxially stretched as necessary.

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

The mixed dicarboxylic acid component refers to a dicarboxylic acid component having a sulfonic acid salt (a dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof) in an amount of 5 to all dicarboxylic acid components in a water-soluble polyester copolymer. ~
It is a dicarboxylic acid component containing 15 mol%.

As the dicarboxylic acid having a sulfonic acid salt and / or the ester-forming derivative thereof used in the present invention, those having a group of a sulfonic acid alkali metal salt are particularly preferable,
For example, alkali metal salts such as 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5- [4-sulfophenoxy] isophthalic acid; The ester-forming derivative thereof is used, but 5-sulfoisophthalic acid sodium salt or the ester-forming derivative thereof is particularly preferred. The dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof is particularly preferably used in an amount of 6 to 10 mol% based on the total dicarboxylic acid component from the viewpoint of water solubility and water resistance.

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 an ester-forming derivative thereof) and the like can be mentioned.

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

In the present invention, the aromatic dicarboxylic acid component is preferably used in a range of 50 to 80 mol% based on the total dicarboxylic acid component, and furthermore, the terephthalic acid component and the isophthalic acid component are in a molar ratio of 30/70 to It is particularly preferable to use in a range of 70/30 from the viewpoint of applicability to a polyester film and solubility in water.

Specific examples of the aromatic dicarboxylic acid component include phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and aromatic dicarboxylic acids such as biphenyldicarboxylic acid and the like. Ester-forming derivatives.

Examples of the alicyclic dicarboxylic acid and / or its ester-forming derivative include 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid.
Cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 4,4 ′
-Bicyclohexyldicarboxylic acid or the like, or an ester-forming derivative thereof is used, and these are preferably used in an amount of 10 mol% or more based on the total dicarboxylic acid component from the viewpoint of the aqueous solution viscosity of the resin. It may be high and may cause problems in coatability.

In the present invention, a linear aliphatic dicarboxylic acid and / or an ester-forming derivative thereof may be used within a 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 linear aliphatic dicarboxylic acid component is too large, not only blocking becomes easy, but also the water resistance of the adhesive becomes poor.

In the present invention, it is preferable to use ethylene glycol in an amount of 50 mol% or more based on the total glycol components in view of the mechanical properties of the polyester copolymer and the adhesiveness to the polyester film. The glycol components used in the present invention include, in addition to ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, and triethylene glycol. And polyethylene glycol and the like.

As a polymerization method of the water-soluble polyester copolymer in the present invention, various ordinary methods can be used. For example, a transesterification reaction of dimethyl ester of dicarboxylic acid and glycol is carried out, methanol is distilled off, and then polycondensation is carried out under reduced pressure and high vacuum, or dicarboxylic acid is added to glycol. After distilling off the generated water, the pressure is gradually reduced, and high vacuum is applied to conduct polycondensation, or when using dimethyl ester of dicarboxylic acid and dicarboxylic acid as raw materials, dicarboxylic acid There is a method in which a transesterification reaction between a dimethyl ester of an acid and a glycol is carried out, then a dicarboxylic acid is added to carry out an esterification reaction, and then polycondensation is performed under high vacuum. As the transesterification catalyst, manganese acetate, calcium acetate, zinc acetate and other known ones can be used, and as the polycondensation catalyst, antimony trioxide, germanium oxide,
Other known materials such as dibutyltin oxide and titanium tetrabutoxide 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 stabilizers. However, various conditions such as a polymerization method, a catalyst, and a stabilizer are not limited to the above examples.

Although the water-soluble polyester copolymer used in the present invention has substantially water solubility, the substantially water-soluble described in the present invention does not mean strictly physicochemically, but water. And those that dissolve and / or finely disperse in water.
The intrinsic viscosity of the water-soluble polyester copolymer used in the present invention is in the range of 0.25 to 0.55 dl / g.

A particularly preferred intrinsic viscosity range is from 0.3 to 0.5 dl / g. On the other hand, a water-soluble polyester copolymer having an intrinsic viscosity of more than 0.55 dl / g cannot be applied because the viscosity in an aqueous solution becomes extremely high or becomes a gel at room temperature. Conversely, when using a water-soluble polyester copolymer having an intrinsic viscosity of less than 0.25 dl / g, the water resistance becomes too low,
Sufficient adhesiveness cannot be obtained.

Examples of the conductive polymer used in the present invention include polymers having at least one conductive group selected from sulfonic acid groups, sulfate groups, quaternary ammonium salts, tertiary ammonium salts, and carboxyl groups. Particularly, a polymer having a sulfonic acid group, a carboxyl group, a sulfate group or / and a salt thereof is preferable. The conductive group is required to be 5% by weight or more per polymer-1 molecule.

In the conductive polymer, hydroxy groups, amino groups,
It may contain an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group.

The molecular weight of the polymer is 500 or more and 5000 or less, preferably 7
00-4000. If the molecular weight exceeds 5,000, the undercoat layer tends to become cloudy and lose transparency. If it is less than 500, it is difficult to obtain conductivity.

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

In addition, ▲ ▼ indicates an average molecular weight (in the present specification, the average molecular weight indicates a number average molecular weight), and GPC expressed in terms of polystyrene sulfonic acid soda (HLC-8020 manufactured by Toso Corporation).
It is based on the measurement value by.

Particularly preferred repeating units of the repeating unit constituting the conductive polymer of the present invention include the following,
It is not limited to these.

A crosslinking agent may be added to the undercoat layer coating solution of the present invention. Examples of the crosslinking agent used in the present invention include an epoxy compound, an aziridine compound, a block isocyanate compound, a block methylol compound and the like. Those having more than one are preferred. The crosslinking agents may be used in combination.

The epoxy compound used in the present invention may be any compound having an epoxy group, and is not particularly limited.
Preferably, one having two or more epoxy groups is preferred.

 Specific examples of typical epoxy compounds are shown 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
As a commercial product, there is Denacol series (manufactured by Nagase Kasei Kogyo Co., Ltd.), and Denacol EX-614B, EX-61
5A, EX-512, EX-521, EX-421, EX-313, EX-830, E
Specific examples include, but are not limited to, X-841, EX-861, EX-911, EX-920, and the like.

 Further, two or more epoxy compounds may be used in combination.

The block isocyanate compound is preferably a compound having two or more functional groups. A commercially available product is Elastron Series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Elastron H-3, E-37, C- 9, F-29, H-38, W-11,
MF-25, BN-08, BN-11 and the like can be mentioned, but are not limited thereto. Two or more block isocyanate compounds may be used in combination. In order to further promote the reaction, a reaction promoting catalyst may be used. Examples of the catalyst include Elastron Catalyst 64 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), but are not limited thereto.

Further, the aziridine compound is preferably a bifunctional or more functional compound, particularly preferably a bifunctional or trifunctional compound having a molecular weight of 1,000 or less.

Specific examples of typical aziridine compounds are shown below, but are not limited thereto.

Two or more aziridine compounds may be used in combination.

The undercoat layer coating solution contains the water-soluble polyester copolymer, the conductive polymer, and the crosslinking agent as the polyester copolymer:
Conductive polymer: crosslinker = 90 to 30% by weight: 10 to 50% by weight:
It is preferably contained in a proportion of 0 to 20% by weight.

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

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, 1 represents 0 or 1, and n ₁ represents 0 to represents an integer of 50, m ₁ represents an integer of 0 to 4, M ₁ represents a cation of alkali metal ions, alkaline earth metal ions, ammonium ions or quaternary ammonium salt ions. 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 an integer of 0 to 4 And M ₂ is a general formula D-
It has the same meaning as M ₁ of [I].

Hereinafter, specific examples of the anionic surfactants represented by the general formulas D- [I] to D- [II] are shown.

Exemplary anionic surfactant _{D-14 C 12 H 25 OSO} 3 Na D-15 C 16 H 33 -OCH 2 CH 2 O 6 CH 2 4 SO 3 Na D-16 C 12 H 25 OCH 2 CH 2 O 6 SO 3 Na Formula D- [III] R ₄ J ₁₃ OCH ₂ CH _{2 On 3} H wherein R ₄ represents an alkyl group or an alkenyl group having 6 to 20 carbon atoms, and J represents Or Wherein l ₃ represents 0 or 1, and n ₃ represents an integer of 5 to 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] Wherein the sum of n ₇ and n ₉ is an integer of 5 to 100, n ₈ is 1
Represents an integer of ~ 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. Provided that at least one of n ₁₀ and n ₁₁ is 5 or more.

Hereinafter, specific examples of the nonionic surfactants represented by the general formulas D- [III] to D- [VI] are shown.

Exemplified nonionic surfactant _{D-19 C 13 H 27 OCH} 2 CH 2 O 9 H D-20 C 18 H 37 OCH 2 CH 2 O 20 H D-21 C 18 H 35 OCH 2 CH 2 O 9 H Although the typical specific examples of the compounds preferably used in the present invention have been shown above, these are further examples of the compounds included in the above general formula, and the compounds used in the present invention are: It is not limited to this. These may be used in combination.

The content of the surfactant of the present invention is preferably 0.05 to 10 g per kg of the undercoat layer coating solution.

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

Further, the coated polyester film support of the present invention is coated with the undercoat layer coating solution of the present invention on at least one surface of the polyester film before completion of the orientation crystallization, dried, stretched in at least one direction, and heat-set. Then, it is preferable to obtain by cooling and completing the oriented crystallization.

To apply the undercoat layer coating solution to the polyester film,
It is also possible to apply a normal coating step, that is, a method of applying the undercoat layer coating liquid in a separate step by separating the polyester film after completion of the orientation crystallization from the manufacturing step of the film,
Such a process requires a separate process, which is disadvantageous in cost. Therefore, from such a viewpoint, a method of applying the undercoat layer coating solution in the polyester film production 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 point before the completion of the orientation crystallization in the process as described above. The unstretched film obtained by cooling the polyester resin on a cooling drum is preheated and then vertically stretched, then the undercoat layer coating solution of the present invention is applied, dried and further preheated, horizontally stretched, heat-fixed and cooled. Such a method is performed. Before applying the undercoat layer coating solution of the present invention, the polyester film may be subjected to a surface treatment such as corona discharge or glow discharge.

In the present invention, the polyester film before completion of the orientation crystallization is an unstretched film obtained by hot-melting a polyester polymer into a film, or the unstretched film is stretched in one of the vertical and horizontal directions. It refers to a uniaxially stretched film, or a film that has been stretched biaxially in the vertical or horizontal direction, and is a biaxially stretched film before re-stretching in any one of the vertical and horizontal directions to complete orientation crystallization.

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

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

Various known methods can be applied as the coating method. For example, roll coat method, gravure roll method, spray coat method
The coating method, the air knife coating method, the bar coating method, the impregnation method, the curtain coating method, and the like can be applied alone or in combination.

The polyester film before completion of the orientation crystallization applied as described above is guided to a process such as stretching and heat setting after drying. 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 adhesiveness and hydrophilicity to hydrophilic colloids such as polyvinyl alcohol and gelatin.

The coated polyester film support of the present invention is provided with at least one hydrophilic colloid layer thereon, and can 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 coated polyester film support of the present invention.

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 sulfates; Sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as pyrazole can be used, but gelatin is preferably used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull Society Science Photography Japan (Bull. Soc. Sci. Phot. Japan), No. 16,
Oxygen-treated gelatin as described on page 30 (1966) may be used, or a hydrolyzate or enzymatic degradation product of gelatin may be used. Further, a gelatin derivative, a graft of gelatin with another polymer may be used. Polymers can also be used.

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 conventional 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.

Further, an antifoggant, a stabilizer, a hardener and the like can be added to the silver halide emulsion. The hydrophilic colloid as described above is used as a binder for the emulsion, but gelatin is advantageously used.

The silver halide emulsion layer and other hydrophilic colloid layers
The hardening agent can be used to increase the film strength. Examples of such hardening agents include aldehyde, aziridine, isoxazole, epoxy, vinyl sulfone, acryloyl, carbodiimide, triazine, and triazine. Molecular hardening agents, maleimide-based, acetylene-based, and methanesulfonic acid ester-based hardening agents can be used alone or in combination. A plasticizer, a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer, a coupler, a coating aid, an antistatic agent, a formalin scavenger,
A fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder, a bleaching accelerator, and the like can be contained.

In the photographic material, the hydrophilic colloid layer other than the silver halide emulsion layer includes a protective layer, a filter layer,
There are auxiliary layers such as a back coating layer, an anti-halation layer, an anti-irradiation layer and an intermediate layer.

The coated polyester film support of the present invention can be applied to supports of various photographic light-sensitive materials such as an X-ray light-sensitive material, a print light-sensitive material, a photographic light-sensitive material, and an ornamental light-sensitive material.

[Effects of the Invention] (1) The water-soluble polyester copolymer used in the present invention has no problems in terms of working environment such as toxicity and flammability and environmental pollution, and the equipment is simplified as compared with the case where an organic solvent is used. it can.

(2) The polyester film support coated with the undercoat layer coating solution of the present invention is transparent, has excellent antistatic properties and excellent adhesion to the hydrophilic colloid layer, and exhibits excellent water resistance.

(3) Since the undercoat layer coating solution used in the present invention has an appropriate viscosity as an aqueous solution, it exerts a particularly excellent effect on application to a polyester film before completion of oriented crystallization.

(4) Since the surface tension of the undercoat layer coating solution of the present invention is low, the undercoat layer coating solution exerts an excellent effect on finishing a smooth and uniform surface with no burrs when coating a polyester film.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.

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

(1) Intrinsic viscosity: Measured at 20 ° C. in a mixture of phenol / 1,1,2,2-tetrachloroethane = 60/40 (weight ratio).

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

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

(4) Coatability: Each of the prepared undercoat layer coating solutions was applied to a uniaxially stretched polyethylene terephthalate with a predetermined coating thickness using a wire bar. The coating state at that time was visually evaluated. The evaluation criteria are shown below.

Evaluation of vertical and horizontal unevenness of coating No unevenness Class A For weak unevenness Class B For strong unevenness Class C Trouble of coating evaluation Evaluation Without twist A Class With weak twist B Class With strong twist C (5) Adhesion to polyester film support; polyethylene terephthalate having an intrinsic viscosity of 0.65 was passed through
Melt extrusion into a film at ℃, apply static electricity, about 30 ℃
An unstretched film (thickness: 1000 μm) obtained by quenching on a cooling drum is preheated to 75 ° C., vertically stretched (3 times), corona-discharged, and coated with an undercoat layer coating solution on the surface-treated support surface. Coated, dried and preheated in a tenter, stretched horizontally (100%) at 100 ° C, heat-set at 220 ° C, and subbed at a film thickness of 0.3 g / m ² (in terms of polymer). A finished polyethylene terephthalate film was obtained.

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

(6) Adhesion to gelatin; a gelatin layer containing a hardener is applied on the film having an undercoat layer obtained in (5), dried and hardened, and then cut at 45 ° in the same manner as in (5). And the cellophane was pressure-bonded and rapidly peeled off, and the area from which the gelatin layer was peeled was evaluated on a five-point scale.

(7) Water resistance of adhesion: The film obtained in (6) was immersed in an aqueous solution of potassium hydroxide having a pH of 10.2 at 35 ° C. for 15 seconds, and the surface was scratched with a pen tip. The peeled area of the layer was evaluated on a 5-point scale.

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

 1: The adhesion is very weak and completely peeled off.

 2: 50% or more is peeled.

 3: About 10 to 50% is peeled off.

 4: Adhesive strength is quite strong, less than 10% peel off.

 5: Adhesion is very strong and is not peeled off 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) is Tera-Ohm Meter VE-30 manufactured by Kawaguchi Electric Co., Ltd.
Was measured under the conditions of an applied voltage of 100 V, 23 ° C. and 55% RH.

(9) transparency; the transparency of the film obtained in (5) is
Haze was measured with TURBIDIMETER MODEL T-2600DA manufactured by Tokyo Denshoku Co., Ltd.

Example 1 38.74 parts by weight of dimethyl terephthalate, 31.95 parts by weight of dimethyl isophthalate, 10.34 parts by weight of sodium dimethyl 5-sulfoisophthalate, 54.48 parts by weight of ethylene glycol, 0.073 parts by weight of calcium acetate monohydrate, and tetramanganese manganese acetate 0.024 parts by weight under nitrogen flow 170-220 ° C
After distilling off methanol, a transesterification reaction was carried out, followed by addition of 0.05 parts by weight of trimethyl phosphate, 0.04 parts by weight of antimony trioxide as a polycondensation catalyst and 17.17 parts by weight of 1,4-cyclohexanedicarboxylic acid, and 220 to 235 At a reaction temperature of ° C., almost the theoretical amount of water was distilled off to carry out esterification. afterwards,
The pressure was reduced to 0.2 mmHg and the temperature was raised to 280 ° C. However, the polycondensation reaction was performed for 2 hours.

When the obtained water-soluble polyester copolymer (A) was analyzed, the intrinsic viscosity was 0.45 dl / g. The water-soluble polyester copolymer was stirred in hot water of 95 ° C. for 3 hours, and 15% by weight
An aqueous solution was used.

Using the aqueous solution of the water-soluble polyester copolymer (A) and the conductive polymer (B-3), (A) and (B-
(A) is 75% by weight based on the total weight of 3), and (B-3) is
An aqueous solution was prepared so as to be 25% by weight and the total weight of (A) and (B-3) was 8% by weight.
Was added at a ratio of 0.5 g per 1 kg of the prepared solution to obtain 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 an undercoat layer of 0.3 g / m ² by dry weight. In addition, a film was prepared by laminating gelatin on the film having the undercoat layer by an ordinary method, and the film was evaluated for adhesiveness and the like.

 The evaluation is shown in Table 1.

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

C-1 Examples 3 and 4 The same procedure as in Example 1 was repeated except that the conductive polymer was replaced with (B-3) and (B-24) and (B-23) were used. A biaxially stretched polyethylene terephthalate film having the following formula and a film laminated with gelatin were prepared.

Example 5 An undercoat layer was prepared in the same manner as in Example 1 except that the amounts of the polyester copolymer, the conductive polymer, the crosslinking agent, and the surfactant were adjusted in the proportions shown in Table 1. A biaxially stretched polyethylene terephthalate film having the following formula and a film laminated with gelatin were prepared.

Examples 6-7 Biaxially stretched having an undercoat layer was prepared in the same manner as in Example 1 except that the crosslinking agent of Example 3 was replaced with C-1 and Elastron H-38 · (C-XII) was used. A polyethylene terephthalate film and a film laminated with gelatin were prepared.

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

Comparative Examples 2 and 3 Same as Example 1 except that in Example 1, either the polyester copolymer (A) or the conductive polymer (B-3) was not added, and the composition was changed as shown in Table 1. Thus, a biaxially stretched polyethylene terephthalate film having an undercoat layer and a film laminated with gelatin were prepared.

Comparative Example 4 The same procedure as in Example 3 was carried out except that the conductive polymer of Example 3 was of the same type as (B-21) and had a number average molecular weight of 7,000.

Example 8 On a biaxially stretched polyethylene terephthalate film having an undercoat layer obtained by applying the undercoat layer coating solution obtained in exactly the same manner as in Example 1 to a vertically stretched polyester film support A photosensitive layer for X-ray photography was applied thereon by a conventional method to prepare a photosensitive material sample. Filming of the obtained photosensitive material sample in a dry state before development processing (interlayer adhesion)
(Hereinafter referred to as a raw film), with a wet film during the development process,
The film adhesion in the dry state after the development treatment (hereinafter referred to as “dry film adhesion”) was measured by the following method to evaluate the interlayer adhesion. Table 2 shows the results.

Evaluation method with film (with raw film and dried film) The surface of the photographic hydrophilic colloid layer of the sample which has been dried before development processing or after development processing reaches the support at an angle of 45 ° with a razor blade After the scratches are formed in a grid and an adhesive tape (cellophane adhesive tape) is pressed thereon, the tape is rapidly peeled at an angle of about 45 °. At this time,
The area of the photographic hydrophilic layer that peels off with the tape
In comparison with the area to which the tape was attached, the evaluation was performed according to the following five grades.

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

(With a wet film) During the various development processes, the surface of the photographic hydrophilic colloid layer of the sample is scratched to reach the support with a sharp needle in a grid,
Thereafter, the surface of the layer is rubbed vigorously for 10 seconds while keeping it wet. At this time, the area of the photographic hydrophilic colloid layer that peeled off was compared with the lattice area, and the evaluation was performed in five steps.
The evaluation criteria are the same as those for the raw and dry films.

(Melting) A sample cut to 1 cm × 8 cm was immersed in a 1.5% aqueous solution of caustic soda kept at 50 ° C. without stirring to measure the time until the emulsion layer was separated from the undercoat layer. The evaluation was performed in the following three stages.

Examples 9 to 14 The undercoat layer coating solutions containing the polyester copolymer are listed in Table 1.
A photosensitive material sample was prepared in the same manner as in Example 8, except that the sample was changed as shown in FIG. 2, and the same evaluation as in Example 8 was performed, and Examples 9 to 14 were performed. Table 2 shows the results.

As is evident from Table 2, the samples of the X-ray photographic material prepared from the coated polyester film support having the undercoat layer of the present invention were all coated with a raw film, with a wet film and with a dry film, particularly with a wet film. It was found to be excellent in film formation and melting.

This effect was obtained not only for X-ray photographic materials but also for various photographic materials (photosensitive materials containing color emulsions, emulsions for printing photographic materials, etc.).

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tohru Kobayashi 1 in Sakura-cho, Hino-shi, Tokyo Konica Corporation (72) Inventor Noriaki Tachibana 1 in Sakura-cho, Hino-shi, Tokyo In Konica Corporation (56 References JP-A-58-124651 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 27/36 C08L 67/00-67/04 C09D 167/00-167/04

Claims (4)

(57) [Claims] An undercoating layer coating solution containing at least a water-soluble polyester copolymer, a conductive polymer having a number average molecular weight of 500 to 5,000 and a surfactant of at least 0.05 to 10 g per kg of the undercoating layer coating solution. A coated polyester film support coated on at least one surface. 2. The molar ratio of (a) terephthalic acid and / or its ester-forming derivative (terephthalic acid component) to isophthalic acid and / or its ester-forming derivative (isophthalic acid component) Is 30/70 to 70/30, (b) a dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof is 5 to 15 mol% based on all dicarboxylic acid components, and (c) an alicyclic dicarboxylic acid and / or Or an ester-forming derivative thereof, and (d) ethylene glycol in an amount of 50
2. The coated polyester film support according to claim 1, comprising at least mol% of components. 3. The coated polyester film support according to claim 1, wherein the conductive polymer having a number average molecular weight of 500 to 5000 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—;
Represents an alkylene group or a phenylene group having 1 to 6 carbon atoms, a and b represent an integer of 0 or 1, and M represents a hydrogen atom or a cation. ) 4. A water-soluble polyester copolymer, a conductive polymer having a number average molecular weight of 500 to 5000, and 1 kg of an undercoat layer coating solution
An undercoat layer coating solution containing at least 0.05 to 10 g of a surfactant is coated on at least one surface of the polyester film support before completion of orientation crystallization, and then stretched in at least one axis to further orientation and crystallization. A method for producing a coated polyester film support, which is completed.