JPH06240033A - Method for producing easily-adhesive polyester film - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a method for producing an easily-adhesive polyester film which is excellent in adhesiveness to a photosensitive layer and excellent in heat distortion resistance and is useful as a photosensitive material, particularly a photographic undercoat film. [Structure] Thickness 20 to 300 in which oriented crystallization is not completed
Polyester, acrylic modified polyester, polyurethane, acrylic resin, vinyl resin, vinylidene chloride resin, polyethyleneimine, polyvinyl alcohol, on at least one side of a μm polyalkylene naphthalate film,
An aqueous coating solution containing at least one easily adhering substance selected from the group consisting of modified polyvinyl alcohol and gelatin is applied, followed by drying, stretching and heat treatment to complete orientational crystallization and application of the first primer layer. A photosensitive film having a light transmittance of 70% or more, characterized in that a coating liquid containing gelatin is applied onto the first primer layer and then a second primer layer is applied by drying. A method for producing an easily-adhesive polyester film.

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 an easily-adhesive polyester film, more specifically, a photosensitive material having excellent adhesion to a photosensitive layer and excellent heat distortion resistance.
In particular, the present invention relates to a method for producing an easily-adhesive polyester film which is useful as a photographic undercoat film.

[0002]

2. Description of the Related Art Polyethylene terephthalate film is widely used as a base film such as a film for X-ray photography because of its excellent transparency, mechanical properties and chemical properties.
However, polyethylene terephthalate has a second-order transition point of about 70 ° C. and is not so stable against heat,
At temperatures higher than 70 ° C., the flatness of the film tends to be lost. In addition, the rigidity is not sufficiently high, and the film has a drawback that it is easily deformed. For this reason, for example, a photographic film has various processing processes in practical use and is unstable when the temperature rises.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a method for producing an easily-adhesive polyester film having excellent adhesiveness to a photosensitive layer and excellent thermal deformation resistance. .

[0004]

The object of the present invention is to:
According to the invention, a thickness of 20
Of at least one selected from the group consisting of polyester, acrylic modified polyester, polyurethane, acrylic resin, vinyl resin, vinylidene chloride resin, polyethyleneimine, polyvinyl alcohol, modified polyvinyl alcohol and gelatin on at least one side of a polyalkylene naphthalate film having a thickness of up to 300 μm. An aqueous coating solution containing an easily-adhesive substance is applied, and then dried, stretched and heat-treated to complete oriented crystallization and a first primer layer is applied to form a film, and then gelatin is applied on the first primer layer. It is achieved by a method for producing a photo-sensitive adhesive polyester film having a light transmittance of 70% or more, which comprises applying a coating solution containing the same and then performing drying to apply a second primer layer.

In the present invention, the polyalkylene naphthalate is a naphthalenedicarboxylic acid component such as 2,6-naphthalenedicarboxylic acid or 1,5-naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol,
It is a polyester made from an alkylene glycol component such as 1,4-butanediol. Specifically, polyethylene-2,6-naphthalate is preferable. Some of these polyesters may be replaced with other dicarboxylic acids or other glycols.

The polyester film of the present invention is
It can be manufactured by a conventionally known method. For example, the polyester is dried and then melted, and a die (for example, T die, I
It can be manufactured by extruding from a die or the like) onto a cooling drum to rapidly cool the unstretched film, stretching the unstretched film biaxially, and further heat-fixing the unstretched film. The thickness of the film is 20 to 300 μm. If the thickness of the film is less than 20 μm, the stiffness of the film is weak, while it is 300 μm.
If it exceeds, the workability is poor.

As the polyester film, a film containing no lubricant is preferable from the viewpoint of surface flatness, but in order to control the surface roughness, a lubricant, for example, inorganic fine particles such as calcium carbonate, kaolin, silica, titanium oxide and / or catalyst residue is used. It may be a film containing fine particles of the above, or may be a film containing other additives such as an antistatic agent such as sodium dodecylbenzenesulfonate and a color tone adjusting agent.

In the present invention, the aqueous coating liquid used for forming the first easily adhesive primer layer is polyester, acrylic modified polyester, polyurethane, acrylic resin, vinyl resin, vinylidene chloride resin, polyethyleneimine, polyvinyl alcohol, modified polyvinyl alcohol. And an aqueous coating liquid containing at least one easily adhering substance selected from the group consisting of gelatin.

As the polyester, a copolyester having a sulfonic acid alkali base, a carboxylic acid alkali base or the like in the molecule is preferably exemplified in order to impart hydrophilicity. Specifically, terephthalic acid-isophthalic acid-5Na
-Sulfoisophthalic acid-ethylene glycol-diethylene glycol-neopentyl glycol-based copolyester and the like are preferable.

Examples of the acrylic modified polyester include modified polymers obtained by grafting an acrylic monomer on the above polyester. Specifically, terephthalic acid-5Na-sulfoisophthalic acid-diethylene glycol-1,4-butanediol copolymerized polyester (50
%) In the presence of methyl methacrylate-ethyl acrylate-ammonium acrylate-butyl acrylate (50
%) And modified polymers obtained by polymerizing

Preferred examples of the polyurethane include hydrophilic polyurethanes having an alkali sulfonate group or an amine carboxylate group in the molecule. Specifically, polyethylene glycol-diphenylmethane diisocyanate-ethylenediamine, dimethylolpropionic acid amine salt-based polyurethane and the like are preferable.

Examples of the acrylic resin include methyl methacrylate-ethyl acrylate-ammonium acrylate-
Acrylamide copolymer, methacrylamide-butyl acrylate-sodium acrylate-methyl methacrylate-N
-Methylol acrylamide copolymers and the like are preferable. Acrylic resins can be manufactured and obtained as acrylic emulsion, acrylic aqueous solution, acrylic dispersion and the like.

Examples of the vinyl resin include vinyl acetate, vinyl chloride, methyl vinyl ether, vinylpyrrolidone,
Styrene, acrylate, sodium styrene sulfonate,
A copolymer such as itaconic acid salt is exemplified. Specifically, vinyl acetate-sodium maleate-vinyl chloride-sodium acrylate copolymer, vinyl acetate-styrene-butyl vinyl ether copolymer, polyvinyl butyral and the like are preferable. These resins are preferably mixed with other resins.

Preferred examples of the vinylidene chloride resin include vinylidene chloride homopolymer emulsions and copolymer emulsions of vinylidene chloride and other vinyl monomers. Specifically, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-ethyl acrylate-sodium acrylate copolymer and the like are preferable.

The polyethyleneimine is a polymer of ethyleneimine, and its molecular weight can be arbitrarily selected. In addition to linear polymers, graft polymers to other polymers are also included.

As the polyvinyl alcohol, various polyvinyl alcohols having different saponification degrees are preferably exemplified. As the modified polyvinyl alcohol, a derivative obtained by modifying the hydroxyl group of polyvinyl alcohol by esterification, etherification, reaction of isocyanate, etc. is preferably exemplified. Any known gelatin may be used as the gelatin, and examples thereof include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, derivative gelatin, modified gelatin, phthalated gelatin, and low-molecular gelatin.

These resins are used alone or as a mixture of two or more. Also, with these resins, amino resin,
A crosslinkable resin such as a phenol resin, an epoxy resin, or a polyisocyanate, or another resin can be used in combination.

In the present invention, the aqueous coating liquid can be used by adding a necessary amount of a surface active agent such as an anionic surface active agent, a cationic surface active agent or a nonionic surface active agent.

As these surfactants, those capable of lowering the surface tension of the coating solution to 50 dyne / cm or less, preferably 40 dyne / cm or less and promoting wetting to the polyester film are preferable, and examples thereof include polyalkylene oxide and polyalkylene oxide. Oxyethylene alkyl phenyl ether, polyoxyethylene-fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfate, alkyl sulfonate, alkyl sulfosuccinate, quaternary ammonium chloride salt, alkyl amine hydrochloric acid, etc. Can be mentioned.

In addition to the above, an antistatic agent, an ultraviolet absorber, a pigment, an organic filler, an inorganic filler, a lubricant, an antiblocking agent, a dispersant and the like can be added.

In the present invention, the aqueous coating solution is applied to one side or both sides of the polyester film before crystal orientation is completed.

Here, the polyester film before the crystal orientation is completed is an unstretched film obtained by heat-melting polyester to form a film as it is; the unstretched film is oriented in the longitudinal direction (longitudinal direction) or the transverse direction (width). Uniaxially-stretched film oriented in one of the two directions (direction), and further oriented in a low-magnification stretch direction in both the longitudinal and transverse directions (finally reoriented in the longitudinal or transverse direction for oriented crystallization). Biaxially stretched film before completion) and the like.

The solid content concentration of the above aqueous coating liquid is usually 30% by weight or less, more preferably 10% by weight or less. The coating amount is 0.5 to ²⁰ g per 1 m ² of the running film,
Further, 1 to 10 g is preferable.

As a coating method, any known coating method can be applied. For example, kiss coat method, reverse coat method,
A die coating method, a reverse kiss coating method, an offset gravure coating method, a Meyer bar coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method and the like may be applied alone or in combination.

The polyester film applied with the aqueous coating solution and before the completion of crystal orientation is then dried and stretched.
The crystal orientation is completed by being guided to a process such as heat setting. For example, a longitudinally uniaxially stretched polyester film coated with an aqueous coating liquid is introduced into a stenter, laterally stretched, and heat-set into a biaxially stretched film. During this time, the coating liquid is dried,
A first easy-adhesive primer layer is formed.

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

In the present invention, a coating liquid containing gelatin is further applied onto the first easy-adhesive primer layer and dried to form a second easy-adhesive primer layer. This gelatin may be the same as or different from the gelatin that can be used for the first easily adhesive primer layer,
The same is preferred. As this gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, derivative gelatin, modified gelatin, phthalated gelatin, low-molecular gelatin and the like can be used. Further, copolymers of gelatin and other polymers can also be used. Examples thereof include copolymers of gelatin with acrylic acid, methacrylic acid and their derivatives such as esters and amides, and vinyl monomers such as acrylonitrile and styrene.

The blending ratio of gelatin in the second easily adhesive primer layer is 30 to 90% by weight, more preferably 50 to 80%.
It is preferably in the weight%.

An antistatic agent is preferably contained in the second easily adhesive primer layer. The antistatic agent is not particularly limited, and various kinds can be used, and broadly classified into an ion conductive type and an electron conductive type.

As the ion conductive type antistatic agent,
Examples of anionic fatty acid amine salt, alkyl phosphate type, alkyl sulfate type, alkylallyl sulfate type and the like, as cationic type alkyl amine sulfate type, quaternary ammonium salt type, quaternary ammonium resin type, Examples thereof include pyridinium type and morpholine derivatives, and examples of nonionic compounds include sorbitan type, ether type, amine type, amide type, ethanolamide type, fatty acid glycerin ester, alkylpolyethyleneimine, etc. Alkyl betaine type, alkyl imidazoline derivative,
Examples thereof include N-alkyl β-alanine type.

Examples of the electron-conducting type antistatic agent include a dispersion of metal fine particles such as carbon black and antimony-doped tin, and a metal complex represented by TCNQ-TTN complex, which utilizes radical hopping.

The proportion of the antistatic agent in the second easy-adhesion primer layer is 10 to 30% by weight, more preferably 10 to 20% by weight.
It is preferably in the weight%.

In the second easily adhesive primer layer, it is possible and preferable to use another resin as a third component in order to firmly fix gelatin or an antistatic agent. Preferred examples of the other resin include polyester, polyurethane, acrylic resin, epoxy resin, cellulose resin, polyvinyl alcohol and the like. The amount of the other resin compounded is preferably 0 to 40% by weight.

The above-mentioned coating liquid may be water-based or solvent-based. A known method can be applied as a method of applying the coating liquid. For example, a spray coating method, an air knife method, a reverse coating method, a kiss coating method, a gravure coating method, a Meyer bar method, a roll brush method, a die coating method and the like can be applied. The coating liquid concentration varies depending on the coating method, but is generally 0.5 to 50% by weight. The wet coating amount is preferably 1 to 20 g / m ² , and the dry film thickness is 0.5 μm or more, further 1 μm.
It is preferably m or more.

The easily adhesive polyester film thus obtained has a light transmittance of 70% or more. When the light transmittance is less than 70%, it is not preferable for optical use such as photography.

The easily-adhesive polyester film of the present invention exhibits excellent adhesiveness to the photosensitive layer, particularly has a large adhesive force to the gelatin-based photosensitive layer and is suitable for alkali and acid treatments such as development and fixing. It is durable and water resistant.

[0037]

EXAMPLES The present invention will be further described below with reference to examples. The properties in the examples were evaluated by the following methods.

1. Adhesiveness (a) Preparation of photosensitive emulsion 10 ml of 1N ammonium bromide solution, 0.5 ml of 1N potassium iodide, 6 g of gelatin and 40 ml of water were mixed to obtain 40
Emulsion N is prepared by adding 10 ml of a 1N ammoniacal silver nitrate solution dropwise to the mixture under stirring at -50 ° C over 2 minutes.

(B) Evaluation of Adhesiveness The photosensitive emulsion N prepared in (a) above is applied to the surface of the sample film on which the easily adhesive is applied, and dried to form a film having a thickness of 3 μm. Next, it is immersed in a sodium hydroxide aqueous solution having a pH of 11 at 32 ° C. for 2 minutes. Further, it is immersed in an acetic acid aqueous solution (containing 1% of sodium acetate) having a pH of 4.2 at 32 ° C. for 2 minutes. Then, after washing with water and drying for one day, cellulose is applied and a peeling test is performed. A three-level evaluation is given according to the peeling state. A: The coating film does not come off at all. B: A part of the coating film is peeled off. C: The entire coating film is peeled off.

2. Antistatic property After leaving the film at 23 ° C x 50% RH for 24 hrs, the vibration capacitance type potentiometer TR-84M type (manufactured by Takeda Riken)
Measure with and display the value.

3. Heat-deformation-resistant film sample (30 cm x 20 cm) at 120 ° C for 10
Hold for a minute, observe the change in the flatness of the film before and after that, and make the next evaluation. A: Flatness is maintained. B: The film is deformed.

[0042]

Examples 1 to 12 Polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.64 measured in 35 ° C. o-chlorophenol was melt extruded onto a rotating cooling drum maintained at 20 ° C., quenched and unstretched. A film, and then the unstretched film was stretched in the machine axis direction by 3.4 times, and then the first layer coating agent (4% by weight concentration) having the composition shown in Table 1 was applied to one side of the film by the kiss coating method. (Wet application amount 20g /
m ² ). Subsequently, the film is stretched 4.5 times in the transverse direction, and further 22
Heat treatment was performed at 0 ° C. to obtain a primer-coated polyester film having a thickness of 110 μm.

Further, the second layer coating composition (10% by weight concentration) having the composition shown in Table 1 was coated on the above-mentioned primer-coated polyester film by the reverse coating method (10 g /
m ² ). Subsequently, it was dried at 80 ° C. for 2 minutes to obtain a polyester film coated with two layers. The characteristics of this film are shown in Table 1.

[0044]

[Comparative Example 1] The same procedure as in Example 1 was carried out except that no coating agent was applied. The results are shown in Table 1.

[0045]

Comparative Example 2 Polyethylene terephthalate having an intrinsic viscosity of 0.63 measured in o-chlorophenol at 35 ° C.
It is melt extruded on a rotary cooling drum maintained at 0 ° C. and rapidly cooled to give an unstretched film, and then the unstretched film is stretched 3.5 times in the machine axis direction, and then the coating composition of Example 1 (4 wt. % Concentration) was applied to one side of the film by the kiss coat method (wet application amount 15 g / m ² ). Subsequently, the film was stretched 3.9 times in the transverse direction and further heat-treated at 215 ° C to obtain a thickness of 13
A 0 μm primer-coated polyester film was obtained.

Further, the second layer coating composition (10% by weight) having the composition shown in Table 1 was coated on the above primer-coated polyester film by the reverse coating method (10 g / m ² ). Subsequently, it was dried at 80 ° C. for 2 minutes to obtain a polyester film coated with two layers. The characteristics of this film are shown in Table 1.

[0047]

Comparative Examples 3 to 4 In Example 1, the first layer or the second layer
The procedure was the same except that no layer was applied. The results are shown in Table 1.

[0048]

[Table 1]

1) Types of coating agents <Polyethyleneimine type A> Polyethyleneimine / polyvinyl alcohol / melamine resin / polyoxyethylene nonylphenyl ether = 50/20/20/10 (w)
t%).

<Acrylic B> Methyl methacrylate-ethyl acrylate-Na-N-methylol acrylate (55 wt%) / polyvinylidene chloride (20
wt%) / polyvinyl alcohol (10 wt%) / melamine resin (5 wt%) / polyoxyethylene nonyl phenyl ether (10 wt%).

<Polyurethane type C> Polyoxyethylene glycol (MW = 2000) -tolylene diisocyanate-ethylenediamine dimethylol propionate amine salt type polyurethane (75 wt%) / polyethyleneimine (10 wt%) / polyoxyethylene nonylphenyl ether ( 15 wt%).

<Polyester type D> Terephthalic acid-isophthalic acid-5Na sulfoisophthalic acid-ethylene glycol-diethylene glycol-neopentyl glycol copolymerized polyester (60 wt%) / polyethyleneimine (20 wt%) / melamine resin (10 wt%) / polyester Oxyethylene nonyl phenyl ether (10wt
%).

2) Type of gelatin G-0176K (made by Nitta Gelatin)

3) Types of Antistatic Agent <Antistatic Agent x> Sodium Sulfonate Newcol 271A (Nippon Emulsifier) <Antistatic Agent y> Tin Oxide Dispersion Ceramate F (Taki Chemical Co., Ltd.) <Antistatic Agent z> Etosulfate type Elegan 264A (made by NOF Corporation)

4) Types of surfactants Polyoxyethylene nonylphenyl ether NS-21
0 (Made by NOF Corporation)

[0056]

According to the present invention, it is possible to provide a method for producing an easily-adhesive polyester film which is excellent in adhesiveness to a photosensitive layer and is excellent in heat distortion resistance.

Claims (1)

[Claims] 1. The thickness 20 to which the oriented crystallization is not completed.
At least one surface of a 300 μm polyalkylene naphthalate film is selected from the group consisting of polyester, acrylic modified polyester, polyurethane, acrylic resin, vinyl resin, vinylidene chloride resin, polyethyleneimine, polyvinyl alcohol, modified polyvinyl alcohol and gelatin. An aqueous coating solution containing an adhesive substance is applied, followed by drying, stretching and heat treatment to complete oriented crystallization and a film coated with a first primer layer, and then gelatin is applied on the first primer layer. A method for producing a polyester film for photosensitizer easily adhering, which has a light transmittance of 70% or more, which comprises applying a coating solution containing the same and then performing drying to apply a second primer layer.