JPH08201969A - Flame retardant photographic polyester film - Google Patents

Abstract

PURPOSE: To improve transparency, handleability, dimensional stability, transportability and adhesiveness to a photographic sensitive material and a magnetic medium by incorporating P atoms derived from specified P compds. into polyester as the material of a substrate film. CONSTITUTION: A substrate film is made of polyester having ethylene-2,6- naphthalate units as the principal repeating untis and <=0.1wt.% P atoms derived from a P compd. represented by the formula O=P-[R1 -(OR2 )n -X]3 [where each of R1 and R2 is 1-20C divalent hydrocarbon, X is an ester forming functional group and (n) is 0-500] and 0.01-3wt.% P atoms derived from a P compd. represented by the formula are incorporated into the polyester so that the total P atom content of the polyester is regulated to 0.05-3wt.%. In the latter formula, R3 is 1-20C divalent hydrocarbon, R4 is 1-10C monovalent hydrocarbon and each of R5 and R6 is H or 1-10C monovalent hydrocarbon having an ester forming functional group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant photographic polyester film, and more particularly to a polyester film for a photographic system using a novel cartridge system. More specifically, it is flame-retardant, transparent, easy to handle, heat resistant, and dimensionally stable.
The present invention relates to a photographic polyester film having good transportability, good adhesion to a photographic sensitive material and a magnetic medium, little curl curl, and excellent image sharpness.

[0002]

Photographic light-sensitive materials are generally manufactured with a plastic film as a support. This plastic film includes triacetyl cellulose (hereinafter referred to as "TA
A fibrous polymer represented by C) and a polyester polymer represented by polyethylene terephthalate (hereinafter referred to as “PET”) are used. By the way, since polyester is generally flammable, it has recently been desired to impart flame retardancy to various polyester film products. Further, in recent years, a new patrone system has been recently proposed in order to meet the demands for downsizing and thinning of photographs and systematization with various electronic devices. In addition to the properties required in the past, the photographic plastic film for this new system has (1) improved curl during long-term storage in a small cartridge (before and after development), (2) in camera -Characteristics such as transportability in developing processor / printer and (3) adhesiveness with magnetic media are newly required. Therefore, the one using TAC (JP-A-4-218037), hydrophilic PET
(Japanese Patent Application Laid-Open Nos. 4-250446 and 4-26)
Japanese Patent No. 8551) has been proposed, but the conventional TA
A polyester film mainly composed of C or PET cannot satisfy all of the above characteristics.

Further, in Japanese Patent Application Laid-Open No. 50-109715, polyethylene-2,6-naphthalenedicarboxylate has been proposed as a plastic film replacing TAC or PET, but it is still insufficient and put to practical use. Has not reached. Further, since the films proposed above are flammable, they do not meet the requirement of imparting flame retardancy. Further, the film provided with flame retardancy generally has a problem that the easy adhesion is poor and the adhesion to the photographic material layer and the magnetic medium is not sufficient.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to impart flame retardancy and to improve transparency, handleability, heat resistance, dimensional stability, transportability, adhesion to photographic sensitive materials and magnetic media. It is an object of the present invention to provide a flame-retardant photographic polyester film which is good, has less curling curl, and has excellent image clarity.

[0005]

The flame-retardant photographic polyester film of the present invention for this purpose is a polyester whose main repeating unit is ethylene-2,6-naphthalate and whose polyester film is a polyester film. In contrast, 0.01 to 1% by weight and 0.01 to 3% by weight of phosphorus atoms derived from the phosphorus compound represented by the following formula,
% By weight, and the total phosphorus atom content in the polyester is 0.05 to 3% by weight. _{O = P- [R 1 - (} OR 2) n-X] ₃ wherein, R _1, R ₂ are each a divalent hydrocarbon group having 1 to 20 carbon atoms, X is an ester-forming functional group Yes, n
Is 0 to 500.

[0006]

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In the formula, R ₃ is a divalent hydrocarbon group having 1 to 20 carbon atoms, R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ₄ is
₅ and R ₆ are each a hydrogen atom or a monovalent hydrocarbon group having an ester-forming functional group having 1 to 10 carbon atoms.

Further, it is desirable that an easy-adhesion layer is provided on at least one surface of the base film.

The easy-adhesion layer has a temperature of 25 ° C. and a relative humidity of 65%.
It is preferable that the surface specific resistance is 5 × 10 ¹² Ω / □ or less, and the contact angle between the surface of the easily adhesive layer and water is 50 ° or more.

Further, an easily adhering layer is provided on both sides of the substrate film, a photographic sensitive material layer is provided on the surface on one side, and a magnetic layer is provided on the surface on the opposite side. The polyester film for use is more preferable because the above-mentioned various properties are satisfied.

The polyester in the present invention is a polyester whose main repeating unit is 2,6-naphthalenedicarboxylic acid as an acid component and ethylene glycol as a diol component, and whose main repeating unit is ethylene-2,6-naphthalate.

The polyester of the present invention contains a small amount of an acid component, for example, isomers of naphthalenedicarboxylic acid such as 2,7, 1,4 and 1,5 terephthalic acid,
It may contain components such as isophthalic acid, diphenoxyethanedicarboxylic acid, dichlorophenoxyethanedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenylketonedicarboxylic acid and anthracenedicarboxylic acid. Further, as a diol component, a small amount of trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol and other alkylene glycol components, cyclohexanedimethanol and other alicyclic diol components, polyethylene glycol and polytetraethylene. Glycol,
It may also contain a polyalkylene glycol component such as.

The method for producing the polyester of the present invention may be any of the conventionally known transesterification method and esterification method. Further, in producing the above polyester, a reaction catalyst for an alkali metal compound, an alkaline earth metal compound, a zinc compound, a lead compound, a manganese compound, a cobalt compound, an aluminum compound, a phosphorus compound, an antimony compound, a titanium compound, a germanium compound, etc. Is used as appropriate.

In the present invention, two types of phosphorus compounds need to be copolymerized. First, the first phosphorus compound is a phosphine oxide derivative, and specifically, is represented by the following formula. O = P- - in _{[R 1 (OR 2) n} -X] 3 ( wherein, a divalent hydrocarbon group of R _1, R ₂ are carbon atoms respectively 1 to 20, X is an ester-forming functional group And
n is 0-500. )

Specific examples of the first phosphorus compound include tris (hydroxymethyl) phosphine oxide, tris (2-hydroxyethyl) phosphine oxide, and tris (hydroxyalkyl) phosphine oxide. Examples include tris (carboxyalkyl) phosphine oxide derivatives such as phosphine oxide derivatives, tris (carboxypropyl) phosphine oxide, tris (carboxyoctyl) phosphine oxide, and alkylene oxide adducts of tris (hydroxyalkyl) phosphine oxide derivatives. You can

The content of phosphorus atoms derived from the phosphine oxide derivative to be copolymerized with the polyester of the present invention in the polyester must be 0.01 to 1% by weight, preferably 0.05 to 0. 5% by weight,
More preferably, it is 0.1 to 0.3% by weight. If the phosphorus atom content derived from the phosphine oxide derivative is less than 0.01% by weight, the flame retardancy of the polyester is insufficient and 1
When it exceeds the weight%, the mechanical properties of polyester deteriorate.
The "(phosphorus compound) -derived phosphorus atom" in the present invention
Means a phosphorus atom belonging to the phosphorus compound specified among the two types of phosphorus compounds copolymerized with the polyester.

The second phosphorus compound of the present invention is a carboxyphosphinic acid derivative, specifically, the compound represented by the following chemical formula 3.

[0018]

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In the formula, R ₃ is a divalent hydrocarbon group having 1 to 20 carbon atoms, R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ₄ is
₅ and R ₆ are each a hydrogen atom or a monovalent hydrocarbon group having an ester-forming functional group having 1 to 10 carbon atoms.

Specific examples of the second phosphorus compound include carboxymethyl-methylphosphinic acid, carboxyethyl-methylphosphinic acid, carboxypropyl-methylphosphinic acid, carboxymethyl-ethylphosphinic acid,
Examples thereof include carboxyphosphinic acids such as carboxymethyl-phenylphosphinic acid, carboxymethyl-cyclohexylphosphinic acid, and carboxyphenyl-methylphosphinic acid, alkylene glycol condensates thereof, and intramolecular ring-closing compounds.

The content of the phosphorus atom derived from the carboxyphosphinic acid derivative copolymerized with the polyester of the present invention in the polyester must be 0.01 to 3% by weight, preferably 0.05 to It is 2% by weight, and more preferably 0.1 to 1.5% by weight. The phosphorus atom content derived from the phosphine oxide derivative is 0.01
If it is less than 5% by weight, the flame retardancy of the polyester is insufficient, and if it exceeds 3% by weight, the hydrolysis resistance of the polyester is lowered, which is not preferable.

The method of adding the phosphorus compound of the present invention to the polyester is not particularly limited, and it can be added at any stage of the polyester production process, and during the esterification or transesterification reaction, the polycondensation reaction. It may be any time, and it is preferably between the end of the esterification or transesterification reaction and the beginning of the polycondensation reaction. It is also a preferable method to add the phosphorus compound after previously mixing or dissolving it in a diol component such as ethylene glycol or other solvent or condensing it by heating.

The hydrolysis resistance of the polyester of the present invention is
Intrinsic viscosity change (ΔIV) of polyester when polyester chips were vacuum dried at 160 ° C for 3 hours
You can judge with. ΔIV = intrinsic viscosity of polyester before drying−intrinsic viscosity of polyester after drying The polyester of the present invention has a low ΔIV of about 0.05 or less and shows good hydrolysis resistance.

The mechanical properties of the polyester of the present invention can be evaluated by the presence or absence of cracks when the film obtained from the polyester is folded in two, and the film made of the polyester of the present invention has a film surface even when folded in two. It is preferable because it does not crack and has good mechanical properties.

Further, the polyester film of the present invention may be blended with another type of polymer within a range not impairing the object of the present invention, and a crystal nucleating agent, an ultraviolet absorber,
Various additives such as heat stabilizers, antistatic agents, lubricants, pigments, dyes, inorganic and / or organic particles, and waxes may be added to the extent that they are usually added.

The flame retardancy of the polyester of the present invention can be evaluated by the vertical flame test method of UL94 flame retardancy test standard for plastic materials issued by Underwriter Laboratories, and the obtained polyester is 94 VTM-2 or more. It can be determined that, and further, 94VTM-0 standard can be achieved, showing good flame retardancy.

In the case of polyethylene-2,6-naphthalene dicarboxylate film, it has a high refractive index,
It tends to cause the light piping phenomenon. A method of adding a dye is known as a method of avoiding the light piping phenomenon. The dye used for film dyeing is not particularly limited, but gray dyeing is preferable for the general tone of the light-sensitive material for the color tone, and the dye has excellent heat resistance in the film formation area of the polyester film, and is compatible with polyester. Those having excellent solubility are preferable. Regarding the dyeing density, the color density in the visible region is measured with a color densitometer manufactured by Macbeth Co., and preferably at least 0.01 or more, more preferably 0.03 or more.

Further, the polyester film of the present invention can be provided with slipperiness for the purpose of improving the processability in the film forming process, the handleability of the obtained film, the workability and the commercial value. The means for imparting slipperiness is not particularly limited, but addition of inert particles to polyester is used as a general method. Here, the type of the inert particles is not particularly limited, but examples thereof include inorganic particles and organic particles. Specifically, natural products are crushed and classified, or silica and alumina produced by a synthetic method,
Inorganic compound particles such as titania, zirconia, ceria, molybdenum oxide, tungsten oxide, calcium carbonate, calcium phosphate, barium sulfate, iron oxide, kaolin, talc and carbon, organic resin such as silicone resin, silicone rubber, crosslinked polystyrene, polyimide and epoxy resin Examples thereof include compound particles. Further, it is also possible to use slipperiness imparted by internal particles that deposit a catalyst or the like during the polyester polymerization reaction.

These slipperiness imparting means are not particularly limited, but since transparency is an especially important requirement for photographic use, calcium carbonate, silica, crosslinked polystyrene-based particles having a refractive index relatively close to that of polyester, or Those having no internal coarse particles are preferred. Coarse particles are 5
It has a diameter of μm or more.

The intrinsic viscosity of the polyester film of the present invention is preferably 0.4 or more, more preferably 0.5 or more, and particularly preferably 0.55 or more.

The haze value of the polyester film of the present invention is preferably 10% or less, more preferably 5% or less,
It is particularly preferably 2% or less. If the haze value exceeds 10%, the photographic image tends to be blurred and unclear, which is not preferable.

200 of the polyester film of the present invention
The heat shrinkage at 30 ° C. for 30 minutes is preferably 2% or less, more preferably 1.5% or less, and particularly preferably 1.2%.
It is the following. The heat shrinkage ratio at 80 ° C. for 8 hours is preferably 0.7% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less.

The elastic modulus of the polyester film of the present invention is preferably 400 kg / mm ² or more, more preferably 450 kg / mm ² or more, and particularly preferably 500 k.
g / mm ² or more. The elastic modulus when immersed in distilled water at 38 ° C. for 30 minutes is preferably 350 kg / mm ²
More preferably, it is 450 kg / mm ² or more.

The tear propagation resistance of the polyester film of the present invention is preferably 200 g / mm or more, more preferably 300 g / mm or more. The breaking strength is preferably 10 kg / mm ² or more, more preferably 15
kg / mm ² , particularly preferably 18 kg / mm ² .

The surface morphology of the polyester film of the present invention has a center line average roughness Ra of preferably 0.02.
0 μm or less, more preferably 0.015 μm or less, particularly preferably 0.010 μm or less, and the maximum surface roughness Rt is 0.3 μm or less, more preferably 0.2 μm.
m or less, particularly preferably 0.15 μm or less. If the center line average roughness Ra exceeds 0.020 μm or the maximum surface roughness Rt exceeds 0.3 μm, it becomes difficult to obtain a clear photographic image. Further, when measured by a multiple interference method with a wavelength of 540 nm, the number of protrusions showing second, third, and fourth order interference fringes is
130 pieces / mm ² or less, 30 pieces / mm ² or less,
15 pieces / mm ² or less is preferable.

The polyester film of the present invention is a film having a thickness of 1000 μm or less, preferably 3 to 50.
The thickness is 0 μm, more preferably 4 to 200 μm.

The polyester film of the present invention has a partial melting temperature Tp of 80 to 170 ° C., preferably 85 to 165.
C., particularly preferably 80 to 160.degree. Tp is 80
When the temperature is lower than 0 ° C, the stability of the polyester molecule is insufficient, resulting in poor dimensional stability, curling curl, and the like.
On the other hand, if Tp exceeds 170 ° C., the curl curling property is significantly deteriorated, which is not preferable.

Next, an example of the method for producing the polyester film of the present invention will be described. After the polyester is sufficiently dried, it is melt extruded into an unstretched sheet, and then biaxially stretched and heat-treated to obtain a desired film. Biaxial stretching may be either longitudinal or transverse sequential stretching or biaxial simultaneous stretching, and the stretching ratio is not particularly limited, but usually longitudinal and transverse 2.0 to 6.0 times are suitable. Alternatively, it may be stretched in the machine direction or in the transverse direction after stretching in the machine direction or in the transverse direction.

Next, the biaxially stretched film is heat treated.
The heat treatment conditions in this case may be any of a fixed length, a relaxed state, and a finely stretched state. In the case of the polyester film of the present invention, the heat treatment temperature is 20 from the melting point of the polyester.
It is preferable to carry out the treatment at a temperature of -80 ° C lower and a time of 0.5 to 60 seconds. Further, it is possible to further perform a relaxing process.

Then, while the polyester film is wound on a roll and tension is applied, heat treatment is performed at a temperature not higher than the glass transition temperature of the film. The processing temperature is a glass transition temperature of the film −50 ° C. to a glass transition temperature of the film,
The glass transition temperature of the film is preferably -40 ° C to the glass transition temperature of the film-5 ° C. The processing time is
It is 10 minutes to 150 hours, preferably 2 hours to 48 hours. For example, 105 to 115 ° C. and 24 hours are preferable heat treatment conditions, but the treatment may be performed at a lower temperature for a longer time, or may be performed before or after coating with a photographic sensitizer or the like. When the glass transition temperature is exceeded, the partial melting temperature disappears, so it is necessary that the temperature is not higher than the glass transition temperature. The tension applied to the film is preferably substantially equal to the heat absorption stress of the film at the processing temperature.

In the present invention, the easy-adhesion layer provided on at least one side of the base film has a temperature of 25 ° C. and a relative humidity of 65.
%, The surface specific resistance is 5 × 10 ¹² Ω / □ or less, preferably 1 × 10 ¹² Ω / □ or less, and more preferably 5 × 10.
^It has an antistatic property of ¹¹ Ω / □ or less, and has a contact angle with water of 50 ° or more, preferably 60 ° or more, more preferably 70 ° or more. If the surface specific resistance exceeds 5 × 10 ¹² Ω / □, the antistatic effect is small, and dust is likely to adhere during processing such as coating and slitting, resulting in a high possibility of becoming a photographic image defect. If the contact angle with water is less than 50 degrees,
Adhesion to the coating on the easy-adhesion layer, for example, the photographic material layer and the magnetic layer becomes insufficient, which is not preferable.

In order to obtain such an easy-adhesion layer, it is usually difficult to achieve it by using an antistatic polymer which does not have a reactive functional group or which is easily deposited on the surface, such as a conventional surfactant, and thus it is difficult to crosslink. Antistatic polymers having functional groups are preferred. As the antistatic polymer, a monomer (monomer) having a sulfonic acid group and / or a salt thereof or a phosphoric acid group and / or a salt thereof, a monomer (monomer) having a reactive (crosslinkable) functional group, and other monomers. Those copolymerized with (monomer) are preferable.

Typical examples of the monomer include styrene sulfonic acid and / or a salt thereof (as a salt, ammonium, lithium, sodium, potassium, etc.) and a monomer having one unsaturated bond and a phosphate group. Can be mentioned as. In particular, a monomer containing an alkylene oxide and a phosphoric acid group and / or a salt thereof is preferable, and among them, it is preferable that the alkylene oxide and a phosphoric acid group and / or a salt thereof are present in one monomer,
Further, it is more preferable that the phosphoric acid group exists in the side chain of the polymer after the polymerization with the alkylene oxide interposed therebetween.

Here, the alkylene oxide is a repeating unit in the molecule represented by the following formula, and preferred examples include ethylene oxide, propylene oxide,
Examples thereof include those containing both ethylene oxide and propylene oxide. -(R-O) n- (R: alkylene group and derivatives thereof, n: integer selected from 1 to 9)

The phosphate group can be arbitrarily selected as long as it is formed by the addition of a cation, and the cation is a monovalent salt such as lithium salt, sodium salt, potassium salt, rubidium salt and ammonium salt. Of these, potassium salts and rubidium salts are particularly desirable in terms of antistatic properties. The phosphoric acid group is obtained by a method of providing a cation to a free phosphoric acid group after copolymerization, or a method in which a monomer having a phosphoric acid group is phosphorylated by a neutralization method in advance as one component of the monomer. be able to.

Examples of the monomer in which the phosphoric acid group is present through the alkylene oxide are acid phosphooxyethyl acrylate, acid phosphooxyethyl methacrylate, acid phosphooxy (polyoxyethylene glycol) monoacrylate, and acid phospho. Oxy (polyoxyethylene glycol) monomethacrylate, acid phosphooxy (polyoxypropylene glycol) monoacrylate, acid phosphooxy (polyoxypropylene glycol) monomethacrylate, 3chloro-2 acid phosphooxypropyl acrylate, 3chloro 2 acid phosphooxypropyl Methacrylate etc. can be mentioned as a typical example.

Further, for the purpose of imparting a crosslinkable functional group, it is important to copolymerize the following monomers having a crosslinkable functional group in order to satisfy the requirements of the present invention. As such a crosslinkable functional group, a carboxy group,
Examples include hydroxyl group, methylol group, sulfonic acid group, amide group or methylolated amide group, amino group (including substituted amino group), or alkylolated amino group, epoxy group, acid anhydride, etc. it can.

Illustrative of the above monomer, acrylic acid,
Methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinylsulfonic acid, styrenesulfonic acid, acrylamide, methacrylic acid Examples include, but are not necessarily limited to, amides, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and those obtained by methylating the above amino groups, glycidyl acrylate, glycidyl methacrylate, and the like. Absent. The copolymerization ratio of the monomer is not particularly limited, but is preferably 1 to 30% by weight, and more preferably 3 to 20% by weight from the viewpoint of easy adhesion.

As the other monomer component (monomer), known ones can be used. In particular, alkyl acrylate, alkyl methacrylate (as the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-
Acrylic monomers such as ethylhexyl group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group) are preferably used as the basic skeleton.

The above-mentioned monomer and other monomer (monomer) can be copolymerized at any ratio, but preferably, the monomer is 20% by weight or more, more preferably 30% by weight or more, further preferably 40% by weight or more. Is desirable in terms of antistatic property.

In addition to the above, the following compounds,
For example, acrylonitrile, methacrylonitrile, styrenes, monomers or dialkyl esters of maleic acid and itaconic acid, vinyl chloride, vinylidene chloride, vinyl acetate, vinylpyridine, vinylpyrrolidone, alkoxysilanes having a vinyl group, etc. You may use it as a copolymerization component of 1 part. Further, the molecular weight of the antistatic polymer is preferably 100,000 or more, more preferably 300,000 or more from the viewpoint of easy adhesion.

The antistatic polymer can be obtained by a known acrylic resin polymerization method. However, when it is applied to the in-line coating method, it is preferably dissolved or dispersed in water. A water dispersion made by the method is preferred.

In the present invention, it is preferable to use the above antistatic polymer in combination with another resin in order to satisfy the requirement of easy adhesion. The resin to be mixed is not particularly limited, for example, acrylic resin, polyester resin,
Examples thereof include polyurethane resin, polyamide resin, polyester graft acrylic resin, and the like. Among these, those having a crosslinkable functional group are particularly suitable as in the above antistatic polymer.

An example of a suitable acrylic resin is a copolymer of an acrylic monomer having a carboxy group, a hydroxyl group, a methylol group as a crosslinkable functional group, the polymer having a glass transition temperature of 0 to 45 ° C. and a molecular weight of Is preferably 10,000 or more. The mixing ratio of the antistatic polymer and the other resin is not particularly limited, but a preferable range is a weight ratio of the antistatic polymer in the easy-adhesion layer of 10 to 70.
%, Preferably 20 to 60%, more preferably 30 to
50%.

In the present invention, it is preferable to use a cross-linking agent in combination in order to bring out the effect more remarkably. As the cross-linking agent, known ones such as melamine-based cross-linking agent, isocyanate-based cross-linking agent, epoxy-based cross-linking agent, silane coupling agent, organic titanate compound and the like can be mentioned. Among them, the melamine-based crosslinking agent is effective in increasing the contact angle with water. Examples of the melamine-based crosslinking agent include those having an imino group, a methylol group, or an alkoxymethyl group as a functional group in one molecule, and among them, a methylolated melamine resin is most preferable. Addition of an organic titanate compound, especially titanium lactate, is effective in terms of antistatic effect. The amount of these cross-linking agents added is 1 to 40% by weight, preferably 3%, in each of the easy-adhesion layers.
It is desirable that the content is -20% by weight.

In the present invention, it is necessary that an easy-adhesion layer is provided on at least one surface of the base film. In particular, in the case of applying the new patrone method in which the photographic light-sensitive material is provided on one side and the magnetic layer is provided on the other side, it is preferable from the viewpoint of adhesiveness to provide the easy adhesion layer on both sides. The thickness of the easy-adhesion layer is not particularly limited, but in the present invention, it is 0.
01 to 2.0 μm is preferable, and 0.04 is more preferable.
To 1.0 μm, more preferably 0.06 to 0.5 μm
Is.

Further, in order to bring out the effect of the present invention more remarkably, it is preferable to stretch in the state that water is present in the easy-adhesion layer in the process of stretching after coating, and therefore the concentration of the coating agent is set. It is effective to lower the stretching temperature or lower the stretching temperature in a range where there is no film tearing, necking stretching, or undried coating film after stretching heat treatment. Specifically, the coating agent concentration is 0.5 to 10% by weight, preferably 1 to 5% by weight, and the stretching temperature is 85 to 135 ° C, preferably 95 to 13%.
It is good that it is 0 ° C.

In the easy-adhesion layer of the present invention, known additives such as antioxidants, heat stabilizers, weathering stabilizers, ultraviolet absorbers, organic or inorganic easy additives are used as long as the effects of the present invention are not impaired. Lubricants, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents and the like may be added. In particular, a biaxially stretched product in which inorganic particles are added and blended into the easy-adhesion layer of the present invention is more preferable because it has improved slipperiness.

Typical examples of the inorganic particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like. The average particle diameter of the inorganic particles is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, still more preferably 0.08 to 2 μm, and the compounding ratio to the solid content in the easy-adhesion layer is particularly limited. No, but weight ratio is 0.05
-8 parts are preferable, and 0.1-3 parts are more preferable.

The easy-adhesion layer may be applied by a known application method, for example, reverse coating method, gravure coating method,
Any method such as a rod coating method or a die coating method can be used.

As the photographic light-sensitive material layer of the present invention, any known black-and-white or color layer may be used. In the case of color, at least one silver halide emulsion for each of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer may be provided, and the halogenated emulsion layer and the non-photosensitive layer may be provided. There is no particular limitation in the order of numbers and layers.

Further, the magnetic layer may be applied or applied transparently or opaquely on the entire surface opposite to the photographic material layer uniformly or in the form of stripes. As magnetic powder, γ-Fe ₂
O ₃ , Co-γ-Fe ₂ O ₃ , and metal powder can be selected, and the binder can be selected from thermoplastic resin, thermosetting resin, radiation curable resin, reactive resin, and the like. For example, vinyl acetate, chloride Vinyl-based resins such as vinylidene chloride, rubber-based resins such as acrylonitrile / butadiene copolymers, acryl and / or methacryl-based resins that may have functional groups, cellulose-based resins such as acetyl cellulose and nitrocellulose, epoxy -Based resins, phenol-based resins, monomeric isocyanates, modified isocyanates, urethane prepolymers, polyurethane resins such as blocked isocyanates, silicone-based resins, polyamide-based resins, polyester-based resins, polyether-based resins, polycarbonate-based resins and these Blended with, copolymerized with, etc. And the like. Further, known cross-linking agents, dispersants, lubricants, antistatic agents, stabilizers, plasticizers and the like can be added within the range not impairing the object of the present invention.

When the photographic material layer and the magnetic layer are provided on the polyester film having the easily-adhesive layer of the present invention, a generally known coating method can be used. For example, a reverse coating method or a gravure coating method. Method, rod coating method, die coating method or the like can be used.

[Characteristic Measuring Method and Evaluation Method] The characteristic value measuring method and effect evaluating method of the present invention are as follows. (1) Intrinsic viscosity Measured at 25 ° C using o-chlorophenol as a solvent, according to ASTM-1601 (unit: dl / g).

(2) Total phosphorus atom content of polyester It was measured by a colorimetric method.

(3) Phosphorus atom content derived from each phosphorus compound Polyester was dissolved in a soluble solvent such as hexafluoroisopropanol, deuterium trifluoroacetate substitution product, deuterated chloroform, and the peak area of each component in ³¹ P-NMR. It was calculated from the ratio and the total phosphorus atom content.

(4) Hydrolysis resistance of polyester As a measure of the hydrolysis resistance of the polyester chip, the change in the intrinsic viscosity when the polyester chip was vacuum dried at 160 ° C. for 3 hours was judged. Decrease in intrinsic viscosity of polyester = Intrinsic viscosity of polyester before drying-Intrinsic viscosity of polyester after drying ◎: Intrinsic viscosity decrease of 0.03 or less. ◯: The decrease in intrinsic viscosity exceeds 0.03 and is 0.05 or less. X: The decrease in intrinsic viscosity exceeds 0.05.

(5) Flame Retardancy of Polyester Judgment was made by the vertical flame test method of UL94 flame retardancy test standard for plastic materials issued by Underwriter Laboratories. ⊚: 94 VTM-0 is achieved. A: Achieved 94 VTM-2. X: 94VTM-2 is not achieved.

(6) Mechanical Properties of Polyester The superiority or inferiority was judged by the presence or absence of cracks when a film obtained from polyester was folded in two.

(7) Glass transition temperature Tg The glass transition temperature Tg was measured using a differential scanning calorimeter (hereinafter also simply referred to as DSC; for example, DSC-II type manufactured by Perkin Elmer Co., Ltd.). The measurement conditions of DSC are as follows. That is, set 10 mg of the sample in the DSC device, and
After melting for 5 minutes at a temperature of ° C, it is quenched in liquid nitrogen.
This rapidly cooled sample was heated at a rate of 10 ° C./min to give a glass transition temperature T
g is detected.

(8) Partial melting temperature Tp A DSC pan containing 10 mg of a film sample was set in a differential scanning calorimeter (DSC) and heated from 20 ° C. at a heating rate of 20 ° C./min under a nitrogen stream. Iki, at least 23
It was measured up to 0 ° C. The partial melting temperature Tp is the measured DS
A baseline is drawn on the C curve, and it is defined as an arithmetic mean value ((T1 + T2) / 2) of a temperature T1 at which the temperature starts to shift from the baseline to the endothermic side and a temperature T2 at which the endothermic side returns to the baseline.

(9) Tear propagation resistance Using a light load type tear tester (manufactured by Toyo Seiki Co., Ltd.), A
It was measured according to STM-D-1922. The sample size was 51 × 64 mm, and a notch of 13 mm was made, and the indicated value when the remaining 51 mm was torn was read.

(10) Surface Roughness Ra, Rt Cutoff of 0.000 according to JIS-B0601-1976.
25 mm, measuring length 4 mm, center line average roughness Ra (μm)
And the maximum roughness Rt (μm).

(11) Heat Shrinkage A film having a test length of 200 mm and a width of 10 mm was heated in a hot air oven having a constant temperature under a load of 3 g for 30 minutes, and the shrinkage was calculated from the length before and after heating.

(12) Breaking strength, Young's modulus According to JIS-Z1702-1976, width 10 mm,
A strip having a length of 100 mm was measured at a tensile speed of 300 mm / min when measuring the breaking strength and a Young's modulus of 20 mm / min.

(13) Film haze Measured according to ASTM-D1003-52.

(14) Thickness of easily-adhesive layer: Obtained from a photograph of a cross-section of a biaxially oriented polyester film provided with a coating layer, using a transmission electron microscope HU-12 manufactured by Hitachi, Ltd. The thickness was an average value of 30 pieces in the measurement visual field.

(15) Surface resistivity After being left for 24 hours in a normal state (25 ° C., relative humidity 65%), a digital ultrahigh resistance / micro ammeter R8 was placed in that atmosphere.
340A (manufactured by Advantest Co., Ltd.) was used and the measurement was performed at an applied voltage of 100V. The unit is Ω / □.

(16) Contact angle with water After standing for 24 hours in a normal state (25 ° C., relative humidity 65%), a contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.) was used under the atmosphere. The contact angle with water was measured using distilled water stored under the same conditions. The measured value was an average value of 10 pieces.

(17) Durability The following adhesion evaluations were used, and “⊚” and “∘” were evaluated as good durability. (A) Adhesiveness-1 (Adhesion between the base film and the easy-adhesion layer) 100 crosscuts of 1 mm ² were put in the easy-adhesion layer, and cellophane tape manufactured by Nichiban Co., Ltd. was stuck on top of it and strongly adhered with a finger. After pressing, it was rapidly peeled off in the direction of 90 ° C., and the number of remaining pieces was used to perform a four-level evaluation. ◎: 100/100 (remaining number / measured number) ○: 80/100 or more and less than 100/100 △: 50/100 or more and less than 80/100 ×: less than 50/100 (b) Adhesiveness-2 (photographic feeling Adhesion of material layer) After forming a silver halide emulsion layer film of a blue color sensitive layer, a green color sensitive layer, and a red color sensitive layer on the easy-adhesion layer, adhesion is performed in the same manner as in (a) above. The sex was evaluated. (C) Adhesiveness-3 (adhesion to magnetic layer) 100 parts by weight of Daiheracoat CAD4301 (manufactured by Dainichiseika Co., Ltd.) on the easy-adhesion layer and 1 part by weight of Sumijour N-75 (manufactured by Sumitomo Bayer Co., Ltd.) Solid content of 20
Create a paint by weight% and apply it with a bar coater.
It was dried at 00 ° C. for 5 minutes. The adhesion was evaluated in the same manner as in (a) above.

(18) Ash Test A polyester film provided with an easily adhesive layer was rubbed well with an untreated polyester film, and then the ash of a well-dried tobacco was brought close to the ash test. It was judged. ○: No adhesion △: Slight adhesion ×: Significant adhesion

(19) Curling curl property (a) Curling curl recovery property The film was sampled in a size of 30 mm in the width direction and 135 mm in the longitudinal direction and wound on a core having a diameter of 10 mm.
Treatment at 70 ° C, 30% RH for 72 hours, then
Release from the core and soak in distilled water at 38 ° C for 30 minutes, then 3
With 0 g tension applied, dry for 5 minutes in a hot air oven at 50 ° C. The diameter of the cylinder formed when the treated film sample was placed on a flat surface was measured. The curl curl recovery property was evaluated according to the following 5 grades. A score of 4 or more is considered good. 5: The film was not curled and became flat 4: The diameter of the cylinder was 60 mm or more 3: The diameter of the cylinder was 40 mm or more and less than 60 2: The diameter of the cylinder was 20 mm or more and less than 40 1: The diameter of the cylinder was less than 20 mm (b ) Width-direction curl property A film having a photographic sensitive material layer formed on an easy-adhesion layer is sampled in a size of 30 mm in the width direction and 135 mm in the longitudinal direction, and left still on a flat plate with the photographic material layer facing down. To do.
The degree of curl in the width direction after development processing was evaluated as follows. A value of “Δ” or more is considered good. ◯: The film became flat without curling Δ: The film was slightly curled in the width direction and the clearance between the convex portion and the flat plate was 2 mm or more and less than 5 mm ×: The film was curled and the clearance between the convex portion and the flat plate was 5 mm that's all

[0083]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1 A mixture of 150 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 70 parts by weight of ethylene glycol was subjected to transesterification reaction according to a conventional method using magnesium acetate as a catalyst, and then tris (3-hydroxypropyl) phosphine oxide 3 was used. After dissolving 6 parts by weight and 9.1 parts by weight of carboxyethyl-methylphosphinic acid in ethylene glycol and adding and stirring for 5 minutes, 0.04 parts by weight of antimony trioxide as a polycondensation reaction catalyst was added, and the mixture was heated under reduced pressure at high temperature. Was subjected to a polycondensation reaction to obtain a polyester having an intrinsic viscosity of 0.69 and a total phosphorus atom content of 1.8% by weight. The phosphorus atom content derived from each phosphorus compound in the obtained polyester was ³¹ P.
As a result of calculation from —NMR spectrum, phosphorus atoms derived from tris (3-hydroxypropyl) phosphine oxide and carboxyethyl-methylphosphinic acid were 0.3% by weight and 1.5% by weight, respectively. The hydrolysis resistance of the obtained polyester was good, showing a value of ΔIV of 0.03. The obtained polyester was sufficiently vacuum dried, melt-extruded at 300 ° C., wound around a casting drum at a refrigerant of 20 ° C. by an electrostatic cast method, cooled and solidified to obtain an unstretched film. This unstretched film was brought into contact with a roll heated to 130 ° C. and stretched 4.5 times in the longitudinal direction to obtain a uniaxially stretched film. Both sides of this uniaxially stretched film were subjected to corona discharge treatment, and the treated surface was coated with the following water-based coating material. After the application, while continuously gripping the edges with clips, guide it to a heating zone of 140 ° C, preheat and dry it, and then stretch it 4.5 times in the width direction.
Heat treatment was performed while allowing the film to relax, to obtain a biaxially oriented polyester film having a base polyester film thickness of 90 μm and an easy-adhesion layer thickness of 0.1 μm. The surface roughness of this film was 0.09 μm, which was smooth. While the film is in roll form and tension is applied in the longitudinal direction of the film, 1
Heat treatment was performed for 24 hours in a hot air oven at 05 ° C. The flame retardancy of the film thus obtained was good at 94-VTM-0 level, and the mechanical properties were good even when the film was folded in two and did not crack.

[Water-based coating material] (A): Acid phosphooxy (polyoxyethylene glycol) monomethacrylate (repeating unit of oxyethylene glycol n =) neutralized in advance with potassium hydroxide
5) / butyl acrylate / acrylic acid 70/25 /
Aqueous dispersion of antistatic polymer having a molecular weight of about 150,000, which was emulsion-polymerized at a ratio of 5 (% by weight) (B): methyl methacrylate / butyl acrylate /
Acrylic emulsion copolymerized with acrylic acid in a ratio of 55/35/10 (C): hexamethylolated melamine (A) / (B) / (C) in a solid content weight ratio of 35/55 /
It was mixed with 10 and further diluted with water to obtain a 3 wt% liquid.

The above water-based coating material was applied on both sides to form a stripe-shaped magnetic layer on one surface of the film having an easily adhesive layer formed thereon, and then a photographic light-sensitive material layer was provided on the opposite surface. The photographic polyester film thus obtained was evaluated. As shown in Tables 1 and 2, the transparency, dimensional stability, curl curl property, adhesiveness, etc. were good. The transportability was also good.

Examples 2 and 3 Except that the total phosphorus atom content was changed in Example 1,
A polyester film having a thickness of 90 μm was formed by the same method. Thus, the thickness of the base polyester film is 90
A biaxially oriented polyester film having a thickness of 0.1 μm and an easy-adhesion layer thickness of 0.1 μm was obtained. The surface roughness of this film is 0.08
It was as smooth as μm. This film was heat-treated in a hot air oven at 105 ° C. for 24 hours in a roll-like state with tension applied in the longitudinal direction of the film. The flame retardancy of the film thus obtained was good at 94-VTM-0 level, and the mechanical properties were good even when the film was folded in two and did not crack. Then, in the same manner as in Example 1, a photographic polyester film was obtained. The photographic polyester film thus obtained was excellent in transparency, dimensional stability, curl curl property, adhesiveness and the like as shown in Tables 1 and 2. The transportability was also good.

Examples 4 to 8 The mixing ratio of the water-based coating material (A) / (B) / (C) of Example 1 was 70/20/10, 60/30/10, 50/40.
A photographic polyester film was prepared in the same manner except that the film thickness was changed to / 10, 20/70/10, 30/70/0. As shown in Tables 1 and 2, the flame retardancy, transparency, dimensional stability, curl curl property, adhesiveness, etc. were good. The transportability was also good.

Example 9 A photographic polyester film was prepared in the same manner as in Example 1, except that the sodium salt of polystyrenesulfonic acid (molecular weight: 50,000) was used in place of the water dispersion component (A) of Example 1. did. As shown in Tables 1 and 2, the results are flame retardant,
The transparency, dimensional stability, curl curl property, and adhesiveness were good. The transportability was also good.

Example 10 Example 1 was repeated except that the polystyrene sulfonate ammonium salt / ethyl acrylate / acrylic acid (65/30/5 (wt%)) was used instead of the water dispersion component (A) of Example 1. A polyester film for photography was prepared in the same manner as in. As shown in Tables 1 and 2, the results were good in flame retardancy, transparency, dimensional stability, curling curl property, adhesiveness and the like. The transportability was also good.

Comparative Example 1 An intrinsic viscosity of 0.68 and a total phosphorus atom content of 3.8 were obtained in the same manner as in Example 1 except that only 25.2 parts by weight of carboxyethyl-methylphosphinic acid was used as the phosphorus compound.
4% by weight of polyester were obtained. The flame retardancy of the film obtained from the polyester thus obtained is 94 VTM-0 level, which is good, but the hydrolysis resistance is Δ.
The IV was poor at 0.3.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

The photographic polyester film obtained by the present invention is flame-retardant and has transparency, handleability, heat resistance,
It has excellent dimensional stability, transportability, adhesion to photographic materials and magnetic media, little curling curl, and excellent image clarity. Further, since it is excellent in hydrolysis resistance and mechanical properties, it is suitable as a roll-shaped photographic film for general use. In addition, for X-ray photography, printing plate making, microfilm, electrophotography, diazo photography, etc., and O.
It can be used for photographs such as HP. Further, if it is whitened, it can be used for photographic paper or the like.

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Claims (4)

[Claims] 1. A base film is a polyester whose main repeating unit is ethylene-2,6-naphthalate, and a phosphorus atom derived from a phosphorus compound represented by the following formula: 0.01
-1% by weight and 0.01-3% by weight, and the total phosphorus atom content in the polyester is 0.05-3% by weight, which is a flame-retardant photographic polyester film for photographic use. O = P- - in _{[R 1 (OR 2) n} -X] 3 ( wherein, a divalent hydrocarbon group of R _1, R ₂ are carbon atoms respectively 1 to 20, X is an ester-forming functional group And
n is 0-500. ) [Chemical 1] (In the formula, R ₃ is a divalent hydrocarbon group having 1 to 20 carbon atoms, R _3
4 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ₅ and R ₆ are each a hydrogen atom or a monovalent hydrocarbon group having an ester-forming functional group having 1 to 10 carbon atoms. ) 2. The flame-retardant photographic polyester film according to claim 1, wherein an easy-adhesion layer is provided on at least one surface of the base film. 3. The easily adhesive layer has a relative humidity of 65 ° C. and a temperature of 25 ° C.
% Surface resistivity is 5 × 10 ¹² Ω / □ or less,
The flame-retardant photographic polyester film according to claim 1 or 2, wherein the contact angle between the surface of the easily adhesive layer and water is 50 degrees or more. 4. The easy-adhesion layer is provided on both surfaces of the base film, the photographic sensitive material layer is provided on one surface of the base film, and the magnetic layer is provided on the opposite surface of the base film.
The flame-retardant photographic polyester film as described in any one of 1 to 3 above.