JPS5922217B2 - Polyester film undercoating method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for priming polyester films.

In particular, the present invention relates to a process for priming biaxially oriented crystallized linear polyester for photographic purposes. In the past, various undercoating methods have been attempted, but as is well known, polyester polymers generally have high crystallinity and are linear chains that do not have active functional groups in their chemical structure. Due to the fact that it is a macromolecular substance, it is extremely hydrophobic, and it has been difficult to obtain good adhesion with hydrophilic photographic emulsions.

Conventional methods for making polyester polymers hydrophilic include surface treatments such as chemical treatment, electric discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Direct coating of photographic emulsion to obtain adhesion (for example, US Pat. No. 2,764,520, 3,497,407, 31,452)
No. 42, No. 3376208, No. 3072483, 347
No. 5193, No. 3360448, British Patent No. 78836
No. 5, etc.), and a method in which an undercoat layer is applied to the polyester after these surface treatments. Various efforts have been made to apply the coating method, including a multilayer method in which a hydrophobic resin layer that adheres well to polyester and has good solubility is applied as a layer, and a hydrophilic resin layer is applied as a second layer. There is a single layer method in which a resin layer containing hydrophobic groups and hydrophilic groups is applied during coalescence.

Since the method of applying the undercoat layer is excellent, much research has been conducted in this field, and many attempts have been made to date, including copolymers such as vinylidene chloride and acrylic acid as the type of resin used. However, it has been pointed out that the bonding method is complicated or the bonding strength is not sufficient. To compensate for this, it is inevitable that the undercoat solution contains a large amount of an etching agent that is highly polar, has a high boiling point, and is expensive, as a solvent that swells or dissolves the polyester. These etching agents include, for example, aromatic rings (benzene ring, naphthalene ring, pyridine ring, pyrrole ring, or their condensed rings, or alkyl, alkoxy, acyl, nitro, cyanide, halogen atoms, hydroxy, formyl, carboxy, carbomethoxy, hydroxy). , alkyl, carbamoyl, hydroxyalkoxy, aminoalkyl, etc.) or a compound having a partially hydrogenated aromatic ring, or alcohol, ketone, carboxylic acid, ester, aldehyde, etc. For example, British Patent Nos. 772600, 776157, 785789
No. 797425, US Patent No. 2830030, German Patent No. 1020457, Specification of German Patent No. 1092652, etc.)
There is. Specific examples of the above-mentioned solvents include benzoic acid, salicylic acid, salicylic acid ester, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-nitropropanol, benzyl alcohol, benzaldehyde, acetonylacetone acetylphenol. , benzamide, benzonitrile, benzyl alcohol, nitrobenzyl alcohol, chlorobenzyl alcohol, pyrrole, chloral hydrate, benzylamine, methyl nicotinate, and the like.

Other well-known polyester solvents or swelling agents include phenol, orthochlorophenol, parachlorophenol, cresol, resorcinol, and other phenol derivatives, which are often used. However, since these etching agents, especially phenolic substances, generally have a high boiling point of 150°C or higher, they require considerable heating time when drying the undercoat, and therefore, during the drying process, especially at the beginning, the penetration of the solvent may occur. Due to the increase in crystallinity, the support expands and its elastic modulus decreases, and in the later stages of this expansion, the support shrinks, which tends to significantly impair flatness.

Furthermore, phenols have strong skin permeability and reduce workability. Furthermore, if these substances are contained in factory exhaust or wastewater, they cause environmental destruction and require complete recovery. And this requires a huge amount of investment and equipment. Even with these methods, sufficient adhesive strength has not yet been easily obtained. In other words, in addition to the problems with handling and processing operations mentioned above, these methods require long processing times in order for these reagents to be effective, making high-speed processing almost impossible. It was hot. In view of the above points, the present invention provides a novel
Moreover, during the actual gluing operation, the length of 100 m during the manufacturing process was
The present invention was developed as a result of intensive research to develop a polyester undercoating formulation that would enable high-speed processing that could withstand the above processing, while also giving sufficient consideration to pollution issues, and that would provide excellent adhesive strength. It has been reached. That is, in the present invention, after subjecting a biaxially oriented crystallized linear polyester support to surface treatment by flame treatment, a polymer containing maleic acid or maleic anhydride and a specific addition-polymerizable monomer are added. An undercoat layer is provided by applying an undercoat liquid in which the polyester is dissolved or dispersed, thereby obtaining good adhesive strength between the polyester and the silver halide emulsion layer.

According to the undercoating method of the present invention, it is not necessary to include any of the above-mentioned etching agents in the undercoating solution, but if desired, specific components from among the above can be included in the undercoating solution.

The polymeric component of the basecoat composition comprises any suitable polymer, copolymer or terpolymer that provides suitable adhesion to the support film. Alternatively, one or more copolymers can be used to form a composite polymer component. The polymer containing maleic acid or maleic anhydride for the undercoating solution generally has a molecular weight of 5,000 to 500,000.
Polymers with a molecular weight of 100,000 to 400,000 are particularly effective.

In the case of copolymerization, monomers include styrene, methylstyrene, styrene sulfonic acid, chlorostyrene, styrene of acrylic acid or methacrylic acid (for example, methyl, ethyl, 2-700-3-hydroxypropyl, hydroxyethyl, 2, (3-dihydroxypropyl butyl, ethylhexyl, phenyl, styrene, etc.) or amides such as acrylamide, methacrylamide, acryloylmorpholine, diacetone acrylamide, vinyl esters such as acrylonitrile, vinyl acetate, vinyl propionate, vinyl benzoate, etc., and methyl vinyl ether , vinyl ethers such as butyl, vinyl ether, chloroethyl vinyl ether, and phenyl vinyl ether, and vinyl pyrrolidone. Alternatively, itaconic acid, acrylic acid, itaconic anhydride, vinylbenzoic acid, methacrylic acid, etc.
Hydrolysis of mono- or copolymers using β-unsaturated carboxylic acid esters, amides, etc. as starting monomers can also be used. Alternatively, a copolymer of maleic anhydride can be used as it is, in the form of hydrolysis, or in the form of a half ester. In particular, copolymers are advantageous from the viewpoint of ease of handling such as solubility in solvents.

In this case, it is advantageous for the proportion of maleic acid or maleic anhydride in the polymer to be, for example, from 40 to 80 mol percent, in particular from 50 to 75 mol percent.

These amounts are selected primarily to provide a composition that does not suffer from wet adhesion tests and in which the addition polymerizable monomer can be safely dispersed at room temperature. Further, addition polymerizable monomers to be used in combination with these maleic acid or maleic anhydride-containing polymers include the monomers mentioned above for use in copolymerization, such as acrylic acid, acrylamide, acryloylmorpholine, Diacetone acrylamide, methyl acrylate, butyl acrylate, amyl acrylate, ethyl/xyl acrylate, phenyl acrylate, methacrylamide, methyl methacrylate, hexyl methacrylate, methoxyethyl methacrylate, hydroxyethyl methacrylate, butyl vinyl ether, styrene In addition to so-called monofunctional monomers such as vinyl propionate, methyl itaconate, and butyl itaconate, divinylbenzene, diaryl phthalate,
Hexahydro 1,3,5-triacryl-S-triazine, N,N'-bisacryloylpiperazine, N,
Polyfunctional monomers such as N'-methylenebis-acrylamide and acryloxyethyl methacrylamide are effective, and one or more of these may be used. Among these, those having an acrylamide group or a methacrylamide group are particularly effective. In addition, the types of these monomers were selected with the focus on being able to be safely dispersed in water-soluble or water-dispersible copolymers, and the amount added was determined to be stable over time, including cooling operations if necessary. It is important not to cause a sudden increase in viscosity due to the water-soluble or water-dispersible copolymer.
~60% is added.

Alternatively, if necessary, a thermal polymerization inhibitor such as an aromatic ketone or an aromatic quinone may be contained in an amount of about 0.01 to 5% based on the addition polymerizable monomer. The undercoating solvent used in undercoating liquids containing these polymers and addition-polymerizable monomers may be water, and depending on the selection of copolymers, some organic solvents may not be necessary at all, but if desired, organic solvents may be used. Solvents can also be used. When using organic solvents, alcohol solvents such as methanol, ethanol, methoxyethanol, acetoxyethanol, and ethoxyethanol, ketone solvents such as methyl ethyl ketone, acetone, and acetophenone, ether solvents such as tetrahydrofuran, dioxane, and dimethoxyethane, or dimethylformamide, A polar solvent such as methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, or a mixed solvent of these with water is selected as necessary.

These contain the above polymer and addition polymerizable monomer at 0.01
It is selected so as to be dissolved or uniformly dispersed by about 10% by weight. Alternatively, the undercoating solution may contain other additives such as a reinforcing support for the undercoat layer or improving adhesion to the emulsion layer, an antistatic agent, a matting agent, and the like.

In addition, in order to prevent the decrease in intrinsic viscosity due to surface treatment of polyester and to ease the treatment conditions for the purpose of enabling repeated use, carboxyl groups, methylol groups, hydroxyl groups, oxirane groups, epoxy groups, isocyanate groups,
A crosslinking agent having an acetal group, a vinyl group, an oxy group, a carbodiimide group, a phenolic hydroxyl group, or a metal crosslinking agent may be added. There is no particular limit to the amount of the undercoating solution applied to the polyester, but it is generally advantageous to use an amount of about 1 to 109, particularly about 2 to 59, per square meter. Further, as the polyester used in the present invention, polyesters whose main components are aromatic dicarboxylic acids and aliphatic diols, and polyesters whose starting materials are aromatic carboxylic acids having aliphatic hydroxyl groups are used. Among them, aromatic dicarboxylic acids such as terephthalic acid, naphthalene dicarboxylic acid, and isophthalic acid, ethylene glycol, 1,4
- Polyesters with butanediol, propanediol, etc. are effective, and polyethylene terephthalate is particularly convenient from the viewpoint of availability of raw materials. Therefore, examples using this will be mainly described below. The present invention relates to a method for treating the surface of polyester, and although the thickness of the polyester used is not particularly relevant, it is a linear polyester that has been biaxially stretched and crystallized since it is used as a photographic support that requires dimensional stability. is valid.

The photographic emulsion to be coated is an emulsion containing gelatin, and is not limited by the materials dispersed or contained in the emulsion, such as color negative, color positive, black and white.

The method of the present invention is generally practiced as follows.

An undercoating liquid prepared by surface-treating a biaxially oriented crystallized linear polyester film support and then dispersing or dissolving a carboxyl group-containing polymer and an addition polymerizable monomer on the treated surface in the coating section. is applied and adjusted to the required amount using a squeeze roll or air knife, dried in the drying section, and wound up. An emulsion layer is applied onto this undercoat layer. Evaluations of adhesion tests between photographic film supports and emulsion layers conducted in the following examples are as follows. 1) Adhesion test when drying: Using a razor blade, make about 4 linear scratches in a mesh pattern on the emulsion side of the raw film, processed film, and dried film.
Apply adhesive tape that adheres well (for example, Scotch Permacel tape) on top of it and instantly peel it off.

In this method, if the peeled part is O~5% or more, it is classified as A grade.
A case of 5 to 30% is classified as B class, and a case of 30 to 100% is classified as C class. 2) Adhesion test during wet processing At each stage of development, fixing, and washing, two scratches were made crosswise on the emulsion surface of the film using a metal brush in the processing solution.
The scratched area is rubbed with the tip of a finger in a direction perpendicular to the line, and if the emulsion layer does not peel off more than the scratch, it is graded A, if the maximum peeling is within 511, it is graded B, and if it is larger than this, it is graded C.

Next, the present invention will be specifically explained with reference to operation examples and examples.

Example 1 30? A polyethylene terephthalate film support having a width of 200 μm and a thickness is subjected to flame treatment on both sides at the same time.

Polyethylene terephthalate film support is 100m
A flame is applied vertically at a speed of /MUL at a distance of 3 degrees to the treatment surface, and treatment is performed using combustion gas composition 1 described below. Furthermore, undercoat composition 1 was applied at a completely isolated application area at 140°C.
, let dry for 5 minutes. The area of the crater was 30 x 0.5 m. The base coating liquid is approximately 80% per square meter of polyester.
m1 was used. A photographic photosensitive film produced by coating and drying a gelatin-silver halide emulsion on a polyethylene terephthalate film support provided with this undercoat layer has an adhesive strength of A in a dry state, and an adhesive strength of A in a wet state after processing. It was hot.

Moreover, the photographic performance of the photosensitive film thus obtained was good. Example 2 The combustion gas composition was 2 and the processing speed was 500 m/min.

Thereafter, undercoat composition 1 was applied and dried at 150°C for 2 minutes. The photographic light-sensitive film thus obtained had a grade A adhesive strength both in dry and wet conditions, and had good photographic performance.

Actual example 3 Surface treatment was carried out under the same conditions as in Actual Example 1.

Thereafter, undercoat composition 2 was applied and dried for 2 minutes at 15'C. Approximately 80% of the undercoat liquid was used per square meter of polyester. Undercoat Composition 2 The photographic light-sensitive film thus obtained had a grade A adhesion strength both in dry and wet conditions and had good photographic performance.

Actual example 4 Surface treatment was carried out under the same conditions as in Actual Example 1.

Thereafter, the mother liquor was adjusted to pH 5 with aqueous ammonia, and undercoat composition 3 was applied, followed by drying at 150° C. for 2 minutes. Undercoating liquid composition 3 When drying the photosensitive film thus obtained,
Both the adhesive strength and the A-class photographic performance in the wet state of the treatment were good.

Actual example 5 Surface treatment was carried out under the same conditions as in Actual Example 1.

Thereafter, undercoat composition 4 was applied and dried for 15 minutes for 2 minutes. Undercoat Composition 4 The photographic light-sensitive film thus obtained had adhesive strength of Class A in both dry and wet conditions.

Extreme example 6 Surface treatment was carried out under the same conditions as in Actual Example 1.

Thereafter, undercoat composition 5 was applied and dried at 150°C for 12 minutes. Undercoating Liquid Composition 5 The photographic light-sensitive film thus obtained had a grade A adhesion strength both in dry and wet conditions, and had good photographic and adhesive properties.

Extreme example 7 Surface treatment is performed under the same conditions as Leprosy Example 1.

Thereafter, undercoat composition 6 was applied and dried for 15 minutes for 2 minutes. Undercoat Composition 6 The photographic light-sensitive film thus obtained had a grade A adhesive strength both when dry and when wet during processing, and had good photographic performance.

Actual example 8 Surface treatment was carried out under the same conditions as in Actual Example 1.

Thereafter, undercoat composition 7 was applied and dried for 15 minutes for 2 minutes. Undercoating Liquid Composition 7 The photographic light-sensitive film thus obtained had a grade A adhesion strength both in dry and wet conditions, and had good photographic performance.

Actual example 9 Surface treatment was performed under the same conditions as Example 1.

Thereafter, undercoat composition 8 was applied and dried for 15 minutes for 2 minutes. Undercoating liquid composition 8 The adhesive strength of the photographic photosensitive film thus obtained when dry and in the wet state of processing is both A grade and
Photographic performance was also good.

Preferred embodiments of the present invention are as follows.

1) In the claims, the polyester is linear polyester.

2) A polyester with an aliphatic diol containing terephthalic acid as an acid component in 1).

3) In the claimed polymers, the maleic acid or maleic anhydride is 50 to 75 mole percent.

Claims (1)

[Claims] 1 A polyester whose surface has been made hydrophilic by flame treatment, a polymer containing maleic acid or maleic anhydride, and acrylic acid, acrylamide, acryloylmorpholine, diacetone acrylamide, methyl acrylate, butyl acrylate, amyl acrylate , ethylhexyl acrylate, phenyl acrylate, methacrylamide, methyl methacrylate, hexyl methacrylate, methoxyethyl methacrylate, hydroxyethyl methacrylate, butyl vinyl ether, vinyl styrene propionate, methyl itaconate, butyl itaconate, divinylbenzene, diaryl phthalate, hexahydro
1,3,5-triacryl-s-triazine, N,N'
- Adhesion between the polyester and the silver halide emulsion layer by applying an undercoating liquid containing an addition polymerizable monomer selected from bisacryloylpiperazine, N,N'-methylenebis-acrylamide, and acryloxyethyl methacrylamide. A method for undercoating a polyester film, which is characterized in that it provides the following properties: