JPS63249842A - Photographic supporting body - Google Patents

Abstract

PURPOSE:To obtain an undercoated layer of the titled body having excellent transparency and anti-blocking property by incorporating a vinylidene chloride latex in the undercoated layer, and said undercoated layer coated with an aqueous polyester is provided on at least one surface of a photographic polyester film which is treated with corona discharge. CONSTITUTION:The vinylidene chloride latex is incorporated in the undercoated layer coated with the aqueous polyester. The used aqueous polyester is composed of a high polymer polyester formed by polycondensating a dibasic said and a dihydroxy alcohol, and especially, is composed of the polyester obtd. by dispersing polyethylene terephthalate in water. Thus, the titled body which has the excellent transparency and anti-blocking property, and has strong sticking power between the polyester film and a photographic hydrophilic colloid layer is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a support for a photographic polyester film for firmly adhering a photographic gelatin composition to a polyester film for a photographic light-sensitive material.

CB) Prior art and its problems It is well known that various methods have been tried in the past for subbing polyester films. However, polyester films generally have high crystallinity, are chemically stable, and are extremely hydrophobic, making it difficult to obtain good adhesion to hydrophilic photographic emulsion layers.

Conventional techniques that have been attempted to overcome such difficulties include chemical treatment, mechanical treatment, Discharge treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment,
A method of applying a photographic emulsion directly after processing such as laser treatment, mixed acid treatment, or ozone oxidation treatment to obtain adhesive strength;
On the other hand, there are two methods in which, after these surface treatments, a subbing layer is provided and a photographic emulsion is coated on top of this. Of these, the latter method is the most effective and widely used.

All of these surface treatments are believed to make the surface of polyester, which was originally hydrophobic, more or less hydrophilic by creating some copolar groups on the surface.

It is considered that as a result, the affinity between the polar groups contained in the undercoat layer and the polyester surface increases.

The method for applying the subbing layer is described in Japanese Patent Application Laid-Open No. 52-49019.
, No. 52-42114, No. 52-104913, a method in which a layer that adheres well to a polyester film is provided as a first layer and a hydrophilic resin layer is applied thereon as a second layer, and a method in which a hydrophilic resin layer is applied as a second layer; There is a method of applying only one resin layer containing both hydrophilic groups.

For example, copolymers using vinylidene chloride, vinyl chloride, methacrylic acid and acrylic acid and their esters, maleic anhydride, styrene, butadiene, etc. as starting materials, as well as JP-A-47-24270 and JP-A-51-30274
As shown in Figure 1, the grafted gelatin or nitrocellulose is dissolved in an organic solvent, and a compound such as p-chlorophenol or resol 7nol, which is a solvent or swelling agent for the support film, is added to support the subbing liquid. A method of applying it to the body film is used.

However, in the processing methods using these solvent-based subbing liquids, when the subbing liquid is applied and dried, solvent vapors that are harmful to the environment are emitted, which often interferes with the work. For this reason, it is necessary to invest a large amount of money in installing a solvent recovery device. In particular, the inclusion of the solvent or swelling agent for the support film in the subbing liquid not only releases harmful vapors, but also causes the film to lose its transparency, impairs the flatness of the film, and reduces the quality of the finish. Significantly worse alignment often occurs.

Therefore, as an undercoat processing method that improves this drawback, a method has been adopted in which an aqueous dispersion containing a copolymer of various monomers is used as a subbing liquid instead of a solvent-based subbing liquid. For example, a subbing method using an aqueous dispersion containing a butadiene-styrene copolymer and a subbing method containing a vinylidene copolymer are known. However, in order to provide excellent adhesion by applying an aqueous dispersion containing a copolymer to a hydrophobic film, the type of aqueous dispersion, processing conditions,
Selection is difficult and it is difficult to ensure sufficient adhesion.

Another method is to strengthen the undercoat layer by adding a polymer latex with a high Tg point to the undercoat layer. For example, JP-A-52
There is a method of including a synthetic copolymer having a glass transition point (CTg point) of 45°C or higher, such as -119919, in a copolymer of a diene monomer. There is a method of adding styrene particles to an acrylic acid ester copolymer. these are,
Both are methods of adding polymer latex that do not substantially form a film, and are undesirable because they have problems with the film-forming properties and transparency of the coating film.

In addition, the patent featuring polyester is
There are combinations of water-soluble polyester and gelatin cross-linking agents such as -53939, but this method inevitably causes blocking.

In addition, if a water-soluble polyester having a high Tg point is used for the purpose of avoiding blocking, the undercoat layer, which causes complete film formation, will be destroyed, resulting in insufficient adhesion, which is undesirable.

(C) Object of the Invention The first object of the invention is to provide a photographic support having a subbing layer with excellent transparency and excellent blocking resistance.

A second object of the present invention is to provide a photographic support having strong adhesion between a polyester film and a photographic hydrophilic colloid layer.

The third object of the present invention is that since it does not require the use of swelling or dissolving agents for polyester, no harmful organic solvents are released into the exhaust air or wastewater, and the photographic material can be used without causing pollution. It is to provide support.

A fourth object of the present invention is to provide a photographic support with excellent flatness.

A fifth object of the present invention is to provide a photographic support having a subbing layer comprising a subbing composition that can be stably and easily produced.

A sixth object of the present invention is to provide a photographic support having a subbing layer comprising the undercoat composition having good storage stability.

A seventh object of the present invention is to provide a photographic support that can be stably manufactured without causing fluctuations in undercoating performance even when the coating and drying conditions in the undercoating process vary.

CD) Structure of the Invention As a result of research on the subbing layer of a photographic polyester film support, the present inventors added vinylidene chloride latex to the subbing layer coated with water-based polyester at 25% of the total solid content of the subbing layer. - By containing the following, it was possible to obtain a desired photographic support particularly excellent in transparency and blocking resistance. This vinylidene chloride latex is commercially available under the name of Kureha Chemical ■Yo Shifure Halon Latex and Asahi Kasei ■Yo Shisaran Latex.

The water-based polyester used in the present invention is a high molecular weight polyester formed by polycondensation of a dibasic acid and a dihydric alcohol, particularly polyethylene terephthalate, which is dispersed in water. These are commercially available from Gooh Kagaku Co., Ltd., Nippon Gosei Kagaku ■, and Toyobo 0. The following exemplified compounds are shown as these commercially available polyesters.

Exemplary compound (1) Plus coat Z-450 same
(2) Polyester-XWR-930 (3)
Same as Polyester Indicates a copolymer.

Exemplary compound storage Fullhalon latex DOAX-2 (commercially available from Kureha Kagaku Yoshi) Same β) Saran latex 2-5
02 (Asahi Kasei Yoshi commercially available) The above two components are essential components of the present invention, but in addition, water-soluble polymers such as gelatin and cellulose, crosslinking agents such as compounds containing two epoxy groups in one molecule, etc. , inorganic fine particles such as colloidal silica, etc. may be added.

(E) Examples The invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

The evaluation of the adhesive strength between the support of the photographic polyester film and the emulsion layer in the following Examples was as follows.

(1) Adhesion test during drying Use a razor blade to make shallow scratches on the emulsion surface of the dry film in a mesh pattern, press adhesive cellophane tape on top of the scratches, and instantly remove the scratches. In this method, the case where the peeling part is 0 to 2% is marked with ○, and the case where it is 2 to 30% is Δ
mark, 30% to 100% is marked x.

(2) Adhesion test when processing is wet Make two cross-cutting scratches on the emulsion surface of the film in the processing solution using a metal pencil, then rub the scratched area with your finger in a direction perpendicular to the line to confirm that the emulsion layer Q: If it does not spread beyond the scratch
If the maximum width of the scratch spreads beyond the scratch, it is marked Δ, and if the scratch spreads beyond the scratch, it is marked X.

The evaluation of blocking resistance was as follows.

Cut the double-sided subbing layer film into a size of 50cm x 50m, stack 10 sheets together and apply a load of toKf to 50±
Leave it in an atmosphere of 5°C and 60±5% RH for 7 days. Take it out, peel off the film, measure the blocking area, and tally it up. As a result, θ~5chi is ○, 5~20
% is Δ, and 20 inches or less is X.

Transparency was evaluated by stacking 10 subbing layer films and examining their color tone. Those with good quality and no difference from the unsubbed film were rated 01, which was rated as Δ, and those with noticeable coloring were rated as X. In addition, those in which something like a precipitate was observed on the surface were also marked as x.

In the example, a subbing liquid of the following composition was applied to the corona-treated surface of an axially stretched and heat-set polyethylene terephthalate film with a thickness of 100 μm at a thickness of 10 μm per square meter using an air knife coater at 60°C. and dried for 1 minute. A silver iodobromide emulsion was coated thereon.

Subbing liquid 1° Example 2 A coating liquid as shown below was prepared and the same operation as in Example 1 was performed.

Subbing liquid 2° Example 3 A coating liquid as shown below at °C was prepared and the same operation as in Example 1 was carried out.

Subbing liquid 3゜Example 4 A coating liquid as shown below was prepared and the same operation as in Example 1 was performed.

Subbing liquid 4° Example 5 A coating liquid as shown below was prepared and the same operation as in Example 1 was performed.

Subbing liquid 5° The photographic films of Examples 1 to 5 thus prepared had good adhesion between the film support and the photographic emulsion layer, both in the dry state and during the development process, and were evaluated as O. The blocking resistance, photographic properties and transparency were also good.

Comparative example Comparative compounds used as comparative examples outside the present invention are shown below.

Comparative Compound (qPolystyrene Emulsion (Hoechst Synthesis ■, commercially available as Simo Vinyl)) The following subbing liquid was prepared and the same procedure as in Example 1 was carried out to prepare a comparative photographic film.

The results of the adhesion, transparency, and anti-blocking properties of the photographic film made in this manner are shown below.

CF) Effect of the invention As is clear from the above examples and comparative examples, a corona discharge treated photographic polyester film is provided with a subbing layer coated with water-based polyester, and the subbing layer is coated with chloride. It was confirmed that the photographic support, which is characterized by containing vinylidene latex, exhibits excellent adhesion to coating materials, excellent transparency, and good photographic properties.

Claims (1)

[Claims] (1) Photographic polyester film treated with corona discharge, at least one surface of which is provided with an undercoat layer coated with water-based polyester, and the undercoat layer contains vinylidene chloride latex. support.