JPS63246741A - Photographic supporting body - Google Patents

Abstract

PURPOSE:To improve the antiblocking and sticking properties of the titled body by incorporating <=40% a particle composed of 50-99% inorg. fine particle and 1-50% resin component in an undercoating layer coated with a vinylidene chloride latex, on the wt. basis of the total solid matter of the under coating layer. CONSTITUTION:The undercoating layer contains 5-40% particle composed of 50-99% inorg. fine particle and 1-50% resin component, and 60-95% vinylidene chloride latex, and the titled body provides with the undercoating layer so as to have the coating amount of said layer of 0.1-1g/m<2>, preferably, 0.2-0.8g/m<2> base don the solid matter contd. in said layer.Said two component of the inorg. fine particle and the resin component are essential components. However, a water soluble high polymer such as gelatin, cellulose, etc., and a cross-linking agent such as a compd. contg. two epoxy groups in one molecule, etc., may be incorporated in the undercoating layer. Thus, the anti-static and anti-blocking properties of the titled body are especially improved, and the strong sticking strength between a polyester film and a photographic hydrophilic colloidal 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 these difficulties include surface treatment of polyester-based polymer compounds, particularly hydrophilic treatment, to obtain adhesive strength with the photographic emulsion layer, including chemical treatment and 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, once these surface treatments have been completed, the undercoat Jl't
There are two methods: - providing a photographic emulsion and coating it with a photographic emulsion. Of these, the latter method is more effective and widely used.

All of these surface treatments seem to make the polyester surface hydrophilic by creating some copolar groups on the surface of the polyester, which was originally hydrophobic, and as a result, the polyester surface becomes hydrophilic. It is thought that the affinity between the polar group of the moiety 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 of forming a layer that adheres well to a polyester film as a first layer and coating it with a hydrophilic resin as a second layer; There is a method of applying only one resin layer containing both of the functional 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, a subbing liquid made by dissolving grafted gelatin or nitrocellulose in an organic solvent and adding a compound such as p-chlorophenol or resorcinol, which is a solvent or swelling agent for the support film, is applied to the support film. A coating method is used.

However, in the processing methods using these solvent-based subbing liquids, when the subbing liquid is applied and dried, organic solvent vapors that are harmful to the environment are emitted, which often causes problems in 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 transparency and flatness, resulting in poor quality. A permanent condition that significantly worsens the condition 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. In addition, blocking tends to occur on the undercoated surface coated with the aqueous dispersion.

Furthermore, a method of adding inorganic particles to a polymer undercoat layer to improve adhesion is described in JP-A-54-70029, but in general, inorganic particles and aqueous polymer dispersions have poor compatibility; for example,
In the case of colloidal silica, the subbing layer added to an aqueous dispersion of styrene-butadiene latex and gelatin becomes cloudy and does not have good adhesion, and has relatively good film formation properties below MPTO°C. The compatibility of colloidal silica with acrylic emulsions is also poor.
Furthermore, a subbing layer in which colloidal alumina is added to gelatin is described in JP-A No. 51-141620, but colloidal alumina is less transparent when coated than colloidal silica, and has poor compatibility with gelatin. inferior in terms of Also,
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-52-11
There is a method of incorporating a synthetic copolymer having a glass transition point (CTg point) of 45° C. or higher, such as No. 9919, into a copolymer of diene monomers. There is also a method of adding styrene particles to the acrylic ester copolymer. Both of these methods involve adding polymer latexes having different Tg points, which are undesirable because they have problems with the film-forming transparency of the coating film.

Furthermore, in an example using an aqueous vinylidene chloride dispersion, gelatin, and a plastic swelling agent as shown in JP-A-52-114670, adhesion was poor when the aqueous vinylidene chloride dispersion alone was used. Since a polyester swelling agent is used, this method is unfavorable from an environmental and manufacturing standpoint.

(C) Object of the Invention The first object of the present invention is to provide a photographic support that is particularly excellent in antistatic ability and antiblocking ability.

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. The purpose is to provide support.

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

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.

(D) Structure of the Invention As a result of research on the subbing layer of a photographic polyester film support, the inventors found that the subbing layer, which was completely coated with vinylidene chloride latex, contained 50 to 99% inorganic fine particles and 1 to 50% resin content. The desired photographic support could be obtained by including the particles in the subbing layer in such a manner that the content of the particles was 40% or less of the total solid content in the subbing layer. Particles consisting of inorganic fine particles and resin are described in JP-A-59-71316 and are commercially available from Dainippon Ink Chemical Co., Ltd. For example, these particles are made by using 1% or more of acrylic ester as a resin component and stabilizing the coupling of inorganic particles such as silica with a silane coupling agent.
9 inches, preferably 50 to 85 inches is effective.

The vinylidene chloride latex used in the present invention contains vinylidene chloride as a main component, and is commercially available from Kureha Chemical Co., Ltd. and Asahi Kasei Co., Ltd., for example.

The following exemplified compounds are shown as these commercially available vinylidene chloride latexes.

Exemplary compound (1) Flehalon latex DOAX-1
Same (2) Fullhalon latex DOAX-2 Same
(3) Saran Latex L-302 (4) Saran Latex L-502 Commercially available particles consisting of inorganic fine particles and resin that are effective in the present invention are exemplified compound (A) Silica 70 Ethylhexyl acrylate 30% (same) 50% silica 2-
Ethylhexyl acrylate 50% (both (A) and 03) are commercially available as Dainippon Ink Chemical ■Yoshibon Coat DV series). The average particle size of these particles is generally between 0.05 and 0.
．． It is 2μ.

As shown in the examples, in the present invention, vinylidene chloride latex t-60 to 95 t, inorganic fine particles 50 to 99 t, and resin content 1
Particles consisting of ~50% are mixed at a ratio of 5 to 40%, and the solid content coating amount is 0.1 to 1 t/r? , preferably 0.2
~0.8f/rr? The object of the present invention can be achieved if the subbing layer is coated so as to achieve the following.

The above two components are essential for the present invention, but water-soluble polymers such as gelatin and cellulose, crosslinking agents such as compounds containing two epoxy groups in one molecule, etc. may also 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 is 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 onto the scratches, and peel off instantly. In this method, when the peeled portion is 0 to 2 inches, it is marked ◯, when it is 2 to 30%, it is marked Δ, and when it is 30 to 100%, it is marked X.

(2) Adhesion test when processing is wet Make two cross-cutting scratches on the emulsion surface of the film using an iron brush in the processing solution, and then rub the scratched area with your finger in a direction perpendicular to the line to remove the emulsion layer. Q: If the damage does not spread beyond the scratch,
mark, if the maximum width is less than 5 baits, it is marked Δ, and if it spreads beyond the scratch, it is marked X.

The evaluation of blocking resistance was as follows.

Cut the double-sided draft film into a size of 50cm x 50m, stack 10 sheets together, apply a load of 10 to 9, and cut the film to 50±
Leave it in an atmosphere of 5°C and 60±51RH 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% or less is ×.

Transparency was evaluated by stacking 10 subbed films and examining their color tone. A good film with no difference from an unsubbed film was given O1 coloring as Δ, and a markedly colored film was given tx. In addition, samples in which something like a precipitate was observed on the surface were also rated as "X".

Example 1 On the corona-treated surface of a biaxially stretched and heat-set polyethylene terephthalate film with a thickness of 100 μm, a subbing solution of the following composition was coated with an air/oil 7 coater at a concentration of 20 − per square meter at 60°C. Dry 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 was prepared and the same operation as in Example 1 was performed.

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.

The photographic films of Examples 1 to 5 prepared in this manner showed good adhesion between the film support and the photographic emulsion layer, both in the dry state and during development. It was a mark judgment. The blocking resistance, photographic properties and transparency were also good.

Comparative example A lumi compound used as a comparative example outside the present invention is shown.

Comparative compound (Q silica 30% 2-ethylhexyl acrylate 70% (Dainippon Ink Chemical ■ Yo Shipon Coat D
(Commercially available as V) The same robolysterene emulsion (Commercially available as Hoechst Synthetic ■Yoshimo Vinyl) Same (
5) Acrylic acid ester emulsion (commercially available from Toagosei Kagaku Yoshi) Comparative Example A subbing liquid as shown below was prepared and the same operation as in Example 1 was carried out to prepare a comparative photographic film.

Lowering liquid 6° Lowering liquid 7° Lowering liquid 8° Lowering liquid 9° Lowering liquid 10° Lowering liquid 11° The results of the adhesion, transparency, and blocking resistance of the photographic film made in this way are as follows. show.

(F) Effect of the invention As is clear from the above examples and comparative examples, a subbing layer is provided on a photographic polyester support by coating an aqueous dispersion of a synthetic polymer containing 0% or more of vinylidene chloride fnia. When the undercoat layer contains 40 or less particles containing 50 to 95% inorganic fine powder, the obtained photographic polyester film support has excellent blocking resistance,
In addition, it was confirmed that the coating material had excellent adhesion to the coating material.

Claims (1)

[Claims] (1) A subbing layer coated with vinylidene chloride latex is provided on at least one surface of a corona discharge-treated photographic polyester film, and the subbing layer contains 50 to 99% inorganic fine particles and 1 to 50% resin content. Contains particles consisting of %,
A photographic support characterized in that the content of the particles is 40% or less of the total solid content in the subbing layer.