JPS62232646A - Photographic support - Google Patents

Abstract

PURPOSE:To form a photographic support having strong adhesion between a polyster film and a photographic hydrophilic colloidal layer by incorporating in a subbing layer, grains composed of fine inorganic particles and a resin component in an amount of >=40wt% of the total solid of the subbing layer obtained by coating with an aqueous dispersion of polyester. CONSTITUTION:The subbing layer obtained by coating with an aqueous dispersion of polyester, such as linear saturated high-molecular weight polyesters obtained by polycondensation of dibasic acid and divalent polyol, especially, polyethylene terephthalate, contains, in an amount of >=40wt% of the total solid of the subbing layer, the grains composed of 50-99% fine inorganic particles and the 1-50% resin component. for example, these grains are composed of the >=1% acrylate ester as the resin component, and the fine inorganic particles, such as silica, stabilized by coupling it with a silane coupling agent or the like, and it is preferred to use the fine inorganic particles in an amount of 50-90%, especially 50-85%.

Description

DETAILED DESCRIPTION OF THE INVENTION 4. 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.

(Bl Prior art and points of interest) It is well known that many methods have been tried for subbing polyester films.However, polyester films generally have high crystallinity and are chemically stable. It has been difficult to obtain a hydrophilic photographic emulsion layer and good zonal strength because of its extremely strong hydrophobicity.

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,
One method is to apply a photographic emulsion directly after treatments such as laser treatment, mixed acid treatment, and ozone oxidation treatment to obtain adhesive strength.
There are two methods: t is provided and a photographic emulsion is applied thereon. Of these, the latter method is more effective and widely practiced.

All of these surface treatments are thought to make the surface of the polyester, which was originally hydrophobic, more or less hydrophilic by creating copolar groups on it, and as a result, the surface of the polyester, which was originally hydrophobic, becomes hydrophilic. It is thought that the affinity between the polyester group 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 the g1 layer and applying a hydrophilic resin layer as a second layer thereon, and a method of applying a hydrophilic resin layer with a hydrophobic group There is a method of applying only one resin layer containing both of the functional groups.

Examples include co-monomers 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-B No. 47-24270 and JP-A No. 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, processing methods using these solvent-based subbing liquids, except for coating and drying the subbing liquid, emit vapors of surface-like solvents that are harmful to environmental hygiene, and often cause 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, containing the bathing agent or swelling agent for the support film in the subbing liquid not only releases harmful vapors, but also causes loss of film transparency and poor finish quality, such as impairing the flatness of the film. Alignment 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 various heptad copolymers 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, hydrophobic films can be subbed with aqueous dispersions containing copolymers to provide excellent adhesion.

In order to reduce the adhesive strength, it is difficult to select the Si type and processing conditions of the aqueous dispersion, and it is difficult to ensure sufficient adhesion.

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, when it is added to an aqueous dispersion of styrene-butadiene latex gelatin and coated, the sublayer becomes cloudy and has poor adhesion. Furthermore, as will be described in Examples, colloidal silica is not well-compatible with acrylic emulsion at temperatures below MPTO° C., which has relatively good film-forming properties. Furthermore, a subbing layer in which colloidal alumina is added to gelatin is described in JP-A-51-141620, but colloidal alumina is
It has poor transparency when applied and poor compatibility with gelatin. Also, there is a method of adding a polymer latex with a high Tg point to the undercoat layer to strengthen the undercoat layer. For example, there is a method of incorporating a synthetic copolymer having a glass transition point (Tg point) of 45 DEG C. or higher into a copolymer of diene monomers, as disclosed in JP-A No. 52-119919. 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.

In addition, the patent featuring polyester is
Although there are combinations of water-soluble polyester gelatin cross-linking agents such as -53939, this method does not prevent the occurrence of blocking.

Furthermore, 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 not preferred.

Further, as shown in Examples, when fine powder particles such as colloidal silica are added for the purpose of preventing blocking, the transparency of the undercoat film and the adhesive strength at the @i threshold decrease.

(Q. Purpose of the Invention The first object of the present invention is to provide a photographic support having strong adhesive strength between a polyester film and a photographic hydrophilic colloid layer.

The second object of the present invention is that it does not require the use of lubricants or solubilizers for polyester, so it does not release harmful organic solvents into exhaust gas or waste water, and it is a cost-effective solution. It is an object of the present invention to provide a photographic support that can be used in the following manner.

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

A fourth object of the invention is to provide a photographic support having a subbing layer comprising the undercoat composition which can be stably and easily produced.

A fifth object of the invention is to provide a photographic support having a subbing layer comprising the undercoating composition which has good storage stability.

A sixth object of the present invention is to provide a photographic support that can be stably manufactured without causing fluctuations in subbing performance even when the head cloth and drying conditions change during the subbing coating process.

A seventh object of the present invention is to provide a photographic support having a sublayer that is excellent in antistatic ability and antiblocking ability.

Plow Structure of the Invention As a result of research on the subbing layer of photographic polyester film supports, the inventors found that 12 points were found in the subbing layer coated with water-based polyester at a temperature of 50°C or less, containing 50 to 99% of inorganic fine particles.
and particles having a resin content of 1 to 50%, and are incorporated into the subbing layer so that the content of the particles is 40% or less of the total solid content of the subbing layer, thereby forming the desired photographic support. I was able to obtain Particles consisting of inorganic fine particles and resin are described in JP-A-59-71316 and are commercially available, for example, 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 coupling and stabilizing inorganic particles such as silica with a silane coupling agent. 50 to 85 rice cakes are effective.

The aqueous polyester used in the present invention is a linear polymer formed by polycondensation of a dibasic acid and a dihydric alcohol, and a saturated polyester, particularly polyethylene terephthalate, is dispersed in water.

These are commercially available from Nippon Gosei Kagaku Csu and Toyobo. The following exemplified compounds are shown as these commercially available polyesters.

Exemplary compound (1) Polyester-XWR-930 (Tg
=0℃) Same (2) Polyester-XWR-950 (
Tg=34℃) Same (3) Pyronal MD-1
400 (Tg=19℃), same (41 pyronal
MD-1530 (15°C) Polyester; Polyester Pyronal manufactured by Nippon Gosei Kagaku@; Polyester manufactured by Toyobo@ In addition, examples of commercially available particles consisting of non-imitation particles and resin that are effective in preventing inventions are listed below. Silica 70% 2-ethylhexyl acrylate 30%mt
(Bl 50% silica, 50% 2-ethylhexyl acrylate ((3), both sold for 7 hours as Boncourt DV series by Dainippon Ink Chemical ■). The average particle size of these particles is generally 0.05-0.2μ
It is.

As shown in the examples, in the present invention, the water-based polyester is
95%, Muden 9i particles 50-99% and resin content 1-50%
(mixed at a ratio of 5 to 40, with a solid content of 50 to 600, preferably 100 to 500
The object of the present invention can be achieved if the entire undercoat layer is coated so as to have a ratio of 1 q/d.

The above two components are essential components for the present invention, but in addition, a water-soluble polymer such as gelatin cellulose,
A linking agent such as a compound containing an epoxy group may be added.

(g) Examples The invention will be further explained in more detail with examples, but the embodiments of the present invention are not limited thereto.

In addition, the evaluation of the adhesion force between the support of the photographic polyester film and the emulsion layer in the following examples was performed using the following i! It is 19.

(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, then crush the cellophane tape that adheres well on top of it and peel it off instantly. In this method Haku 4
If the L part is 0 to 2 inches, mark ○, and if it is 2 to 30%, mark Δ
mark, 30% to 100% is marked x.

(2) Adhesion test when processing is wet Use a pencil to make two scratches on the emulsion surface of the film in the processing solution, and then rub the scratched area with your finger in a tenth direction perpendicular to the green. Make sure the emulsion layer does not spread beyond the scratches.
mark, Δ mark if it spreads beyond the scratch and the width is within 5W, and mark X if it spreads beyond the scratch and is hard to heal.

The evaluation of blocking resistance was as follows.

Cut the double-sided double-sided film into a size of 50mm x 50mm, stack 10 sheets together, apply a load of 10Kf, and cut the film to 50mm x 50cm.
Leave it for 7 days in an atmosphere of 5° C. and 60±5% R, )i. Take it out, peel off the film, measure the blocking area, and total it. As a result, 0~5% is Q, 5~
201% is Δ, and 20% or less is ×.

In addition, the transparency was evaluated by stacking 10 subbed films and examining their color tone. Those with no difference from the unsubbed film were rated ○, those with color were Δ, and those with noticeable color were rated ×. . Also, those in which something like a precipitate was observed on the surface of the 7IC were also rated as "X".

In the example, a subbing liquid of the following composition was applied to the corona-treated surface of a 100 μm thick polyethylene terephthalate film that had been axially stretched and heat-set at a concentration of 10 −/m2 using an air knife coater and dried at 60° C. for 1 minute. did. A conjugated silver iodo emulsion was applied thereon.

The photographic film thus produced had good contact between the film support and the photographic emulsion layer both in the dry state and during the development process, and had an O-print rating. Photographic properties and transparency were also good.

Example 2 A liquid solution as shown below was prepared and the same operation as in Example 1 was carried out.

Subbing liquid 2° The photographic film thus produced had good adhesion between the film support and the photographic emulsion layer, both in the dry state and during development, and was judged as O.

The photographic properties and transparency were also good.

Example 3 Blood as shown below was prepared and the same operations as in Example 1 were performed.

Subbing liquid 3° The photographic film thus produced had good adhesion between the film support and the photographic emulsion layer, both in the dry state and during the current processing, and was evaluated as ○.

The photographic properties and transparency were also good.

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

Undercoat 7 nights and 4° The photographic film thus produced had a good clear layer between the film support and the photographic emulsion layer both in the dry state and during the development process and was evaluated as ○.

The photographic properties and transparency were also good.

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

Subbing liquid: 5° The photographic film thus produced had good contact between the film support and the photographic emulsion layer, both in the dry state and during development, and was evaluated as ○.

The photographic properties and transparency were also good.

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

Comparative compounds (Q 30% silica, 70% 2-ethylhexyl acrylate (commercially available as Boncoat DV from Dainichi Ink Chemical Co., Ltd.) Polystyrene emulsion (commercially available as Movinyl from Hoechst Synthesis ■) Pyronal MD -1200 (Tg=67°C) (Aqueous polyester commercially available from Toyobo) 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.

Subtraction liquid 6° Subtraction liquid 7° Subtraction liquid 8 Subtraction liquid 9 Subtraction g10 Subtraction liquid 11 The results of the adhesion, transparency, and blocking resistance of the photographic film thus prepared are shown below.

(F) Effect of the invention As is clear from the above examples and comparative examples, a subbing layer containing a polyester having a Tg point of 50°C or less is provided on a photographic polyester support, and the subbing layer is made of an inorganic material. The photographic polyester film support obtained when the undercoat layer contains 40% or less of particles containing 50 to 95 particles of fine powder has excellent blocking resistance and excellent adhesion to the coating material. It was confirmed that it was.

Claims (1)

[Claims] A subbing layer coated with a water-dispersed polyester having a Tg point of 50°C or less is provided on at least one surface of the corona discharge-treated photographic polyester film, and the subbing layer contains 50 to 99% of inorganic fine particles and a resin content. 1-50% of the particles, and the content of the particles is 40% of the total solids in the subbing layer.
% or less.