JPS5858660B2 - Shashinyouso - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to photographic elements, and more particularly to photographic elements provided with subbing layers containing certain components.

Conventionally, various subbing layers have been studied in the field of photographic science in order to provide a hydrophilic layer on a hydrophobic support.

For example, natural polymers such as gelatin and synthetic polymers such as vinylidene chloride copolymers are being considered as binders for the undercoat layer.

By the way, the conventional undercoating method using organic solvents is complicated and has the risk of explosion and pollution.In recent years, undercoating methods and undercoating liquid compositions that do not require the use of organic solvents have been developed. Product development is booming.

We have already investigated an undercoat layer that does not use an organic solvent in Japanese Patent Application No. 39527.

There, it was shown that water dispersion is particularly effective as a constituent of the undercoat layer.

However, when an undercoat layer containing water-dispersed silica is applied to a photographic film support and dried, depending on the composition of the undercoat liquid, the undercoat layer develops a milky white color and becomes opaque (hereinafter referred to as a whitening phenomenon). Sometimes.

If the whitening phenomenon occurs in the undercoat layer, it will remain as a haze on the photographic film even after the photographic film is developed.
It may impair photographic performance.

In general, when a low-boiling organic solvent is used as a solvent for an undercoating liquid, a so-called brushing phenomenon tends to occur, but it is known that this can be prevented by adding a high-boiling organic solvent.

However, the cause of the whitening phenomenon that occurs when water is used as the solvent of the undercoating liquid as in the present invention is different from the brushing caused by the influence of moisture when an organic solvent is used.

That is, it is thought that this is caused by a change in the dissolution or dispersion state of water-dispersed silica during the drying process.

However, no technique for preventing the whitening phenomenon of the undercoat layer due to such causes has been proposed so far.

An object of the present invention is, first, to provide a photographic element using certain components as a subbing layer.

A second object of the present invention is to provide a photographic element coated with an undercoating solution containing water-dispersed silica, which prevents the whitening phenomenon that tends to occur when drying.

A third object of the present invention is to provide an undercoat composition using an aqueous solvent.

That is, the present invention provides a photographic element provided with an undercoat layer containing water-dispersed silica and an alkali aluminate salt.

Each component used in the present invention will be explained in detail.

Component (A): Water-dispersed silica As the water-dispersed silica, a colloidal solution in which fine particles of silicic anhydride of about 5 to 200 mμ are dispersed using water or methanol as a dispersion medium is used.

These colloidal solutions of silicic anhydride include the following commercially available products, which can be used particularly conveniently.

For example, 6 Cyton'' manufactured by Monsanto Company in the United States, ``Ludotux'' manufactured by DuPont, Nalcog manufactured by Nalco Chemical Company, and Snowtex manufactured by Nissan Chemical Company are commercially available.

Other water-dispersed silicas described in Japanese Patent Application No. 50-39527 can also be used.

Although there are no particular limitations on the physical properties of the water-dispersed silica used in the present invention, particle diameters of approximately 1 to 100 mμ are particularly preferred.

Furthermore, water-dispersed silica alone has little effect on matting the surface of the undercoat layer.

Therefore, when matting is required, it is more convenient to separately add a matting agent.

The water-dispersed silicas described above have antistatic properties, which also provide advantageous performance to the photographic elements of this invention.

(B) Component; alkali aluminate salt The alkali aluminate salt includes aluminum oxide,
Refers to salts formed from metal oxides that are more basic than these.

There are various methods for producing aluminate, and the aluminate can be synthesized by a well-known method.

For example, sodium aluminate is produced by mixing and heating aluminum oxide and sodium oxide.

Alternatively, it is synthesized by reacting sodium hydroxide with aluminum hydroxide.

These are not special products and can be easily obtained commercially.

In the present invention, the aluminate includes hydrated metaaluminate, hydrooxoaluminate, and anhydrous aluminate.

Specific examples thereof include sodium aluminate, sodium metaaluminate, anhydrous potassium metaaluminate, calcium aluminate, barium aluminate, and the like.

Among these, potassium aluminate, sodium aluminate, and the like are particularly advantageous in terms of ease of handling and effectiveness.

In the present invention, it is important to contain both of these (4) and CB), and thereby various effects described below can be achieved.

Water is suitable as the undercoat solvent of the present invention, but an organic solvent or a combination of water and an organic solvent can also be used if necessary.

When using an organic solvent, it is desirable to use one that is highly miscible with water, such as methanol, ethanol, acetone, dioxane, and the like.

Among these, those skilled in the art can easily select one or more of them with reference to solubility, ease of drying, reactivity, odor, compatibility with water, price, etc.

Generally, there are only a few base coating liquid compositions in which water or an aqueous solution of an organic solvent that is compatible with water can be used as a base coating solvent, and the bark of the present invention provides one of them. .

The amount of these solvents is 0.001 for the above country, component (B)
It is selected so that about 20% by weight can be dissolved or uniformly dispersed.

It is more convenient to add various additives to the undercoat layer of the present invention in addition to these components.

For example, etching agents, undercoating polymers, etc. are particularly effective in improving adhesion.

The undercoating polymer may be a synthetic resin (generally a polymer or copolymer) or a natural polymeric substance such as gelatin.

The term gelatin referred to herein also includes gelatin obtained by graft polymerization of so-called vinyl monomers.

The undercoat polymer also includes a so-called latex polymer.

Regarding these, U.S. Patent No. 3,193,386, U.S. Pat.
, No. 411,911, No. 3.488,708, No. 3,
No. 589,906, No. 3.615,556, etc., and the components can be selected from these.

Etching agents include phenol, resorcinol,
There are aromatic compounds having one to three hydroxyl groups, such as phloroglucin.

These are used in an amount of about 0.1 to 5 ji/rrr.

Moreover, it can contain various other additives as required.

For example, coating aids, anionic, nonionic, or cationic surfactants for the purpose of improving wetting (e.g., saponin, polyethylene glycol ether described in U.S. Pat. No. 2,831,766, U.S. Pat.
, acylated taurine described in U.S. Pat. No. 739,891, maleopimarate salts described in U.S. Pat. In addition, matting agents such as silica particles and polymer matte particles (for example, JP-A-48-85130, JP-A-49-5125, US Pat. No. 3,247,127, US Pat. No. 3,653,905, US Pat. No. 3,653,905, No. 379,533, No. 3.658,670,
Dyes and pigments such as manganese dioxide, etc. described in British Patent No. 584,609, etc.); Dyes or pigments for antihalation, dyeing, etc.; Antistatic compounds (for example, U.S. Pat. No. 3,525,621, No. 3,658,573, No. 3,630,742, No. 2,074,647,
2.279,410, Japanese Patent Publication No. 46-24158, etc.); Appropriate hardening agents such as formaldehyde, aldehyde compounds such as glyoxal, mucochromic acid, tetramethylene 1,4-bis ( Compounds with ethyleneimino groups such as ethylene urea), hexamethylene-1,4-bis(ethylene urea), active vinyl compounds such as metaxylene divinyl sulfone, and active halogens such as 2-methoxy4,6-dichlorotriazine. compounds having epoxy groups such as bisphenol glycidyl ether, isocyanates, and other polymers, copolymers, or dispersions thereof for the purpose of improving one-dimensional stability.

With conventional undercoating fluids, it is often not possible to obtain sufficient adhesion between the polyester and the photographic emulsion layer by simply applying a single layer to the surface of the polyester. It is common practice to coat polyester with appropriate additives and then coat a second layer thereon.

Gelatin, which has good adhesion to the hydrophilic layer, is often used as one of the components of the second layer.

Both components (4) and (B) of the present invention may be applied to either of the above layers.

In addition, according to the present invention, (B) a single layer of the subbing layer containing both components is sufficient for the hydrophobic film base and the various layers (described below) provided on the subbing layer. It has strong adhesive strength.

There is no particular restriction on the amount of components (4) and (B) used in the undercoat layer, but usually when this undercoat composition is applied directly to the polyester surface, the amount of component (4) is 1×10 -6
9/m to 5 g/m, preferably 0.05 to 0
．． 3g/m': degree, the ratio of component (B) to the solid content of component (4) is 1. It is convenient to add OX 10-' to 200 wt%, preferably 1.0 x 10-2 to 50 wt%.

The photographic film support on which the undercoat layer containing these components is provided may be a hydrophobic polymer compound such as cellulose ester (specifically, cellulose acetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butylene). polystyrene, polycarbonate, polyolefin, polyester (specifically polyethylene terephthalate, poly1
．． 4-Cyclohexane-dimethylene terephthalate and polyethylene-1,2-diphenoxyethane-4,4
'-dicarboxylate).

Among these, the most preferred from the viewpoint of physical properties is biaxially stretched polyethylene terrestrial film.

According to the present invention, a coating solution containing the above components is applied to a biaxially stretched and heat-set polyester film without any special surface treatment (e.g., mixed acid treatment, flame treatment, corona discharge treatment, etc.). However, these surface treatments may be performed as necessary.

It can also be applied to unstretched or uniaxially stretched polyester films.

On the undercoat layer containing the components of the present invention, in addition to photographic gelatin layers such as a photographic gelatin silver halide emulsion and an antihalation layer, for example, a diffusion transfer image-receiving layer, a diazo photosensitive composition, a photosensitive resin composition, a magnetic material, etc. Even if various types of adherent substances are applied, they will be firmly adhered and their properties will not be impaired.

The undercoating composition of the present invention and each layer of the photographic material may be coated by various coating methods including dip coating, air knife coating, curtain coating, or extrusion coating using a popper as described in U.S. Pat. No. 2,681,294. It can be applied by method.

U.S. Pat. No. 2,761,791, 3.5 as appropriate.
08,947, 2,941,898 and 3.526
, No. 528, etc. can also be used.

Since the photographic element of the present invention has an undercoat layer coated with an undercoat liquid containing the above-mentioned components (4) and (B), this provides good adhesion between the hydrophobic film surface and the photographic emulsion layer. be able to.

Since the photographic element of the present invention can be so-called aqueous undercoated using water as the main solvent, the manufacturing process can be simplified compared to the conventional method, and there is no risk of explosion or pollution that tends to occur when organic solvents are used. There is no sex.

Since the photographic element of the present invention has a novel undercoat layer containing both components (4) and (B) as described above, it is possible to prevent the whitening phenomenon that tends to occur when water-dispersed silica is used.

This is an unpredictable and completely new effect.

Since the constituent components of the undercoat layer used in the present invention do not contain anything that would degrade photographic performance, very favorable results can be obtained as a photographic element.

Furthermore, the photographic elements of this invention have improved antistatic properties.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

The numerical values in the following examples indicate weight % unless otherwise stated.

EXAMPLE A solution having the following composition was applied to an axially stretched polyethylene terephthalate film support using a roll coater at a rate of 20 cc per liter.
It was applied at.

Then, it was dried at 125°C for 5 minutes.

Latex polymer (composition, molar ratio: vinylidene chloride/methyl acrylate/acrylic acid = 83/15/2) 3.00 saponin 0.02 resorcin
3. OO distilled water
93.98 Divide the film obtained here into three equal parts and divide them into the following I,
The undercoat composition II was applied using a 20CC roll coater per 177+'', and then dried at 120° C. for 5 minutes.

Liquid I Seven Latin Saponin Chrome Muuno Kun Colloidal Silica (Nichichi Kagaku Snowtex N) Resorcin Distilled Water Liquid R Gelatin 0.60 0.02 0.01 0.20 3.00 96.17 0.60 Saponin 0.02 Chrome Miyuunokun 0.01 Colloidal Silica
0.20 (Nichichi Kagaku Snowtex N) Potassium aluminate 0.0 Lusorcin
3.00 Distilled water 96.1 Comparing the surface condition of the film coated with liquid I and ■, I
Although the liquid caused surface whitening, a transparent surface was obtained with the liquid (2).

Example 2 The following undercoating liquid compositions I and IV were applied to a biaxially stretched polyethylene terephthalate film support at a rate of 2 times per 1r11'.
After coating with a 0cc roll coater, it was dried at 125°C for 5 minutes.

■Liquid gelatin 0.30 Colloidal silica 0.60 (Nichikagaku Snowtex N) Resorcin 3.00 Saponin
0.02 distilled water
96.08 ■Liquid gelatin 0.30 Colloidal silica 0.60 (Snowtex N manufactured by Nichikagaku Co., Ltd.) Resorcin 3.00 Saponin
0.02 Sodium aluminate
0.04 Distilled water 96.0
4 Comparing the surface conditions of the films coated with these liquids (2) and (2), liquid whitening and repellency were observed with liquid (2), but no whitening or repellency was observed with liquid (2).

In addition, a photographic emulsion was coated on a polyethylene terephthalate base that had been primed with liquid (1), but the photographic emulsion and film base support had good adhesion during drying of the emulsion coating and during processes such as development, fixing, and water washing. was obtained, and no problems occurred with respect to photographic performance, such as fog and sensitivity.

Claims (1)

[Claims] 1. A photographic element characterized by being provided with an undercoat layer containing water-dispersed silica and alkali aluminate.