GB2026201A - Photographic material having a writing quality-imparting layer - Google Patents

Abstract

A photographic material having on the image-viewing side thereof an image for the picture and a non-image portion, e.g. a border or margin, and on the surface of the non-image portion alone a layer comprising a binder and a matting agent which allows writing, e.g. with a pencil or an aqueous ink, to be readily made on the non-image portion. The matting agent comprises particles, e.g. of silica. When the non-image surface is hydrophilic, e.g. gelatin, the binder thereon can be a protein, cellulose ether, sugar derivative or hydrophilic polymer. When the surface is hydrophobic, e.g. a cellulose ester polyester or acrylic polymer, the binder thereon is one which is soluble in a solvent for the hydrophobic surface, such as a vinyl or vinylidene chloride (co)polymer, cellulose ester, amorphous polyester, polydiene or polymer of (meth)acrylic acid. On a hydrophobic surface a mixture of a hydrophobic and hydrophilic binder is preferred, e.g. on a cellulose ester a mixture of a cellulose ether and cellulose ester. The surface layer is coated in strips or on the margins of a material for making a light-sensitive silver halide photo- graphic material, e.g. a diffusion- transfer unit.

Description

SPECIFICATION Photographic material having a writing quality-imparting layer This invention relates to a photographic material and, more particularly, to a photographic film unit having a layer thereon capable of being written on with a pencil, a fountain pen, a marking pen, or the like (hereinafter this layer is referred to as a writing quality-imparting layer) at a non-image portion on the image-viewing side of the unit.

The materials are generally silver halide photographic materials.

On the side of a photographic material from which the image is viewed there is an image portion 1 in which the picture appears and a non-image portion 2 which is generally a white border or margin which frames the image portion las shown in Figures 1 and 2. Specific examples include color photographic prints, black-and-white photographic prints and diffusion transfer type film units.

These photographic materials are widely used among amateurs. The surface of the image-viewing side of the units is usually (i) a smooth surface comprising a hydrophilic polymer like gelatin, (ii) a smooth surface comprising a hydrophobic polymer like diacetyl cellulose, (iii) a so-called matt surface comprising gelatin and organic or inorganic fine particles (for example, fine particles of polymethyl methacrylate, silicon dioxide, or the like having a particle size of about 0.1 to 10 > ), or (iv) an uneven gelatin surface formed by embossing a polyethylene film surface and coating thereon a silver halide emulsion layer and a surface-protecting gelatin layer such as the surface of so-called "non-glossy paper" for color photographic prints.These surfaces on an image-viewing side have the same surface qualities in both the image portion and a non-image portion, and the two portions are not different from each other in the surface smoothness (or surface roughness). The non-image portion has almost no ability to be written on with a pencil, fountain pen, marking pen, ball-point pen, etc.

Some matt surfaces comprising gelatin and a matting agent (described in (iii) above) have a slight writing ability but when the matting agent is used in amounts large enough to impart sufficient writing quality, the image quality of the image portion is seriously reduced. Thus, there is a limit on the amount of the matting agent that can be used and from the standpoint of writing quality it is quite insufficient.

The ability to write photograph data such as the date and the place the photograph was taken and some memoranda on the surface of the image-viewing side of a photographic material is extremely convenient and hence photographic materials enabling such writing have been eagerly desired.

In particular, diffusion transfer type film units, as described in Japanese Patent Applications (OPI) Nos.

153628175 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application") and 42217173 and U.S. Patent 3,954,476 have, on the image-viewing side, a surface comprising a polymer such as a cellulose ester and have almost no writing quality. It is very desirable for diffusion-transfer type film units to have writing quality in the non-image portion of the surface on the image-viewing side in view of their special uses and the special manner for using them.

We have now discovered that a photographic material having writing quality in a non-image portion can be obtained, without reduction of image quality in an image portion, by providing a writing quality-imparting layer on the surface of the image-viewing side in the non-image portions only.

The photographic material of the present invention has a writing qualfty-imparting layer on the surface of the image-viewing side in the non-image portion only and hence the image portion and the non-image portion are different from each other in surface smoothness.

In the accompanying drawings: Figures land 2 are planar views showing the image-viewing sides of conventional photographic film units each having an image portion (1) and a non-image portion (2) on the image-viewing sides; Figure 3 shows a support for a diffusion-transfer type light-sensitive material, which has three writing quality-imparting layers (2, 2', 2") on support (1) as used in Example 2; and Figure 4 is a planar view showing a photographic film unit according to the present invention having a writing quality-imparting layer (3) on a non-image portion (2) on the image-viewing side.

The writing quality-imparting layer in accordance with the present invention is a layer comprising a matting agent and a binder. The matting agent consists of fine particles of an organic material like polymethyl acrylate or fine particles of an organic material such as silicon dioxide (silica), calcium carbonate, magnesium carbonate, titanium oxide, aluminum oxide, barium sulfate or glass dust. Of these, fine particles of silicon dioxide are particularly preferred. The particle size of the matting agent is preferably in the range of from 0.1 to 10 , in particular 1 to 8y.

In the present invention, the binders for the writing quality-imparting layer include various hydrophilic and hydrophobic polymers. These binders are selected such that there is good adhesion between the non-image portion and the writing quality-imparting layer, they are compatible with the matting agents, and can be coated consecutively to the layer forming the non-image portion.

Where the surface of the non-image portion comprises a hydrophilic polymer such as gelatin, proteins such as gelatin and casein, cellulose ethers such as methyl cellulose, hydroxyethyl cellulose or carboxymethyl cellulose, sugar derivatives such as sodium alginate or starch derivatives, and hydrophilic polymers such as polyvinyl alcohol, poly-N-vinylpyrrolidone or polyacrylic acid can be used as the binder for the writing quality-imparting !ayer. If necessary, hardeners for hydrophilic polymers, such as formaldehyde, chromium alum or 2,4-dichloro-6-hydroxy-s-triazine, antistatic agents or pigments may also be present in the latter layer.

Where the surface of the non-image portion comprises a hydrophobic polymer like a cellulose ester polymer, a polyester or an acrylic polymer (e.g., a polyacrylate or polymethacrylate), those binder which are soluble in a solvent capable of dissolving or swelling the hydrophobic polymer forming the surface of the non-image portion can be used as the binderforthewriting quality-imparting layer.

For example, where the hydrophobic polymer forming the surface of the non-image portion is a cellulose ester polymer, such as diacetyl cellulose, triacetyl cellulose or nitrocellulose, there can be used as the binder for said layer any of (1) vinyl chloride or vinylidene chloride homo- and copolymers such as polyvinyl chloride a copolyer of vinylidene chloride and vinyl acetate, a copolymer of vinylidene chloride and maleic anhydride or a copolymer of vinyl chloride and an acrylic acid monomer; (2) cellulose ester polymers such as diacetyl cellulose, triacetyl cellulose, nitrocellulose, acetylbutyl cellulose or acetylpropyl cellulose; (3) amorphous polyesters such as a terpolymer of terephthalic acid, isoterephthalic acid and ethylene glycol; (4) polydienes such as polybutadiene; (5) polyvinyl acetal, polyvinyl formal or polyvinyl butyral; and (6) homopolymers of an acrylic ester or methacrylic ester, and copolymers thereof with acrylic acid, methacrylic acid or vinyl chloride, such as a copolymer of methyl or ethyl acrylate and acrylic acid.

The use of a hydrophilic polymer in admixture with the above described hydrophobic polymers used upon a hydrophobic non-image portion surface serves to further improve the writing quality, in particular, the writing quality with a fountain pen using an aqueous ink. Suitable polymers for this combination are cellulose ether polymers, such as methyl cellulose, ethyl cellulose or carboxymethyl cellulose and polyvinyl alcohol. Of these, methyl cellulose is particularly preferred.

In the case of using a hydrophobic polymer and a hydrophilic polymer in combination as a binder, the weight ratio of hydrophobic polymer to hydrophilic polymer is preferably in the range of from 0.5:10 to 4:10.

Where the surface of the non-image portion comprises a cellulose ester, a mixture of a cellulose ether resin and a cellulose ester is most preferable as the binder for the writing quality-imparting layer. The cellulose ether resins used in the present invention include methyl cellulose, ethyl cellulose and carboxymethyl cellulose. Of these, a methyl cellulose resin is particularly preferred.

In the methyl cellulose resin preferably used in the present invention, about two of the three hydroxy groups in the glucose units contained in the cellulose are substituted by methoxy groups (-OCH3). In addition, methyl cellulose resins wherein about two hydroxy groups are similarly substituted by methoxy groups and only a small portion thereof are substituted by hydroxypropoxy groups (-OC3H6OH) to increase the miscibility of the cellulose ester resin with organic solvents and prevent the cellulose ester resin from becoming too hydrophilic are also included. The proportion of methoxy groups in one glucose residue is preferably about 10 to 40 wt%, particularly preferably about 18 to 32 wt%.

The proportion of hydroxypropoxy groups in one glucose residue is preferably 2 to 15 wt%, particularly preferably 4 to 12 wt%.

As commercially available methyl cellulose resins suitable for use in the present invention there are Metholose SM, Metholose SOSH, Metholose 65SH, and Metholose 90SH (all made by Shinetsu Chemical Industry Co., Ltd.).

As the cellulose ester resins used in the present invention there are illustrated diacetyl cellulose, triacetyl cellulose, and cellulose nitrate as referred to above. Of these, diacetyl cellulose and/or triacetyl cellulose are particularly preferred.

Where the hydrophobic polymer forming the surface of non-image portion is polyethylene terephthalate, acrylic polymer, or polycarbonate, the binder for the writing quality-imparting layer can be selected similarly to the case of the above-described cellulose ester polymers.

A suitable coating amount for binder in the writing quality-imparting layer is about 0.2 to 20 gum2, preferably about 0.4 to 10 git2, and a suitable coating amount for the matting agent is about 0.01 to 6 gum2, preferably about 0.02 to 3 g/m2. The weight ratio of binder to matting agent is preferably about 10:0.5 to 10:3.0.

In the present invention, in order to provide a writing quality-imparting layer comprising (1) a cellulose ether resin, (2) a cellulose ester resin, and (3) an inorganic matting agent on, for example, a film having cellulose ester surface, it is preferable to dissolve or disperse the two resins and the inorganic matting agent in a suitable organic solvent and coat the composition according to generally well known methods, for example, doctor coating, extrusion coating, slide coating, roller coating, gravure coating, or the like.

As the organic solvent for the composition, those which dissolve the two resins, which form a stable coating solution, and which provide strong adhesion between the writing quality-imparting layer and the cellulose ester surface after coating are used. For example, there are a methanol/methylene chloride/acetone mixed solvent, a methanol/cyclohexanone/acetone mixed solvent, a methanol/benzene/acetone mixed solvent, a methanol/ethylene chloride/acetone mixed solvent, etc.

The content of the cellulose ether resin in 100 g of the coating solution is preferably about 1 to 30 g and in particular about 2 to 10 g. The content of the cellulose ester resin is preferably about 0.05 to 12 g and in particular about 0.1 to 4 g per 100 g solution. The content of the matting agent is preferably about 0.05 to 13 9 and in particular about 0.1 to 4 g per 100 g of coating solution.

Also, the weight ratio of the content of cellulose ether resin to that of cellulose ester resin is preferably about 10:0.5 to 10:4.0.

If the content of the cellulose ester resin is above this range, poor ink-receptivity in the writing quality-imparting layer results, in particular, poor writing quality for an aqueous ink is obtained. On the other hand, if the content is less than the above range, poor adhesion between the resin and the support film and poor surface hardness of the writing quality-imparting layer result, thus writing quality for a hard pencil or a fountain pen is deteriorated.

Also, the mixing ratio of the matting agent based on the mixture of the cellulose ether resin and the cellulose ester resin is preferably about 10:0.5 to 10:3.0 by weight. If the amount of the matting agent is more than this, the continuity and uniformity of the coating of the writing quality-imparting layer is poor, which results in defective portions having insufficient writing quality and deteriorates the adhesion between the resin and the support film, leading to unfavorable writing quality. On the other hand, if the amount of the matting agent is less than this range, poor writing quality for pencil results, such amount being unfavorable.

In the present invention, a coating solution having the above-described composition is coated in an amount of about 10 to 400 g, in particular about 20 to 200 g per 1 m2 and dried to form a writing quality-imparting layer.

The writing quality-imparting layer of the present invention may be coated on the marginal portions of a photographic material upon production of the photographic material or upon forming previously produced photographic film into a commercial product (hereinafter referred to as working steps).

As methods for coating upon production, the writing quality-imparting layer may be coated on a cellulose ester layer simultaneously with or after formation of the cellulose ester layer on a support, and the coating of light-sensitive layer or layers on the opposite side of the support; and a cellulose ester layer may be provided on a support and, after coating a light-sensitive layer or layers on the opposite side, the writing quality-imparting layer may be coated on the cellulose ester surface.

As methods for coating during working steps, there is a method of coating the writing quality-imparting layer simultaneously with slitting a wide light-sensitive material into strips of a given width, or before or after the slitting step.

In general, such photographic films are coated as a wide film and then cut to size. Therefore, in the case of coating the writing quality imparting layer before cutting, multi-stripe coating is conducted. There are various methods for stripe coating such as doctor coating, extrusion coating, slide coating, roller coating, gravure coating, etc. Multi-stripe coating can be conducted by using these coating heads in sequence.

In one embodiment of applying the writing quality-imparting layer of the present invention, doctor coating is employed using a coater equipped with a plurality of liquid-providing nozzles. In order to improve mechanical accuracy, it is possible to use a multi-stripe liquid-providing device comprising a wide liquid-providing nozzle having inserted therein spacers. As to specific methods for stripe coating, the descriptions given in Japanese Patent Applications (OPI) Nos. 25503/73,25504/73, 138037/75, 15533/77, 3208176,65606/76, 140703/76, Japanese Patent Publication No.4221/54, U.S. Patents 3,062,181,3,227,165 and 4,038,422 and British Patent 1,417,442 can be referred to.

In addition, in the case of providing the writing quality-imparting layer on a photographic material, it is also possible to provide the layer on only a limited portion of a non-image portion or to provide the layer after completion of development processing. In such a case, the coating solution of the writing quality-imparting layer is coated according to gravure coating or by stamping after the cutting step.

The present invention is characterized in that the writing quality-imparting layer is provided only on the non-image portion of the photographic material, for example, a marginal area framing an image portion of a diffusion transfer film unit. With photographic film units, it is not preferable to provide the writing quality-imparting layer on the image portion as well because it leads to deterioration of image quality. A wide variety of data such as the photograph date, scene, the photographed object, etc., may be written in the margin of the photographic material after photographing and development processing and, in such a case, the ability to write with any writing tool in accordance with the present invention is particularly important.In this case, providing the writing quality-providing layer only on the marginal portion serves to save the coating solution and increase the coating efficiency several times without deteriorating image quality.

Diffusion transfer photographic film units are generally retained in groups of about 10 in a cartridge and superposed one over the other before photographing and designed to be released one-by-one immediately after photographing (for example, as described in U.S. Patent 3,954,476 or Japanese Patent Applications (OPI) Nos. 153628/75 and 43317/73). A blocking phenomenon occurs under some environmental conditions within the cartridge, and one-by-one separation becomes impossible, resulting in a malfunction of the photographic film units. Application of the present invention to such film units is particularly effective for providing universal writing quality and obtaining sufficient function as photographic film units without the blocking phenomenon under ordinary photographic conditions in a camera or under storage.

The writing quality-imparting layer of the present invention can optionally be colored. Coloration of the writing quality-imparting layer gives beautiful effects and can be used for quality control in production of photographic film units.

Example 1 A photographic film unit was prepared according to U.S. Patent 3,954,476, Example 8.

Light-Sensitive Element: On a transparent polyethylene terephthalate film base (1) were coated, in sequence, an image-receiving layer (2), a titanium dioxide layer (3), a carbon black layer (4), a cyan dye-providing layer (5), a red-sensitive layer (6), an interlayer (7), a magenta dye-providing layer (8), a green-sensitive layer (9), an interlayer (10), a yellow dye-providing layer (11), a blue-sensitive layer (12), and a surface-protecting layer (13).

Cover Sheet: On polyethylene terephthalate film (20) were coated an acidic polymer layer (21) and a timing layer (22).

On the opposite side of transparent polyethylene terephthalate film (1)was previously coated a 0.5 u thick layer comprising diacetyl cellulose, and coating solutions (1) and (2) were coated in the areas of the diacetyl cellulose layer corresponding to the non-image portion to form a writing quality-imparting layer.

Coating Solution (1) Solution A: Metholose 60SH 5g Methylene chloride 76 g Methanol 19 g Solution B: Diacetyl cellulose 1 g Acetone 15.2 g Methanol 3.8 g 20 g of solution B was mixed with 100 g of solution A, and 60 g of acetone was added thereto. Further, 0.6 g of silica (average particle size: 4.0 # was added thereto followed by mixing and dispersing in a ball mill to prepare a coating solution.

Coating Solution (2) Gelatin 6g Silica (average particle size: 4.0 ) 0.6 g Water 1809 Phenol 0.3g Each of the photographic film units was exposed, and a developing solution was spread between the light-sensitive element and the cover sheet to obtain an image.

Writing quality and blocking property of the photographic film units having the writing quality-imparting layer in the non-image portion were tested to obtain the results shown in Table 1.

The anti-blocking property was tested by exposing 5 sheets per each unit of each sample for 1 hour under the conditions of 500C and 80% RH, then superposed one over the other under the same conditions for 24 hours while placing thereon a 30 g/cm2 pressure followed by visually examining for possible blocking phenomenon.

In Table 1, sign "o" indicates a sufficient property, whereas sign "x" an insufficient or bad property.

Table 1 Sample Coating Writing Quality Anti-Blocking No. Solution *1 *2 *3 *4 Property 1 (*) (1) 0 0 0 0 0 2(**) (2) 0 0 0 o x 3 (**) -- x x o x o (*) present invention, (**) comparative sample *1 pencil, *2 ball-point pen, *3 oily ink, *4 aqueous ink As is clear from Table 1, the photographic film unit having a writing quality-imparting layer of the present invention in the non-image portion (sample 1) showed universal writing quality and did not result in blocking phenomenon when superposed under high humidity atmosphere. Further, no detrimental influences were observed on the transparency of the image, and the like. On the other hand, sample (2) having the writing quality-imparting layer formed by applying coating solution (2) showed a poor anti-blocking property, though it exhibited in good writing quality, thus not being practically usable. Sample (3) having no writing quality-imparting layer showed almost no writing quality, since the surface of the non-image portion was diacetyl cellulose.

Example 2 On a 200 #thick, 29.1 cm wide polyethylene terephthalate film was coated a 2 lithick nitrocellulose layer.

Then, the coating solution of the following formulation was coated in three stripes of 1.8 cm width as shown at 2,2', 2" in Figure 3, to form writing quality-imparting layers.

Coating Solution Triacetyl Cellulose 10 g Polyvinyl Alcohol 1 g Tetrachloroethane 90 g Methanol 10 g Silica (particle size: 4 ) 1.5 g The above-described mixture was stirred at high speed (4,000 rpm) at 800C to prepare a dispersion and the solvent which evaporated off during stirring was replaced with a mixed solution of ethylene chloride and methanol (1:1) to prepare a coating solution containing 10 wt% solid ingredients.

On the opposite side of the support were coated in image-receiving layer (1), a reflection layer (2), an opaque layer (3), a cyan dye layer (4), an interlayer (5), a red-sensitive emulsion layer (6), an interlayer (7), a magenta dye-releasing layer (8), a green-sensitive emulsion layer (9), an interlayer (10), a yellow dye-releasing layer (11), a blue-sensitive emulsion layer (12), and an overcoating layer (13) as described in U.S. Patent 4,030,925, col. 34, line 63 to col. 35, line 35, to prepare a self-processing type light-sensitive material.

This light-sensitive material was slit into pieces 9.7 cm in width and 10.1 cm in length, and exposed so that the writing quality-imparting layer (1.8 cm in width) became the non-image portion as shown in Figure 4 (image portion: 9.1 cm x 6.7 cm), and the processing solution described in U.S. Patent 4,030,925, col. 32, lines 45 to 54 was spread between the material and the cover sheet described in the same U.S. Patent, col.

32, lines 37 to 44. Thus, there were obtained photographic film units having a writing quality-imparting layer of the present invention in the non-image portion.

Claims (16)

1. A photographic material having on the image-viewing side thereof an image portion and a non-image portion, and on the surface of the non-image portion alone a writing quality-imparting layer comprising a binder and a matting agent.

2. A photographic material as claimed in Claim 1, wherein the surface of the non-image portion comprises a hydrophobic polymer.

3. A photographic material as claimed in Claim 2, wherein said polymer is a cellulose ester polymer, a polyethylene terephthalate polymer, a polycarbonate or an acrylic polymer.

4. A photographic material as claimed in Claim 2, wherein said polymer is a cellulose ester.

5. A photographic material as claimed in any of Claims 2 to 4, wherein the binder for said writing quality-imparting layer is a vinyl chloride polymer or copolymer, a vinylidene chloride polymer or copolymer, a cellulose ester polymer, an amorphous polyester, a polydiene, an acrylic acid polymer, polyvinyl acetal, polyvinyl formal or polyvinyl butyral.

6. A photographic material as claimed in Claim 1, wherein the surface of the non-image portion comprises a hydrophilic polymer and the binder of said writing quality-imparting layer is a protein, cellulose ether, sugar derivative, polyvinyl alcohol, poly-N-vinyl pyrrolidone or polyacrylic acid.

7. A photographic material as claimed in Claim 1, wherein said binder is a mixture of a hydrophobic polymer and a hydrophilic polymer.

8. A photographic material as claimed in Claim 7, wherein the weight ratio of said hydrophobic polymer to said hydrophilic polymer is in the range of from 0.5:10 to 4:10.

9. A photographic material as claimed in Claim 7 or 8, wherein said binder is a mixture of a cellulose ester resin and a cellulose ether resin.

10. A photographic material as claimed in Claim 9, wherein said cellulose ether resin is methyl cellulose, ethyl cellulose and/or carboxymethyl cellulose.

11. A photographic material as claimed in Claim 10, wherein said cellulose ether resin is methyl cellulose.

12. A photographic material as claimed in Claim 9, wherein said cellulose ester resin is diacetyl cellulose, triacetyl cellulose and/or cellulose nitrate.

13. A photographic material as claimed in any of Claims 8 to 12, wherein the weight ratio of the matting agent to the mixture of said cellulose ether resin and said cellulose ester resin is 10:0.5 to 10:3.0.

14. A photographic material as claimed in any preceding claim, wherein said photographic film is a diffusion-transfer type of film unit.

15. A photographic material as claimed in any preceding claim, wherein said writing quality-imparting layer is colored.

16. A photographic material as claimed in Claim 1, substantially as hereinbefore described with reference to Figure 3 or 4 of the accompanying drawing or to Sample (I) of Example 1 or to the materials of Example 2.