JPS5941174B2 - Film with writability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a film that has writability, and in particular, the surface of a cellulose ester resin film is modified so that it can be used for pencils, etc.
It provides excellent writing performance for all types of writing instruments, including ballpoint pens, oil-based inks, and water-based inks, and can be used even when stacked and left in environments with high temperatures and humidity.
This invention relates to a film that prevents adhesion between films due to blocking.

Conventionally, methods for imparting writability to synthetic resin films include roughening the surface by sandblasting, embossing, etc., roughening the surface by etching it with sulfuric acid, etc., and using magnesium carbonate or silicon dioxide. There are known methods of roughening the surface by applying a resin liquid in which inorganic and organic fine particles (hereinafter referred to as matting agents) such as (silica) and polymethyl methacrylate are dispersed. Films provided with this have been used, for example, as matte films for drafting.

Regarding these methods, for example, Japanese Patent Publication No. 44-2523
No. 8, No. 44-29385, U.S. Patent No. 314258
No. 1, No. 3607473, No. 3078178, British Patent No. 817184, etc. However, in the method of roughening the surface of a synthetic resin film by chemically etching it with sulfuric acid or the like, the degree of roughening is insufficient and sufficient writability cannot be obtained.

In addition, when the surface is physically roughened by sandblasting etc., writing with a pencil is sufficient, but there is almost no writing ability with water-based ink such as a fountain pen or water-based felt-tip pen, and after writing, the surface is rubbed by hand. If you do so, the ink may rub off and disappear, or it may become contaminated. On the other hand, as a method for improving the writing properties of water-based inks, for example, a layer in which a matting agent is dispersed in a binder made of a hydrophilic resin such as polyvinyl alcohol or gelatin is provided on the surface of a synthetic resin film. One possible method is to roughen the surface.

A synthetic resin film whose surface has been roughened by such a method is not only writable with a pencil but also has sufficient writability with water-based ink, and from the viewpoint of writability alone, it has sufficient writability. It can be said that the performance is close to that of an all-purpose writing film.

However, in the case of a writable film using a general hydrophilic resin such as polyvinyl alcohol or gelatin as a binder, the hydrophilic resin absorbs moisture when exposed to a humid environment. This causes an adhesion phenomenon called blocking, making it impossible to separate the films one by one. Therefore, the writability imparting film of this embodiment has a major drawback in that it cannot be used in applications where the films are left in a stacked state and then separated and used one by one.

One way to improve this drawback is, for example, to use a large amount of matting agent with respect to the binder, but if a large amount of matting agent is used with respect to the binder, the synthetic resin film and the matting agent will be mixed together. There is a drawback that the adhesive strength with the layer decreases, and when writing with a hard pencil or fountain pen, the writability imparting layer containing the matting agent easily peels off.

Therefore, there has been a strong demand for a universal writable film that solves all of these drawbacks.

On the other hand, non-image portions of ordinary color photo prints, color slides, black and white photo prints, etc. have almost no writability. It would be extremely convenient to be able to write notes such as the conditions at the time of shooting in the non-image area (usually the surrounding margins) of color photo prints, etc., but it has excellent writing performance with all writing instruments and is easy to stack. There was no color photographic print or the like that would not cause the blocking phenomenon even if left unused.

Therefore, the first object of the present invention is to provide a universal writable film which has sufficient writability for all types of writing implements and which does not cause the blocking phenomenon even when stored in stacks.

A second object of the present invention is to provide a photographic film unit which has universal writing ability only in necessary areas without impairing the image quality of the image area and which does not cause the blocking phenomenon due to humidity.

Here, the photographic film unit is a photographic film comprising an image portion and a non-image portion on one side of a support such as a plastic film or paper having a plastic film surface, such as a color photographic print,
These include black and white photographic prints, color slides, and self-processing photographic film units using the diffusion transfer method.

These objects of the present invention are such that (1) cellulose ether resin, (
2) cellulose ester resin, and (3) average particle size 0
．． This was achieved by a writable film provided with a writability imparting layer made of a matting agent of 1 to 10 .mu.m, particularly 1 to 10 .mu.m.

When this technique is applied to a photographic film unit, the layers consisting of (1), (2) and (3) described above are provided only on the non-image portion of the photographic film unit having a cellulose ester surface, thereby forming the desired photographic film. You can get units.

In the present invention, a film having a cellulose ester surface refers to a film made of cellulose acetate and cellulose nitrate, or a film made of these cellulose esters such as paper, other plastic films (for example, polyethylene terephthalate film, polystyrene film, polyethylene film, etc.). It is a film obtained by coating or laminating on the surface of a cellulose ester.In short, any film whose surface is made of cellulose ester may be used.

As cellulose acetate, diacetyl cellulose (DA
C) and triacetyl cellulose (TAC).

Regarding the manufacturing method of cellulose ester film, etc., reference may be made to, for example, Toshio Miyagawa's "Plastic Materials Course (7) Cellulose Resin" (published by Nikkan Kogyo Shimbun, 1963).

The cellulose ether resins used in the present invention include methylcellulose, ethylcellulose, and carboxymethylcellulose, and methylcellulose resin can be particularly preferably used.

The methylcellulose resin preferably used in the present invention is
Approximately two of the three OH groups in one glycol residue contained in cellulose are substituted with methoxy groups (-0CH3), or alternatively, approximately two OH groups are substituted with methoxy groups (-0CH3). is substituted with a methoxy group, but a small portion of it is substituted with a hydroxypropoxy group (-0
C? 60H) is also included. The proportion of methoxy groups in one glycol residue is preferably 10 to 40% by weight, particularly 18 to 32% by weight.

Commercially available methylcellulose resins include, for example, Metrose SM1 Metrose 60SH1 Metrose 65SH
and Metrose 90SH (both manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the matting agent having an average particle diameter of 0.1 to 10 .mu.m used in the present invention include inorganic fine particles such as silica, calcium carbonate, magnesium carbonate, titanium oxide, aluminum oxide, and glass powder.

In the present invention, the cellulose ester resin that is used in combination with the cellulose ether resin and the matting agent to form the writability imparting layer includes diacetyl cellulose, triacetyl cellulose, and cellulose nitrate as described above in the section of the cellulose ester film. Among them, diacetylcellulose and/or triacetylcellulose are particularly preferred. In the present invention, in order to provide a writability imparting layer consisting of (1) cellulose ether resin, (2) cellulose ester resin, and (3) inorganic matting agent on a film having a cellulose ester surface, two types of The resin and the inorganic matting agent are dissolved and dispersed in a suitable organic solvent, and then the resin is dissolved and dispersed in a suitable organic solvent, and then the resin is dissolved and dispersed in a suitable organic solvent, and then the resin is dissolved and dispersed in a suitable organic solvent.
It is preferable to apply by a roller coating method, a gravure coating method, or the like.

The organic solvent is an organic solvent that dissolves the two types of resins, is stable as a coating liquid, and has a strong adhesive force between the writability imparting layer and the cellulose ester surface after coating, such as A mixed solvent of methanol/methylene chloride/acetone, a mixed solvent of methanol/cyclohexanone/acetone, a mixed solvent of methanol/benzene/acetone, a mixed solvent of methanol/ethylene chloride/acetone, etc. can be used.

The content of the cellulose ether resin in the coating liquid 1007 is preferably 1 to 30 y, particularly preferably 2 to 10 y, and the content of the cellulose ester resin is 0.05 to 127, particularly 0.1 to 10 y.
4y is preferable, and the content of the matting agent is 0.05 to 13y.
, particularly preferably 0.1 to 4y.

Moreover, the weight ratio of the content of cellulose ether resin and the content of cellulose ester resin is preferably 10:0.5 to 4.0. If the content of the cellulose ester resin is greater than this range, the ink receptivity of the writability imparting layer will be poor;
In particular, the writability with water-based ink becomes unfavorable.

On the other hand, if the content of the cellulose ester resin is less than the above range, the adhesive strength with the support film and the surface hardness of the writability imparting layer will be poor, and writability with hard pencils, fountain pens, etc. will be unfavorable. Further, the mixing ratio of the matting agent to the mixture of cellulose ether resin and cellulose ester resin is preferably 10:0.5 to 3.0 by weight.

If the amount of the matting agent is larger than this range, the continuous and uniform application of the writability imparting layer will deteriorate, resulting in defective areas with insufficient writability, or the adhesive force with the support film will deteriorate, making it difficult to write. Sexuality becomes undesirable. On the other hand, if the amount of the matting agent is less than this range, the writing properties with a pencil will be poor, which is not preferable. In the present invention, the coating solution having the above-mentioned composition is applied at a rate of 10 to 4,007 mm per square meter, particularly 20 to 200 mm per square meter. It is applied and dried to form a writability imparting layer.

In the present invention, the writability imparting layer can be provided on the cellulose ester surface of the support film without any particular pretreatment, but if necessary, the cellulose ester surface may be subjected to electrical discharge treatment, ultraviolet irradiation treatment, undercoating, etc. Pretreatment such as processing may be performed.

The writable film of the present invention can be used as a drafting film, ID
When used for cards, tags, name plates, etc.
A writability imparting layer is often provided on the entire surface of the film, but when used as a photographic film unit, it is not necessary to provide a writability imparting layer on the entire surface;
For example, the writability imparting layer may be provided only in the surrounding margins. On the contrary, in the case of a photographic film unit, if the writability imparting layer is provided even in the image area, the image quality will deteriorate, which is not preferable. A photographic film unit has an image viewing area and a margin area, and there is a possibility that articles about the date of photography, scene, and subject will be written in the margin area of the photographic film unit after photography and processing. The effect of being able to write with any type of writing instrument is particularly important. In this case, if the writability-imparting layer according to the present invention is applied only to the margin portion, the writability-imparting liquid, which does not cause deterioration in image quality as described above, will not be wasted and the efficiency will be increased several times. Furthermore, photographic film units (for example, U.S. Pat. No. 3,954,476,
(described in JP-A-50-153628, JP-A-48-43317, etc.), under some environmental conditions the photographic film unit causes a blocking phenomenon in the cartridge, adheres and separates one by one. If this becomes impossible, the function as a photographic film unit will no longer be fulfilled.

If you want to give the above-mentioned photographic film unit universal writability while also fully fulfilling its function as a photographic film unit without causing the blocking phenomenon even under normal camera shooting environment conditions or photographic film unit storage environment conditions, this book is useful. Application of the invention is very effective. The method of applying the writability imparting layer according to the present invention only to the margins of a photographic film unit includes a step of processing the photographic film into a product form (hereinafter referred to as a processing step) during or after manufacturing the photographic film. There is a method of coating.

The method of coating during production is to coat a writability imparting layer on the cellulose ester layer at the same time as or after forming the cellulose ester layer on the support, and then apply a photosensitive layer on the opposite side of the support. There is a coating method, and a method in which a cellulose ester layer is provided on a support, a photosensitive layer is coated on the opposite side, and then a writability imparting layer is coated on the surface of the cellulose ester.

The method of coating during the processing process is to apply the writability imparting layer when slitting a wide photosensitive material into a predetermined width, at the same time as the slitting, or before or after the process of processing the slit into a product form. There is a method.

Generally, such photographic film is coated with a wide width and then subjected to a cutting process, so if the film is coated before the cutting process, a multi-striped coating is performed. Various methods can be considered for stripe coating, such as general coating methods such as doctor coating, extrusion coating, slide coating, roller coating, and gravure coating. As an example of the application of the present invention, a doctor coat equipped with multiple liquid injection nozzles was used, but in order to improve the mechanical accuracy of these injection nozzles, a wide liquid injection nozzle was used. It is also possible to use a multi-line liquid injector consisting of a spacer inserted into a liquid nozzle.

Specific methods for stripe coating include, for example, Japanese Patent Application Laid-open Nos. 48-25503, 48-25504, and 48
-98803, 50-138037, 52-1
No. 5533, No. 51-3208, No. 51-6239, No. 51-65606, No. 51-140703, Japanese Patent Publication No. 29-4221, U.S. Patent No. 3062181,
The description in the specification of 3227165 can be referred to.

In addition, when applying a writability imparting layer to a photographic film unit, the writability imparting layer may be applied only to a limited portion of the non-image area, or after the development process is completed.
A writability imparting layer can also be provided.

In this case, the writability imparting layer coating liquid can be applied by a gravure coating method, or can be applied by a stamp method after cutting. Next, the present invention will be further explained with reference to Examples.

Example 1 Coating liquid prescription (1) 20y of liquid B was mixed with 100f7 of liquid A, 60f of acetone was added thereto, and silica (average particle size 4.0
μ)0.6y was mixed and dispersed in a ball mill for 10 hours to prepare a coating solution.

Coating liquid formulation (2) Coating liquids (1) and (2) were coated on a triacetyl cellulose film (thickness 100 μm) by the slide coating method.
), 200 f7 per square meter was applied and dried to form sample films (1) (invention) and (2) (for comparison).
was created.

The writability and blocking properties of these sample films were compared with those of a commercially available sandblast writable film (Toray Sandmat, manufactured by Toray Industries, Inc.), and the results shown in Table 1 were obtained.

However, for the blocking property test, 5 sheets of each sample were
After being exposed to conditions of 0°C and 80% for about 1 hour, the samples were stacked together and a 307/Crii weight was placed on them under the same conditions. was determined visually.

In Table 1, the mark ○ indicates that the performance is sufficient, and the mark X indicates that the performance is insufficient or unacceptable.

As is clear from Table 1, the writability-imparting film of the present invention has sufficient writability for all types of writing instruments, and does not cause the blocking phenomenon.

Example 2 A photographic film unit was prepared according to Example 8 of US Pat. No. 3,954,476.

2 photosensitive elements: transparent polyethylene terephthalate film base (1), (2) image-receiving layer, (3) Ti
O2 layer, (4) carbon black layer, (5) cyan dye supply layer, (6) red photosensitive layer, (7) intermediate layer, (8) magenta dye supply layer, (9) edge photosensitive layer, (self) intermediate A layer, an AD yellow dye supply layer, a blue photosensitive layer, and a moth surface protection layer were sequentially coated. On the cover sheet polyethylene terephthalate film (20), an acid polymer layer and a timing layer was applied.

The transparent polyethylene terephthalate film (1) has a thickness of 0.5
A layer of μ diacetylcellulose is applied in advance,
Furthermore, the coating solutions (1) and (2) used in Example 1 were applied to the positions corresponding to the non-image areas of the diacetylcellulose layered soil.
) was applied to provide a writability imparting layer.

An image was obtained by exposing the photographic film unit and spreading a processing solution between the photosensitive element and the cover sheet.

The photographic film unit provided with the writability imparting layer in the non-image area was tested for writability and blockability in the same manner as in Example 1, and the results shown in Table 2 were obtained.

As is clear from Table 2, the photographic film unit (sample (self)) comprising the writability imparting layer according to the present invention in the non-image area has all-purpose writability and can be stacked under high humidity. However, no plotting phenomenon occurred.

Claims (1)

[Claims] 1. On a film having a cellulose ester surface, (
A writable film comprising: 1) a cellulose ether resin; (2) a cellulose ester resin; and (3) a writability imparting layer comprising inorganic fine particles having an average particle diameter of 0.1 to 10 μm. 2. A photographic film unit comprising a writability imparting layer according to claim 1 in a non-image area having a cellulose ester surface.