JPH0415640A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having superior whiteness, sharpness and glossiness by forming a white plastic film base from a biaxially oriented polyester film having a laminated structure composed of two or more layers including a layer contg. titanium oxide and a layer contg. a void forming polymer. CONSTITUTION:A white plastic film base is formed from a biaxially oriented polyester film having a laminated structure composed of two or more layers including a layer contg. titanium oxide and a layer contg. a void forming polymer. The layer contg. titanium oxide consists essentially of polyester resin and titanium oxide. The void forming polymer may be polystyrene or polyolefin such as PE or PP. A silver halide photographic sensitive material having superior whiteness, sharpness and glossiness can be obtd.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has a white plastic film support and has good whiteness, gloss, and sharpness. This invention relates to an excellent silver halide photographic material.

[Prior Art] Conventionally, as a support for a reflective photographic element, a polyethylene-coated paper is generally used, which is a base paper made from a bulb and a polyethylene layer kneaded with a white pigment or the like provided thereon. However, reflective photographic elements using polyethylene-coated paper as a support suffer from unevenness on the surface of the base paper support, which results in a glossy surface with rough ripples, which impairs the brightness and sharpness of the photographic image. The aesthetic appearance is significantly impaired. Additionally, although both sides of the base paper of the support are coated with a water-impermeable thin polyethylene film, the cut surface of the base paper is not coated, so during the development process, the processing solution, etc. seeps into this area, causing coloration. Therefore, several methods have been proposed in which only a thermoplastic resin film is used as a support without using base paper.

In particular, as a technique using polyester resin, British Patent No. 1,563,591 and British Patent No. 1,563,592 disclose a method of adding barium sulfate to polyester and stretching the polyester. However, this method does not provide sufficient whiteness as a support for reflective photographic elements. This is clear from the extensive use of optical brighteners and other pigments in the Examples described in the above specification. In addition, as a result of stretching, voids are formed around the barium sulfate particles, resulting in insufficient resolution of images obtained when a photographic layer is applied. Japanese Patent Publication No. 56-4901 discloses a technique in which barium sulfate and titanium oxide are used together. Although the publication states that saturated polyester resins are also suitable as thermoplastic resins that can be used in addition to various resins, polyester resins cannot be used for the following two reasons. That is, the first point is that the refractive index values of barium sulfate and polyester are close, and suitable whiteness cannot be obtained unless stretched, and the publication does not disclose anything about the case where barium sulfate is added to polyester resin. The second point is that when titanium oxide is directly added to a polyester resin and stretched, voids are formed around the particles, which not only makes it impossible to obtain suitable whiteness, but also results in insufficient resolution of photographic images.

Also, JP-A-1-241548 and JP-A-1-24154
No. 9 discloses a white polyester film support filled with calcium carbonate, but since the white polyester film also forms voids around the particles, the resolution of photographic images is insufficient.

Related to these drawbacks, Japanese Patent Application Laid-Open No. 61118
No. 746 contains polyester with an average particle size of 0.1 to 05μ.
A reflective photographic element is disclosed in which the emulsion is coated on a film having a surface-treated titanium oxide of m and whose film thickness and total visible light transmittance are within a specified range.

[Problems to be Solved by the Invention] However, since the titanium oxide-filled white polyester film has a high specific gravity of titanium oxide, the weight of the entire film and the entire photosensitive material coated with a silver halide emulsion increases. When displaying on a wall,
Printed photographic elements may be punched and hung.
In such cases, a problem arises in that the photographic element tears under its own weight.

Therefore, an object of the present invention is to provide a silver halide photographic material having a white plastic film support, which has excellent whiteness, sharpness, and gloss, and has a weight suitable for practical use. .

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned object of the present invention is to provide a photosensitive material in which a silver halide photographic emulsion layer is coated on a white plastic film support. A silver halide photographic light-sensitive material, wherein the white plastic film support is made of a biaxially stretched polyester film having a laminated structure of two or more layers including a titanium oxide-containing layer and a void-forming polymer-containing layer. In particular, we have found that this can be achieved by providing the silver halide photographic light-sensitive material in which the titanium oxide-containing layer is the outermost layer on the side on which the silver halide photographic emulsion layer is coated on the white plastic film support. Ta.

The present invention will be explained in more detail below.

In the present invention, the white plastic film support is a biaxially stretched polyester film having a two-layer or more-layered structure consisting of a titanium oxide-containing layer and a void-forming polymer-containing layer.

The titanium oxide-containing layer is a layer mainly composed of polyester resin and titanium oxide.

As the titanium oxide used, both rutile type and anatase type can be used, but the anatase type is more preferably used because of its bluish color tone.

Titanium oxide having an average particle diameter of 01 to 05 μm is preferably used, and surface-treated titanium oxide may also be used. This surface treatment is AI, Ce
, Mg, Ti, Sb, Si, Sn,
Zn.

Inorganic treatment to deposit one or more selected from metal hydroxides such as Zr, hydrated oxides, phosphates, basic sulfates, etc. and/or fatty acid metal salts, various coupling agents, This is an organic treatment in which alcohols, amines, siloxane polymers, various ester compounds, phosphoric acid compounds, etc. are adsorbed onto the surface of titanium oxide.

In the present invention, the titanium oxide used is classified and/or
Alternatively, it is preferable to use a pulverization treatment to remove coarse particles having a particle size of 3 μm or more. The classification treatment and/or the pulverization treatment may be performed before or after the surface treatment step of the titanium oxide mentioned above, or between the inorganic treatment and the organic treatment if the surface treatment involves both inorganic treatment and organic treatment. You may do so.

In the present invention, the polyester used as the resin constituting the titanium oxide-containing layer is not only a thermoplastic resin consisting only of polyester, but also other polymers, as long as the resin properties of the main component polyester are not practically changed. It also includes those to which additives and the like are added.

The polyester used in the present invention includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid, ethylene glycol, 1,3
- Propanediol, l.

Examples include polymers of condensates with glycols such as 4-butanediol, such as polyethylene terephthalate, polyethylene 2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and copolymers thereof. The polyester used in the present invention includes polyethylene terephthalate (hereinafter referred to as
(abbreviated as PET) is preferred. PET film is impermeable to water, has excellent smoothness, has excellent mechanical properties such as tensile strength and tear strength, has excellent dimensional stability such as heat shrinkage, and has excellent chemical resistance during development processing. It is something.

In the polyester used in the present invention, the intrinsic viscosity measured at 20°C in a mixed solvent of phenol/1,1,2.2-tetrachloroethane (60/40 weight ratio) is 0.
4 to 1.0 is preferable, more preferably 0.5 to 0.8
It is.

In the present invention, the proportion of titanium oxide contained in the polyester is from 10 to 100 parts by weight of the polyester from the viewpoint of whiteness, stretchability, etc. of the support film.
It is preferably 50 parts by weight, more preferably 15 to 30 parts by weight.

In the present invention, along with titanium oxide, zinc oxide, barium sulfate, which is generally used as a white pigment in the industry,
One or more inorganic pigments such as silica, talc, and calcium carbonate can be used in combination. However, the white pigment that can be used in combination with the polyester 100 of the present invention
It should not exceed 10 parts by weight.

In the present invention, as a method for adding titanium oxide to polyester, a method of cross-dispersing titanium oxide in the molten state of polyester is used, but a method of adding titanium oxide during polymerization of polyester is also used.

In the present invention, the kneading machine for cross-dispersing titanium oxide into polyester includes an extruder with a rotor or blades for kneading, a twin-screw kneading extruder that rotates in the same or different directions, and a -shaft continuous extruder. Continuous kneading machines such as kneaders, batch kneading machines such as three rolls, Panbury mixers, Henschel mixers, kneaders, etc. are used. Among these, a continuous twin-screw extruder that rotates in the same direction or in different directions is preferably used because it can continuously knead while applying a strong shearing force.

When added during polymerization, it is preferable to add a slurry in which titanium oxide is dispersed in an ester-forming polyhydric alcohol, such as ethylene glycol.

In the present invention, the polyester composition obtained as described above may be partially pelletized and then subjected to film forming, or may be subjected to film forming while in a molten state.

In either method, the composition may be molded with the pigment concentration as it is, or a composition with a high pigment concentration, a so-called masterbatch, may be prepared and then diluted and molded.

In the present invention, the void-forming polymer contained in the void-forming polymer-containing layer constituting the white plastic film support is not compatible with the polyester resin,
It is an inert resin and refers to a polymer that creates voids around the particles when stretched. Such polymers may be either thermoplastic or thermosetting. The void-forming polymer preferably has an average particle size of 0.01 to 50 μm when dispersed in the polyester forming the polymer-containing layer. As for the method of adding and dispersing it into the polyester, it may be added during polymerization or may be added by melt-kneading.

Specific examples of void-forming polymers used in the present invention include polyolefins such as polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, triacetyl cellulose, diacetyl cellulose, polycarbonate, nylon resin, polyphenylene. Examples include sulfide.

In addition, polyester copolymers such as PET copolymerized with isophthalic acid, PE with increased degree of polymerization through solid phase polymerization, etc.
Polyesters that are not compatible with PET, such as T, liquid crystalline polyester, and polyethylene-2,6-naphthalate, can also be used.

Furthermore, by three-dimensional crosslinking with a curing agent, PET
It is also possible to use resins that are incompatible with the resin, such as styrene-divinylbenzene copolymer particles, and polybutylene ethylene phthalate to which a crosslinking agent is added.

The void-forming polymer used in the present invention is not limited to these specific examples, and any other polymer that can be added to PET and whitened by forming voids by stretching may be used.

Further, in the present invention, it is preferable to add a dispersion aid in order to improve the dispersibility of the void-forming polymer. Dispersion aids include fatty acid metal salts such as zinc stearate, various coupling agents such as silane coupling agents and titanium coupling agents, polyhydric alcohols such as trimethylolpropane and trimethylolethane, and siloxanes such as polydimethylsiloxane. Polymers, maleic anhydride, and any other polymer that can finely disperse a void-forming polymer in the polyester and can form voids during stretching are preferably used.

In the present invention, the above-mentioned void-forming polymer is employed in order to reduce the specific gravity of the formed film.
Various inorganic particles may be included as long as they do not contradict the purpose of the present invention. For example, in the polyester film manufacturing process, it is common practice to collect and reuse so-called selvedges that do not become products. For example, when collecting and reusing the selvage portions of the polyester film of the present invention, The titanium oxide in the laminated titanium oxide-containing layer will also be mixed into the void-forming polymer-containing layer of the newly formed film, and this layer will substantially contain inorganic particles other than the void-forming polymer. However, the present invention can also include such a case.

As the resin constituting the void-forming polymer-containing layer, a polyester resin that is adhesive to the titanium oxide-containing layer constituting resin is selected. Among them, PET is preferably used.

Methods for laminating the void-forming polymer-containing layer with the titanium oxide-containing layer include dry lamination, melt lamination, bonding with an adhesive, and coextrusion, among which coextrusion is preferably used. .

The white plastic film support according to the present invention may be composed of two or more layers, but it is preferable that the titanium oxide-containing layer is the surface layer on the side on which the silver halide emulsion layer is coated.

In addition, in the case of lamination, a method in which the polyester containing a void-forming polymer as a base material is formed into a film, for example, after melt extrusion, after completion of longitudinal stretching, after completion of transverse stretching, etc. Alternatively, a method may be adopted in which the layers are laminated after the molding is completed.

The method of film forming is to extrude the polyester composition in a molten state through a slit die, place it on a rapidly cooling surface such as a rotating drum, form an amorphous sheet, and then extrude the polyester composition at a temperature above the glass transition temperature (Tg) of the polyester and below 130°C. Within this range, it is possible to take a method of sequentially or uniaxially simultaneous stretching in the longitudinal or transverse direction and the axial direction. At this time, in order to satisfy the mechanical strength and dimensional stability of the film support, and to form sufficient voids and whiten the film, the area ratio is 4 to 25 times larger.
More preferably, the stretching is performed in a range of 6 to 16 times. Further, it is preferable to perform heat setting and heat relaxation subsequent to stretching.

Furthermore, when forming a film, it is preferable to filter it using an appropriate grade filter.

In the present invention, the thickness of the white plastic film support is preferably 50 to 300 μm, more preferably 7 μm.
It is 5 to 250 μm. If it is thinner than 50 μm, it will not be stiff as a support and will wrinkle easily. Also, 300μ
If the thickness exceeds m, there may be problems such as being too thick and inconvenient to handle.

In the present invention, to the extent that the purpose of the present invention is not impaired,
The support may contain various commonly used additives, such as optical brighteners, dyes, ultraviolet absorbers, antistatic agents, and the like.

At least one silver decagenide photographic emulsion layer is coated on the opaque and whitened film support formed as described above to produce the silver decagenide photographic light-sensitive material of the present invention. In this case, if necessary, surface activation treatment such as corona discharge and/or
Alternatively, a subbing layer can be applied.

Particularly useful methods for coating silver halide photographic emulsion layers are extrusion coating and curtain coating, which allow two or more layers to be coated simultaneously. Further, the coating speed can be arbitrarily selected, but from the viewpoint of productivity, a speed of 50 m/min or more is preferable.

The silver halide photographic light-sensitive material of the present invention includes various commonly used light-sensitive materials, but those corresponding to so-called reflection photographic elements are preferably mentioned.

Here, the term "reflective photographic element" refers to a so-called transmission photographic element that projects a photographic image using transmitted light and utilizes the projected image.
As mentioned above, an opaque material with a total visible light transmittance of 20% or less is used as a support, and a photographic layer is provided thereon, and the photographic image formed on the photographic layer is directly viewed by reflected light. It refers to photographic elements such as those commonly called photographic paper.

The above-mentioned reflective photographic element can be applied to any photographic element using the support according to the present invention, for example, there are no restrictions on black and white, color, etc., and even in the photographic constituent layers, the light-sensitive silver halide photographic emulsion layer , intermediate layer, protective layer, filter layer,
There are no particular restrictions on the number and order of layers such as the back coat layer, and the invention can be applied.

As the silver halide photographic emulsion layer in the silver halide photographic light-sensitive material of the present invention, various known silver halide emulsion layers can be applied. For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, etc. Emulsions of silver, silver chloroiodobromide, etc. can be preferably used. It is also possible to include a coupler for creating a color image in the silver halide emulsion layer, and gelatin or other hydrophilic polymer substances such as polyvinyl alcohol, polyvinylpyrrolidone, etc. can be used as a binder. It is also possible to include Furthermore,
The silver halide emulsion layer can be sensitized in the wavelength range by using spectral sensitizing dyes such as cyanine dyes and merocyanine dyes, and may also contain various other photographic additives such as antifoggants, gold, and sulfur. Chemical sensitizers, hardeners, antistatic agents, etc. can be preferably added. Therefore, the present invention is effective regardless of whether the silver halide photographic material of the present invention is developed in black and white or in color.

[Example] The present invention will be explained in more detail with reference to Examples below.

Example 1 Anatase type titanium oxide with an average particle size of 027 μm was
The surface was treated with alumina and silica of 1.0% by weight in terms of ltos and 0.5% by weight in terms of 5ift. Furthermore, the surface was treated with 0.6% by weight polydimethylsiloxane by a dry method.

The obtained surface-treated titanium oxide was classified into coarse particles of 3μ or more using a turbo classifier manufactured by Nisshin Engineering ■, and then PET with an intrinsic viscosity (IV) of 0.65 was processed using a co-rotating twin-screw kneading extruder (automatic Company Z CM5
3/60) so that the titanium oxide content was 20% by weight. At this time, the screw rotation speed is f6
At 0 rpm, PET, titanium oxide, and PET were supplied in this order, and a vent hole was installed downstream of each supply port. I To
Vented with rr. The discharge rate was 150 kg/hour, and a filter was installed downstream of the kneading machine to filter out coarse particles and foreign matter, and then molded into pellets. (Selected as Beret (A))
On the other hand, the film of the edge portion obtained in the PET film forming process was crushed and dried at 200° C. and I Torr for 7 hours.

After drying, when an attempt was made to dissolve it in a solvent for IV measurement, most of it did not dissolve and remained solid. The obtained dried pulverized product and IVo, 65 PET chips were mixed in a weight ratio of 30:70.
Mix in a twin-screw kneading extruder (Japan Steel Works ■) that rotates in different directions.
TEX65) and kneaded. A ventro is provided downstream of the supply port, and 0. Vented at I Torr. The discharge amount is 2
After kneading at 00 kg/hour, the mixture was passed through a filter and formed into pellets. (referred to as pellet (B)) Pellets (A) and (B) are each supplied to an extruder, and a titanium oxide-containing layer is formed into a 220 μm 5PET by a coextrusion die.
An unoriented sheet was obtained by coextruding two layers to a thickness of 1500 μm.

Next, this sheet was stretched 35 times in the machine direction at 95°C, then 30 times in the transverse direction at 105°C, heat-set at 210°C, and then relaxed 2% in the transverse direction at 150°C in the middle zone. After applying the coating, it was cooled to room temperature and rolled up.

The obtained biaxially stretched film has a thickness of 160 μm and a transmittance of 5.
%, a white opaque film with a specific gravity of 10 (Film A
).

After applying a subbing layer consisting of a terpolymer of styrene-butadiene-maleic anhydride to the titanium oxide-containing layer side of the film, corona discharge was applied, and gelatin, which is normally used in color photographic paper, was applied on top of this. - A silver halide photographic light-sensitive material sample was prepared by applying a silver halide photographic emulsion to a dry film thickness of 15 μm.

The whiteness, resolution, gloss, and protrusion defects of the obtained sample were measured as described below, and the evaluation results are shown in Table 1.

[Measurement method] a Gokiou 1 The raw base before emulsion coating and undercoating was measured at 380 to 780 nm using Color Analyzer Model 607 (manufactured by Hitachi ■).
The spectral reflectance of J I 5-Z-8722 (1
The tristimulus values were determined according to 982), and the L0 value was calculated according to the CIE method, which was defined as whiteness.

A density line chart for measuring resolution is printed onto a reflection photographic element sample. After exposure, it is developed in the usual way, and the optical density difference of the wire print image is measured using a microdensitometer PDM-
5 (manufactured by Konica ■), and the value expressed by the following formula was defined as the resolution.

The number of visible surface projections per 100 crrr of reflective photographic element samples was counted and evaluated according to the following criteria.

0 to 30 pieces 7100 cm...○Excellent flatness.

31~100 pieces/100 crr?・−・ΔFlatness is not very good.

101 or more/100crr? ... × Poor flatness.

If the level is 0 or higher, there will be no practical problem, and the result will be a reflective photographic element with excellent gloss.

At a level below Δ, the surface looks rough and lacks luster.

Example 2 Using pellets (A) and (B) of Example 1, a three-layer coextrusion die was used to form a layer with pellet (B) of 150
A pellet (A) is placed on both sides of the layer so that the thickness is 0 μm.
A film B was obtained by forming a film in the same manner as in Example 1, except that the layers using the above were coextruded so that each layer had a thickness of 220 μm. Film B has a film thickness of 180 μm and a transmittance of 3.
It was a white film with a specific gravity of 11.

A silver halide photographic emulsion was coated on the obtained film B in the same manner as in Example 1 to prepare a silver halide photosensitive material sample. Table 1 shows the results of evaluating the obtained sample in the same manner as in Example 1.
Shown below.

Example 3 When making the pellet (B) in Example 1, a pellet (C) was prepared by using a polypropylene resin (Propaten P

A film C was obtained by forming a film in the same manner as in Example 2, except that the pellet (C) prepared above was used in place of the pellet (B).

The thickness, transmittance, and specific gravity of Film C were comparable to those of Film B.

A silver halide photographic emulsion was coated on the obtained film C in the same manner as in Example 1 to prepare a silver halide photosensitive material sample. Table 1 shows the results of evaluating the obtained sample in the same manner as in Example 1.
Shown below.

Examples 4 to 7 Styrene-divinylbenzene copolymer particles (Example 4), polyethylene naphthalate resin (Example 5), and crosslinking aid were used in place of the polypropylene resin used in the preparation of pellet (C) in Example 3. Using polybutylene terephthalate resin (Example 6) or triacetyl cellulose resin (Example 7) that was blended with and crosslinked by electron beam irradiation,
Film D1 film E1 film F1 film G were respectively created.

The thickness, transmittance, and specific gravity of the obtained films DG were comparable to those of the film B.

A silver halide photographic emulsion was coated on each of the obtained films DG in the same manner as in Example 1 to prepare silver halide photosensitive material samples. The obtained samples were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 8 Example 2 except that in the preparation of the pellet (B) of Example 1, the ears from film B were used as the ears of the film.
A film H was obtained by molding the film in the same manner as described above. Therefore, the center layer of film H contains a small amount of titanium oxide.

The thickness and transmittance of Film H were approximately the same as those of Film B, and the specific gravity was slightly larger.

A /SS rosin silver photographic emulsion was coated on the obtained film H in the same manner as in Example 1 to prepare a silver halogenide photosensitive material sample. The obtained sample was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 Barium sulfate particles with an average particle diameter of 0.3 μm and IV065
The PET resin was kneaded using a twin-screw kneading extruder TEX65 so that the barium sulfate content was 20% by weight, and pellet molding was performed.

The obtained pellet was extruded using a single layer extruder to a thickness of 1900 μm to form an unoriented sheet. Film I was then obtained in the same manner as in Example 1 including the stretching conditions.

Film I has a thickness of 180 μm, a transmittance of 4%, and a specific gravity of 1.
It was 3.

A silver halide photographic emulsion was coated on one side of the obtained film I in the same manner as in Example 1 to prepare a silver halide photosensitive material sample. The obtained sample was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 Film J was obtained in the same manner as in Example 2, except that calcium carbonate having an average particle size of 06 μm was used instead of titanium oxide.

The thickness and transmittance of Film J were approximately the same as those of Film B, and the specific gravity was slightly smaller.

A silver halide photographic emulsion was coated on one side of the obtained film J in the same manner as in Example 1 to prepare a silver halide photosensitive material sample. The obtained sample was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 A film K was obtained by forming a film in the same manner as in Comparative Example 1, using the pellet (A) instead of the pellet in Comparative Example 1. However, the unstretched sheet thickness was 1400 Atm, and the stretching ratio was 2.6 times in length and 30 times in width.

The thickness and transmittance of the film were almost the same as those of film B, and the specific gravity was 15.

A silver halide photographic emulsion was coated on the obtained film K in the same manner as in Example 1 to prepare a silver halide photosensitive material sample. Table 1 shows the results of evaluating the obtained sample in the same manner as in Example 1.
Shown below.

As is clear from Table 1, all of the light-sensitive material samples of the present invention using any of Films A to H as a support were excellent in whiteness, sharpness, and gloss.
In addition, the weight was appropriate, they did not float on water, many sheets could be transported at the same time, and they were easy to handle.

On the other hand, samples using films I and J as supports had poor sharpness, and in particular, those using film J did not have a smooth surface due to voids generated in the surface layer, resulting in prints with no gloss. Ta.

In addition, since the samples using Film K had a large specific gravity and were heavy, they tended to tear when hung after making a hole, and were poor in handling when handling a large number of sheets at the same time.

[Effects of the Invention] As explained in detail above, the present invention provides a silver halide photographic light-sensitive material having a white plastic film support that has excellent whiteness, sharpness and gloss, and has a weight that is appropriate for practical use. It is possible to provide a silver halide photographic material having the following.

Claims (2)

[Claims] (1) A photosensitive material in which a silver halide photographic emulsion layer is coated on a white plastic film support, wherein the white plastic film support is a laminate of two or more layers including a titanium oxide-containing layer and a void-forming polymer-containing layer. A silver halide photographic material comprising a biaxially stretched polyester film having a structure. (2) The silver halide photographic photosensitive material according to claim (1), wherein the titanium oxide-containing layer is the outermost layer on the side on which the silver halide photographic emulsion layer is coated in the white plastic film support according to claim (1). material.