JPH08286318A - Photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic material having excellent printing suitability and excellent stain-repelling property. SOLUTION: This photographic material comprises a supporting body having at least one layer of photosensitive silver halide emulsion layer in one side and at least one layer of reverse side layer in the other side and the reverse side layer consisting of at least one layer contains at least one kind of vinylidene chloride copolymers and at least one kind of low molecular weight glycidol compounds.

Description

Detailed Description of the Invention

The present invention is directed to at least one light sensitive silver halide emulsion layer on one side and at least one reverse side layer on the other side (reverse side).
It relates to a photographic material having a support with a delayer and characterized by good printability and good stain repellency. The support is preferably reflective.

Photographic materials having a reflective support, such as those used in photographic prints, must be printable on their reverse side.

Dot matrix printers, thermal printers and ink jet printers are also used among others. First, there is a need for good absorption of the applied printing inks, but also for good retention and high stain resistance so that the printed images are easy to read after processing.

Printing is conventionally done prior to processing. Thus, it is necessary that the quality of the image printed is not degraded by the processing.

On the other hand, however, contamination of the photographic material, which can be caused by, for example, oxidative developer components, must be avoided or easily removed.

In summary: The print must adhere and the stain must not adhere.

The object of the present invention is to provide such a material.

It has now been found that this object can be achieved by combining two substances placed in the reverse side layer.

The present invention therefore provides a photographic material of the above type which comprises in the reverse side layer, at least one of which is present, at least one vinylidene chloride copolymer and at least one low molecular weight glycidol compound.

Low molecular weight compounds are understood as compounds having a molecular weight of up to about 2000.

The vinylidene chloride polymers are 20 to 95 mol%, preferably 70 to 93 mol% of vinylidene chloride and 5 to 80 mol%, preferably 7 to 30 mol% of one or more comonomers, especially chlorides. Vinyl, (meta)
It is preferred to include acrylic acid or (meth) acrylic acid derivatives such as amides, nitriles and C ₁ -C ₄ -alkyl esters.

Vinylidene chloride polymers are especially 10 to 3
It is used in an amount of 00 mg / m ² , preferably 50 to 150 mg / m ² . They are 10 to 1000 nm, especially 30
It is preferably used as a dispersion having an average particle diameter of ˜300 nm.

Examples of vinylidene chloride polymers to be used in accordance with the present invention are: wt% average particle diameter P1 vinylidene chloride / vinyl chloride (85/15) 80 nm P2 vinylidene chloride / butyl acrylate (87/13) ) 65nm P3 vinylidene chloride / methyl acrylate (90/10) 134nm P4 vinylidene chloride / butyl methacrylate (80/20) 210nm P5 vinylidene chloride / methyl methacrylate (84/16) 95nm P6 vinylidene chloride / methyl acrylate (86) / 14) 123nm P7 vinylidene chloride / methyl methacrylate / acrylic acid (88/8/4) 197nm P8 vinylidene chloride / acrylic acid (93/7) 234nm P9 vinylidene chloride / methacrylic acid (91/9) 158nm P10 vinylidene chloride / Acrylic acid (88/12) 110nm P11 Vinylidene chloride / methacrylamide (93/7) 73nm P12 Vinylidene chloride / Methyl acrylate / (82/4/11/3) 139nm Acrylonitrile / Acrylic acid P13 vinylidene chloride / methyl acrylate / itaconic acid (88/10/2) 65nm P14 vinylidene chloride / acrylonitrile / (85/6/9) 80nm P15 vinylidene chloride / methacrylonitrile (91/9) 140nm methacrylic acid The methyl glycidol compound preferably has the general formula (I)

[0014]

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[Wherein R is a branched or unbranched, saturated or unsaturated alkyl residue having 5 to 20 carbon atoms, A is an unsubstituted or substituted aromatic residue, n is 5
Is an integer of 15 and m is an integer of 0 to 5].

These compounds are 1 to 100 mg / m ² ,
It can be preferably applied in an amount of 10 to 30 mg / m ² .

Examples of glycidol compounds according to the invention are:

[0018]

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[0019]

In a preferred embodiment, the reverse side layer, of which at least one is present, comprises at least one anionic or nonionic wetting agent and at least one antistatic substance. Suitable wetting agents are fluorinated surfactants, alkyl sulphonates, alkylaryl sulphonates, succinic acid half-esters, sulphosuccinic acid esters, saponins, alkylarylalkyl ethers, the choice being the type described. It is not necessary to be limited to the compounds of

Suitable antistatic agents are substantially ion-conducting compounds, metal oxides and organic compounds having a highly conjugated bond system capable of electronic conduction.

Among the ion-conducting materials, cationic and anionic active electrolytes are described. Materials with high molecular weight are preferred. These can contain, for example, quaternary nitrogen groups, sulfo groups or carboxyl groups. For example, it is preferred to use salts of polystyryl-sulphonic acid and its copolymers.

Among the metal oxides used are Si, A
It is an oxide of 1, Zn, Sn, Ti, Mo, W, and V.

Antistatic agents having a highly conjugated bond system are EP 0 440 957 and EP 0 593 1
11 are described.

These substances are conjugated systems capable of electron conduction, in contrast to ion-conducting compounds. A dispersion of polythiophene is described, which is suitable as an antistatic agent for plastic substrates. Certain thiophenes can be polymerized in the presence of polyacids and can be used as stable compositions in water for further applications. These compounds can be used to make transparent antistatic coatings on plastic materials that are unaffected by atmospheric humidity.

Antistatic agents having a highly conjugated bond system are preferred in the present case because they have no negative impact on stain repellency and printability. In particular, the formula (I
I):

[0027]

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[Wherein R ₁ and R ₂ independently of one another represent hydrogen or a C ₁ -C ₄ alkyl group or, taken together, are optionally substituted C ₁ -C ₄ alkylene. Residues, preferably methylene residues, which may optionally be substituted by alkyl groups, 1,2-ethylene residues, 1,3-propylene residues or optionally C ₁
Form a 1,2-cyclohexylene residue which may be substituted by —C ₁₂ alkyl or phenyl groups] using the oxidizing agents conventionally used for the oxidative polymerization of pyrrole. , And / or oxygen or air in the presence of polyacids, preferably in an aqueous medium, at a temperature of 0-100 ° C.

[0029]

[Chemical 4]

Obtained in the presence of polyanions by the oxidative polymerization of 3,4-dialkoxythiophenes of the formula [wherein R ₁ and R ₂ have the meanings given for formula (II)]. To be Due to oxidative polymerization, polythiophenes receive a positive charge, which is not shown in the formula, as their number and position cannot be determined accurately.

In the case of polymerization, the thiophenes of formula (III), the polyacid and the oxidizing agent are dissolved in an organic solvent, or preferably water, and the solution is stirred at the intended polymerization temperature until the polymerization is complete.

When air or oxygen is used as the oxidant, the solution containing thiophene, polyacid and optionally catalytic amounts of metal salts is filled with air or oxygen until the polymerization is complete.

The polyanions used are the anions of polymerized carboxylic acids such as polyacrylic acids, polymethacrylic acids or polymaleic acids, and polymerized sulphonic acids such as polystyrene sulphonic acids and polyvinyl sulphonic acids. These polycarboxylic acids and polysulfonic acids can also be copolymers of vinylcarboxylic acids and vinylsulfonic acids with other polymerizable monomers such as acrylic acid esters and styrene.

The molecular weight of the polyacids providing the polyanions is preferably 1000 to 2,000,000, particularly preferably 2000 to 500,000. Polyacids or their alkali metal salts are commercially available, eg polystyrene sulphonic acids and polyacrylic acids, or else can be prepared using known methods (eg Houben-Weyl, Methoden.
der organischen Chemie, v
olumin E20, Makromolekulare
Stoffe, part 2, (1987), pag
See es1141 et seq.).

Preparation of 3,4-polyethylenedioxythiophene solution: 20 g of free polystyrene sulphonic acid ( _Mn approx. 40,000), 21.4 g of potassium peroxydisulfate and 100 mg of iron (III) sulphate.
Is first stirred in 2000 ml of water. 8g 3,4
-Add ethylenedioxythiophene with stirring.
The solution is stirred at room temperature for 24 hours. Both, 100 g anion exchanger and 100 g cation exchanger moistened with water are then added and stirred for 8 hours.

Ion exchangers are removed by filtration. A prepared solution with a solids content of about 1.2% by weight is obtained.

In addition to the additives mentioned, the reverse side layer can contain further additives. Spacers, for example particles of polymethylmethacrylate, can be considered, which can also be wax-coated to act on the lubricity. Particles of matting agents such as SiO ₂ , TiO ₂ , starch or polyacrylonitrile are also considered to improve the surface roughness and thus for example some handling or to improve the suitability of the surface for marking with pencils. You can Pigments for shading the white can also be added with the optical brightener. Substances having an adhesive action for improving spliceability can also be considered.

The front side of the material can contain any desired structure common in photographic materials as the light-sensitive silver halide emulsion layer or optionally further layers.

This structure is preferably the conventional layer structure for color negative papers, in this case blue-sensitive,
A yellow coupling, a green-sensitive, a magenta-coupled and a red-sensitive, a cyan-coupled silver halide emulsion layer are applied in this order on the support, the silver halide in the emulsion layer being of the order of at least 95 mol%. Contains silver chloride. The photosensitive layers are conventionally separated by an intermediate layer. At least one protective layer is applied on top of the top photosensitive layer.

In another preferred embodiment, layers of black and white paper can also be applied. Fixed-tone and variable-tone papers are included, the latter conventionally sensitized for the blue and green spectral regions. The gradation can be adjusted to a desired value by selective exposure in the blue or green region.

[0041]

【Example】

TEST CRITERIA Tests were performed on color negative paper with a polyethylene coated paper support on both sides. After exposure, processing (developing, bleaching / fixing, etc.) was performed using the standard E92 method.

Contamination Repulsion The test medium was a highly oxidized CD92 developer.
This is an absorbent roller (absorbent roll)
er) was applied to the test material. The sample treated in this way is then hand-sprayed.
It was rinsed with r) and the degree of contamination of the surface of the layer was evaluated visually. Rating systems 1-5 with increasing pollution: rating 1, none; rating 5, very severe pollution.

Printability Tests were carried out using conventional dot matrix printers and thermal printers. The printed images were evaluated before and after processing. Evaluation system 1 with decreasing print density
5: Rating 1, highest print density; Rating 5, lowest print density.

Antistatic property The surface resistance was measured. Measurement electrodes with lengths of 10 cm and 1 cm apart were used. The value described is the surface resistance per 1 cm in length, and will be described as Ω / in the subsequent sentence. Sample is 50%
Preconditioned for 24 hours at room temperature (20 ° C.) at relative humidity of. The measurements were carried out before and after the treatment of the test samples. Development was carried out using the method described above.

Examples Example 1 (Invention) The reverse side of paper coated with polyethylene on both sides was first subjected to corona discharge treatment. An aqueous formulation having the following preparative ingredients was then applied on the surface: P-
3 about 59% by weight aqueous, anionic dispersion; solid application ratio 150 mg / m ² ; poly- (3,4-ethylene-
Dioxythiophene) / polystyrene sulfonic acid dispersion liquid, total solid application ratio 15 mg / m ² ; 5 of compound I-1
0% by weight aqueous solution, solid application ratio 15 mg / m ² ; Formula (I
V)

[0046]

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1% by weight aqueous solution of the compound of, solid application ratio 5
mg / m ² .

Example 2 (Comparative) As Example 1, but without the compound I-1.

Example 3 (Comparative) As Example 1, but with 1 m instead of compound I-1.
Formula of 30mg per ²

[0050]

[Chemical 6]

The compound of was used.

Example 4 (Invention) As in Example 1, but using 55% by weight anionic dispersion of P-2, solid application ratio 80 mg / m ² , instead of vinylidene chloride / methyl acrylate. The following was also applied: Poly-according to Example 1 at a solid application rate of 8 mg / m ^2.
(3,4-ethylenedioxythiophene) dispersion, 12
1 wt% aqueous solution of the compound of formula (IV) in mg / 50 wt% aqueous solution of Compound I-1 in application rate of m ^2, and a solid application rate of 5 mg / m ^2.

Example 5 (Invention) As in Example 4, but using a 55% by weight aqueous anionic dispersion of P-12.

Example 6 (Invention) As in Example 4, but using a 55% by weight aqueous dispersion of P-6.

Example 7 (Invention) As in Example 4, but using a 45% by weight aqueous dispersion of P-5.

Example 8 (Comparative) As Example 7, but without the addition of P-5 and Compound I-1.

Samples from the examples were examined using Method E92, untreated (u) and after treatment (p). The following values have been determined:

[0058]

[Table 1]

Example 9 (Invention) The layer used was a biaxially oriented polyester film with uniformly distributed micropores to render the support opaque. The polythiophene composition of Example 1 was added to a substrate layer consisting of a ternary polymer of vinylidene chloride / methyl acrylate / itaconic acid 88/10/2 blended with colloidal silica gel with a specific surface area of 100 m ² / g to form a layer The solid application rate at was adjusted to 4 mg / m ² . An aqueous formulation having the following preparative components was then applied on this substrate: 59% by weight aqueous anionic dispersion of P-3, solid application rate 100 mg / m ² . Poly- (3,4-ethylenedioxythiophene) dispersion in the composition described in the case of Example 1, solid application ratio 5 mg / m ² . Formula (I-
50% by weight aqueous solution of the compound according to 1). Solid application rate of 15 mg / m ² in layers. 1% by weight aqueous solution of the compound of formula (I), solid application ratio 5 mg / m ² in layers.

Example 10 (Invention) Similar to Example 9, but the antistatic layer was applied without adding the poly- (3,4-ethylenedioxythiophene) dispersion.

The tests of Examples 9 and 10 revealed the following results:

[0062]

[Table 2]

Example 11 An antistatic coating is first applied on the reverse side of a corona discharge-treated layer support of polyethylene coated paper on both sides, then the following layers are applied on the front side in the order listed. This produced a multi-layer color photographic material. For all amounts given are 1 m ^2, the amount of silver halide is described as AgNO _3: the first layer (substrate layer) Gelatin second layer of 0.10 g (blue - sensitive layer) 0.50 g AgNO _3, and 1 0.25 g gelatin 0.42 g yellow coupler Y-1 0.18 g yellow coupler Y-2 0.50 g tricresyl phosphate (TCP) 0.10 g stabilizer ST-1 0.70 g blue sensitizer S-1 Blue-sensitive silver halide emulsion prepared from 0.30 mg of stabilizer ST-2 (99.5 mol% chloride and 0.5 mol% bromide, mean particle diameter 0.9 μm) Second layer (intermediate) layer) 1.10 g TCP fourth layer of scavenger O-2 0.12 g of scavenger O-1 0.06g of gelatin 0.06g (green - sensitive layer) 0.40 g AgNO _3, and 0 .77 g of gelatin 0 41 g magenta coupler M-1 0.06 g stabilizer ST-3 0.12 g scavenger O-2 0.34 g dibutyl phthalate (DBP) 0.70 mg green sensitizer S-2 0.50 mg Green-sensitive silver halide emulsion prepared from stabilizer ST-4 (99.5 mol% chloride and 0.5 mol% bromide, average particle diameter 0.47 μm) Fifth layer (UV-protective layer) 1.15 g Gelatin 0.50 g UV absorber UV-1 0.10 g UV absorber UV-2 0.03 g scavenger O-1 0.03 g scavenger O-2 0.35 g TCP 6th layer (red - sensitive layer) 0.30 g of AgNO _3, and 1.00g of gelatin 0.46g of cyan coupler C-1 0.46g of TCP 0.03 mg of red sensitizer S-3 0.60 mg of stabilizer Red-feel prepared from ST-5 -Sensitive silver halide emulsion (99.5 mol% chloride and 0.5 mol% bromide, average particle diameter 0.5 μm) Seventh layer (UV protective layer) 0.35 g gelatin 0.15 g UV absorber UV-1 0.03 g AV absorber UV-2 0.09 g TCP 8th layer (protective layer) 0.90 g gelatin 0.05 g optical brightener W-1 0.07 g polyvinylpyrrolidone 1.20 mg silicon Oil 2.50 mg of polymethylmethacrylate microspheres (average particle diameter 0.8 μm) 0.30 g of hardener H-1 color photographic recording material is exposed through a step optical wedge. During the exposure an additional filter is introduced in the beam path of the exposure in such a way that the wedge appears as neutral at an optical density of D = 0.6. The exposed material is processed using the following method: Step Time Temperature Development 45 seconds 35 ° C Bleach / Fix 45 seconds 35 ° C Rinse 90 seconds 35 ° C The processing solution was of the following composition: Color Developer Tetra. Ethylene glycol 20.0 g N, N-diethylhydroxylamine 4.0 g (N-ethyl-N- (2-methanesulfonamido) ethyl) 5.0 g-4-amino-3-methylbenzenesulfate potassium sulfite 0.2 g Carbonic acid Potassium 30.0 g Polymaleic anhydride 2.5 g Hydroxyethanediphosphonic acid 0.2 g Optical brightener (4.4′-diaminostilbene sulfonic acid derivative) 2.0 g Potassium bromide 0.02 g Water to make 1 liter Adjust the pH value to 10.2 using KOH or H ₂ SO ₄ .

Bleaching / fixing solution Ammonium thiosulfate 75.0 g Sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (iron / ammonium salt) 45.0 g Water to 1 liter, pH value adjusted to 6.0 with ammonia or acetic acid .

[0065]

[Chemical 7]

[0066]

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[0067]

[Chemical 9]

[0068]

[Chemical 10]

[0069]

[Chemical 11]

Pouring of Antistatic Layer An aqueous mixture prepared from the following ingredients was applied on the reverse side of the material: a) 59% by weight aqueous anionic dispersion of P-3; solid application ratio 150 mg / m ² ; b) Poly-3,4-ethylenedioxythiophene / polystyrene-sulphonic acid dispersion, ratio 1: 7; solid application ratio, 25 mg / m ² ; c) 50% by weight aqueous solution of compound I-1; solid application ratio 20.
mg / m ² , d) 1 wt% aqueous solution of compound IV; solid application ratio 5 mg /
m ² .

Example 12 Similar to Example 11, but without a) in the antistatic layer.

Example 13 Same as Example 11, but with the following changes to the antistatic layer:

A) Solid application rate of only 100 mg / m ²
B) In place of the poly-3,4-ethylenedioxythiophene / polystyrene dispersion, 1 of polystyrene sulfonic acid is used.
Solids application rate of 20 mg / m ² with 0% by weight solution.

Example 14 (according to EP 394 791) Same as Example 11 but with an antistatic layer of the following composition: a) 58 mol% styrene, 38.5 mol% butadiene and 3.5. 50% by weight aqueous dispersion of a copolymer prepared from mol% acrylic acid; solid application rate 15 mg / m
² , b) 20 of octadecene succinic acid monobenzyl ester
Wt% aqueous dispersion; solid application ratio of 85 mg / m ² , c) 10 wt% solution of sodium polystyrene sulfonate; solid application ratio of 45 mg / m ² , d) 10 wt% solution of compound IV; solid application ratio of 9 mg /
m ² .

The samples of Examples 11-14 were examined in untreated (u) and treated (p):

[0076]

[Table 3]

The main features and aspects of the present invention are as follows.

1. At least one light-sensitive silver halide emulsion layer on one side, and at least one light-sensitive silver halide emulsion layer, characterized in that the reverse side layer, at least one of which is present, comprises at least one vinylidene chloride copolymer and at least one low molecular weight glycidol compound. A photographic material having on its side a support having at least one reverse side layer.

2. The photographic material as described in the above item 1, wherein the support is reflective.

3. 20-9 vinylidene chloride copolymer
Photographic material according to claim 1, characterized in that it consists of 5 mol% vinylidene chloride and 5-80 mol% of one or more comonomers.

4. Vinylidene chloride copolymer 10-3
The photographic material according to the above item 1, which is used in an amount of 00 mg / m ² .

5. The glycidol compound has the formula

[0083]

[Chemical 12]

[Wherein R is a branched or unbranched, saturated or unsaturated alkyl residue having 5 to 20 carbon atoms, A is an unsubstituted or substituted aromatic residue, n is 5
Is an integer of -15, and m is an integer of 0-5].

6. Glycidyl compound 1-100 mg /
The photographic material according to the above item 1 used in an amount of m ² .

7. Photographic material according to claim 1 characterized in that the reverse side layer further comprises at least one anionic or nonionic wetting agent and at least one antistatic substance.

8. The substance having an antistatic effect used is represented by the formula

[0088]

[Chemical 13]

[Wherein R ₁ and R ₂ independently of one another represent hydrogen or a C ₁ -C ₄ alkyl group or, together, are optionally substituted C ₁ -C ₄ alkylene. Residues, preferably methylene residues, which may optionally be substituted by alkyl groups, 1,2-ethylene residues, 1,3-propylene residues or optionally C ₁
Form a 1,2-cyclohexylene residue which may be substituted by -C ₁₂ alkyl or phenyl groups] by oxidative polymerization of 3,4-dialkoxythiophenes in the presence of polyanions formula

[0090]

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The photographic material as described in the above item 7, which is at least one compound of the formula: wherein R ₁ and R ₂ have the above meanings.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Alfred Kolberg Germany 51061 Cologne Huerland Schutlerse 110 (72) Inventor Beate Beber Germany 42799 Reichlingen Johannisberg 16 (72) Inventor Gujunter Herring Germany 51519 Odenthal Indahirdscheid 16 (72) Inventor Friedrich Jonas Germany 52066 Aachen Krugenaufen 15 (72) Inventor Berner Kraft Germany 51377 Lef Erkusen Naue Nasichtraße 29

Claims (1)

[Claims] 1. At least one layer on one side, characterized in that the reverse side layer, at least one of which is present, comprises at least one vinylidene chloride copolymer and at least one low molecular weight glycidol compound. A photographic material having a light sensitive silver halide emulsion layer and a support having at least one reverse side layer on the other side.