JPH07119960B2 - Photographic recording material with improved protective layer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a separating agent that is soluble in an alkaline processing liquid in at least one protective layer.
And high molecular weight particles (high mol
A photographic recording material containing ecular weight particles).

Hydrophilic colloids such as gelatin present in the outer layers of photographic recording materials, especially silver halide recording materials, cause tackiness of the recording materials at elevated temperatures and high atmospheric moisture.
s) so that such materials tend to stick together when packaged, for example as a stack. This tendency of different parts of the recording material to stick together or to one another in contact with one another gives rise to many difficulties.

The outer layer of the recording material is delustered by incorporating finely divided inorganic compounds such as silicon dioxide, manganese oxide, titanium dioxide or calcium carbonate or organic compounds such as polymethylmethacrylate or cellulose acetate propionate, whereby It is known to overcome the above drawbacks by reducing their tackiness.

The photographic light-sensitive material disclosed in DE-A-2,758,767 has an outer non-light-sensitive gelatin layer containing colloidal silica particles having a size of 7 nm to 120 nm and a polymer latex composed of particles having a size of 30 nm to 80 nm. This gelatin layer is said to confer on the photographic material increased break resistance and dimensional stability.

However, one drawback of photographic materials with such layers is that the additives reduce the transparency of the layers and that the materials are wound especially at temperatures in the range 35 ° C to 40 ° C and High moisture content (eg 85% or more relative humidity)
Then, sensitometric proper
That is, contact patches that impair ties will inevitably occur.

According to DE-OS 2,919,822, there are preformed alkali-insoluble and water-insoluble polymer particles which have a relatively narrow particle size distribution and are suitable for use as a matting agent in photographic layers. It is obtained by suspension copolymerization of maleic anhydride and 1-olefins (German Publication Nos. 2,919,822 and 3,144,793). The particles are left on the surface after the photographic material has been processed.

Numerous attempts have been made to find alkali-soluble polymer particles which are removed from the surface when the photographic material is treated with an alkaline processing liquid; US Pat. No. 2,322,037.
See U.S. Pat. No. 878,520, U.S. Pat. No. 4,094,848, U.S. Pat. No. 4,142,894, U.K. Patent No. 2,012,978, U.K. Patent No. 1,055,713, and German Patent Publication No. 3,331,542.

Graft polymers based on methacrylic acid and methylmethacrylate on styrene-maleic acid half-ester copolymers as graft base and soluble in alkaline medium are disclosed in DE-A-3,331,542. These graft polymers partially dissolve at pH values of 6.2 to 6.5 when cast in the absence of gelatin. This premature dissolution of the particles is due to the casting solution
It is particularly disadvantageous to include an additive such as silica sol adjusted to an alkaline pH as part of the method of making the silica sol and for the purpose of stabilizing the solution. The break strength and surface wear resistance of layers containing silica sol are severely compromised. DE-A-3,333,142 discloses the addition of copolymers containing polymethylmethacrylate units.

In a photographic recording material comprising a support, at least one information recording layer, and optionally other layers, at least one layer comprises an alkali-soluble separating agent and a water-insoluble high molecular weight compound.
Contains HM (but does not contain colloidal silica),
A photographic recording material, wherein the high molecular weight compound HM has the following formula: Where R ¹ , R ² , R ³ may be the same or different and represent hydrogen, alkyl, especially alkyl or halogen having 1 to 4 carbon atoms, especially Cl, L A photographic recording material has now been found which is characterized in that it contains a repeating unit of a chemical bond or a commonly used linking member, and X represents a reactive group.

"Reactive group" means a group capable of performing addition or condensation reaction with a substance containing NH _2, COOH or OH groups forming such materials and chemical bonding. In particular, they include groups capable of reacting with gelatin in a defined manner.

The layer also generally includes a binder. The ratio of binder to high molecular weight compound HM to separating agent is preferably 1: 0.2-5.0: 0.3-
Within the range of values of 2.0, especially about 1: 1.1: 0.5. Preferably, the layer thickness is in the range 0.2 μm to 5 μm.

Reactive group X of the following are particularly preferred: -Cl, -Br, -J, -OSO 2 -R 4, −CO ₂ CH ₂ CN, −CO ₂ CH ₂ CO ₂ C ₂ H ₅ , −CO ₂ CH ₂ CONH ₂ , −CO ₂ −CH ₂ COCH ₃ , _{-CO 2 N = CHCH 3, -CO} 2 N = C (CH 3) 2, −CO ₂ CH ₂ CH ₂ Br, −CO ₂ CH ₂ CH ₂ CN, In the above formula, R ⁴ is alkyl, aryl or aralkyl.

In a particularly preferred embodiment, the repeating unit of the high molecular weight compound HM has the following structure: (In the formula, R ¹ , R ² , R ³ and X have the above-mentioned meanings, L ¹ represents CONH, COO or a phenylene group, L ² represents an alkylene group having 1 to 20 carbon atoms or a carbon atom.
Represents an arylene group having 6-20, L ³ represents a COO, OCO, CONH, NH—CO—O, NHCO, SO ₂ NH, NHSO ₂ or SO ₂ group or O, and m represents 0 or an integer. , N represents 0 or an integer).

In another particular embodiment, X is halogen at the terminal position,
Epoxy, _{imide, NCO, CH = CH 2,} C (CH 3) = CH 2 or CN
Represents a group substituted by. The following are particularly preferred examples of these repeating units: In another particularly preferred embodiment, the high molecular weight compound HM
In addition to the above-mentioned repeating units, in particular, substituted or unsubstituted, structurally different repeating units CM derived from acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds or acrylonitriles. To do. In a preferred embodiment, the high molecular weight compound HM has a glass transition temperature of at least 50 ° C. The glass transition temperature can be adjusted to a desired value by proper selection of the above monomers.

Examples of Monomer CMs are found in Polymer Handbook, Chapter III,
“Glass transition temperature of polymer” (Polymer Handbook, se
ction III, “The Glass Transition Temperatures of
Polymers "). Examples include ethylmethacrylate, methylmethacrylate, isobornylmethacrylate, phenylmethacrylate, cyclohexylchloroacrylate, methylchloroacrylate, 4
-Tert-butyl styrene, 2.5-dimethyl styrene, styrene, vinyltoluene, acrylonitrile and methacrylonitrile.

Examples of suitable high molecular weight compounds are shown in the formulas below, in which the monomer content is given in weight percent.

The alkali-soluble separating agent is preferably a separating agent which is soluble in conventional alkaline processing baths, especially at pH values above 9.0. The separating agent preferably has an average particle size of 0.5 μm to 6 μm, in particular 1 μm to 3 μm.

Conventional alkali-soluble separating agents can be used. As disclosed in German Official Gazette No. 3,331,542,
Graft copolymer particles obtained from methacrylic acid and methyl methacrylate on a graft base of α-olefin- or styrene-maleic acid half amide or maleic acid copolymer having a particle size of 0.5 μm to 8 μm and a particle size distribution of ± 1 μm. Is particularly preferable.

Alkyl-hydroxyalkyl-
Cellulose derivatives which are substituted by-) and by partial esterification of dicarboxylic acids are also suitable alkali-soluble separating agents. Other alkali-soluble separating agents are described in U.S. Pat. No. 2,992,101, U.S. Pat. No. 4,094,848, U.S. Pat. No. 4,142,894 and British Patent No. 1,055,713.

The separating agent is preferably 30-500 mg / m ² , especially 50-200 m per layer.
The high molecular weight compounds HM to be used according to the invention used at g / m ² preferably have an average particle size of 0.02-0.5 μm, in particular 0.05-0.20 μm.

Water-insoluble high molecular weight compounds used according to the invention
HM is preferably a copolymer. They can be prepared by emulsion polymerization or by polymerization of the monomers in an organic solvent, followed by dispersion of the solution in latex form in an aqueous solution of gelatin.

Free-radical polymerization of ethylenically unsaturated monomers involves the thermal decomposition of chemical initiators by the action of reducing agents on the oxidizable compounds (redox initiators) or by physical action such as irradiation by ultraviolet rays or other high-energy radiation, high frequency, etc. It is started by the addition of the free radicals formed by. Some examples of the most important chemical initiators are persulfates (eg ammonium persulfate, potassium persulfate, etc.) Hydrogen peroxide, peroxides (eg benzoyl peroxide or tertiary butyl peroctoate, etc.) Azonitrile compounds (eg 4,4′-azo-bis-4-cyanovaleric acid, azo-bis-isobutyronitrile, etc.) and the like are included. An example of a conventional redox initiator is hydrogen-
Included are iron (II) salts, potassium persulfate, sodium pyrosulfite and cerium-IV salt-alcohols and the like. Examples of initiators and their function are described in F.F. A. Bovey (FA
Bovey), Emulsion Polymerization, Interscience Published Incorporated., New York, 1955, pp. 59-93 (Emulsion Polymerisation, In
terscience Publishers Inc., New York, 1955, pages 5
9 to 93). The emulsifier used in the emulsion polymerization can be a compound having a surface-active effect. Preferred examples of such compounds include soaps, sulphonates, sulphates, cationic compounds, amphoteric compounds and high molecular weight protective colloids. Specific examples of emulsifiers and their function can be found in Belgian Chemical Industry, 28, 16-20, 1963 (Belgische Chemische.
Industrie, Volume 28, pages 16 to 20, 1963).

Production Example (High Molecular Weight Compound B) Alkyl diphenyl ether disulfonate
A solution of 4 g of phenyl ether disulphonate) and 500 g of water is heated to 70 ° under nitrogen. A mixture of 150 g of methyl methacrylate and 40 g of chloroethyl methacrylate, a solution of 1 g of potassium peroxodisulfate in 50 of water and a solution of 0.5 g of sodium metabisulphite in 50 g of water is added simultaneously within 90 minutes. The reaction mixture is stirred for 2 hours, then the pH is adjusted to 7 and a portion of the water is distilled off until the solids content is 20%.

The layer containing the separating agent and the high molecular weight compound HM is preferably an outer layer generally containing a hydrophilic colloid.

The following are examples of suitable hydrophilic colloids: proteins such as gelatin, gelatin derivatives such as acetylated gelatin, phthaloyl gelatin and succinyl gelatin, albumin, casein, acacia, agar, alginic acid, cellulose derivatives such as An alkyl ester of carboxymethyl cellulose, preferably a methyl or ethyl ester, hydroxyethyl cellulose, carboxymethyl cellulose, a synthetic polymer,
For example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid salt, polymethacrylic acid salt, polymaleic acid salt or polystyrenesulfonic acid salt, preferably sodium or potassium salt, and at least one monomer of the polymer. A copolymer containing. Among these hydrophilic colloids, amphoteric polymer electrolytes such as gelatin, gelatin derivatives, casein and other protein compounds have a particularly pronounced effect. The hydrophilic colloids can be used alone or in combination. Gelatin, gelatin derivatives, casein and other protein compounds are among the preferred colloids.

From 0.1 to 1% by weight of surfactant, based on the weight of water present, can be added to the casting solution for these layers. Examples of suitable surfactants include saponins and other naturally occurring compounds, nonionic surfactants,
For example, polyalkylene oxides, glycerol compounds such as monoglycerides or glycidol compounds and one or more acid groups such as one or more carboxylic acids, sulfonic acids, phosphoric acids, sulfonic acid esters or phosphorus. Anionic surfactants containing acid ester groups are included. Particularly suitable surfactants are
U.S. Pat.Nos. 2,271,623, 2,240,472, 2,288,226,
No. 2,676,122, No. 2,676,924, No. 2,676,975, 2,691,566
No., 2,721,860, 2,730,498, 2,742,379, 2,739,8
91, 3,068,101, 3,158,484, 3,201,253, 3,21
0,191, 3,294,540, 3,415,649, 3,441,413, 3,
442,654, 3,475,174 and 3,545,974, German published gazette 1,942,665, British patent 1,077,317 and 1,198,
No. 450 and Ryohei Oda et al., "Synthesis of surfactants and their applications" (Kansho, 1964) ["Kaimen Kasseizai No Gosei
to Sono Ohyo ", Ryohei Oda et al (published by Maki
Publishing Co, 1964)], J. W. Perry and A. M. Schwartz (JW Perry and AMSchw
"Surface Active Agent" by artz)
s ") [published by InterScience Publications, Inc. in 1958 (published by
Interscience Publications Inc., 1958)], J.
Pee. “Encyclopedia of Surface Active Agents, by JP Sisley”
Volume 2 ("Encyclopedia of Surface Active Agents",
Volume 2) [published by Chemical Publishing Co, 196
4)], "Surfactant Handbook" 6th edition (Sangyo Tosho, 1966 1)
February 20) ["Kaimen Kassei Zai Binran" 6th Edtion
(Published by Sangyo Tosho Co., 20th December 196
6)], etc. For example, German publication number
Wetting agents containing fluorine can also be used, as described in 1,961,638.

These surfactants can be used alone or in the form of a combination. Particularly preferred compounds are those containing an OSO ₃ M group, such as those of the general formula R—O—SO ₃ M or R— (OCH
₂ CH ₂ ) _n- OSO ₃ M (wherein R represents an alkyl group having 8 to 30 carbon atoms, M represents an alkali metal or ammonium ion, and n represents an integer having a value of up to 20). ) Ordinary alcoholic sulfonic acid esters and the general formula: (Wherein R ′ represents hydrogen or an alkyl group containing 1 to 18 carbon atoms, R ″ represents an alkyl group containing 1 to 18 carbon atoms, and M represents an alkali metal ion or Represents an ammonium ion, m represents a positive integer having a value of 0 to 20, and n represents the number 3 or 4).

The recording material according to the invention is preferably a material comprising at least one photosensitive silver halide emulsion layer. The layer to be used according to the invention is preferably
It is arranged as the outermost layer, ie the outermost layer on the front and / or back surface of the material. The usual types of silver halide emulsions can be used and they are preferably chemically and spectrally sensitive. The materials are conventional additives such as brightening agents, anti-fogging agents stabilizers, filter layers, binders, hardeners, plasticizers, lubricants.
cants), antistatic agents, color couplers, etc .: Research Disclosure 1978 17
643, pp. 22-31 (Research Disclosure 17643 of 1978, p.
ages 22 to 31) and Research Disclosure 197
9-16, pp. 647-651 (Research Disclosure 18716 of 197
9, pages 647 to 651). The recording material can be, for example, a color negative material, a color reversal material or a paper material. They can be processed by known methods. Methods for processing color reversal materials are shown, for example, in German publication No. 3,113,009 and German publication No. 3,226,163. For processing color photographic paper materials, for example, German Official Gazette No. 3,
107,173, and the processing of color negative materials is described in DE-A-3,029,209.

The layer according to the invention can be used to provide a hardener to the gelatin layer of a photographic material. In this known method of curing by applying a coating of hardener, the hardener diffuses into the underlying layer. This method allows color photographic multilayer materials to be cured, for example, in a single step. So-called rapid hardening agents can be used for this purpose. Examples of such hardeners include N-carbamoyl- and N-carbamoyloxy-pyridinium compounds (US Pat. No. 3,880,665), free betaines or N-carbamoylpyridinium compounds containing sulfo groups in the form of metal salts (US Pat. Patent No. 4,036,952), 2-alkoxy-N-carboxy-dihydroquinoline esters (U.S. Pat. No. 4,013,468), isoxazolium salts (U.S. Pat. No. 3,321,313) and carbodiimides (German Pat. No.) is included.

The compounds according to the present invention not only effectively prevent tackiness, but also the breaking strength and wet scratch strength.
Improving both ngth) (resistance to surface wear) is both surprising and unexpected. Adhesion-reducing substances, such as silica sols, usually cause a significant reduction in breaking strength and surface abrasion resistance.

Examples Casting solutions for coating layers are made from the following materials: ¹ ) The graft copolymer of DE-A-3,331,542 was used as the separating agent.

The pH of the solution is 6.0 to 6.5 and the wet application
ation) was 50 g / m ² .

The hardener has the following formula: Equivalent to.

The coating layer solution is cast onto an uncured color negative film and dried.

After drying, the presence of glossy patches,
Ease of removal from the cartridge, yellow spots (yell
The samples were inspected for the presence of ow patches and graininess as described in DE-OS 3,331,542. The breaking diameter and wet scratch strength (Newton) were determined as follows: a) Breaking strength The breaking diameter of the photographic recording material is Research Disclosure.
No.25 302, May 1985 (Research Disclosure No.25 3
02, May 1985).

b) Wet scratch strength Place the photographic material on a horizontal sample holder in a bath filled with water at 38 ° C, 10 ° DH with the active layer facing upwards. The sample to be measured was completely covered with water. After allowing the sample to swell in water for 5 minutes, a firmly held steel ball is passed over the sample at a speed of v = 30 mm / sec. The force (Newton) by which the steel ball presses the outermost protective layer of the sample is 0 to 10 Newton (10) when the steel ball passes through the path of 20 cm in length.
N) is adjusted to increase continuously. The force at which an indication of damage to the layer becomes visible after drying the sample along the measurement path is taken as a measure of the wet scratch strength (Newton) of the photographic material.

The values obtained are shown in the table below: For a given antifogging effect and an influence on a given granularity, the material C according to the invention shows, after swelling in water, a marked improvement in the breaking strength combined with a reduction of the surface wear.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Prem Larvani Federal Republic of Germany Day-5090 Lef Elksen 1 Indenderen 15 (56) References JP-A-60-156056 (JP, A) JP-A-60- 209732 (JP, A) JP-A-53-112732 (JP, A) JP-A-58-34444 (JP, A)

Claims (10)

[Claims] 1. A photographic recording material comprising a support, at least one information recording layer, and optionally other layers, at least one layer containing an alkali-soluble separating agent and a water-insoluble high molecular weight compound HM. (Provided that colloidal silica is not included), the high molecular weight compound HM has the following formula: (Wherein R ¹ , R ² and R ³ may be the same or different and represent hydrogen, alkyl or halogen, L represents a chemical bond or a conventional linking member, and X represents a reactive group. A photographic recording material containing a repeating unit of 2. The repeating unit has the following structure: (In the formula, R ¹ , R ² , R ³ and X have the meaning described in claim ¹ , L ¹ represents a CONH, COO or phenylene group, and L ² represents ^{1 to} 20 carbon atoms. An alkylene group or carbon atom having
Represents an arylene group having 6-20, L ³ is COO, OCO, CONH, NHCO- O-, NHCO, SO 2 NH, NHSO 2
Or a SO ₂ group or O, m represents 0 or an integer, and n represents 0 or an integer), The material according to claim 1. 3. X is a group substituted at the terminal position by halogen, epoxy, imide, NCO, CH═CH ₂ , C (CH ₃ ) ═CH ₂ or CN. First
Item or the material according to Item 2. 4. The high molecular weight compound HM is a copolymer further containing a substituted or unsubstituted repeating unit derived from acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds or acrylonitriles. The material according to any one of claims 1 to 3, which is characterized in that 5. Material according to any of claims 1 to 4, characterized in that said material comprises at least one photosensitive silver halide emulsion layer. 6. The alkali-soluble separating agent used comprises particles of a graft copolymer of methacrylic acid and methyl methacrylate on a graft base of an α-olefin- or styrene-maleic acid half amide or maleic acid copolymer. The material according to any one of claims 1 to 5, characterized in that: 7. The material according to any one of claims 1 to 5, wherein the alkali-soluble separating agent used is a substituted cellulose derivative. 8. The high molecular weight compound HM is 0.02 μm to 0.5.
8. Material according to any of claims 1 to 7, characterized in that it is in the form of particles having an average particle size of μm. 9. The material according to any one of claims 1 to 8, wherein the high molecular weight compound HM is a copolymer having a glass transition temperature of at least 50 ° C. 10. A layer containing an alkali-soluble separating agent and a water-insoluble high molecular weight compound HM is an outer layer of a photographic recording material, according to any one of claims 1 to 9. The material according to any one.