DE2505017A1 - PHOTOGRAPHIC MATERIAL - Google Patents

Description

PATENT ANWXLTE

DR. E. WIEGAND DIPL-ING. W. NISMAKN DR. M. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMBURG 2505017

TELEPHONE = 555476. 8000 MD NCHEN 2, '

TELEGRAM ₁ KARPATENT MATHILDENSTRASSE 12

TELEX: 5 29 068 K A R P D,

V. 42 258/75 - Ko / Ne- 'February 6, 1975

Photo Film Co., Ltd. Minami Ashigara-Shi, Kanagawa (Japan)

Photο graphis ehe s material

The invention relates to a photographic material in particular a photographic material, which is a photographic layer of a hydrophilic colloid a carrier with a hydrophobic surface.

According to the invention there is a photographic material with a carrier with at least one thereon photograph! see layer indicated, the layer being adjacent to the carrier non-volatile ^ or low volatile contains liquid droplets with diameters smaller than the thickness of the layer adjacent to the support, as well a method for producing this photographic material.

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ORIGINAL INSPECTED

Polyethylene terephthalate, cellulose triacetate, polystyrene, Polyolefin coated papers and. Like. Are generally up to now for conventional photographic supports Applied because of their excellent transparency and / or flexibility. Unfortunately, however, all have such materials highly hydrophobic surfaces, so it is very difficult to make a photographic layer of a hydrophilic Colloids, generally made of gelatin, closely adhere to the supports.

The previously used method to overcome the above difficulties to achieve an effective Adhesion strength between a photographic emulsion layer and the surface layer of the support by means of surface treatment, in particular surface treatment Making the hydrophobic surface of the support hydrophilic include the following two types of methods:

(1) Applying a surface activating treatment, for example chemical treatment, mechanical treatment, corona discharge, flame treatment, UV irradiation, radio frequency treatment, Glow discharge, active plasma treatment, laser treatment, mixed acid treatment or ozone oxidation with subsequent direct absorption of the photographic emulsion for liability training.

(2) Formation of a primer layer or undercoat after the above surface treatments and peeling a photographic emulsion layer thereon, e.g. B. U.S. Patents 2,698,241, 2,764,520, 2,864,755,.

2 864 756, 2 972 534, 3 057 792, 3 071 466, 3 072 483,

3 143 421, 3 145 105, 3 145 242, 3 360 448, 3 376 208,

3 "462,335 and 3,475,193 and British patents 788 365, 804 005 and 891 469 are given.

The latter method (2) is more effective and is therefore widely used.

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It is believed that in all such surface treatments the surface of the carrier is hydrophilic due to the formation of polar groups, more or more less on the surface of the support, which is of the hydrophobic type and the like, is made and, consequently, the affinity the surface for the polar groups of the components contained in the primer and the like. Is increased.

Various methods have heretofore been used for drawing up a primer layer, and these include the so-called Double shift process, in front of a first shift, the one exhibits excellent adhesion to the support is formed and then a second layer of a hydrophilic resin, is drawn onto it, as well as a single-layer process, with only one resin layer, which is both hydrophobic Contains groups as well as hydrophilic groups, is drawn.

All such procedures have been carefully studied and various resins have been examined for their suitability for use as a primer layer, for example "a-" finally copolymers of vinyl chloride, vinylidene chloride, Methacrylic acid, acrylic acid, itaconic acid, maleic anhydride and the like, as well as polyethyleneimine, epoxy resins, grafted Gelatin nitrocellulose and the like. However, these methods have inevitable the following defects: (A) Insufficient adhesive strength

In particular, with respect to supports made of polyethylene terephthalate, polystyrene and the like, the adhesive strength obtained only by the surface activating treatment described in (1) above cannot satisfy all practical requirements for photographic materials. Moreover show in rearing a primer ^a: resin having a good affinity for the hydrophobic carrier and an excellent adhesion to the hydrophobic carrier generally has a poor affinity for a hydrophilic

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photographic / to be affixed layer and an insufficient one Liability. In contrast, show hydrophilic resins having a good affinity for photographic Layer, if used as a primer layer, excellent adhesion to the photographic layer, However, insufficient adhesion to the carrier.

(B) The primer coating processes require numerous steps and a lot of time.

Because gelatin is often used as a resin for photographic binders is used, the photographic layer becomes extremely drawn up at low temperatures and dried, e.g. the gelatine is cooled to a temperature below about 10 ° G and then at temperatures below about 50 ° G is dried, making use of the advantageous specific property of gelatin, since it is at gelled at lower temperatures. However, if the above specified polymers are used as a primer layer, these polymers have to cool down to higher levels Temperatures, for example about 100 C or more Drying are heated as they are general of the property are free from gel formation at low temperatures. In addition, these synthetic compounds require high molecular weight often use organic solvents as solvents instead of water when they are in place of Gelatin can be used. This makes additional coating equipment for these organic solvents separate from those for the photographic layers necessary. These coating and drying steps must be performed two or three times in the double primer coat process be repeated.

(C) Problems of toxic gases, skin irritation, environmental pollution and the like.

A further improvement in the adhesive strength of the

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primer layer described above results from various measures applied, e.g. solvents, which swell or dissolve the carrier, or so-called etchants, which have a high polarity and a high Have boiling point and are expensive, but must be incorporated into the primer in large quantities. For example include the etchants for polyester compounds having an aromatic ring such as benzene ring, a Naphthalene ring, a pyridine ring, a pyrrole ring or a condensed ring thereof or "such" with a or more alkyl, alkoxy, acyl, nitro, cyano, hydroxy, formyl, carboxy, alkoxycarbonyl, hydroxyalkyl, Aminoalkyl or haloalkyl groups, halogen atoms or the like. substituted aromatic rings, alcohols, ketones, carboxylic acids, esters, aldehydes or the like. As for example in British patents 772 600, 776 157, 785 789 and 797-4-25, U.S. Patent 2,830,030 and German patents 1 020 457 and 1 092 652 are given. Specific examples of such etchants are benzoic acid, salicylic acid, salicylic acid ester, monochloroacetic acid, Dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, methanesulphonic acid, trifluoromethanesulphonic acid, Nitropropanol, benzyl alcohol, benzaldehyde, acetylacetone, acetylphenol, benzamide, benzonitrile, anisole, nitrobenzyl alcohol, Chlorobenzyl alcohol, pyrrole, chloral hydrate, Benzylamine, xylylenediamine, nicotinic acid amide and nicotinic acid ester.

More examples of these etchants work particularly well known and widely used are compounds with phenolic hydroxyl groups, such as phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, phenylphenol, chlororesorcinol, Fluoroglycine, orcine, pyrogallelic, gallic acid,

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o-cresol, m-cresol, p-cresol, resorcinol or methoxyphenol. However, it is known that these etchants are usually difficult to handle and harmful to the user
are human bodies. Furthermore, phenolic compounds often pose serious problems in work because they are very irritating and penetrating into the skin. If these compounds are still contained in waste water or waste gases, they cause environmental damage and must therefore essentially be recovered, which makes additional waste treatment facilities necessary.

(D) Unevenness of the film surface

With the previous methods, considerably high temperatures are required to dry the primer layer, as stated above under (B) and (C).

In particular, since phenolic compounds generally have a high boiling point above about 180 ° G, requires the drying of the primer layer from these compounds requires heating for a fairly long period of time. Therefore, expansion and reduction of the modulus of elasticity in the polyesters undesirably occur during the drying, especially in the earlier stage of drying, due to the increase in the extent of through the penetration of the solvent into the polyester carrier caused crystallinity and shrinkage of the Polyester takes place in the later stage of drying, so that there is a striking unevenness of the surface adjusts.

(E) Difficult temperature control in drying the primer layer

Since the etchability of the solvent is strongly dependent on temperature, the adhesive strength as such is also

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if by an anchoring effect of the resin to the Carrier caused is highly dependent on the at the stages of coating, drying and the like. Applied temperatures.

This poses a serious problem from the point of view production in a stable manner.

The invention has been developed with a view to avoiding the foregoing errors in the prior art.

A first object of the invention is therefore in a photographic material having a strong adhesive strength between the support and the photographic Layer.

A second object of the invention is a photographic material which einerGrundierschicht for simultaneously mounting a photographic layer, and thus to simplify the production steps and reducing the number of production ^stages: is capable.

A third object of the invention is a photographic material that is free from environmental pollution caused. I. E. the drying of the organic solvents is not always necessary for the production of photographic Materials required according to the invention, which prevents toxic organic solvents will be released into exhaust gases or waste water.

A fourth object of the invention is "a photographic material, a primer comprising is less irritating to the skin.

A fifth object of the invention is a photographic one Material with a surface of excellent evenness.

A sixth object of the invention is to provide a photographic material with a wide tolerance range

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regarding changes in temperature in the stages.

A seventh object of the invention is a photographic material which does not have a primer layer requires.

An eighth object of the invention is a photographic material wherein the primer layer is in essentially also works as a dye emulsion layer.

These and other objects of the invention will become apparent from the following description of the invention.

The invention provides a photographic material consisting of a support having at least one thereon photographic layer, the layer adjacent to the support being non-volatile or less volatile contains liquid droplets with diameters smaller than the thickness of the layer adjacent to the support.

The invention provides a preferred embodiment of a photographic material consisting of of a carrier with a primer layer thereon of a resin, v / which as at least one component Droplets of a non-volatile or low-volatile Liquid immiscible with the resin and a photographic layer formed on the primer layer contains.

When using the primers according to the invention it is generally not necessary to incorporate the above-mentioned etching agents into the primer, However, they can be incorporated therein if desired.

Although the use of such etchants for the carrier is indispensable when using conventional primers and the adhesion due to an anchoring effect between the primer layer and the carrier due to the effect of the etchant is obtained, a sufficient

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Appropriate adhesion without the use of such caustic agents when applied of the primer according to the invention and this constitutes one of the significant effects of the invention represent.

Carriers that can be used according to the invention, include all carriers of high molecular weight substances. Particularly suitable carriers for use in the Photography are, for example, cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate or cellulose nitrate, styrofoam polymers such as polystyrene, Styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers or poly-a-methylstyrene, polyester, such as Polyethylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate or polycarbonate, polyolefins, such as polyethylene or polypropylene, or papers from the point of view transparency, flexibility and other chemical properties. The supports can be or can be transparent contain a dye or pigment such as titanium dioxide. Furthermore, the carrier can comprise layer films, wherein a plastic coated on a paper or plastic films whose surfaces have been treated as described in U.S. Patent 3,515,567. .

Resins coated on the support are often those resins which have a good affinity for hydrophilic photographic Have layers and which generally have high polarity are used. Therefore, the carrier is preferably one subjected to the surface activations described above. Particularly preferred methods for surface activation are corona discharge, glow discharge, electrodeless discharge, flame treatment, and the like, in view of easy implementation and the effect achieved.

Devices and methods for these activating treatments are described in the patents outlined above and are used to advantage.

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The photographic layer used according to the invention, which includes non-photosensitive layers and photosensitive layers will be briefly discussed below.

Examples of suitable binders for photographic layers (hydrophilic organic protective colloids), the can be used according to the invention, include synthetic or natural hydrophilic high molecular weight compounds, for example gelatine, acylated gelatine, such as phthalated gelatine or gelatine, cellulose derivatives, such as carboxymethyl cellulose or hydroxyethyl cellulose. Graft gelatin obtained by grafting acrylic acid, methacrylic acid or amides thereof on gelatin, polyvinyl alcohol, polyhydroxyalkyl acrylates, polyvinylpyrrolidone, Vinylpyrrolidone-vinyl acetate copolymers, casein, agarose, albumin, sodium alginate, polysaccharides, agar agar, Starch, grafted starch, polyacrylamide, acylated polyethyleneimine or homopolymers of acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-substituted acrylamide or N-substituted methacrylamide, copolymers thereof or partially hydrolyzed products thereof. These binders can can be used both individually and in a mixture.

In the context of the invention, it is not particularly v / i ent ig what kinds of additives are incorporated in the binder, if the above-mentioned hydrophilic high molecular weight ones Connections are used as binders. To this However, binders are usually various additives including light-sensitive substances such as silver halide, physical development nuclei, for example the silver sulfide used in the diffusion transfer process, or diazo compounds, color couplers, from emulsion polymerizations obtained latex polymers and the like. Added.

Since all of the binders of the photographic layer are hydrophilic as stated above, it was difficult to

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these binders adhere directly and tightly to the hydrophobic carrier.

If desired, a compatible mixture can also be used of two or more of the binders described above can be used. Of the binders described above Gelatin 9τα is most commonly used, but can Gelatine also partially or completely through a synthetic high molecular substance as well as so-called gelatine— derivatives are replaced.

The resins used for the primer layer are conveniently the same as the resins used to form the ' photographic layer applied thereon with a view to good adhesion properties, although also different Resins can also be used. In addition, resins having a relatively hydrophilic group other than the above can be used The resins described can also be used. Regarding the priming method, the adhesion between the hydrophilic resin and the other hydrophilic resin can be used Resin relatively easily obtained due to the strong polar bond strength that develops between them and difficulties arise in adhering the hydrophilic resin closely to the hydrophobic support. .

An advantageous feature of the photographic material according to the invention consists in the constitution of the primer layer in the material and in particular in the dispersion the small in den'polymeren binder of the primer layer incorporated droplets of liquid. If a primer, layer is formed with a structure according to the invention on a carrier, the adhesion between the green ' The layer and the carrier are remarkable compared to the Case of drawing up the same resin alone as a unitary layer regardless of the constituent resin of the primer layer increase.

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As a result, the photographic material produced has very strong adhesion to the support, provided that the adhesion between the resin and the hydrophilic primer layer and the photographic layer is satisfactory. Suitable resins that have good affinity for photographic Layer generally comprise, in addition to the resins described above, polymers of monomers with polar groups in the molecule, such as carboxyl, carbonyl, hydroxy, sulfo, amino, amido, epoxy or acid anhydride groups, for example acrylic acid, sodium acrylate, methacrylic acid, itaconic acid, crotonic acid, sorbic acid, itaconic anhydride, Maleic anhydride, cinnamic acid, methyl vinyl ketone, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxychloropropyl methacrylate, Hydroxybutyl acrylate, vinylsulfonic acid, potassium vinylbenzenesulfonate, acrylamide, N-methylacrylamide, Acryloylmorpholine, dimethyl methacrylamide, N-tert, butyl acrylamide, Diacetone acrylamide, vinyl pyrrolidone, glycidyl acrylate or glycidyl methacrylate or copolamers of the above Monomers with other copolymerizable monomers.

Examples of resins are homopolymers of ethylenically unsaturated Esters or ethylenically unsaturated acids corresponding to, for example, acrylic acid esters, such as ethyl acrylate or butyl acrylate, methacrylic acid esters, such as methyl methacrylate or ethyl methacrylate, acrylic acid or methacrylic acid or acid derivatives thereof or copolymers of these monomers with other vinyl monomers or copolymers of polycarboxylic acids, such as itaconic acid, itaconic acid, anhydride, maleic acid or maleic anhydride with vinyl monomers such as styrene, vinyl chloride, vinylidene chloride or Butadiene or trimers of these monomers with other ethylenically unsaturated monomers. '

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The resins described above can be used as aqueous Solution, as a solution in an organic solvent or as a dispersion as a latex in water.

With regard to the non-volatile or low-volatile liquids for dispersion in the primer layer all such liquids can be used as long as they do not completely dissolve the primer layer diffuse into the primer layer or completely disappear during drying.

The remarkable effect of the invention can be achieved due to the fact that fine droplets always are present in the primer layer within the coating and during and after drying and the effect will be not directly influenced by the chemical properties of the droplets. Therefore, these droplets can be in the Practice depending on the primer resin and the solvent used for the primer, which one can be emulsified and dispersed in the primer without complete miscibility with the mass and additionally For example, droplets which do not disappear when the mass is drawn onto the carrier and then dried can be used.

For example, if gelatin, a widely used hydrophilic resin, is applied as a primer layer, and Water, which is widely used as a solvent, can be selected from the following liquids are: esters or amides, which differ from organic acids or inorganic acids, such as phthalic acid, adipic acid, Phosphoric acid, citric acid, sebacic acid, isophthalic acid, cyclohexanedicarboxylic acid, benzoic acid, caprylic acid, caproic acid, Glycolic acid, pelargonic acid, azelaic acid, tetrahydrophthalic acid, fumaric acid, maleic acid, stearic acid, abietic acid, Oleic acid, sicinoleic acid, lauric acid. Or palmi-

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tic acid, esters or ethers derived from polyhydric alcohols such as ethylene glycol, butanediol, diethylene glycol, Derive propylene glycol, pentaerythritol, glycerine or cyclohexanediol, alkylphenols, alkylnaphthalenes, halogenated paraffins, cyan couplers, magenta couplers or Yellow couplers and vegetable oils, animal oils, mineral oils and the like.

All of the above substances can be used if they are liquid as such or in admixture for example are liquid at about 25 C. Suitable boiling points of the liquids are above 120 ° C., preferably above about 160 C. Furthermore, they preferably have a low solubility in water, which after a simple Attempt by professionals can be determined. The appropriate solubility in water for the liquids lies with a solubility of about 10 g / 100 g water at 25 ° C or less, if liquids immediately after the dispersion be used. The preferred solubility is a solubility of about 0.1 g / 100 g water or less A particularly preferred solubility in water is a solubility of 0.05 g / 100 g water or less from the point of view of shelf life or handling.

Specific examples of suitable liquids are diethyl adipate. Dibutyl adipate, diisobutyl adipate, di-nhexyl adipate, Dioctyl adipate, dicyclohexyl adipate, di-2-ethylhexyl adipate, Dioctyl sebacate, diisooctyl sebacate, dibutyl succinate, octyl stearate, dibenzyl phthalate, tri-o-cresyl phosphate, Diphenyl mono-p-tert-butylphenyl phosphate, honophenyl di-o-chlorophenylpho sphat, honobutyldioc tylpho sphat, 2,4-di-n-amylphenol, 2,4-di-tert.-amylphenol, 4-n-l-tonylphenol, 2-methyl-4-n-octylphenol, Κ, ΙΤ-diethylcaprylaird-d, Ν, Ν-diethyl laurylamide, glycerine tripropionate, glycerine tri- · butyrate, glycerol monolactate diacetate, tributyl citrate, ace-

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ethyl triethyl citrate, di-2-ethylhexyl adipate, dioctyl sebacate, Diisooctyl azelate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethyl citrate, tri- (2-ethylhexyl) citrate, Acetyl-tri-n-butyl acetate, di- (isodecyl) -4-, 5-epoxytetrahydrophthalate, Oligovinyl ethyl ether, dibutyl fumarate, polyethylene oxide (degree of polymerization.> «> 16), glycerol tributyrate, Ethylene glycol dipropionate, di- (2-ethylhexyl) isophthalate, butyl laurate, tri- (2-ethylhexyl) phosphate, triphenyl phosphate, Tricresyl phosphate, silicone oils, dimethyl phthalate, diethyl phthalate, dipropylene phthalate, dibutyl phthalate, Diisooctyl phthalate, diamyl phthalate, di-n-octyl phthalate, Diaiaylnaphthalene, triamylnaphthalene, monocaprine, \ Monolaurin, monomyristin, monopalmitin, monostearin, monoolein, Dicaprin, Dilaurin, Dimyristin, Dipalmitin, Di- * Stearin, diolein, i-stearor-2-palmitin, i-palmito-3-stearin, i-Palmito-2-stearin, triacetin, tricaprin, trilaurin, trimyristin, Tripalmitin, tristearin, triolein, tripetroselin, Trierucin, Triricinolein, Linoleo-distearin, Linoleo-dilinolein, Oleodierucin, linoleodierucin, palmitooleolinolein, Paraffin, drying oils such as linseed oil, perilla oil, Tung oil, hemp oil, kaya oil, walnut oil, soybean oil, poppy seed oil, Sunflower oil, catalpa oil, arrowhead oil or safflower oil, semi-drying oils, such as cottonseed oil, corn oil, sesame oil, rapeseed oil, Rice husk oil, croton oil, mustard oil, Eapok oil or dehydrated bhizinus oil, peanut oil, olive oil ,, tsubakiöΓ, Sasanoqua oil, tea seed oil, castor oil, hydrogenated castor oil, Almond oil, bean oil or Chaulmoogra oil.

Of the substances described above, particularly those substances with a melting point of up to about 50 C preferred and also mixtures with two or more of this and with a melting point of up to about 50 ° C.

These compounds are already known and for example in US Patents 2,322,027, 2,533

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2 588 765, 2 960 404, 3 121 060 and 3 287 134, the German U.S. Patent 1,152,610, the British Patents 955 061 and 1,272,561, Japanese Patent Laid-Open 21 766/68, Japanese Laid-Open Application 14322/73 and Kuwata, Fats and Oils Chemistry, Iwanami, 1968, Tokyo.

Of these compounds, esters of adipic acid, phthalic acid, succinic acid, fumaric acid, azelaic acid, Isophthalic acid or phosphoric acid and esters of glycerol are used advantageously as they do not detrimentally affect the photographic Affect photosensitive materials and are easily accessible, are chemically stable and therefore can be handled easily.

Of all these materials, the more hydrophobic liquids have a significant effect on adhesion, if water is used, for example as a solvent for the primer layer, possibly on Reason for the easy formation of fine droplets of the materials.

When using primer resins other than gelatine and a solvent other than water, the Droplets are formed by choosing liquids that are incompatible or poorly compatible with one another.

The droplets can be produced using emulsifying agents or dispersion methods generally used in the field of photographic emulsions, cosmetics and the like be trained.

This means that non-volatile or low-volatile liquids can be in a sufficiently fine state dispersed or emulsified in the primer resin composition by mixing the resin composition with the liquid, and then a strong shear force can be applied to the using a mixer, homogenizer, ultrasonic wave and the like

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Mixture, can be applied.

It is preferred in the formation of the droplets to have one generally to improve the effectiveness of the emulsification or to stabilize the emulsified dispersion formed to add the emulsifier used. As such emulsifiers anionic surface-active agents, non-ionic surface-active agents, cationic surfactants or mixtures thereof can be used. From the photographic point of view Properties are anionic and non-ionic surface-active Medium preferred. With regard to the reduction. The particle size of the droplets is reduced in the Japanese Patent Publication 9979/73 anionic surfactants are particularly preferred. However, bubbles are often formed during emulsification. In this case, a defoaming agent can be added become, as it z. B. Japanese Patent Publication 9979/73 is given.

The surfactants are generally in the US patents in addition to the above patents 2 240 472, 2 271 623, .2 288 226, 2 311 021, 2 322 027, 2 360 289, 2 533 514-, 2 739 891, 2 801 170,

2 801 171, 2 852 382, 2 94-9 360, 3 068 101 _r 3 158 4-84, -

3 201 253, 3 210 191, 3 294 540, 3 396 027, 3 415 649, 3,441,413, 3,442,654, 3,475,174, 3,545,974-, 3,619,195 and 3 775 349, the German Offenlegungsschrift 1 942 665, the German patents 1 143 707, 2 045 414, 2,043,271 and 2,045,464 and British patents 1 077 317 and 1 198 450 are given. One or more of the Desired agents can be found under the above surfaces active means can be chosen. The amount of surface active agents Means can be varied as desired. however, at least a sufficient amount will be used

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Formation of a practical, emulsified product used.

Regarding the size of the droplets to be dispersed A smaller size gives a better result in terms of the transparency of the primer layer. the • The thickness of the primer coat is usually less than about 1 micron in most cases, which makes the coat light Damage is caused if the layer is unnecessarily thick. Therefore if a primer coat is applied in a separate step and a photographic layer thereon after drying the primer layer as in a conventional one In the process of being drawn up, the droplets are preferably less than about 1 micron in diameter. Furthermore can in the formation of the photographic material according to the invention gelatin can be used as the primer resin, so that the primer resin as the lowermost layer of the photographic layer at the same time as the photographic layer is drawn up Layers can be poured. In this case, a thick primer layer can be formed because the Primer layer is not damaged if it is thick, with droplets with a diameter even larger than about 1 micron are sufficiently effective in terms of adhesion. In summary, the droplets give a sufficient one Effect as long as its diameter is smaller than the thickness of the primer layer. In practice, however, is the size of the droplets favorably less than 1 micron, since, if the size of the droplets increases, the stability of the liquid as such decreases over time and the transparency of the drawn film formed is lost. On the other hand, there is no lower limit on the diameter the droplets. In fact, if the particle size of the droplets is changed, the volume ratio becomes the droplet-forming liquid to the binder-

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forming resin is kept constant, the transparency of the drawn film is improved and the adhesive strength is improved increases as the size of the droplets decreases.

The droplets can, as described above, by applying a strong shear stress to the liquid -be formed using a mixer or homogenizer and with the aid of a surfactant. According to the usual procedure, droplets are with a average particle size down to about 0.001 microns are easily manufactured and are suitable for the invention.

In general, the objects of the invention can be satisfactory with droplets having an average particle size of about 1 to about 0.01 microns will. In general, the thickness of the primer layer or the photographic layer containing the liquid lies contains droplets, above about 0.01 microns. To the Lowering the size of the droplets, it is advantageous to preferably use a non-volatile liquid together of a volatile liquid to form an emulsion, only the volatile liquid by drying evaporate the same after the absorption and consequently droplets of the non-volatile liquid with a small particle size-obtain. '.

In order to reduce the limiting viscosity to Reason of the treatment to make the surface of the support hydrophilic to make, to prevent and to the treatment conditions to enable a repeated use of the To reduce carrier, for example made of polyester, can if desired in the droplets according to the invention layer containing such compounds are incorporated which are one or more of the following groups

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sit, namely carboxy, methylol, hydroxy, oxirane, epoxy, glycidyl, ethyleneimino, isocyanate, thioisocyanate, Acetal, ketal, vinyl, acryloxy, methacryloxy, Carbodiimide, phenolic hydroxyl, thiol, amino, alkylamino, Acylamino, carbamoyl, thiocarboxy, thiocarbamoyl, Guanidyl, hydrazine, oxime, ureide and thioureido groups. Such compounds are, for example, diepoxy compounds, polyisocyanate compounds and the like.

Furthermore, resins, emulsion polymerization products and the like can be incorporated into the layer. Regarding the latex is z. B. Reference to U.S. Patents 3,142,568, 3,193,386, 3,062,674, 3,220,844, 3,287,289, 3,411,911, 3,411,912, and 3,488,708, and the like are taken and those skilled in the art can readily determine the appropriate ones accordingly the purpose, the types of use and the conditions when applying the according to the inventive method determine formed materials.

The droplets used according to the invention can be obtained by simultaneously mixing one or more Oils can be made emulsions or they can be made into separate emulsions by mixing or re-dispersion will. This means that the emulsion can be used without difficulty can be used, regardless of whether it is a mono-disperse emulsion or a multi-disperse emulsion or whether their particle size distribution is broad or narrow.

Regarding the amounts of the for the primer coat and the amount of the resin dispersed therein to be used, the adhesive strength increases as the The amount of liquid in all combinations of resin and liquid is increased, provided the amount of liquid is increased remains relatively low compared to that of the resin. However, if the amount of fluid is increased too much,

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the adhesive strength decreases again due to the decrease in the strength of the primer layer due to the Decrease in the cohesion of the layer itself or because the droplets are no longer in the resin after drying can hold and thus be driven out of the resin. As a result, the amount of liquid that can be added depends on the film-forming properties of the resin as such and the strength of the film, although the droplets are usually in an amount up to the Jiachen volume amount may be present to the volume of the resin. Particularly preferred amounts of the droplets are in the range of about 1/5 to 2 times the volume to the volume of the resin on a dry basis from the point of view of adhesion, film strength, Transparency, suitability for double-layer coating and the like.

By drawing up the resin composition with a dispersed therein non-volatile or low-volatile liquid on the carrier and subsequent drying, as described above, only the solvent is under Formation finally evaporated on the support of a resin film, wherein only the non-volatile or low-volatile liquid is dispersed as fine droplets ”.

The coating film obtained has very excellent adhesion to the carrier in comparison with a film of the same resin, which does not contain any non-volatile or low-volatile liquid dispersed therein.

It is believed that this improvement in adhesion is due to the fact that the residual stress caused by the shrinkage of the drawn film is increased in the course of the drying of the coated film. _: caused, probably released and markedly reduced due to the fine droplets. This to

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would also be supported by the fact that the Adhesion of the coating film with regard to all priming resins and all dispersed liquids improved is .. Therefore it is also evident that the photographic material according to the invention also has the advantage. that the curl caused by the primer coat, as in the usual method, is not formed, since no shrinkage stresses occur during the drying of the applied film.

Of the photographic materials according to the invention are those that contain gelatin as a primer layer, industrially most advantageous as a basic component of the photographic, on the primer layer formed layer of the resin used for this purpose in most cases made of a hydrophilic resin, in particular Gelatin, and consequently the affinity between the photographic layer and the primer layer is extreme is high. In addition, the primer layer can be applied simultaneously with the application of the photographic layer on the ground the properties of gelatinisation (solidification) are raised at lower temperatures, d. H. simultaneous pouring is possible. Under application this process does not require a specific coating apparatus for the primer layer and, in addition, the Number of stages reduced by one, so that those that occur due to errors that can occur in this stage Difficulties can be avoided.

The invention has a significant advantage in that a gelatin layer is close to a hydrophobic one Carrier can be made to adhere, which previously could not be achieved by applying a primer coat with the Structure is formed according to the invention.

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A feature of the invention is that there are fine droplets in the primer layer, thereby creating the Adhesion strength is improved. It goes without saying that the primer layer also has other components than what is essential for liability, at-r. \. for example antistatic agents, dyes, coating aids agents, matting agents, crosslinking agents and the like "without going out of the scope of the invention. ·. · "" '·,

According to the invention, the same purpose can also be used without specific formation of a primer layer, but by dispersing these droplets directly in a photographic one Layer can be achieved when the change in photographic properties, loss of transparency, reduction the resistance to scratches of the photographic film as such and the like. Can be neglected.

Each layer of the primer according to the invention and the photograph! see photosensitive materials can include various coating processes from immersion coating, air coating coating, curtain coating or extrusion coating using one Funnel according to US Pat. No. 2,681,294. ·

If desired, two or more layers can be applied simultaneously using the methods described in U.S. Patents 2,761,791, 3,508,9-4-7, 2,941,898, and 3,526,528, and in Harasaki and coworkers, Coating Technology, page 253? Asakura, 1973, Tokyo.
Film adhesion test : ■ -.

The photographic layer to be tested was provided with six transverse lines and six longitudinal lines separated from each other 5 mm apart, notched so that 25 squares were formed

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became. An adhesive tape (Scotch Brand, Mending Tape, manufactured by Sumitomo Three M Co., Ltd.) was adhered to the sheet and quickly peeled off at an angle of 180 degrees. The adhesive strength was determined from the number of squares of the The photographic layer peeled off is calculated and divided into five grades in the following manner.

Degree number of peeled squares

A 0-5

B 6-10

C 11-15

D 16-20

E 21-25

Adhesive strength sufficient for practical use as a photographic material corresponds to your Grade B or Grade A, preferably Grade A, of the above five grades.

All of the adhesion tests given below were carried out using this procedure.

The invention is illustrated in detail by means of the following examples. Unless otherwise stated, All parts, percentages, ratios and the like are based on weight.

y example 1

To 200 g of an aqueous solution containing 10% by weight of gelatin, which was kept at 50 ° G, was added 15 g of an aqueous solution Solution with 5% by weight of sodium dodecylbenzenesulfonate (emulsifier) and a certain amount of dioctyl adipate (non-volatile liquid) as indicated in Table 1 was added. That Mixture was applied for 20 minutes using a

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Mixer for the production of the primer stirred.-The the mean diameter of the liquid droplets was approximately 0.5 microns.

The primer thus produced was drawn down to a film thickness of 2 microns on a dry basis on a polyethylene terephthalate film with a thickness of 0.1 mm, which had been treated with corona discharge, off .- '. educated whereupon solidified at about 5 ° C for 1 minute and then dried at 25 C for 30 minutes. The corona discharge was with a discharge discharge of 200 V with an electrode gap of 0.8 mm while moving the film with a width of 30 cm at a speed ' of 2 m / min.

A conventional silver bronze gelatin emulsion, which contained 2.5 mol 1% silver iodide, became a silver cover on the film provided with the primer coating

of 3 g per m and a gelatin cover of

ρ
3 »5 gd ^em ^ - ^{it received} film. Then the film was at

Solidified at 5 ° C for 1 minute and then at 30 ° C during Dried for 30 minutes.

The photographic film thus obtained was subjected to the adhesion test by the above-mentioned method. The results obtained are shown together en m with the amount of dioctyl adipate in Table I below.

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Table I.

Amount of dioctyl adipate bond strength Cg)

0 (control) E. 15th A. 20th .A 25th A.

The application of dioctyl adipate in an amount in the

On the order of 5 S was ineffective.

Example 2

The same procedure as in Example 1 was carried out using polyethylene terephthalate supports with a Thickness of 0.2 mm, which had been treated with glow discharge or flame treatment.

The glow discharge was carried out under a low pressure of 0.05 mm Hg and with an output of 200 W for 5 seconds. "The flame treatment was carried out by moving the Polyäthjlen-terephthalatfilmes ir. With a width of JO c. at a speed of about 80 m / min, which is perpendicular to a burner at a distance of 3.5 cm was held. The composition of the for the The fuel gas used for flame treatment was a mixed gas of (1) propane gas (0.9 kg / hour) and (2) oxygen gas (2.1 kg / hour) and the area of the burner was about 31 cm 0.45 mm. The results obtained are shown in Table II listed.

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Amount of dioctyl adipate

(s)

15 20

25th

Table II liit plammbe-
act treated
eld film 'E _: Adhesion strength A. With glimment
charge behan
eld film A. E. A. '. ■ A A. A. Example 5

The same procedure as in Example 1 was carried out under Use of a polystyrene carrier with a thickness of 0.1 mm. The results obtained are in the table III listed.

• Table III

Amount of dioctyl adipate (g)

Adhesion Strength

0 Example 4 • E 20th A. 25th A '

One by heating 20 g of di-n-alkyl phthalate with Alkyl groups of different carbon atoms as shown in Table IV and 0.8 g of sorbitan monolaurate (Defoaming agent) at 60 ° C. was obtained in 200 ml of an aqueous solution with a content of 15 S.

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Gelatin and 1.5 g of p-myristic acid amide-benzenesulfonic acid, sodium salt poured at an elevated temperature of 60 ° C. The mixture was applied for 25 minutes a high-speed agitator (20,000 rpm) stirred to produce a primer.

The average size of the resulting droplets was 0.4 microns and the particle size distribution was almost equal to the normal distribution.

The primer thus obtained was applied to a polyethylene terephthalate film drawn, v / elcher previously with a corona discharge under the same conditions as in Example 1 to form a film thickness of 1 micron on a dry basis, followed by at 5 ° C solidified for 1 minute and then dried at 25 ° C. for 30 minutes.

On the primer coated in this way The support became a silver halide photographic emulsion drawn up for black and white photography of the following composition. The men-

The amounts of coating per m of the film are in each case: 3 * 5 S Silver chlorobromide with a content of 3 »5 Mo1% bromine, 13 »0 g of gelatin grafted with hydroxyethyl methacrylate (Graft ratio 30% by weight), 0.1 g of formaldehyde (37% strength aqueous solution), 0.03 S polyethylene oxide (degree of polymerisation = 12) and 130 ml of water. The resulting photographic Film was tested for adhesion strength. The results obtained are summarized in Table IV.

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Di-n-alkyl phthalates

Di-n-butyl phthalate di-n-amyl phthalate Di-n-o c tyl phthalate di-n-lauryl phthalate Without (control)

2505017 5 Tabel "IV /'..■'■ Adhesion Strength A ■ ··; ' ^: A - A '·'. ■ A ■ E "..-: ·.
- _ " example

To 100 g of an aqueous latex solution with a content of 20% by weight polymethyl methacrylate with an average particle size of 0.05 microns became 7 cm aqueous solution with 5% by weight sodium dodecylbenzenesulfonate ■ and 10 g of dibutyl phthalate were added. The mixture. Was stirred for 10 minutes using a mixer to prepare a primer. The average The diameter of the resulting liquid droplets was about 0.4 microns.

The primer thus obtained was applied to a polyethylene terephthalate carrier with a thickness of 0.1 mm drawn up, the previous with a corona discharge underneath treated under the same conditions as in Example 1, resulting in a pilm thickness of 2 microns on a dry basis and then dried at 80 ° C for 20 minutes. A silver halide gelatin emulsion such as

2 "'■

in example 1 to a silver coverage of 3 g per m and

a gelatin cover of 3.5 g D © ^ of the carrier. pulled, solidified at 5 ° C for 1 minute and then dried at 30 ° G for 30 minutes.

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The photographic film obtained thereby had adhesive properties graduation A when using a primer that did not contain dibutyl phthalate, while the formed photographic film has an adhesive property graduation C.

This big difference is probably caused by because granular solids such as latex polymers and droplets contribute to the adhesion according to the invention.

Example 6

To 200 g of an aqueous solution with 10% by weight gelatin, which was kept at 50 C, 20 g of an aqueous Solution with 5% by weight sodium dodecylbenzenesulfonate and 25 g Dibutyl phthalate added. The mixture was stirred for 20 minutes using a mixer and then 10 g Potassium poly-p-styrenesulfonic acid salt continues as Thickening agent added so that a primer was obtained. The average diameter of the obtained Liquid droplets were about 0.4 microns.

The primer obtained in this way as the first layer and the photographic emulsion according to Example 4 as the second Layer were simultaneously by the slip coating method on a polyethylene terephthalate support a thickness of 0.1 mm, which had been treated with corona dewatering, pulled up, solidified at 5 ° C. for 2 minutes and then dried at 30 ° C. for 30 minutes. The film thickness was 2 microns for the primer coat and 5 microns for the photographic one Dry-based layer.

The adhesion property of the film obtained was tested and was graded A. The film was exposed and then developed and gave an excellent picture.

The invention was described above in detail using " preferred embodiments described without them ' .is limited to this.

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Claims (11)

Claims 1. Photographic material, characterized by a carrier with at least one photographic material located thereon Layer, the layer adjacent to the carrier being non-volatile or low-volatile droplets ! Contains liquid with a diameter smaller than the thickness of the layer abutting the carrier. 2. Photographic material according to claim 1, characterized in that the layer containing the droplets is a primer coat. 3. Photographic material according to claim 1, characterized featured having a primer coat and a photographic layer successively on the support and the primer layer contains the droplets. 4. Photographic material according to claim 3> characterized in that the primer layer is a resin with a good affinity for the resin on the primer layer contains applied photographic layer. 5. Photographic material according to claim 3 _? characterized in that the primer layer contains at least one resin which is the same as the resin of the photographic layer applied to the primer layer. 6. Photographic material according to claim 3i thereby characterized in that the primer layer is at least one the materials gelatin, gelatin derivatives or compounds with carboxyl groups, carbonyl groups, hydroxyl groups, Contains amino groups, amido groups, epoxy groups or hydroxyl groups in the molecule or with an acid anhydride structure. 7 · Photographic material according to claim Λ to 6, characterized in that the droplets of the non-volatile or low-volatile liquid from a liquid which is liquid at about 25 ° G and a 3832/0961 Has boiling point above about 120 ° C, or a mixture of liquids which are liquid at around 25 ° C and has a boiling point above about 120 ° C. 8. Photographic material according to claim 7, characterized in that the non-volatile or low- "volatile" Liquids made from esters or amides of organic or inorganic acids, esters or ethers of polyhydric alcohols, alkylphenols, alkylnaphthalenes, halogenated paraffins, color couplers, vegetable oils, animal oils or mineral oils. 9. Photographic material according to claim 7, characterized in that the non-volatile or low-volatile liquids have a melting point of up to about 50 ° G. 10. Photographic material according to claim 8, characterized characterized in that the liquid is composed of an adipate, azelate, citrate, fumarate, glycerine iyate, isophthalic acid derivative, Phthalic acid derivative, phosphoric acid derivative or Sebacic acid derivative consists. 11. Photographic material according to claims 1 to 10, characterized in that the average diameter of the droplets is less than about 1 micron. • {12 \ Process for the production of a photographic Material, characterized in that at the same time on a carrier a primer, which droplets a non-volatile or low-volatile liquid with diameters smaller than the thickness of the primer layer contains, and a photographic layer is coated. 13 · The method according to claim 12, characterized in that a quantity of the droplets from the non-volatile or low-volatile liquid in the primer layer of about 1/5 to 2 parts by volume per part by volume of the primer layer is applied on a dry basis. 0.9832 / 096