DE2001727A1 - Photographic element - Google Patents

Description

c NTA N WKL, C

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

MÖNCHEN HAMBURG

TELEPHONE: 555476 8000 M ü N C H E N 15,

TELEGRAM ₁ KARPATENT NUSSBAUMSTr ^ SE ₁ P

14-. January 197o

W. 14 637/69 13AS

Puji Photo PiIm Co., Ltd. Kanagawa (Japan)

Photographic element

The invention relates to a photographic light-sensitive halogen silver element with an auxiliary or subbing layer, in which in particular sticking is prevented. The term used here "Sticking" denotes such a phenomenon that when an underlayer is bonded to another layer or to an object surface brought into contact and stripped off again, the touched surface is contaminated with contact marks and in extreme cases the Underlayer or support surface is even stripped or scratched.

In making a silver halide photographic element (hereinafter referred to as "photographic element" referred to) is a hydrophobic PiIm used as a carrier on one side with a hydrophilic Halosilver emulsion layer and on the other side

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te covered with a backing layer, whereby in this Pail the adhesion of the surface of the carrier to the Halogen silver emulsion layer or the backing layer the creation of a class or underclass or one Substrate is reinforced in between. Since this underlayer is generally hydrophilic, sticking is very common or adhesion between the sub-layers applied as a coating to both surfaces of the support, the sub-layer and one on the other surface as over | train applied calogensilver emulsion layer or the Underlayer and a backing layer applied to the other surface during the preparation stages of one photographic element when wound in the form of a Roll or spool or when stacked in the form of sheets or webs. In addition, sticking or Adheres between the underlayer and a roller or spool when the underlayer is heated Roll brought into contact during the manufacturing stage will.

Previous attempts to prevent such sticking by incorporating water or organic * ..eheη fine particles insoluble in solvents, e.g.

Starch, barium sulfate, silicon dioxide gel or titanium dioxide, in a protective layer, undercoat or backing layer of a photographic element to thereby cover the surface matting are unsatisfactory and, in particular, have various difficulties in dispersing of such material in an overcoat solution for an underlayer of a photographic element.

Namely, when a coating solution to which such a material has been added is allowed to stand for a long period of time, the material will settle to accumulate or aggregate.

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Y / e.in the solution has a low viscosity, such as a Coating solution for an underlayer of a photographer! - element, the stability of the dispersion is so low that the above-mentioned material, da3 for the lamination of the surface was added to itself drops off. Therefore, it is hardly possible to produce a stable dispersion for an undercoat.

The object of the invention is to create a! .Lasse for an underlayer for a photographic element, which has resistance to storage for a long period of time. Another purpose of the Invention is to provide an auxiliary or underlayer of a photographic element which has sufficient Has a protective effect against sticking or sticking.

The above-mentioned purposes can according to the Invention by incorporation in an auxiliary layer of a photographic element of a homopolymer! Glycidyl methacrylate (hereinafter referred to as "GI.IA") or of glycidyl acrylate (hereinafter referred to as "GA") or a copolymer of a vinyl monomer with GKA or GA can be achieved.

The auxiliary or intermediate layer according to the invention with a content of a homopolymer of GLIA or GA or a lüischpolymerisat of a vinyl monomer with GIlA. or GA has a sufficient protective effect against sticking or sticking. This is possibly due to the fact that the above said fine polymer particles matt the surface of the film and that the gelatin hardening effect of the Glycidyl group in the polymer a decrease in the hygroscopic Behavior of the auxiliary or lower layer.

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_BATH

The cash register for the auxiliary or lower layer, which contains a homopolymer of GMA or GA or a copolymer of a vinyl monomer rait GMA or GA, is so stable, in contrast to the known dispersion containing a matting agent, that no accumulation or settling of Graining takes place even after standing for a long period of time. In addition, the above-mentioned component of the auxiliary or lower layer has a photographic W Elemar.t accordance eggs invention no adverse Finfluß on the adhesion of a HalogensilberemuMonsschicht or backing layer to a carrier, which plays one important Rclle at a lower class, but rather it has a tendency to further strengthen the adhesion through the gelatin hardening effect of the glycidyl group present in the above-mentioned polymer.

The polymer to be incorporated into a lower layer of a photographic element according to the invention is a honey polymer from GKA according to the following formula (I) or GA according to the following formula (II) or a mixed polymer from GMA or GA with a vinyl monomer. The copolymer can also be a terpolymer which contains two or more vinyl monomers.

CH,
CH ₉ = C (GMA) (I)

COOCH ₀ -CH-CH ₀

CH ₀ = CH (GA)

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The vinyl monomer to be copolymerized with GMA or GA is one such monomer that is associated with GMA or GA performs considerable interpolymerization with the glycidyl group during emulsion polymerization does not react and is unable to carry out emulsion polymerization due to its high solubility is in water; Examples of such monomers are alkyl acrylates with 1 to 4 carbon atoms in the alkyl group, Alkyl methacrylates with 1 to 4 carbon atoms in the alkyl group, other substituted alkyl acrylates, Acrylamide derivatives, "methacrylamide derivatives," vinyl halides, e.g. vinyl chloride, vinylidene halides, e.g. Vinylidene chloride, vinylpyrrolidone, other N-vinylamides, Vinjrlpyridines, Styrene, styrene derivatives, e.g. α-methylstyrene, Butadiene, isoprene, acrylonitrile, methacrylonitrile or the like. The proportion of GMA or GA in the copolymer of GMA or GA with a vinyl monomer is / is preferred at least 3 mol% or more. This proportion could be lower than 3 mol%, there will be no sufficient effect issued to prevent sticking.

The aqueous polymer dispersion according to the invention is produced by emulsion polymerizing a monomer component in an anionic surfactant such as lauryl alcohol sulfate, sodium alkyl benzene sulfonate and sodium 1,3-p-nonylphenoxy-5,8,11-trioxatridecane isulfonate manufactured. The emulsion polymerization can be carried out in a customary manner. So can a desired aqueous polymer dispersion can be obtained by de-aerated distilled water Monomers in a ratio of 10 to 60% by weight, suitable amounts of the aforementioned anionic surfactant and / of a water-soluble one

as a dispersant

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Polymerization: nitiators, for example, potassium persulfate, and if necessary, poly ~ erisationszusätze added, the mixture is stirred vigorously and then heated for several hours at 50 to 9O ⁰ C.

The particle size of the polymer in the aqueous polymer dispersion according to the invention can by the conditions of the emulsion polymerization in usual V / are regulated, for example by the amount of a surface-active agent as a dispersant, the stirring conditions, reaction time and Reaction temperature. The grain size is preferably in the range of 0.05 to 1 micron.

The amount of the aqueous polymer dispersion according to

of the invention for an auxiliary or sub-layer

2 2

preferably A mg per m to 200 mg per m, based on the weight of the polymer. If this amount is smaller, the anti-sticking effect is poor, while, if the amount exceeds the specified range, the adhesion of an undercoat to an emulsion layer or Backing layer tends to deteriorate. When the sub-layer or sub-layers have been dried were, a conventional gelatin-halosilver emulsion is applied as a coating or coating thereon, whereupon is dried.

In order to eliminate any tendency to screw in, the other surface provided with the aid layer is provided with coated with a topcoat of a gelatin composition which does not contain silver halide, but if desired antistatic agents, filter dyes, antihalation agents or the like. may contain.

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According to the procedure described above manufactured photographic elements are characterized by high adhesion or high adhesion of the Layers on each other and on the hydrophobic film support without sticking are characterized and show excellent Dimensional stability during testing, use and storage conditions.

The photographic silver emulsion layer, Antihalation layer, backing layer or the like. - The are applied as a coating to the film carrier provided with the sub-layer or layers no particular limitation as long as the above described sub-layer is used.

The rialogue silver photographic emulsion may be a Chlorosilver emulsion, bromosilver emulsior., Chlorobromosilver emulsion, Brom, iodosilver emulsion, chlorobromoiodosilver emulsion or the like. contain. Of course, the photographic elements can contain an inverse number of calcium silver emulsion layers exhibit.

According to the invention, an aqueous dispersion of a homopolymer of GMA or GA or a copolymer of GMA or GA with a vinyl monomer can be added as such to a coating solution which is used for an undercoat according to the prior art. The else provided to this V. ^T with the addition solution is applied as a coating or coating on a hydrophobic film support, a subbing layer having a sufficient effect to prevent

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to obtain a change in sticking. The hydrophobic film carrier used is carrier materials made from cellulose derivatives, for example cellulose triacetate, cellulose diacetate, cellulose acetate butyrate and cellulose acetate propionate, polyethylene terephthalate, polycarbonate, polyvinyl chloride or polystyrene .

The composition for the sublayer contains one aqueous gelatin solution, solvent for swelling k of the hydrophobic film carrier, e.g. acetone, methyl chloride, Ethylene chloride, trichloroacetate or phenol and a water-soluble organic solvent, e.g. acetone or methanol, based on the abovementioned polymers. The solvent for swelling the hydrophobic film support and the water-soluble organic solvent can be the same compound. These compounds are in the prior art in terms of bulk or Undercoat compositions are well known and are therefore not particularly limited. Other If necessary, compounds can be added to the compound.

) The invention is illustrated by means of hereafter

position examples and examples explained in more detail, before-in the parts listed are based on weight.

Production example 1

800 parts of distilled, de-aerated water, 120 parts of a purified by distillation

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and 180 parts of butyl methacrylate were placed in a glass-lined closed type reactor equipped with a temperature controller (thermometer), a stirrer, a reflux condenser, a heater and a gas inlet, and the atmosphere of which had been replaced with nitrogen gas. 5.0 parts of sodium laurylbenzenesulfonate was then added as a dispersant and the reaction mixture was stirred vigorously at 500 to 800 rpm to emulsify. Then 0,15'Teile · ammonium persulfate and 0.05 part of acidic sodium sulfite (sodium sulfite acid) were added as polymerization initiators and it was heated with stirring at 90 to 100 ⁰ G. After the reaction was continued for 6 hours, the polymerization was completed; the particle size of the solid polymer in the resulting aqueous dispersion of the copolymer of GMA and butyl methacrylate was about 0.1 to 0.3 microns, measured by means of an electron microscope.

Production example 2

Using the same apparatus as used in Preparation Example 1, there were added 1754 parts of distilled water, 80 parts of GMA, 106 parts of butyl methacrylate, 9.3 parts of C _g H ₁₉ -Q-0 as a dispersant and 0.5 part of potassium persulfate as a polymerization initiator . in a similar ^T ', ^r else as described in preparation example 1, processed to an aqueous polymer dispersion having a copolymerization ratio of GMA to butyl methacrylate of 4: 6

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on a mole basis. The grain size of the solid polymer in the resulting aqueous dispersion was 0.1-0.2 microns.

Production example 3

Using the same apparatus as used in Preparation Example 1, a similar one was made Procedure as described in the preparation example "!, Κ repeated with the modification that 80 parts of GA and 100 parts of styrene were used as monomer, wherein a stable aqueous copolymer dispersion with a grain size of 0.1 to 0.3 microns was obtained.

In the following examples, evaluation or evaluation of the anti-sticking effect of an underlayer was carried out as follows: A sample was cut to a size of 35 mm × 35 nm, and the coated or coated surfaces were faced with each other, one day and one night long in a thermostat at a temperature of 30 ⁰ C and a relative humidity of 80% stand- ψ left, wherein a weight was applied thereto kg of second Then the percentage of a glued area to the total area was measured.

example 1

The both surfaces of a polyethylene terephthalate film support having a thickness of 100 microns and a width of 30 cm, which had been biaxially stretched and heat-set, were at 110 ⁰ C in air using a

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Quecksjlberquarzlarr.pe of 1 kilowatt for 2 min "and überzogen- irradiated directly with a solution for an undercoat layer, preceded 3 at 120 ⁰ C" was now dried. .As Lösungsnittelunterschicht was used a T'ssse the following ¹ composition. A comparison with reference to adhesions is carried out in the cases in which G.05, 1.0 or 1.5 parts of the aqueous dispersion of the copolymer of GKA and butyl methacrylate, which are prepared according to the procedure of preparation example 1 \ jar (copolymerization ^{ratio of G V} A to butyl anethaorylate = 6: 4) had been added.

Parts

Gelatin 1

v: = sser 2

Monochloroacetic acid 2 ".

Phenol 5

Xethanol 35

Methylene chloride 57

3e? Ubiquitous of the resulting lower class.et films was the yerklebunrsstatus of the lower class v; ie in the Table I below.

Table I.

Mo. additional space to v / äSrirer glued area

? ol "T.erisatdist) ersior (f0 (Partial *

" C 25

2 0.5 10

3 r, o ο

4 1.5 0

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From the results in Table I above, it can be seen that a remarkable sticking preventive effect when the aqueous dispersion is added sir.es copolymer of GI-IA and butyl methacrylate was granted.

3e2 st 'el 2

The ce.!. The surfaces of a Pclyäthylenterephthalatf '"support having a thickness of 7 5 microns and a ψ latitude of 31 cm, the biaxially stretched and heat set was wcrder, were irradiated with ultraviolet rays at SO ⁰ C. for 1 min in air using a 1 lc mercury quartz lamp and irradiated directly with a solution for an undercoat of the following composition, Ucerzoren, to which a different aqueous dispersion of a mixed polymer was added before GMA and butyl methacrylate with a different mixed polymer ratio, which was caused at 12C ^C C was dried for 2 min

Gelatin 1

'., £. ε s e r 2

Trichloroacetic acid 2

Methanol 40

Methylene chloride 43

Phenol 6

Tetrachloroethane 6

aqueous dispersion of the copolymer 2

(Polymer solids content approx. 9%)

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For the resulting undercoated films, the bonded state of the undercoat was determined, the results shown in Table II below were obtained.

Table II

No. Mixed polymerisation bonded surface

ratio to mole (%)

based on GMA to butyl methacrylate

1 ΊθΟ: Ο 3 2 40:60 0 • 2 5:95 0 4th 0: 100 20th

It can be seen from the results in Table II above that the homopolymer of butyl methacrylate has no anti-sticking effect, however the homopolymer or copolymer from GM given a remarkable effect.

Example 3

A gelulose triacetate film with a width of 31 cm and a thickness of 100 microns was coated with a solution for an undercoat of the composition given below, to which an aqueous dispersion of a copolymer of GA and styrene (copolymerization ratio based on moles of GA to styrene = 4: 6) was added worden- was followed by drying at 100 min ⁰ C during the second

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Parts

Gelatin 1

V / a ε s er 2

Acetic acid 1

Methanol 60

Acetone 30

aqueous mixed polymer dispersion 1.0

(Polymer solids content about 20%) ■

It was found that the resulting undercoated The film exhibited no sticking between the underlayer and the emulsion layer or backing layer.

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Claims (3)

Photographic element mix a hydrophobic one Film carrier, characterized in that da-15 is the film carrier v / tnigsters on a surface an underlayer with a content of at least one glycidylmsthacrylat-Kcmopoly * r? r.i sat, glycidyl acrylate homopolymer, copolymer before. Glycidyl methacrylate and a vinyl compound that can be mixed with it, copolymer of glycidyl acrylate and of any animalizable animal that can be mixed with it Vinyl compound or mixtures thereof and an over- v / enigstons one of the mentioned sub-layers as a coating applied photosensitive calogensilver emulsion layer having. 2) Photographic element according to claim 1, characterized in that the polymerizable Vinyl compound & us of the group of acrylic acid, methacrylic acid, Alkyl acrylate, alkyl methacrylate with ^ e '/ eils 1 to 4 carbon atoms in the alkyl group, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, II-vinylamide, Styrene, α-methylstyrene, acrylonitrile and methacrylonitrile is selected. 3) Photographer: see element according to claim 1, characterized in that the mixed polymer consists of a C-lycidylme ^J -hacr; - lat-ijutyl methacrylate-mixed polymer or glycidyl acrylate-styrene copolymer. h) Photographic element according to one of claims 1 to 3, characterized in that ca3 the hydrophobic film base is made from a cellulose derivative from the group of 0 0 9 8 3.0 / 1 6 8 9 \