DE1796152A1 - Light-proof protective paper for photographic material - Google Patents

Description

G J 7 8 3

179B15Ü

A 6 F A - G E V A E R T AG LEVERKUSEN

It surely removes the protective paper from the photographic material,

The present invention relates to light-proof protective material, that is suitable for the packaging of photograph! see A

Materials z = B, photosensitive roll film, and represents a Improvement and further development of the patent application X 52 3O8Vlb / 55f, hereinafter referred to as -HauptpatentcLnmeldühg the material described.

Light-proof protective papers are included in the main patent notification described which are impermeable to actinic light rays and as protective paper strips for photographic roll films or for the packaging of X-ray or other

photographic materials are suitable = ^^

The main claim of the main patent registration claims light-proof protective paper for photographic material = this Protective paper consists of a single sheet of pliable black paper with a layer of pigment on one side, which is a polymer cast from aqueous latex as Contains binder for the actinic light absorbing pigment, and one applied to the pigment layer transparent protective layer, whereby that through the rind Paper and the pigment layer formed light-proof protective

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sufficiently impermeable νο around the Durchdiringen, th -Lichtstrahlen η to _verhinderno. , _:

Lentsiöher Sohutzipier according to the main patent application: ``, is't jgenögend impermeable to actinic light rays although it% e ^: fo ^} r Marin -i-js't, ^ .li> not -ftiehr -as -0.1 Γηίϊι =

! As described in Hauptpatentanme dung, can the 'trans' pkrente -protection-SGhicfi't be chosen such that they -Wesentlieh what-serundyrchlass-ig is't and is in Schutzipapier ^packaged; phb: tbgraphisches material thus no damage when exposed to rain. "

It would now be found that, if it was clearer, protective paper for the main patent application would apply as protective paper for: photo- _; Graphic roll film is used, with the uncoated side of the black paper facing the film carrier, the film and the protective paper strips tend too easily to slide on top of each other = according to the invention, this disadvantage is eliminated by means of a protective paper according to the main patent application with the difference, however, that in this case the pigmented polymer layer is one free layer on the other

Side of the paper carrier than the one coated with the protective layer =

For the sake of convenience, the side of the lighter becomes one free pigmented polymer layer with protective paper in the hereinafter referred to as the inside of the protective paper. if light-proof protective paper according to the invention as protective paper

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strip is used for roll film, the coefficient of is sufficient Friction between the film base and the pigmented layer on the inside of the one in contact with the film carrier light-proof paper to prevent unwanted shifting of the light-proof paper over the film.

As mentioned in the main patent application, to printing ink is easier to uniformly over a pigmented polymer layer as applied to a black paper "A erfindungsge mass Schutzpa-pier has no pigmented polymer layer on the outside of the black paper sheet on" If a better printing surface than by the black sheet of paper required, e.g. for attaching information signs, if the light-proof paper is to be used as a protective paper strip for roll film, the outside of the black paper sheet can be coated with a suitable material with good ink acceptance before printing. ■ ·. ■ - '. ■' ...-

The advantages of an improved sliding resistance can be obtained without changing the invention as described in the main claim of the main patent application by coating both the inside and the outside of the black paper sheet with a pigmented polymer layer from an aqueous dispersion this makes the protective paper unnecessarily thicker, but it is still 'usable'. The present invention therefore includes au-oh.> vSchu ^; paper according to the chief

Patent application in which a pigment layer consisting of an aqueous Latex potted polymer containing binder as well as actinic light absorbing pigment is also present as a free layer on the other side of the paper sheet than where the protective layer is »

Although the inventive light-proof protective paper is especially designed for use as protective strips for photographic (φ roll film, it can of course also be used for packaging all other varieties photographic material "Bo such as packaging paper for X-ray film in roll form ,, This packaging paper as can the Method and with the device of our utility model no. 1 971 954 are used.

The black paper, which is used as a carrier for the invention light-proof protective paper is used is very thin and j ^ shows numerous small holes, so that in itself it is insufficient is light-proof and would therefore cause the photographic material to be exposed to light the final protective paper is sufficiently opaque to prevent the To prevent penetration of actinic light rays without endangering the flexibility of the black carrier paper =

Although black kraft paper weighing between approximately 65 and 100 g / m2 works particularly well Any paper made so thin by calendering could be used as a carrier for the protective paper according to the invention it can be seen that the pac ^ rjiut the layers thereon

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preferably does not exceed a thickness of 0.1 mm, application find, provided that it is strong enough and, if with the pigment layer is sufficiently opaque to prevent light rays from penetrating "

In general, a paper which is suitable according to the invention should preferably between about 0.065 and 0.09 mm in thickness, and one on a 15 mm wide strip of paper

have a measured tensile strength of at least 6 kg »^

The pigment layer is preferably made from a dispersion finely divided pigment or a mixture of pigments in a polymer (from aqueous latex) as a binder. wear. Something photographically inert, organic or inorganic pigment that absorbs actinic light find application according to the invention.

Because the light-proof protective paper according to the invention as light-tight protective paper strips for roll film should be used, Ä In general, the pigment used absorb light rays from all parts of the visible spectrum, because usual Roll films are panchromatic. So become black pigments such as soot, oxides of heavy metals, etc. preferably used = but if the light-proof protective paper according to the invention is used Packaging of photographic materials other than photographic materials Roll film is used, these pigments do not necessarily have to be black = in fact, they will E'igmente are then chosen in such a way that they are special paper used all the impermeability required

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ORIGINAL

must give, depending on the species and the emjpfitid ^ i & h-lsei-trdes-2 _; > photographic material. .If e.g. the erfiio.d ^ ng ^ ei ^ sse),; ^; |; light-proof protective paper for packaging X-ray film: an- ,, v. Turn is red, yellow, or ο range. · Μ; 3 # .ο, ηtiß .pder- <-, <'> ^ whose mixtures are used; Pigments; more organic; ::; ·] ■ · 'a, I ^ .. u Heavy metal complexes or heavy metal salts may be used ^ rjipht .. xr-c lii -.-. IH for films to be exposed with X-rays ^ j ^r . because such metal salts or metal complexes have their outline. - ..- χ .: leave behind on the thus exposed film material ,, -, ...-., ·; -, -ι, ..

Carbon black is preferably used as the black pigment. Examples of suitable carbon black dispersions for use in accordance with the present: Invention include: MICRQSOL SCHWARZ 2B, trademark of Ciba AoGo, Basel, Switzerland for an aqueous carbon black dispersion existing paste with 30 wt. * dry substance, and AQUADISPERSE 02/90 Trademark of Kemisk Vaerk Koege A / S, Copenhagen, Denmark, for an aqueous carbon black dispersion »

Any of these _v from;. An aqueous latex polymer brushed, -the filmbiIdende.Eigenschaften has, does not affect the light-sensitive photographic emulsion layer of the film.. and is not sticky after drying, is suitable for _; Encryption · .. application are used as binders in latex form of the pigment "Examples of suitable binder polyvinyl acetate, polystyrene, polyalkyl (meth) acrylates such Polyäthyläcrylat and poly,, _, -. ■ butyl methacrylate eg" PLEXTOL® P 2n (trademark of ^. .Röhn) & Haas GmbH, Darmstadt, for a latex of poly-n-butyl methacrylate with 52.5% by weight dry substance), mixed polymers of styrene, vinyl chloride, vinylidene chloride, alkyl acrylates ^ acrylonitrile, etc.,

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Mixed polymers of styrene and butadiene such as BUTAKON SL 103 (trademark of Imperial Chemical Industries Ltd, London, for an aqueous colloidal dispersion with 46.4% by weight of dry substance), DOW LATEX 512R, DOW LATEX 630 and DOW LATEX are particularly suitable 636 (trademark of Dow Chemical Company, Midland Michigan, VSA ", for a series of latexes of styrene-butadiene copolymers containing 60 to 70 mole percent styrene and 46 to 48 weight percent dry matter), LITEX SB35, LITEX F and LITEX FM (Trademark of Chemische Werke Hüls, AG, Marl / Westf., For a series of latexes of styrene-butadiene copolymers with 60 to 65 mol% styrene and 48-49% by weight dry substance), PLIOLITE LATEX 2108 (trademark of Goodyear Tire & Rubber Company, Akron, Ohio, VoSoAo, for a latex of a styrene-butadiene mixed polymer with 29 mol% styrene and 40% by weight dry substance), HYCAR LATEX 1577 (trademark of BFGoodrich Chemical Company, Cleveland, Ohio, V ₀ SA, for a latex from a copolymer a us styrene, butadiene and acrylonitrile with 29.2 mol% acrylonitrile and 39.8% by weight dry substance) and PERBUNAN Sn LATEX 15M W

(Trademark of the paint factories Bayer A.G., Leverkusen, for a latex made from a copolymer of styrene, butadiene, Acrylonitrile and methacrylic acid with 7.26 mol% acrylonitrile and 15 mol% methacrylic acid, and with 35 wt.% Dry substance, Mixed polymers of butyl acrylate and vinyl acetate such as MOWILITH DMl and MOViILITH DM2 (trademark of Farbwerke Hoechst A.G., Frankfurt / M - Höchst, for latexes with 55% by weight dry matter

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and 26 mol % or 50.5 mol % η-butyl acrylate), copolymers of butadiene and methyl methacrylate such as BUTAKON LATEX ML 501 and BUTAKON LATEX ML 52OS (trademark of Imperial Chemical Industries Ltd., London, for latexes with .39.6 mol % or = 49 mol% butadiene and 48% or 46% by weight dry substance), copolymers of butadiene and acrylonitrile such as BUTAKON LATEX AL 911 (trademark of Imperial Chemical Industries Ltd, London, for a latex with approximately 34 mol % Acrylonitrile and 40 wt. M dry matter), BREON NITRILE LATEX 1561 and BREON NITRILE LATEX 1571 (trademarks of British Geon Ltd., London, for latexes with 42 wt.% Dry matter and 41 mol % or 35.6 mol% acrylonitrile) , CHEMIGUM LATEX 245 CHS (trademark of Goodyear Tire & Rubber Compnay, Akron, Ohio, VSA, for a latex with 42% by weight dry substance and 33 mol% acrylonitrile), LITEX BA65 (trademark of Chemische Werke Hüls AG, Marl / Westf, for a latex of butadiene and acrylonitrile with 40% by weight dry substance un d HYCAR LATEX 1562 (trademark of BoF. Goodrich Chemical Company, Cleveland, Ohio, VSA, for a latex with 40 wt.% Dry substance and approximately 32 mol % acrylonitrile), copolymers of alkyl (meth) acrylates and vinyl chloride and / or vinylidene chloride such as mixed poly (vinyl chloride / vinylidene chloride / butyl acrylate / itaconic acid ) (49/29/20/2) in the form of a latex with 20 wt.% Dry substance, mixed poly

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(Vinylidene chloride / methyl methacrylate / itaconic acid (8S / 1O / 2) in the form of a latex with 20% by weight of dry substance ACRONAL 350 D (trademark of Badische Anilin- & Sodafabrik AG, Ludwigshafen a / Rhein, for a latex of the mixed polymer made of vinyl chloride and n-Buty 1 acryl jit with 44 mol% vinyl chloride and 45% by weight dry substance), DIOPAN 230 D (trademark of the Badische Anilin- & Soda-Fabrik A = G = for a latex of the mixed polymer of alkyl methacrylate and vinylidene chloride with 86 mol % Vinylidene chloride, and 55% by weight dry substance, IXAN WA (trademark of SOLVIC SA, Brussels, Belgium, for a latex of a mixed polymer of methyl methacrylate and vinylidene chloride with 89.5 mol% vinylidene chloride, and 55% by weight dry substance), LUTOFAN 1450 D (trademark of Badische Anilin- & Soda-Fabrik AoGo for a latex of the mixed polymer of vinyl chloride and alkyl acrylate with approximately 76 mol% vinyl chloride and 40% by weight dry substance), VICLAN VL611 (trademark of Imperial Chemical Indus tries, London, for a latex of the mixed polymer ays vinylidene chloride, methyl acrylate and ethyl acrylate with 82 mol% vinylidene chloride and 55.6% by weight dry matter ^ the SARAN LATEX F 122-A 15 and SARAN LATEX F 122-A 20 (trademarks of Dow Chemical Company, Midland, Mich., VSA, for aqueous dispersions of copolymers of vinylidene chloride and acrylonitrile with about 52% by weight of dry substance and 15 or = 20% by weight of dibutyl phthalate as plasticizer).

The dispersions or suspensions of finely divided pigments,

mixed with an aqueous polymer dispersion (latex)

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are, can in any convenient way, but preferably by means of a brush coater, with one with one Air knife or a squeegee provided applicator or metal roller provided with an etched gravure screen, which is arranged in a rotating manner in a watering trough containing an application compound, will be poured onto the black paper carrier Several layers of the same pigment can be applied to the paper backing »

The pigment layer adheres particularly well to the black Backing paper and does not penetrate it, so it retains its flexibility »The pigment composition to be cast is applied in such a way that sufficient impermeability is achieved, i.e. »preferably in the ratio of about 10 to, about 50 g of dry material per square meter of black paper satinised by calendering. The uncoated side of the

• black paper can be printed with e.g. advertising signs,

Film identification marks, frame numbers, warning signs, and signs indicating the film speed.

To obtain maximum visibility of the attached identification marks On roll film through the camera window, it is advisable to have as great a contrast as possible preferable between the pigment layer and the lettering »

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In. For the clarity of the lettering are characters in light colors, such as red, green, blue and yellow on a dark background or characters in dark colors on a light background, which can be shown by negative printing on the uncoated side explained in the following, is attainable, particularly suitable-The used in the description with regard to the labeling The term "color" of course also includes white.

For continuous printing of the characters on the uncoated A rotary printing process, preferably a gravure printing process, is used on the outside of the black paper carrier. that ensures sufficient coverage of the lettering. With these Process, the usual printing inks can be used in one of the above colors »Suitable printing ink compositionsi sum application of the lettering using a rotary printing process are ZoB = alcohol solutions of organic polymers such as Polyvinyl butyral with suitable dyes, e.g. Lead chromate c

Kach a special embodiment for printing the seh .:: ■: ■ · sen paper backing can have the identification marks in negative Be attached in a way, i.e. through unprinted areas. To do this, the backing paper is covered uniformly with printing ink, except for the places of the necessary characters that stand out darkly from the lighter, colored background =

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To see the photosensitive emulsion layer of a photographer To protect the film from the printing ink, if the film and the light-proof protective paper is wound onto a spool touching each other, the lettering is transparent Photographically inert protective layer coated = If the protective paper according to the invention is used for packaging other Photographic materials such as X-ray film are used, this protective layer can serve to protect the protective paper less ^ or more waterproof «This protective layer can be a be a thin polymer layer, which consists of an organic solution or an aqueous dispersion, i.e. a so-called Latex, was cast = examples of such polymers that are normally cast in a dissolved state are cellulose derivatives, ZoBo cellulose nitrate, cellulose acetate, cellulose acetobutyrate and Ethyl cellulose, chlorinated rubber, polyvinyl acetate, polystyrene, and mixed polymers including vinyl chloride, vinyl acetate, vinylidene chloride or contain an alkyl acrylate »

It has been found that a layer of cellulose diacetate and of ethyl cellulose is excellent for protecting a material according to the invention Photographic.Roll film in front of the light-safe Label attached to protective paper Specific examples of polymers, normally made up of aqueous dispersions (latexes), as impermeable to water

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Protective layer can be appliedj are mixed polymers made of vinylidene chloride and acrylonitrile such as SARAM LATEX F 122-A 20 (trademark), mixed polymers made of vinylidene chloride and methyl methcarylate such as IXAN WA 45 (Trade Mark), VICLAN latexes. based on vinylidene copolymers (VICLAN is a trademark of Imperial Chemical Industries, Ltd «, London) such as VICLAN VL 611 (trademark), LUTOFAN 1250 D (trademark the Badische Anilin- & Soda-Fabrik A.G., Ludwigshafen a.Rh =, for a 40% aqueous dispersion of a plastic Based on a vinyl chloride mixed polymer that contains 33% of the plasticizer PALATINOL C (trademark of Badische Anilin- & Soda-Fabrik A.G., for dibutyl phthalate), DIOFAN 300 D (trademark of Badisehe Anilin- & Soda-Fabrik A.G. for a 50% aqueous dispersion of a plastic Based on a plasticizer-free vinylidene chloride copolymer and PLEXTQL 350 η (trademark of Rohm & Haas, a

Philadelphia, Pa. ^ VoS.A.) for a 50% aqueous nonionic Dispersion of a plastic based on an alkyl methacrylate Mixed polymers.

From the above-mentioned latex, a latex itself can both used for the pigment layer as well as for the protective layer will*

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The protective layer is made from a solution in a suitable Solvent or mixture of solvents, or applied from an aqueous dispersion = the layer can be after any suitable application process, j that preferably about 3 to 20 g of dry matter per square meter are present,

(φ As already mentioned, the print quality can be improved by a polymer layer of an aqueous one prior to printing Solution or from a solution in an organic solvent on the uncoated Be te of the paper applies, this The polymer layer may also contain a pigment of the above type for the pigment layer «

Of course, in the case of a second one, it is pigmented Polymer layer on the outside of the black backing paper,

• this second layer preferably the same as this one!. "Art., Der. Inside of this paper *. _; ... _;

The advantages of the modified, light-proof protective paper of the ^! The present invention are principally ^; described in the main sponsor tanmeldühg. In addition, however, when it is used for protective photographic scrolls, the position of the pigment layer on the side of the paper facing the film prevents any shifting of the film over the protective paper strip

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simple assembly and requires the least amount of casting materials.

The thin, light-proof paper according to the invention with a uniform Thickness of 0.1 mm also has the advantage that it possible compared to the usual thicker duplex paper types is, longer strips of roll film on a spool of the usual type to be able to wrap. Because the light-safe according to the invention The protective paper is much more flexible than the usual duplex papers, so there is a risk of the paper springing back or springing back Wraps much less when breaking the roll fastener tape.

The following examples illustrate the invention.

Example 1

A black kraft paper of 75 g / m2 is applied with a Brush coater the following composition so applied that 15 g of dry matter per square meter of kraft paper exist;

MICROSOL SCHWARZ 2B PASTE (trademark) 210 g ACRONAL 350 D (trademark) 275 g

10% strength by weight aqueous solution of COLLACRAL P (Trade mark for a thickener based on the ammonium salt of polyacrylic acid) 75 g

Water 440 g

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The kraft paper coated with the soot is through additional calendering satin finish »The necessary identification marks are uncoated with a yellow printing ink that contains lead chromate as a pigment on the black Layer printed »A post-layer consisting of a solution of cellulose diacetate in acetone and Ethylene glycol monomethyl ether poured in such a way that 3 to 6 g Dry substance per square meter of paper. ~ The cellulose ester solution is prepared by dissolving 10 kg of low-viscosity cellulose diacetate in acetone, the solution volume to 150 l is brought, and this solution .15 1 ethylene glycol monomethyl ether to be added »

Example 2

The procedure is analogous to Example 1, but using DOW LATEX 630 (trademark) as latex instead of the ACRONAL 350 D (.Trademark).

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Claims (1)

- 17 claims ^r lo / light-proof protective paper for photographic material according to the main patent application, modified in that the pigmented polymer layer is a free layer on the other side of the paper than on which the protective layer was applied « 2ο Lightproof protective paper for photographic material according to claim 1 of the main patent application, characterized in that there is also one made of an aqueous latex containing coated layer, consisting of actinic light absorbing pigment particles and a polymer as Binder, as a free layer on the other side of the paper carrier than the one covered with the protective layer 3. Light-proof protective paper according to claim 1, characterized in that that draws the other side of the black paper than the side carrying the pigment layer is printed » 4. Light-proof protective paper according to claim 2, characterized in that that the pigmented layer is printed between the paper carrier and the protective layer, 5 «light-proof protective paper according to one of claims 1 to 4, characterized in that the sheet of black paper is a sheet of black kraft paper. 209814/0403 BAboRlGiNAL Light-proof protective paper according to one of Claims 1 to 5, characterized in that the pigmented polymer layer contains carbon black as pigment » 7ο light-proof protective paper according to one of claims 1 to 6, characterized in that the protective layer is a layer of cellulose diacetate or ethyl cellulose « δ »light-proof protective paper according to claims 1 to 7, characterized in that the black paper has a weight between 65 and 100 g / m2 » 9ο light-proof protective paper according to claims 1 to 8, characterized in that the black paper is between 0.065 and 0.09 mm thick. = Light-proof protective paper according to claims 1 to 9, d £.-Through characterized in that the latex is a mixed polymer of vinyl chloride and butyl acrylate or a mixed polymer from styrene and butadiene is = 209814/0403 BAD ORiGiNAU