DE1914558A1 - Film materials and methods of making them - Google Patents

Description

FATfNTANWXlTE DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPUNG. C. GERNHARDT 1914558 MÖNCHEN HAMBURG PHONE. 555476 8000 MÖNCHEN 15, TELEGRAMS. KARPATENT NUSSBAUMSTRASSE

W. 14 166/69 13 / Loe 2i MäfZ 1969

Bexford Limited Manningtree, Essex, (England)

Film materials and methods of making them.

Addition to the patent «...

Patent application P 14 72 797.0

The invention relates to and improvement of film materials, and more particularly, to film compositions or modification of those described in the German patent (patent application P 14 72-797.0) Invention.

In the German patent specification ....... (patent application P 14 72 797.0) and in the German patent specifications and ....... (patent applications

P 15 97 513.0 and P 15 97 514.1) is a film material

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which comprises a "synthetic linear polyester film backing having a layer of a homopolymer of vinyl halogen ester or a copolymer of a vinyl halogen ester with vinyl acetate and / or vinyl alcohol, an unsaturated carboxylic acid, acrylamide or N-methylolacrylamide, these Layer on the polyester support either before or after the support is fully oriented Orientation of the carrier has been applied.

The footage thus created is for another Covering with an auxiliary or intermediate layer Gelatin and then a gelatin-halosilver emulsion to obtain a light-sensitive photographic film product suitable. On the other hand, the film base thus created can also be provided with a Layer of cellulose acetate, cellulose acetate butyrate, polyvinyl acetate, a partially hydrolyzed polyvinyl acetate or a polyvinyl acetal, this layer being light-sensitive on its surface Carries diazonium salts to obtain a diazo type photosensitive film product.

In these photosensitive film products, the vinyl halo ester polymer layer gives an excellent one Adhesion between the synthetic linear polyester support and the photosensitive layer. In however, it has been found that there is some difficulty in obtaining vinyl halo ester polymer coatings of sufficient uniformity to have significant effects on the properties of the film products of the halosilver or Avoid diazo style.

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The object of the invention is to provide a Polyvinyl halogen ester polymer layer with improved uniformity and excellent adhesion on the synthetic linear polyester carrier and on subsequently applied polymerizate layers in a film material or a film composition of the specified type.

According to the invention, therefore, there is provided a film assembly or film composition comprising a backing of a synthetic linear polyester film, which on at least one surface a layer, hereinafter referred to as layer A, made of a copolymer of a vinyl halo ester with at least one other monomers copolymerizable therewith, said monomers or at least one of the other monomers mentioned is selected so that the end copolymer is a lower softening point than those of either product, that by polymerization in the absence of said chosen monomer or monomers selected monomers is obtained.

The procedure for determining the softening points of polymers vary from those given absolute values. Hence, when referring to the relative softening points, the application is the same Including working method for determining the values to be compared.

The copolymers according to the invention can copolymers of a vinyl halogen ester with a or more of the listed in Table I below

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led monomers that have a softening point lowering effect; possess these monomers an internal plasticizer effect and include alkyl acrylates, Alky! Methacrylates, polyalkylene oxyditaconates and maleates,., Vinyl alkyl ethers, vinyl esters, alkenes, alkadienes and alkyl styrenes.

Table I.

η -butylacrylate

2-ethoxyethyl acrylate

Ethyl acrylate

2-ethylhexyl acrylate

Decyl methacrylate. ■ '

Octadecyl methacrylate

2-ethylhexyl methacrylate

Di (polypropyleneoxy) itaconate

Vinyl butyl ether

Vinyl ethyl ether.

Vinyl methyl ether

Yinyl methyl ether

Vinyl isobutyl ether

Vinyl stearate

Vinyl versatate ■.

Ethylene

1-butene

Butadiene

4-dodecyl styrene

4-nonyl styrene

The copolymers according to the invention can Copolymers of a vinyl halogen ester with one or more of the above-mentioned monomers, which have a softening point lowering effect

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have, if desired together with one or more monomers, in the final copolymer Carboxy, hydroxyl, ester, nitrile, amide, N-monosubstituted or N, N-di-substituted amide, Amino or substituted amino groups result. Suitable such further monomers are shown below Table II listed:

Table II

Itaconic acid Maleic acid Citraconic acid Acrylic acid Methacrylic acid Crotonic acid Diesters and monoesters of unsaturated dicarboxylic acids with monohydric or polyhydric alcohols. Allyl alcohol Vinyl alcohol Esters of unsaturated monocarboxylic acids with polyvalent ones Alcohols, e.g. 2-hydroxyethyl methacrylate. Vinyl acetate acrylonitrile acrylamide methacrylamide N- (1,1-dimethyl-3-oxobutyl) acrylamide N-monosubstituted or N, N-disubstituted derivatives of unsaturated amides, e.g. tertiary butyl acrylamide, Ν, Ν-dimethylacrylamide, N-methylolacrylamide. N-methoxymethylacrylamide, N-acetoxymethylacrylamide N-vinylpyrrolidone dimethylaminoethyl methacrylate

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It should be noted that the expression used here "Monomeres" for the specification of the units that are in the copolymer are present, is used and not necessarily for the determination of the monomers which the copolymer was obtained, i.e. in certain cases the coated polymer can pass through a chemical modification of a preformed copolymer can be obtained, a copolymer in which not all of its units are the same as the monomers from which the pre-formed copolymer has been produced,

The homopolymers of the monomers listed in Table I, for example, usually have

A softening point of below ⁰ ° C. and small proportions of the monomers from Table I lower the softening point of the polymer product in the case of copolymerization with vinyl haloesters (and, if desired, with monomers from Table II). This is shown in the table below, which lists the glass transition temperatures (Tg) determined by a differential calometric method.

Polymeric composition _.

A copolymer of vinyl monochloroacetate and 9o mol% Ίο mole% acrylamide 51 ⁰ C

A terpolymer made from 80 mol% vinyl monochloroacetate, 1o mol% acrylamide and 1o mol% Ethyl acrylate 40 ° C

A copolymer with a content of 72 mol% Vinyl monochloroacetate and 28 mol% polyvinyl alcohol

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A terpolymer with a content of 4o mole% vinyl monochloroacetate, 17 mole% vinyl alcohol and 43 mole% ethylene 21 ⁰ C

Examples of suitable ratios

of monomer units present in the copolymer according to the invention include:

Vinyl halo ester (hereinafter referred to as component I) 50-98 mol%.

Monomers from Table I (hereinafter referred to as Component II designated) 2-3o mol%.

Monomers of Table II (hereinafter referred to as Component III) ο - 2o mole percent. '·

The preferred vinyl halogen esters for component I are vinyl monodi- or vinyl monotrichloroacetates.

The preferred monomers for component II are ethyl acrylate, 2-ethylhexyl acrylate and vinyl isobutyl ether and ethylene.

The preferred monomers for component II are acrylamide, N-methylolacrylamide, itaconic acid, Acrylic acid, vinyl alcohol, N-vinylpyrrolidone and dimethylaminoethyl methacrylate.

The proportions of the three components are chosen so as to achieve a satisfactory balance between adhesion and coating quality. In general, liability assumes the following applied hydrophilic layers are added when the amount of component III is increased; but then must also the Amount of component II can be increased in order to lower the softening point and poor coating behavior to avoid .. The proportions of the components dog III

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can be increased to the limit at which a weakening of the adhesion to the polymer carrier begins.

The composition of the copolymer for layer A is preferably within the following Limits in moles of each constituent monomer expressed are:

Component I 7ο - 95 mol%

Component II 3 - 2o mol%

Component III 2 - 1o Mol-So

The synthetic linear '. ■ polyester support is preferably made of polyethylene terephthalate, polyethylene terephthalate is biaxially oriented always in this use and heat-bonded to give a stronger film base. The procedures for producing such a film base having suitable mechanical properties for use as a support in various photographic film products are well known.

By the term "complete orientation", the process is simultaneous or sequential Longitudinal or transverse stretching of the carrier and crystallization and heat consolidation of the carrier, while holding it to prevent shrinkage.

The vinyl halogen ester copolymers of layer A can be applied to the synthetic linear polyester film support either before or after its complete orientation from aqueous dispersions or latices or as a solution be applied in organic solvents. That

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Application before complete orientation can consist in applying the copolymer to the extruded or pressed amorphous carrier, to the uniaxially stretched carrier or to the biaxially stretched carrier, but before the heat-setting stage.

In general, the copolymers according to the invention are preferably made from aqueous dispersions or latices applied. This avoids the use of expensive organic solvents.

In addition, it is preferred to apply the copolymers to the polyester carrier before complete orientation if the subsequent stretching and / or heat setting of the carrier ensures excellent adhesion of the copolymers to the carrier without the use of swelling agents for the polyester carrier. A particular feature of the copolymers is that when applied in this way, layer A is resistant to stretching and the heat treatment applied during full orientation without becoming discontinuous or producing visible haze. When applied before complete orientation, the aqueous dispersions and / or latices of the copolymers have further advantages over organic solvent solutions in that the possibility of excessive attack by organic solvents on the unoriented or partially oriented carrier is avoided.

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The copolymers according to the invention can be applied to the polyester carrier after it has been more completely Orientation are applied, in order to achieve the optimal possible adhesion of the polymer to the Carrier the fully oriented carrier is preferably treated with a swelling agent or to a Corona discharge is exposed before the polymer is applied.

The treatment with a swelling agent can be in a coating of the film with a solution in an aqueous or organic solvent or with an ₍ aqueous dispersion of the swelling agent and then heating the film for a short period of time to remove the solvent or the dispersion medium, and to enable On the other hand, the swelling agent can be incorporated into the mixed polymer solution or into the dispersion. Suitable swelling agents are halophenols and α-chloro-substituted aliphatic acids, e.g. dichlorophenols, trichlorophenol, p-chloro-m-cresol , p-chlororesorcinol and trichloroacetic acid.

The fully oriented carrier can be conveniently exposed to a corona discharge by passing it between electrodes separated by a distance of 0.25 to 6.35mm and an alternating voltage of 5 to 4o kV at 1o to 1oo kHz wear. The dwell time in the discharge can be up to 5 see *

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It can be seen that the layer A has different constituents than the copolymers indicated above such ingredients, e.g. or fusing, plasticizers and polymeric plasticizers.

The dispersions, latices or solutions for layer A can also contain small amounts of crosslinking agents, so that through during drying Heating the layer is crosslinked. The crosslinking agent may, for example, be dimethylolurea with an amide group containing copolymer or hexamethoxymethylmelamine in the case of a free carboxyl or hydroxyl group be containing copolymer.

The aqueous solutions and dispersions can be applied to the film support in any of the known ways Coating methods are applied, e.g. coating by the immersion process, pearl or bead application process, Slot coating, slot nozzle application process or engraving application process.

The applied moist layers are through Air movement at an elevated temperature or dried by infrared radiation to clear congealed coating of about 0.5 to 10 mg

To obtain polymer per dm. To get together well To ensure that the dispersed polymer particles should preferably have a diameter below Own 5 microns.

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A film material or a film composition of the type described above takes a more hydrophilic layer B (1) with good anchoring or adhesion, e.g., a gelatin-containing thin layer composed of an organic solvent or an aqueous Dispersion has been applied. The organic solution or aqueous dispersion of gelatin can also be synthetic Polymers or resins, crosslinking agents, surface-active Contain agents and adhesion promoters, e.g. polyvinyl acetate, formaldehyde, sodium lauryl sulfate and resorcinol. On this layer containing gelatin can be superimposed with a photosensitive gelatin-halosilver emulsion are applied to obtain a photographic film product which through all the photographic processing steps a shows excellent adhesion of the layer structure.

The film arrangement or construction as described above takes under good anchoring or Adhesion to the surface of layer A is a cellulose acetate layer B (2) or a cellulose acetate? - butyrate layer B (3). These layers can subsequently hydrolyzed on their outer surfaces and impregnated with a light-sensitive diazonium salt or they can be mixed with a light-sensitive • diazonium salt that is in a corrosive solution *. : medium medium. is included, can be impregnated directly, to give a film material of a diaza type.

The film material, as described above, takes on with good anchoring or adherence to the surface layer A has a layer of vinyl acetal B (4),

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by a photosensitive diazonium salt contained in a corrosive solvent medium is, "can be directly impregnated to give a film material of a diazo type.

In addition, the film material of the type described above takes place with good anchoring on the Surface of layer A a layer of polyvinyl acetate or partially hydrolyzed polyvinyl acetate B (5) which includes a photosensitive diazonium salt or which subsequently with such Salt is impregnated.

The film construction or film composition according to the invention as described above is also at suitable for the production of a polyester film material with a matt lacquer coating and according to the embodiment of the invention provides a translucent polyester film material that is clear and legible Marking with pencil or absorbent ink is created, which is a synthetic linear Polyester film base comprises, on at least one surface, a layer A of a copolymer of a vinyl halo ester, as indicated above, this layer on the polyester support before Orientation of the film base, between successive stages in the orientation of the film base or after complete orientation & r film material has been applied, and an adhesive layer B (6) of an organic film-forming in an organic Solvent-soluble material that contains finely divided

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separated particles of an inorganic, translucency-producing interlocking or anchoring agent, or of such interlocking or anchoring means, carries.

Organic film-forming materials for layer B (6) can consist of one or more of the the following are formed:

Cellulose ester, acrylic polymer or copolymer, Urea-formaldehyde resin soluble in organic solvents or modified urea-formaldehyde resin, Melamine-formaldehyde resin soluble or modified in organic solvents Melamine-formaldehyde resin, alkyd resin, polyvinyl acetal, curable epoxy resin, soluble polyamide resin.

These film-forming materials can be used in admixture. For example, a paint grade cellulose nitrate can suitably be mixed with proportions of a Urea-formaldehyde or melamine-formaldehyde resin can be combined together with proportions of an alkyd resin to form a Maintain a balance between flexibility, hardness and scratch resistance; a curable epoxy resin may suitably be combined with portions of an epoxy-reactive polyamide resin.

Fine, inorganic, transparency-producing Anchoring or connecting means can e.g. from the group of silicon dioxide, silicate, frosted glass, chalk, talc, diatomaceous earth, Magnesium carbonate, zinc oxide and titanium oxide can be selected. FeinteiligGs silicon dioxide with a particle size of 0.1 to 15 microns is the preferred anchor or anchor Lanyard with which smaller amounts of the other materials can be incorporated to meet the demand Maintain the degree of transparency and increase the toughness and scratch resistance of the coating.

Layer B (6) should preferably be baked for a short period of time at temperatures around 100 to 120 ^° C. in order to bring about hardening of partially polymerized constituents.

The material content of the layer B (6) is not limited to the materials specified up to now and is smaller Portions of other ingredients can be added in an advantageous manner in order to bring about hardening and

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to regulate the flexibility of the coating and the absorption of static electricity through the. degrade coated film.

The film material or the film structure according to the invention is also in the production of a direct image or a presensitized lithographic printing plate useful and in accordance with this embodiment of the invention a clear polyester film material is created which is a synthetic linear polyester backing comprises which on at least one surface ein.Schlicht A from a copolymer of a vinyl halogen ester, as defined above, this layer on the polyester carrier substrate before the orientation of the film base, between successive stages in the orientation the film base or after the complete orientation of the film base was applied, and one, adhesive or Adhesive layer B (7), which is a water-swellable organic film-forming material that has been made insoluble

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den was, and at least one particulate / organic filler contains.

Suitable, water-swellable organic film-forming Materials for layer B (7) are: cellulose ethers, e.g. methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropylmethyl cellulose, Carboxymethyl cellulose, polyacrylamides, polyvinylpyrrolidone, sodium alginate, natural Gums, e.g. gum arabic, polyvinyl alcohols, carbohydrates, e.g. starch and dextrin, proteins, e.g. casein and Zein, vinyl-maleic anhydride copolymers and Ethylene oxide polymers.

9098U / 1354

The preferred hydrophilic, water-swellable material is polyvinyl acetate which has been hydrolyzed to the extent of 84 to 98%.

These materials can be applied in some cases insoluble in the layer by heat or by the addition of a suitable crosslinking agent, examples of cerium type crosslinking agents are: urea-formaldehyde, melamine-formaldehyde, glyoxal and Dialdehydes in general, formaldehyde and dibasic acids.

The preferred crosslinking agent for polyvinyl alcohol is a methylated melamine-formaldehyde resin.

Suitable finely divided fillers for use in layer B (7) are naturally occurring silicates, e.g. Clay, kaolin, talc, bentonite, sepiolite, and mica, oxides, e.g. '■' ■ itane dioxide, zinc oxide, colloidal silicon dioxide, Diatomaceous silicon dioxide (kieselguhr), carbonates, e.g. calcium carbonate, magnesium carbonate, barium carbonate, and Sulfates, e.g. barium sulfate and calcium sulfate. The preferred fillers are silica, clay and titanium dioxide.

The transparent or translucent polyester film material carrying the layer B (7) defined above, can be made as a direct image lithographic material by recording an image on the fun using a oleophilic medium can be used. On the other hand, the film can be coated with a positive or negative working photosensitive material and then used as a presensitized lithographic printing plate will.

9098417135 /;

Another particular use of the copolymers according to the invention is as an intermediate. layer in the construction or composition described in British Patent 1,080,817. In this The patent specifies that the intermediate layer consists of a copolymer of a vinyl halo ester can, and it has been found that the copolymers of vinyl haloesters according to the invention are useful as such interlayers.

The invention is illustrated below by way of examples explained in more detail.

The film base products of Examples 1 through 19 were made furthermore coated with a photographic gelatin-halosilver emulsion, which is placed directly on top of the applied gelatin coating. The layers of these fully coated photographic films possessed strong adhesiveness to each other and to that Film base so that the film is completely coated without risk of delamination or curling could be treated and processed.

Samples of the polyethylene tesphthalate film from Examples 1-19 were also examined for the quality of the coatings. The vinyl halo ester copolymer coatings were colored with Rhodamine BNS dye and examined manually. Electron photomicrographs were taken of the surfaces of the coatings. The light transmittance "of the polyester supports bearing interpolymer coatings was measured. In all cases the coatings were found to be satisfactorily uniform, free of discontinuities, and optically clear.

In the examples, use was made of such commercially available starting materials as those listed under their trade names are indicated. "These are the following:

nature

Manufacturer

PLURONIC F68
ETHOMEEN T12
HUMIFEN WS25
TEXOFOR FN8
TRITON

Ethylene oxide-propylene oxide condensates

Ethylene Oxide Oleophilic Amine Condensate

Sulphonated oils> ophiler polyester

Condensate of nonylphenyl with 8 moles of ethylene oxide

Sodium salt of alkylaryl polyether sulfate

LISSOCAMINE A Cationic surfactant

Jacobson Van der Berg Ltd.

Armor Hess Ltd.

General Aniline & Film Corp.

Glovers (Chemicals) Ltd.

Rohm & Haas Ltd.

Imperial Chemical Industries Ltd.

FORMVAR 1595E copolyvinyl formal with a Ge-Shawinigen Ltd. contains from 9.5 to 1 ^ % polyvinyl acetate and 5 to 6 % polyvinyl alcohol

AEROSIL TK800
GASIL 64

Amorphous silica

Finely ground (micronized) silicon dioxide 6-14 microns in diameter

TIOXIDE RCR3 Modified titanium oxide

Degussa

Joseph CrossfM-d & Sons Ltd.

British Titon
Products Co., Ltd.

example 1

A glass flask 3000 ml freed of oxygen to water at 40 ° C contained, wherein the water was stirred, was prepared and a slow S ^T ickstoffstrom was provided therein. 50 % of a solution of 0.24 g of ferroammonium sulfate in 120 ml of water and 5 # of a solution of 46.6 g

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Pluronic F68 (Jacobson Van der Berg Ltd.) and 50 g of acrylamide dissolved together in 160 ml of water were added. 5 % of a prepared mixture of 940 g vinyl chloroacetate and 150 g ethyl acrylate was then added.

With continuous stirring at 40 ° C in a nitrogen atmosphere, 10 % of a solution of 1.71 g of ammonium persulfate in 200 ml of water and then 10 % of a solution of 0.25 g of sodium metabisulfite in 200 ml of water were added to initiate the polymerization during the following 15 min added.

^{It was heated and stirred continuously at 2} K) ⁰ C for a further period of 165 min, while the remaining monomer mixture and the remaining aqueous solutions were gradually added. The acrylamide surfactant was kept somewhat in advance of the vinyl chloroacetate-ethyl acrylate mixture during the addition, followed by the persulfate and bisulfite additions.

The letex was stirred for a further 10 minutes at 40 ° C. after all additions. While cooling, the latex was adjusted to a pH of 5 with dilute ammonia. The conversion was 98 % and gave a stable latex with a mean particle size of 0.1 micron diameter.

The following overlays were made on polyethylene terephthalate film upset? The first coating was applied to a uniaxially, i.e., longitudinally stretched film

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applied and consisted of a latex obtained as described above with the following composition:

Coating 1:

^E in terpolymer with a content of 78 mol # vinyl monochloroacetate, 15 M0I-J6 ethyl acrylate and 7 mol # acrylamide

20.0 g

Pluronic F68 0.8 g

Water . 100 g

After drying, the coating weight was about 6 mg /

dm. The coated film turned from the side around one. Factor of 5 ^{stretched at HO 0} C and heat set at 180 ° C.

Coating 2;

Gelatin "3 * 0 g

Formalin (40 % formaldehyde) 0.08 g

Water 100 g

The coating was dried and heated at 110 ° C. for 5 minutes.

The same latex was also applied to a biaxially oriented filin / prior to heat setting at 180 ° C. The gelatin coating was then applied and dried.

Example 2

^ In fully oriented polyethylene terephthalate film , a corona discharge of 50 watts was exposed to each 2.54 cm electrode with a gap of 1 mm between the electrodes.

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A latex having a composition as given in Example 1 was then applied and dried to give a coating weight of 1.5 mg / dm. A second coating with a composition as indicated in Example 1 was then applied and dried and heated ^{at HO 0 C for 3 minutes.}

Example 3

^A fully oriented terephthalate film was coated * with a solution of the composition given below!

4- chlororesorcinol 3.0 g

Ethomeen T12 0.025 g

Water 100 g

The polymer latex coating and the aqueous gelatin coating were then, as described in Example 2, upset.

Example 4

\ A fully oriented polyethylene terephthalate

film was. a corona discharge, as described in Example 2, exposed and the following coatings were applied:

Coating 1:

A terpolymer of 78 mol # vinyl monochloroacetate,

12 mols of ethyl acrylate and 10 mols of acrylamide 20 g

Pluronic F68, 0.8 g

Water 100 g

The coating was dried at 100 ⁰ C.

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Cover 2:

Gelatin j5.0 g

Water 100 g

The coating was dried and heated ^{at HO 0 C for 5 min.}

The latex of Coating 1 was prepared in the same manner as in Example 1.

Example 5

The first coating was applied to a uniaxially stretched polyethylene terephthalate film and consisted of a latex with the following composition:

Coating 1:

A copolymer of 95 mol $ vinyl monochloroacetate and 5 moles of ethyl acrylate 20.0 g

PluroÄic F68 "" 0.8 g

Water 100 g

The coating was dried and the coated film was completely oriented according to that described in Example 1 Way of working.

Coating 2:.

A dispersion of gelatin in an organic solvent, as indicated below:

Gelatin. 1.4 g

Polyvinyl acetate '. "', · 0, \ g

Water 5> ° ^ml

Acetic acid '1.0 ml

Methanol. _ ... -. ,? 4 ml

Formalin (40 % formaldehyde) 0.1 ml

9Q9841M35A.

The coating was dried and heated ^{at 110 ° C. for 5 minutes.}

The latex of Coating 1 was made in the same way prepared as that of Example 1.

Example 6

A first coating was stretched onto a uniaxially Applied polyethylene terephthalate film and consisted of a latex of the following composition:

Cover 1: · '

A terpolymer of 55 mol # vinyl monochloroacetate, 25 moles of ethyl acrylate and 20 moles of acrylamide 20 g

Humifen WS25 0.4 g

Water 100 g

The wet coating weight was 30 mg / dm and, after drying, the coated film was oriented according to the procedure given in Example 1.

Coating 2;

A gelatin solution having the same composition as coating 2 of Example 1 was applied.

The latex of Coating 1 was made in the same manner as produced in example 1.

Example 7. -

The first coating was stretched onto a uniaxially Applied polyethylene terephthalate film and consisted of eggs latex with the following composition:

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Coating 1:

A terpolymer of 65 mol- # Finylmonochloracetat, 30 mol- # 2-ethylhexyl acrylate and 5 Uol-% N-methylol-

acrylamide 20.0 g

Pluronic F68 0.4 g

Water 100 g

The coating was dried to give about 6 mg per dm of polymer and the coated film was as described in Example 1, oriented.

Cover 2:

Gelatin 3.0 g

Formalin (40 % formaldehyde) 0.08g

Water 100 g sodium lauryl sulfate 0.03 g

The film was dried and ^{heated at 110 °} C. for 3 min. The latex of coating 1 was produced in the same way as described in Example 1.

Example 8 "

The first coating was applied to a uniaxially stretched polyethylene terephthalate film and consisted of a latex with the following composition: '

Coating 1;

A terpolymer of 85 mol- $ vinyl monochloroacetate,

10 moles of ethyl acrylate and 5 moles of acrylic acid 20.0 g

Pluronic F68 0.8 g

Water 100 g

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The coating was dried and the coated film became oriented in the same way as in Example 1.

Coating 2;

^E ine Gelatins aqueous solution having the same composition as the coating 2 of Example 1 was applied.

The film was dried and at 110 ^° C. for 5 min

heated.

The latex of Coating 1 was prepared in the same manner as described in Example 1.

Example 9

The first coating was applied to a uniaxially stretched polyethylene terephthalate film and consisted of a latex with the following composition:

Coating 1;

A terpolymer of 60 mol- $ vinyl monochloroacetate, 20 mol # ethyl acrylate and 20 mol # dimethylaminoethyl

methacrylate 10.0 g

Pluronic F68 0.4 g

Water 100 g

The film was dried and fully oriented, and an aqueous gelatin solution was applied like this in Example 1 is described.

The latex of Coating 1 was prepared in the same manner as described in Example 1, produced.

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Example 10

^ in fully oriented polyethylene terephthalate film was coated with the following dispersion:

Coating; 1;

p-chloro-m-cresol 5.0 g

Humifen WS25. 1.0 g

Water 100 g

The coating was heated at 100 ⁰ C for min. 2
The following coatings were then applied:

Coating 2;

A terpolymer of 80 mol # vinyl monochloroacetate,
10 mol- ^ ethyl acrylate and 10 mol- # N-vinylpyrrolidone

10.0 g

Gelatin,: _; 1.0 g

Texofor PNS. 0.4 g

Water "100 g

The coating was dried at 10.0 ⁰ G.

Coating 3:

Gelatin 3.0g

Resorcinol. 3.0 g

Water 100 g

The coating was dried and heated ^{at 110 ° C. for 5 minutes.}

Example 11

A fully oriented polyethylene terephthalate film was coated with the following solution:

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Coating 1;

4-chlororesorcinol. 3.0 g

Sodium lauryl sulfate. 0.01 g

Water 100 g

After drying for 5 min at 100 ^° C., the following coatings were applied:

Coating 2 s

A latex with the following composition:

A terpolymer made from 70 mol- $ vinyl monochloroacetate, 25 mol # ethyl acrylate and 5 mol # monoethyl itaconate . 20.0 g

Texofor FN8 0.4 g

Water 100 g

The coating was dried ^{at HO 0 C for 1 min.}

Coating 3:

A gelatin solution with the same composition as coating 2 of Example 1.

The coated film was heated ^{at HO 0 C for 3 min.}

Example 12

The first coating was applied to a uniaxially stretched polyethylene terephthalate film and consisted of a latex of the following composition: Coating 1:

A terpolymer made from 90 Mpl- $ vinyl monochloroacetate,

8 mol- # .n-butyl acrylate and 2 mol- # methacrylamide 10.0 .g

Texofor PN8 0.4g

Water 100 g

.29- 1SHiSi

The coating was dried and the coated film was fully oriented as described in Example 1 is.

Cover 2:

A dispersion of gelatin in an organic solvent with a composition as in Example 5 was upset.

The coating was dried and heated ^{at HO 0 C for 5 min.}

Example 1J>

60 m.g / dm of a polymer latex was applied to a uniaxially stretched polyethylene terephthalate film. The latex had the following composition:

A terpolymer of 85 mol- $ vinyl monochloroacetate,

10 mole percent ethyl acrylate and 5 mole percent vinyl isobutyl ether 10.0 g

Texofor FN8 0.4 g

Water 100 ml

The film was dried and fully oriented before a gelatin coating as in Example 1 was applied.

Example 14

A vinyl acetate-ethylene-Mischpolymerisatlatex (Mowilith DMlO, Hoechst Chemicals Ltd .; I5OO g) was verdünnn 1125 ml of water and heated with stirring at 95 to 100 ⁰ C. A solution of 697 g potassium hydroxide in 'I500 ml of water was added over one hour while stirring continuously for an additional period of 5 hr. At 95 to 100 ⁰ C.

became. The precipitated product was removed by filtration, fair washed and vacuum dried to give 560 g. The vinyl alcohol-ethylene Mischpolymerisatprodukt was in the amount of 36O g to L440 g of molten chloroacetic acid at 95 ⁰ C was added, followed by. Continuously heated during 5 h and stirred. After cooling to 50 ^° C., 1000 ml of acetone were added and the solution was poured into 20 1 of water. The precipitated polymer was repeatedly dissolved in acetone and W precipitated again in water until it was free of acid. Taking into account the composition of the starting material and by analysis, it was found that the polymer had the following composition: 50 mol vinyl chloroacetate, 30 mol vinyl ethylene and 20 mol vinyl alcohol.

40 g of the copolymer were dissolved in 120 ml of methylene chloride and mixed with a solution of 1.0 g of the surfactant Triton X ^ Ol (Rohm and Haas) in 250 ml of water and passed through an ultrasonic homogenizer. After removal of methylene chloride by passing air through the kept at 4O ⁰ C dispersion, the -Misch "polymer was prepared for use in a stable state.

product, The vinyl alcohol-ethylene copolymer is made by

Hydrolysis of the vinyl acetate-ethylene copolymer described above had been obtained, was heated ^{with 6 times its weight of monobromoacetic acid for 24 hours. At 100 0 C.} The separated by pouring into water, Filtratton and drying had the composition of 60 mol # vinyl bromoacetate, 30 mol ^ ethylene and 10 vinyl alcohol. -

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" ³¹ " 19U558

A fully oriented polyethylene terephthalate film was subjected to a corona discharge as described in Example 2, followed by the following coatings became: -

Coating 1:

Terpolymer from 60 mol- $ vinyl monobromoacetate, 30 moles of ethylene and 10 moles of vinyl alcohol

(prepared as described above) 2.0 g

Acetone 100 g

Hexamethoxymethylmelamine 0.1 g

p-toluenesulfonic acid 0.01 g

The coating was dried for 1 min at 100 ^° C. and a gelatin dispersion with a composition corresponding to that given for coating 2 in example 4 was applied and dried.

Example 15

A fully oriented polyethylene & terephthalate film was coated with an aqueous solution of the following composition:

Coating 1:

4-chlororesorcinol 5 * 0 g

Etomeen T12 0.025 g

Water 100 g The following dispersion was then applied: Coating 2:.

Terpolymer of 60 mol inylmonochlorpropionat $ ^v

30 moles of ethylene and 10 moles of vinyl alcohol 20.0 g

Triton X301. . . . 0.5 g.

Hexamethoxymethylmelamine 0.5 g ...

p-toluenesulfonic acid 0.1 g

Water 100 g

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19H558

The coating was dried and a gelatin coating having the same composition as given for coating 2 in Example 1 was applied, dried and heated ^{at HO 0 C for 3 minutes.} ' , .

Example 16

The vinyl alcohol-ethylene copolymer product, such as Described in Example 14, was with 6 times its weight of dichloroacetic acid for 6 hours. At t heated to 90 ° C. When separated, a copolymer was the Composition of 55 moles- ^ vinyl dichloroacetate-. 30. mol- $ Ethylene - 15 moles of vinyl alcohol obtained. '.

A fully oriented polyethylene terephthalate film was subjected to a corona discharge as described in Example 2. Then the following coating was applied:

A terpolymer of 55 mol- ^ vinyl dichloroacetate, J) O mol- $ Äthjäen and 15 mol- Ji vinyl alcohol

(prepared as indicated above) 20.0 g

Benzyl alcohol 20 g

Triton X30I. 0.8 g

Water x 100 g

* The coating was dried for 2 minutes at 100 ^° C., after which a gelatin _{coating with the composition;} as indicated for the coating 2 in Example, applied and heated ^{at HO 0 C for 5 min.}

Example 17

A fully oriented polyethylene terephthalate film was subjected to a corona discharge as described in Example 2, followed by the application of the following coatings became:

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19U558

Coating 1:

A terpolymer of 85 mol-56 vinyl monochloroacetate,

10 moles of ethyl acrylate and 5 moles of acrylamide 20.0 g

Pluronic F68 0.4 g

Lissocamine A 0.4 g

Water 100 g

The coating was dried at 105 ° C. for 2 minutes.

Cover 2:

A gelatin solution with the same composition as coating 2 of Example 1.

The coated film was dried at 105 ° C. for 5 minutes .

The latex of Coating 1 was prepared in the same manner as that of Example 1.

Example 18

Vinyl chloroacetate-Vinylversatat ^ -Hydroxyäthylmethacrylät were used in molar ratios of 70:25 and were copolymerized in a methyl ethyl ketone solution under reflux for 12 hours and using 0.5 % azobisisobutyronitrile, based on the monomers, as a free radical generating agent.

A fully oriented polyethylene terephthalate film was with an aqueous solution of 4-chlororesorcinol as in Example 3 coated. The following coatings were then applied:

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19H558

Cover 2:

A terpolymer of 70 mol # vinylmanochloroacetate, 25 mol $ vinyl versatate and 5 months 1-5 $ 2-hydroxyethyl methacrylate, prepared as described above 2.0 g

Methyl ethyl ketone 100 g

Hexamethoxymethylmelamine 0.1 g

p-toluenesulfonic acid 0.01 g

The coating was ^{dried at 100 °} C. for 1 min.

Coating 3>:

Composition as for coating 2 in example 5

After drying of the coating, this was heated min at 110 ⁰ C during the fifth

Example 19

A fully oriented polyethylene terephthalate film was coated with an aqueous dispersion of p-chloro-mcresol as described in Example 10. The following coatings were then applied: Coating 2:.

A terpolymer of 85 mol # ^ inyl monochloroacetate, 10 mol JB ethyl acrylate and 5 mol J * N- (1,1-dimethyl-5-oxobutyl) acrylamide 2.0 g

Methyl ethyl ketone * 100 g

The coating was dried for 1 min at 100 ^° C. *

Coating 3? ■ "._ ■■

A gelatin coating composition as for coating 2in Example 5 given

The film was heated ^{at HO 0 C for 5 min.}

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19U558

The terpolymer of coating 2 was prepared in the same way as the terpolymer of Example 1.

Example 20

A latex, which is a terpolymer of 80 vinyl monochloroacetate, 10 mol $ ethyl acrylate and 10 Acrylamide was applied to a uniaxially stretched polyethylene terephthalate film.

The coating was dried to give a clear, uniform layer with a coating weight of 9 mg

Each dm. The coated film was then fully oriented, as described in Example 1.

A similar latex, which, however, is a copolymer of 98 mol vinyl monochloroacetate and 11 mol $ acrylamide, i.e. containing no ethyl acrylate, was also applied to a uniaxially oriented polyethylene terephthalate film. In this Fall, the coating was cloudy after drying, with the intensity the haze increased when the film was fully oriented became.

The following provisions of the light transmission of the two coated films of this example show the improvement in clarity brought about by the incorporation of ethyl acrylate is obtained in the polymer.

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Coating percent light transmission

Uniaxially stretched biaxially stretched film

Vinyl monochloroacetate ethyl

acrylate acrylamide terpoly

merisat 95 99

Vinyl monochloroacetate

Acrylamide copolymer 86 70

The following Examples 21 through 24 illustrate the Utility of the products according to the invention in the manufacture of films for diazo sensitization, drawing purposes and lithographic plates. ·

Example 21

A fully oriented polyethylene terephthalate film, the one adhesive or adhesive layer made of 78 mol $ tänyl monochloroacetate, 15 moles of ethyl acrylate and 7 moles of acrylamide, which has been prepared as in Example 3, has also been dsm with a coating of the following composition overdrawn:

Formvar 1595E 6.4- g

Aerosil TK8OO (amorphous silicon

dioxide) 1.2 g

Gasil 64 1.1 g

Tioxide RCR ^ (titanium oxide) 0.12 g

Butanol. 10.3 g ■

Ethyl lactate 6.4 g

Trichlorethylene 74.5 g

The coating was dried at 105 ° C. for 10 minutes, a coating having a thickness of approximately 10 microns being obtained wuüe «

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19U558

This layer was made with light-sensitive diazonium salts « together with coupling and stabilizing compounds, dissolved in a mixture of ethanol and acetone, impregnated to prepare a diazo type photosensitive film. The layers remained strongly adherent to one another and on the Pünunterlage during all stages of the manufacture and use of the product.

Example 22

^A fully oriented polyethylene terephthalate film having an adhesive layer of 78 moles of vinyl monochloroacetate, 15 moles of ethyl acrylate and 7 moles of acrylamide prepared as in Example 2 was further coated with the following composition:

Cellulose acetate 9.0 g

Acetone 85.0 g

Diacetone alcohol 8.0 g

The layer was dried ^{at 110 ° C. for 15 min.} The dry coating was about 8 to 10 microns thick. It was hydrolyzed to a depth of 4 to 5 microns and then impregnated with an aqueous solution of photosensitive diazonium compounds to produce a photosensitive film of the diazo type.7 The layers were strongly adhered to each other and to the film base during the hydrolysis and subsequent treatment.

example

A fully oriented polyethylene terephthalate film, an adhesive or adhesive layer made of a terpolymer of 78 mol- $ vinyl monochloroacetate, 15 mol- $ ethyl

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19U558

acrylate and 7 MoI- ^ acrylamide carried, as in example 1, was also coated with a compound of the following composition: -

Formvar 1595E 8.9 g Aerosil TK800 1.6 g Gasil 64 (a finely ground (micronized) silicon dioxide) IA g Tioxide RCR ^ (modified titanium oxide) 0.15 g Ethyl lactate 6.0 g Butanol 10.0 g Trichlorethylene 71.5 g

The coating was dried and heated for 15 min at 110 ⁰ C to give a layer having a -thickness of about 5-6 microns. The coating adhered strongly to the base and the drawing properties were excellent.

Example 24

One for use as a drafting film suitable product was as described above Example produced with the modification that the paint applied had the following composition:

Cellulose nitrate 4.5 g

Phenol-formaldehyde resin 8.7 g

Castor oil-modified alkyd resin 4.5 g

Gasil 64 '3.1 g ■. · ■'. '■

Rutri-Titanium Dioxide 0.2 g ^:

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19U558

Technically methylated ethyl alcohol

(Alcohol) 8.0 g

Methyl ethyl ketone x 40.0 g

^{iVi ethyl} cellosolve 22.0 g

Xylene 9.0 g

The coating was dried and placed at "gehä:" for 15 minutes.
Document.

Cured 105 ⁰ C and had excellent adhesion to the

Example 25

fully oriented polyethylene terephthalate film, an adhesive layer of 78 Mo 1- $ vinyl monochloroacetate, 15 mol- ^ ethyl acrylate and 7 mol- # acrylamide, which, like described in Example 3, was further coated with a block of the following composition:

97.7 to 98.4 mole # hydrolyzed polyvinyl acetate &, 0 g

China tone 38.0 g

Tioxide RCR5 25.0 g

Aerosil TK8OO 19.0 g

Methylated melamine ^F ormaldehyd precondensate 10.0 g

Magnesium chloride hexahydrate 1.8 g. Methanol lj 50 ml

V / ater I70 ml

Hydrochloric acid was added to adjust the pH to 4-5.

The coating was dried and heated ^{at 110 ° C. for 20 minutes;} the coating weight was about 60 mg / dm

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The surface of the coated film took a tapped Typeface on and 100 copies were made using an offset copying process without any deterioration the adhesion of the lacquer to the polyester base.

The coated film was also made by applying a solution of a diazonium diphenylamine / formaldehyde resin sensitized and dried to a presensitized to yield lithographic plate (lithographic plate). Liability on the base was during the sensitization, image development and subsequent offset litho printing or -Copy operations good.

9 0 9841 /13.5-4

Claims (1)

19U558 Claims in. Film materials or compositions comprising a synthetic linear polyoster film backing based on at least one surface layer is a layer made of a copolymer made of a vinyl halide ester with at least carries another monomer which can be copolymerized therewith, according to patent (patent application P 14 72 797.0), characterized in that said ester and at least one of said monomers are chosen so that the Final copolymer has a lower softening point than that of the product obtained by polymerization in Absence of said selected monomer or monomers is obtained. 2. Film materials according to claim 1, characterized in that the vinyl halogen ester consists of a vinyl chloroacetate consists" __ ; 3.. Film materials according to Claim 1, characterized in that that the vinyl halogen ester from vinyl monochloroacetate consists. 4. Film materials according to one of claims 1 to J >> characterized in that the selected monomer is selected from the group of alkyl acrylates, alkyl methacrylates, polyalkylene oxyditaconates and maleates, vinyl alkyl ethers, vinyl esters, alkenes, alkadienes and alkyl styrenes. 909841/1354 19U558 5 film materials according to claim 4, characterized in that that the selected monomers from ethyl acrylate, 2-ethylhexyl acrylate, vinyl isobutyl ether and ethylene were chosen are. 6. Film materials according to one of claims 1 to 5 * characterized in that the copolymer consists of a copolymer of a vinyl halogen ester, of one or consists of several of the polymers indicated above and one or more other monomers in the final copolymer Carboxyl, hydroxyl, ester, nitrile, amide, N-mono- or N-di-substituted amide, amino or substituted amino groups result. 7. Film materials according to claim 6, characterized in that said further monomers from the Group of acrylamide, N-methylolacrylamide, itaconic acid, Acrylic acid, vinyl alcohol, N-vinylpyrrolidone and dimetäiylaminoäthylmethacrylat are chosen. 8. Film materials according to one of claims 1 to 7, characterized in that the copolymer 50 to mol % of vinyl halogenate, 2 to 30 mol $ of said selected monomer or said selected monomers and 0 to 20 mol $ of said, further Contains monomers or said further monomers. 9. Film materials according to claim 8, characterized in that the copolymer is 70 to 95 mol- $ vinyl haloester, 3 ois 20 mol- $ of said selected monomer or said selected monomers and 2 to 10 mol-fo . of the further monomers mentioned or the further monomers mentioned. . . 909841/1354 19U558 10. Film materials according to one of claims 1 to 9, characterized in that the film base is biaxial is oriented. 11. Film materials according to one of claims 1 to 10, characterized in that said mixed polymer layer is superimposed on a further layer of one having film-blind material. 12. Film materials according to claim 11, characterized in that that said layer of a gelatin containing Layer consists. · 15 · Film materials according to claim 12, which are for use are suitable as photographic films, characterized in that said gelatin-containing layer consists of a gelatin-halosilver photographic emulsion layer consists. ■ 14. Film materials according to claim 12 for use are suitable as photographic films, characterized in that the gelatin-containing layer itself with a gelatin-silver halide photographic emulsion layer. . 15 film materials according to claim 11, characterized in that that said further layer consists of a layer of cellulose acetate or cellulose acetate butyrate. 909841 / ■! 3 5 Λ ΐβ. Film materials according to claim 15 * for use are suitable in a method of Diazoarfc, characterized in that said further layer has a light-sensitive diazonium compound on its surface or through contains its entire layer thickness. 17. Pilmmaterials according to claim 11, characterized in that shows that said further layer consists of a layer of polyvinyl acetal. 18. Pilmmaterials according to claim 17, for use in are suitable for a method of the diazo type, characterized in that that said further layer has a light-sensitive, borrowed diazonium compound on its surface or through contains its entire layer thickness. 19. Film materials according to claim 11, characterized in that that said further layer consists of a. Layer of polyvinyl acetate or partially hydrolyzed polyvinyl acetate consists. . . . ,. 20. Film materials according to claim 19 * for use in a method of the diazo type. are suitable, characterized that said further layer has a photosensitive diazonium compound on its surface or through it contains their entire layer thickness. 21. Pilmmaterial according to claim 11, which are suitable for use as a drawing film, characterized in that the said further. Layer of one. Layer of an organic film-forming material soluble in an organic solvent containing "finely divided particles" of at least one inorganic transparency yielding Means exists. '' 909841/1354 19H558 22. Film materials according to claim 11 suitable for use as lithographic printing plates, thereby characterized in that said further layer consists of a layer of a water-swellable organic film-forming Material which has been made insoluble and at least one finely divided inorganic filler contains, consists. 23 · Film materials according to claim 22, characterized. indicates that said material consists of a polyvinyl acetate which is hydrolyzed to the extent of 84 to 98%. 24. Film materials according to claim 22 or 2J>, characterized in that said layer contains a crosslinking agent for the organic film-forming material. 25. Film materials according to one of claims 22 to 24, characterized in that said layer is a coating of positive or negative working photosensitive Material carries. 26. Process for the production of film materials or - compositions according to any one of claims 1 to 10, characterized in that said layer is applied to the film base before or after complete orientation the film base applies. 27. The method according to claim 2, characterized in that that the layer is applied to the fully oriented film base and the film base is treated with a Subjecting swelling agent or gorona discharge before said layer is applied. 909841/1354 19U558 28. The method according to claim 26 or 27, characterized in that the layer consists of an aqueous Applies dispersion of said copolymer. 29 · The method according to claim 27, characterized in that that the layer from a solution in an organic solvent or from an aqueous dispersion of the above-mentioned copolymer, the solution or dispersion containing the named swelling agent. 30. The method according to claim 27 or 29, characterized characterized in that the swelling agent consists of a halophenol or an otrchlor-substituted aliphatic acid. ν 909841/1354