DE1447674A1 - Fog free photographic films - Google Patents

Description

The invention relates to photographic films and in particular to transparent taero-plastic films, which have a special custom in the production of photographic films. The j2rfindun _a · concerns primarily the geweroliche üereteilung cast from solutions photo ^ raphisciien jj'ilmbasen which are clear and haze-free essentially at a Dieke that ^ is larger than 7 mils.

The use νςη Karoonatoolymeren high molecular weight to produce films in recent years significantly as a result of their superior chemical, physical and eletctriechen, .ridi; ^ enscaaf-teni ⁱ ~ di & sole ne Joly-rcarbonatMlme- aeigeti · iiit V'er- ¹ iüit films made of anöereiö thermoplastisctien resin material.!

herge.st9-Ilt ·: Bin'eiV ^ lhs'besond'ere -besitzen. ' lolykar-oanatfilme * 'one high resistance to attack by mineral acids, They are easy to weld and are both physiologically harmless and stain-resistant. Furthermore, such films have a high tensile strength and a high notched impact strength, furthermore a great heat resistance, as well as a dielectric strength that of the

BATH ORIGINAL

809811/0904

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• of films made from polyethylene terephthalate are. .

The great S.taoilität, which is a film made of caroonate polymer shows makes such a film particularly suitable for use as a photographic film base. The selection of the poly carbonate film for this purpose is still favored in view of this the unique hydrophobic liatur of such films, which give them gives an independence from climatic conditions to such an extent that these conditions are ignored at all need when the film of its photographic application is fed,

A carbonate polymer, which has particularly excellent properties, and which has been found to be particularly useful for the production of films which can be used as photographic film bases, consists of poly-p, p ^t - (2,2-diphe } iylpiOpan) carbonate. such a polymer may ·· .bis- 2,2-by reaction of (4-hydroxyphenyl) propane having an Karbonatoilder such as phosgene in the presence of a Säureakkeptors such as pyridine are produced. Although this polymer for the preparation of has found widespread use in photographic film bases, its use in this respect is strictly limited, from an industrial point of view, to the production of films having a thickness that is 5 or ^ .Jtfj ^ s ..,.,., because commercially produced films made from solution cast from this polymer _{show veils above, soleher picke.n s} jfpiken ^ and_. and ■ therefore for _: f oiographi ec ^ e ^. ^ jnw.enil.ujt ^ giwfi ^ fJj ,, _, are unsuitable where optical ivlarhei, ^, and, ... SphJ.ei, er ^ rfli— ... neit are necessary.

, Relatively clear and fog-free films with a dtoke

- sheet 3 -

^{1 in} excess of 5 or 6 mils can be made from this polymer by extrusion processes. However, despite their clarity and freedom from fog, extruded films are often permeable

- :. · - ·! "; • ΙθΠίνΙΟι.Ι ', ϋ'-ΓίΓ.' · -. ·· ■;. ■, ι- ■■ - ■ ;. ι ■; ...- .. - ---

optical imperfections marked, for example 'by

- Si-. 5'i9ln: ^ i -.->, i ■ :; ^: '' · ■■■ ··> .., · ■ ■ -.
so-called "fisheye", due to uneven surfaces and dirt

prevent the film from being used as a photographic height Film base "Can be used if only. · Ie phenomena'- ' cannot be tolerated. ·

- '- \'. ^r .:. . · ', .. ■ ·., ■; _ \ ^; ■ - '"" ■ ■' ..-. ■■ ii · ■ ■ i .: - _:. ■ ·. "■■. ■ ■ - - ■ - ■ - .. ·. · , ■■ · ■■■

· * '' · '■'^·;y>"■; ■. '■''■■' * ■ ■■■■ '.. ,, .-.. . ... As far as we know, polycarbonate films cast from solution, which are more than 7 mils thick and which are clear and essentially free of fog, and whose properties are essentially identical to those of the films made of poly-p, p ^t - (2,2-diphenylpropane) - carbonate were produced until ' ^: not yet commercially produced. By suggesting - '^; With the present invention it is now possible to increase the commercial application of such clear, substantially haze-free, solution-cast polycarbonate films in the manufacture of photographic "film material.

It is therefore an essential aim of the present invention to provide a solution-molded, clear and essentially veil-free photographic graphic film base with a thickness of more than 7 mils for monkeys whose hurries are essentially identical to those ' ^J by mimes who are not made of poly-ρ, ρ' - (2,2 diphenylpropane) carbonate.

Am # θί1 ^! ΟΓ ^ · ^Ι; trögötistand the present invention is to Äeö M 'iieuen and improved method for the preparation of

In general, according to the present invention, a clearer

09811 / Q9 <H: ia ;;

1447874

- sheet 4 -

substantially haze-free polycarbonate film having a thickness of more than 7 mils, dadureh be manufactured. that an organic solvent solution of a carborate polymer is poured, which essentially consists of the Heakti ons product of (l) 2,2 bis (4-hydroxyphenyl) propane, (2) a carbonate former, that of the class of carbonate esters, carbonyl halides and haloformates of 2.2 bis (4-hyäroxyphenyl) propane and (3) from about 0.1 to about 6 mole percent, and preferably from 1 to mole percent, of at least one member of the class of isophthalic acid and terephthalic acid based on the number of moles of 2,2 bis (4-hydroxyphenyl) propane and haloformate used 2.2 bis (4-hydroxypnenyl) propane.

The new and improved poly carbonate films according to the present Invention can be achieved by potting the solution of the above Carbonate polymer on one of the well known solution casting techniques getting produced; For example, particularly suitable mushrooms according to the present invention can be used commercially produced that an organic solvent solution of the aforementioned polymer, which is previously filtered and degassed was transferred to a moving belt or drum from a storage or distribution vessel to ensure its purity is abandoned, Jßzteres having an adjustable doctor blade or similar device for control purposes the thickness and uniformity of the polymeric solution applied in this way. The organic solvent can then for example can be removed by evaporation by the tape or the The drum is passed through a controlled environment until the polycarbonate film has formed and become self-supporting is. The Ulm can then be continuously moved from the movable Pad for the purpose of completing drying on a the well-known drying process can be removed.

809 811/0904

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On the other hand, the new and improved film according to the present Invention can also be produced inexpensively in that the polymer solution is poured onto a stationary base, for example onto a smooth glass or metal surface, and that a doctor blade is passed over the surface of the base for the purpose of peeling off the layer of loaujg medium. The organic one Solvent can then be removed leaving the desired polycarbonate film.

In general, any volatile organic material can be used for this casting process Find solvent use, which is inert in the sense that it is the carbonate polymer which is used to produce the Films according to the present invention is used, is not impaired, in this organic solvent the aforesaid Polymer is soluble. Examples of suitable solvents are methylene chloride, 1,2- ^ ichloräthylen and chloroform.

The concentration of the carbonate polymer in the organic solvent solution that is used for film casting in accordance with the teaching of the present invention can vary within wide limits, depending on the nature of the particular solvent used, although a concentration of about 10 to about 30 ° / o Polymer, based on the weight of the solvent used, was found to be satisfactory.

Generally speaking, this can be used to make the film The polymer used in the present invention can be prepared by reacting 2,2 bis (4-hydroxyphenyl) propane, a carbonate former such as PhoBgen, a halogen formate of 2.2 bis (4-hydroxyphenyl) propane or a carbonate ester and from about 0.1 to about 6 mole percent of at least one member of the. Isophthalic acid class and terephthalic acid, based on the number of moles from 2.2 to

809 811/0904

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(4-hydroxyphenyl) propane and bis-halogen formate of 2.2 bis (4-hydroxyphenyl) propane, which the reaction mixture added were used as a carbonate precursor.

Ψβη, η a Karbonatester passes for use, the materials at temperatures of 100 ⁰ G and higher are converted into time periods, which can be 1 to 15 hours. Under these conditions, a ester exchange takes place between the carbonate ester and the 2,2 bis (4-hydroxyphenyl) propane and the acid used. The ester exchange can preferably be carried out at reduced pressures in the order of magnitude of about 10 to about 100 millimeters of mercuric acid, preferably in an inert atmosphere, such as, for example, in nitrogen or argon.

Although the reaction can be carried out in the absence of a catalyst, a customary ester exchange catalyst, for example metallic lithium, potassium, calcium and magnesium, can be used, if desired. Further catalysts and modifications of the ester interchange processes are described in Groggins "Unit Processes in Organic Synthesis" (4th Edition, McGraw Hill Book Company, 1952), pages 616 to 620. The shortage of such a catalyst, if used, is in the generally small, and moves in the order of about 0.001 to about 0.1 ° / o _f based on the number of moles of 2,2 bis- (4-hydroxyphenyl) propane.

The carbonate esters that can be used in this context can be both aliphatic and aromatic in nature, although aromatic esters such as diphenyl carbonate deserve preference. More examples of carbonate esters, which can be used are dimethyl carbonate, diethyl carbonate,

η λ λ

- sheet 7 -

Phenyl methyl carbonate, phenyl tolyl carbonate and di (tolyl) carbonate.

A preferred procedure for producing carbonate polymers which are suitable for creating clear, haze-free films according to the present invention involves the use of carbonyl halides, such as phosgene, as carbonate images (= carbonate supplier). This procedure includes initiation. ..you phosgene in a reaction mixture containing 2.2 bis (4-hydrosyphenyl) propane, further about 0.1 to about 6 fo based on the number of moles of 2.2 bis (4-hydroxyphenyl) propane, in isophthalic acid or terephthalic acid or a mixture of these two and finally an acid acceptor such as a tertiary amine (e.g. pyridine, binethyl aniline, quinoline, etc.). The acid receptor can be used both in undiluted form and also in dilution with an inert organic solvent such as, for example, methylene chloride, chlorobenzene or 1,2 dichloroethane. Tertiary amines are preferred because they are both good solvents and acid acceptors during the reaction.

The temperature at which the Karbony! Halide is reacted, between ⁰ G are below zero to above 10O ⁰ C. The seaction proceeds satisfactorily at temperatures from room temperature (25 ⁰ O) to 50 ° G. Since the reaction is exothermic, the measurement of the phosgene addition can be used to check the heating element. The amount of Äesgeii required will generally depend on the amount that is present

and the acid present.

p react 2 moles of phosgene with one mole of 2.2 fei ^^ (4- ^ ä3? 0aqfFit®Qyl) propane and one mole of acid under Bch> a ££ wag 4 «« ... JEtolye ^ re and of 4 moles of HOl . The 4 moles of HCl are then ousboSl : 4m ^. ,, mmpBen.aen. Acid acceptor swallowed. These are atoeJaioeetric and refer to the thearetic

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Although the concentration of 2,2 bis (4-hydroxyphenyl) propane in addition to the acid in the solvent used can vary within wide limits, a solution is advantageously preferred which contains between about 5 and 2 % of these compounds.

In general, the reaction is carried out by the 2,2 bis (4-hydroxyphenyl) propane and the isophthalic acid or terephthalic acid in an organic base such as pyridine dissolves and then carbony! halide in the « Introducing stirring solution at the rate desired.

Another way of making the carbonate polymers that create ύοώ. Films that can be used in accordance with the present invention consists in adding phosgene to an alkaline aqueous suspension of 2.2 bis (4 - hydroxyphenyl) per pan and acid. This is preferably carried out in the presence of inert solvents such as jjiethylenechlorid, 1,2 dichloroethane and the like. Quaternary ammonium compounds can be used to catalyze the reaction.

A third type of process for making such carbonate polymers includes the action of phosgene on a stirring suspension of anhydrous alkali salts of 2.2 bis (4-hydr'oxyphenyl) propane and acid in one not aqueous media such as benzene, chlorobenzene and toluene. These The reaction is illustrated by the description of the addition of Phosgene to a suspension of the sodium salt of 2.2 to

80981 1/0904

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(4-hydraxyphenyl) propane and the sodium salt, isophthalic acid or terephthalic acid in an inert polymeric solvent such as chlorobenzene. The organic solvent should preferably be a polymer solvent, however it is It is not absolutely necessary that there is a good solvent

represents for the respondents.

In general, a halogen group of. 2,2-bis- (4-hydroxyphenyl) propane, such as, for example, bishalogen formate, which can replace biosgen as carbonate images in all of the procedures described above. However, if a halogen formate of 2,2-bis- (4-hydroxyphenyl) propane is used instead of carbonyl halide, the molar amount of isopthalic acid or terephthalic acid or both added to the reaction mixture must be readily understood by the person skilled in the art the total number of mols of 2,2-bis ~ (4-hydroxyphenyl) propane and of haloformate used, since each mole of haloformate, unlike the other carbonate formers, contributes an alkylidene bisphenyl bond to the polymer chain.

In each of the above-described solution methods of production, the carbonate polymer comes in either one of the heatings dense or la a pseudo-solution, if an aqueous one jfese from j ^ yridine is used as an acid acceptor. The polymer can be precipitated from the solution by using a polymer non-solvent such as heptane or Adds isopropanol. On the other hand, the polymer solution can also are heated for the purpose of evaporation of the solvent.

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8Ό9811 / 090 4

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-It should be emphasized that, albeit in the whole of the present Description always refers to the use of isophthalic acid and terephthalic acid, so that it should not be said that the use of the corresponding acid halides, salts or ßster in the manufacture of the carbonate polymers that are used to create the new and improved castable polycarbonate film solutions according to the present invention, should be used, should be excluded.

In order to further illustrate the practice of the present invention to those of ordinary skill in the art, the The following examples are given for illustration and not of limitation. In the case of property specifications, the measurement according to the following procedures have been performed: basal molars Viscosity numbers (= intrinsic viscosities) were determined at 30.4 ° G 'in dioxane. The jilme were made from a solution of ethylene chloride potted and the tensile strengths in accordance with ASTM regulations on an Instron tensile meter certainly. Melting points were on a Fisher-Johns melting point block with an initial load of around 100 psi. measured. All sizes and percentages relate - if nothing else is said - on the weight.

Example 1:

112.6 parts of 2.2 bis (4-hydroxyljhenyl) propane and 1.126 parts Isophthalic acid was placed in a reaction vessel which contained S) U, 1 part of dry yridine and 643 parts of methylene chloride. Phosgene was then poured into the resulting Gemisii for 1 hour at a rate of 0.85 parts per minute initiated. The resulting reaction mixture was 643 Divide diluted methylene chloride and oil it with aqueous solution

β Λ Ο Λ .Ί 4

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O ^ ilorwas se red acidified off acid. The resulting mixture was washed three times in a row with 760 parts of water and then the methylene chloride layer with 760 'of water mixed and the- · polymer by adding 1,660 ropes of heptane failed. The polymer filtered off was washed with methanol and dried at 125 0. The polymer thus obtained possessed a waemolar viscosity number of 1.04.

50 ropes of the aforesaid polymer were then divided into 150 parts Methylene chloride bottle dissolved, the solution degassed and then Poured from a Yorrate vessel onto a glass plate, whereby the storage vessel had a scraper, which in a Angle was arranged so that a film covering was created, in which the pilm thickness continuously changes from one K, ante to the other Edge varies. The methylene chloride was evaporated for the purpose of obtaining a film that was clear and substantial was haze free and had a thickness in excess of 14 mils lay.

Example 2.r - ■

110.6 parts of 2.2 bis (4-hydroxyphenyl) propane, 1.24 parts Isophthalic acid and 1.24 parts of terephthalic acid were placed in a reaction vessel containing 88.5 parts of dry pyridine andi contained 645 files of methylene chloride. Then it was 1 hour long In .the resulting mixture of phosgene at a rate initiated by 0.85 parts.pxto minute. The resulting fictional worm old 645 parts of methylene chloride diluted and

ait, aqueous hydrochloric acid acidified. Di «<& tatäiiäa & £ iB.itob.uiig was filled three times in a row with 760 . Wa & EFCR washed and then the Methylenchloridacliioiit ■■ & $ _T6O! Vermiecht B'ailen water and the polymer duroh

• ft ft ο a 1 i / η ο η -. /. ■ ~ ¹² ~

- Sheet 12 -

Addition of 1,660 parts of heptane precipitated. The filtered polymer was washed with methanol and dried at 125 ⁰ C. The resulting polymer had an intrinsic viscosity of 0.94 ''

Following the procedure outlined in Example 1, a wedge-shaped "film covering was made from the polymer just described in FIG poured a methylene chloride solution. The Ulm was clear and essentially haze-free and was 17 mils thick.

Table I below shows the results that> were obtained by casting 21% solutions of the specified polymers, the polymers being replaced by the in Example 1 and Example "2 prepared procedures described became. Generally speaking, the films were made by taking the desired polymer in methylene chloride Creation of a $ 21 solution was resolved, under subsequent Degassing of the solution and pouring onto a glass plate from a storage vessel, which is a waste ■ Had scraper, which was arranged at an angle, for the purpose of creating a wedge-shaped .Filmbelages in which the thickness of the film varied continuously from edge to edge. The methylene chloride used in casting the film became thereby evaporating that the film surface of the tree environment

was exposed until the film was easily removed from the glass surface, which was the case in about 4 to 8 hours. Wedge-shaped Film coverings made in this way were tested for haze and were the least Thickness at which fog formation could be detected was measured with a micrometer and called the 'initial fog thickness' designated.

809811/0904 -13-

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Table I.

- $ of used

Acid "at the Basal molars 3ch.leieranfan.gs- example Polymer production Viscosity number thickness 3 . ·. 1> 38 1.00 11.5 4th 1.38 1.10 14th 5 2.08 1.00 12.5 6th 4.24 1.00 25th 7th 4.24 0.86 20th

Isophthalic acid was used in all of the aforementioned examples.

In the following examples (siene oituö l'auelle Ii), circular i'llin samples with a Durctimes :: er of 4 zoii were cast from ke thy leriehlorid solutions under standardized Jedin ^ un ^ en, as will be described below, wooei about 3 ( j-raintn resin in 2o x.iiiLiiiter Methylenotiloriü _o elö '; uv / arsn; i) iQ solutions wuraeti in a covered bucket of a diameter γόη \ inch, which is on a glass 0-ieoyolatte,' velcaQ a ■ i'en.jeratur of .30 ° above sea level,, ouch! Iu ^, eiuyft. jsseri.Die chamber was yriclüftet and the ivIsttiylenchloriddaiEpi using a built-ein.ge Troekeuluftfegers etiti'ernt iun about every 2-1 / 4 iviinuten the Atmospuäre within the chamber. renew,. The film samples were .dried for at least 6 hours, before they were removed for the purpose of the -Pri-ifAAjLiij for the presence or absence of veils or streaks. ,,.., .......,. _: ,

80 9811 / 090A

Sheet 14 -. ...

Table II

Basal molars
Viscosity number Veil initial
thickness 1.02. 10 1.03 15th 0.95 > 14.7 1.04 y ⁱ⁵ Ü, 8Ü ■> ^lj -, 5 1.15 0.98 7th

Mon 1- $ from. used
Acid at the
Example of polymer production

0.502

1.01

2.04

2.56

5.26

5.26. .

0 (control)

Isophthalic acid was used in Examples 9 to 12 and 13 'terephthalic acid in the example.

From the information in Tables I and II it can be seen that clear and essentially haze-free poly-carbonate films cast from solutions and having a thickness of more than 7 mils and in the order of 25 mils can be produced in accordance with the present invention . On the other hand, shows - = α he control test of Example 14 of Table II, oei dem. _; .the film was made from foly-p ^ p ¹ (2.2 diphenylpropane) caroonate, an initial plank egg thickness of 7 mils.

The following-Table III explains the similarity · ,, ·? ■% _t over physical properties of films, which 'were produced from foly- ρ, ρ' (2,2 dipnenylpropane) carbonate with the films, aie according to the teaching of the present above ) rfiriüung 'produced v / urden. The properties of these 'Fiffhe' were at

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8 0 9 8 11/0 9 0 k-

- sheet 15 -

striped patterns one inch and one wide 1 inch / 1 inch stretch rate using a two inch end-pinch break with an Instron stretch machine tested. The tensile deformation under the action of heat was tested in accordance with the regulations aS3M method D-1637-59I.

Table III

Mol- # an
used
Acid to
Polymer
Manufacturing Reason-
molar
Viscose
fact β number 0.98 (Stiff
keits) -
module
PSI Stretch
border
PSI train
firm
speed
FoI DehnDar-.
ice it
Break in Heat dissipation
forming,
'.Tempera
tur JZf ⁰ C (2
deformation 0 (control) 0.96 0.70 220,400 8350 7960 8ü 168 ° 0.502 isophth- 0.85
as acid 0.62 258,700 8080 8980 105 158 ° 0.502 « 0.79 268,200 8570 Ö52O 92 171 ° 1.01 w 0.95 244,600 8090 9Ü5O 108 160 ° 1.38 « 0.73 263,000 8550 7960 99 157 ° 2.04 ^M. 0.77 255.600 8640 9150 108 156 ° 2.04 « & 3 * Χ> α5 - 253,400 8380 8600 97 156 ° 2.56 " 239,300 8610 9450 106 158 ° 5.26 « 230,800 8270 10,000 115 161 ° 5.26 fe3? «Abb, tl 234 * 000 8920 8440 85 ■ 163 °

- * lt »gü

As shown in Table III, the properties of the

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Films according to the present invention compared favorably with the properties of films made from £ olj- p, p * (2.2 di ~ phenylpropane) carbonate and which are listed in the table with "0 fo" (control) are designated.

It is found that the fourth of the modulus, the yield point, the tensile strength and the percentage extensibility (ruch limit) of the films according to the present invention are generally speaking all equal to or greater than the corresponding fourth for films made of poly- p ,, p ^! (2.2 diphenylpropane) carbonate. In the case of the films according to the present invention, ^{the heat deformation temperature varies less than 7> 5 a} / ° with respect to the value of the heat deformation temperature of films made of poly-PjP * (2.2 dipheny / propane) carbonate.

-17-

809811/0904.

Claims (7)

- sheet 17 - Claims Clear and haze-free photographic prints cast from solution Filia base with a - ^ ickness of more than 7 mis, characterized by that it consists essentially of the reaction product of (1) 2,2-bis- (4-hydroxyphenyl) propane, (2) a Carbonate images, of the class of the carbonate esters, the carbonyl halides and halogen formates from 2.2 - «- bis- (4-hyäroxyphenyl) belongs to propane and (3) from about 0.1 to, _about 6 Mole percent of at least one member of the isophthalic acid class and terephthalic acid, decoded on the number of moles of 2,2-bis- (4-hydroxyphenyl) propane and haloformate used of 2,2-bis (4-hydroxyphenyl) propane. 2.) Clear and veil-free photographic images cast from solution Film base greater than 7 mils thick characterized by that they essentially consist of the reaction product of (1) 2,2-bis- (4-hydroxyphenyl) propane, (2) phosgene and (3) from about 0.1 to about 6 mole percent of at least one member of the class of isophthalic acid and terephthalic acid on the number of moles of 2,2-bis- (4-hydraxyphenyl) propane used, consists. 3.) Clear and haze-free photographic images cast from solution i'ilmbasia having a thickness of more than 7 mils, characterized in that that they are formed from the reaction product of (1) 2,2 bis (4-hydroxyphenyl) propane, (2) a carbonate (Carbonate precursor), (Carbonate mediator), of the class of Carbonateeters, the carbonyl halides and haloformates voa 2,2 ^ ia ^ (4 ~ hydr oxy phenyl) propane, belongs to and (5) 809811 / 0ΏΠ /. -. Sheet 18 - about 0.1 to about 6 i'iol percent based on isophthalic acid on the total number of moles of 2,2 bis (4-hydroxyphenyl) propane used and haloformate of 2,2 bis (4-hydroxyphenyl) propane. 4 ·) Clear, sole-free photographic prints cast from solution ]? film base greater than 7 mils thick, thereby characterized in that it consists essentially of the reaction product of (l) 2,2 bis (4-hydroxyphenyl) propane, (2) a Carbonate images from the class of the carbonate esters, carbonyl halides and haloformates of 2,2 bis (4-hydroxyphenyl) propane and (3) from about 0.1 to about 6 mole percent terephthalic acid based on the total number of moles of used 2.2 bis (4-hydroxyphenyl) propane and haloformate of 2.2 bis (4-hydroxyphenyl) propane. 5.) Process for the production of a clear and smear-free photographic film base cast from solution with a thickness of more than 7 xiils, characterized in that a solution of carbonate polymer is cast in an organic solvent, the caroonate polymer being essentially composed of a reaction product of ( 1) 2.2 bis (4-hydroxyphenyl) propane, (2) a carbonate former from the class of carbonate esters, carbonate halides and halogen formates of 2.2 bis (4-hydroxyphenyl) propane and (3) of about 0, 1 'to about 6 mole percent of at least one member of the class of isophthalic acid and terephthalic acid, based on the total number of moles of 2 _r 2 bis (4-hydroxyphenyl) propane and haloformate of 2.2 bis (4-hydroxyphenyl) propane used De-Bteth and that the said organic solvent is then removed. ■ '- U47674 Sheet 19 - 6.) Method of making a clear cast from solution Veil-free photographic glue base with a dioke greater than 7 mils, characterized in that it is a solution of a carbonate polymer in an organic solvent "is cast, the carbonate polymer essentially from the reaction product of (1) 2,2 bis (4-hydroxyphenyl) propane, (2) phosgene and (3) from about 0.1 to about 6 mole percent of at least one member of the isophthalic acid class and ierephthalic acid by weight 2.2 bis- (4-hydroxyphenyl) perJan, and that afterwards said organic solvent is removed. 7.) Process for the production of a clear, fog-free photographic film base cast from solution with a thickness of more than 7 mils, characterized by pouring a solution of a carbonate polymer in methylene chloride, wherein the carbonate polymer consists essentially of the reaction product of (1) 2,2 bis (4-hydroxyphenyl) propane, (2) a colorate-forming agent belonging to the class of carbonate esters, carbonyl halides and halogen formates of 2.2 bis (4-hydroxyphenyl) propane 'and (3) from about 0.1 to about 6 mole percent of at least one member of the class of isophthalic acid and Terephthalic acid based on the total number of moles of used 2,2 bis (4-hydroxyphenyl) propane and haloformate • of. · 2.2 bis (4-hydroxyphenyl) propane and that said Methylene chloride is removed. 8.) Ferfa & ren to produce a clear poured from solution epbl ^ ierfireieo. photographic film base with a thickness of ill® I Ale, characterized in that a solution OiiatpolymerB in an organic solvent isl, wherein the carbonate polymer is essentially '8.09811 / 09 (U - sheet 20 - from the reaction product of (1) 2,2 bis (4-hydroxyphenyl). propane, (2) a carbonate image that corresponds to the mass of carbonate esters, Carbyl analogides and haloformates of 2,2 bis (4-hydroxypnenyl) propane and (3) from 0.1 to about 6 mole percent of isophthalic acid, based on the total molar number of 2,2 bis (4-hydroxyphenyl) propane and haloformate of 2,2 bis (4-hydroxyphenyl) propane used, and that then said organic solvent is removed. · 9.) Process for the production of a solution-cast, clear, veil-free photographic glue base with a thickness of more than 7 MIs, characterized in that one Solution of a carbonate polymer in an organic solvent is cast, wherein the carbonate polymer consists essentially of the reaction product of (l) 2,2 bis (4-hydroxyphenyl) propane, (2) a carbonate blinder belonging to the class of Carbonate esters> carbonyl halides and haloformates of 2.2 bis (4-hydroxyphenyl) propane and (3) 0.1 up to about 6 mole percent of terephthalic acid, based on the total moles of 2.2 bis (4-hydroxyphenyl) propaa and Haloformate of 2,2 bis (4-hydroxyphenyl) propane and that said organic solvent is then removed. ■■ 10.) A method for producing a solution-cast, clear, haze-free photographic 3-film base with a thickness of more than 7 mils, characterized in that a solution of a carbonate polymer is cast in an organic solvent, the carbonate polymer essentially consisting of the heatings product from ( ¹ I) 2 _t 2 bis- (4-hydroxy- -21-ft-ft QQ 1 1 / η ο η ι _r t - Sheet 21 - phenyl.) proj »an, (2) phosgene and (3) from about 0.1 to about ■% of isophthalic acid, based on the number of moles of 2 _% 2 i> Is ~ (4 ^ Üytlroxyphenyl) propane and. that ansehliessenö. . Said organic solvent is removed. Ll.) Verfarireu for the production of a solution poured, clear ■; s.ch3.eiei ^ reieri; photographic jfilmoasis having a thickness of. · Fflöto than 7 Mil's ,, aadureh in that a solution is poured in a KarDonatpolymers Einein organic solvent, wherein the Karbonatpolyaier La essentially · 'from. , the reaction product of (1) 2,2 dis- (4-hydroxypnenyi}, propane, (2) ^ phosgene and (3) from about 0.1 to about 6 MoI-p3roKent; .aQ ·: terephthalic acid, based on the number of moles of -. .... 2.2 bia - * - (4i-l: iydroxyphenyl) propane 'consists' and that'ansohlies- ■'. · -. send said .organic solvent is removed. 12 »); procedure _; for the production of a clear .. · ■ aqaleierfreiea. · photographic ifiimbais jiiit. a thickness of •. more than 7. MiIs, identified by the fact that the solution ■ ^; of an Itorbonatpolyriiers in Methylene hi or id, is, ■ ·; ■■. wooe-i · the cariuonate polymer · essentially from the reaction - .; ■ ·. · '· ■■■■ product vpn (l) 2,2 · bis- (4-hydroxypnenyl) propaii, ■ (2) - Phosphorus. propane oestent and that anscnlieseena said - ■. · - ■ ÄföthylenenchlpiPid .. removed.-isü. · ... - .: ". · ■, .- ■.: -. Jrtv'-;'..- .. ■ ■. 13.) ■ Äerfaai? Ett _t for-hers -teil) a cast, clear- ■ ·: ■ - · ■: · ■ -.j '..renj. ■ - veiled frsieriyf oto ^ raphischen ^ ilm base; niit .eiasr · ■■■:: . '■■' -: Biake -: vöe ^ 'meh ^; alsc · !? iviils ^ ■ gekennaeichnet} "that a /χ-.·" .. i. ^ öeup.g '.-. Qinis ^ Kirpottatpralyfners · in. Methylenehlor Ld' Shed sad OHGINAL 80981 1 / 09οί ^{ηχ Γ} > ^{i> a: 1P} - ²² ~ - sheet 22- is, with the ^ arbonatoolymer im. essential from the reaction product of (1) 2,2 bIs- (4-hydr oxy phenyl) propaa, (2) phosgene and (3) from about 0.1 to about 6 mole percent of terephthalic acid, equivalent to the Mo number of 2.2 bis (4-n.yuroxypüenyi) propane Distist and that said IVIethylene chloride is then removed. W ^- If 80981 1/0904