DK146776B - APPLICATION FOR THE MANUFACTURE OF LIGHT DISTRIBUTION DISCS OF FILES OF GLASS FIBER-FILLED THERMOPLASTIC MATERIALS - Google Patents

Description

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By light scattering discs is meant flat or shaped bodies with wall thicknesses of 0.005 to 20 mm, in which a beam of light perpendicular to the surface of the light scattering discs is deflected from one direction by passage 5 and exit through the discs respectively.

Sheets of fiberglass-filled thermoplastic plastics are known in principle (cf., for example, German Publication No. 2,437,508). They can be made by mixing 10 glass fibers with a plastic melt and this glass-fiber containing plastic melt is extruded through a nozzle.

As the thermoplastic plastics, the various transparent polymers are suitable for this purpose. As fiberglass, all commercially available fiberglass types and types of 15 are suitable, that is, cut glass filaments (long glass fibers and short glass fibers), yarns or staple fibers, if they are post-treated with the polymeric suitable sizing agents used in each case. The length of the glass wires, whether they are bundled into fibers, or the fibers on their side are bundled into yarns, ropes or strings or e.g. is woven for mats or not, for long glass fibers must be between 60 mm and 6 µm / And for short glass fibers, the maximum length should be between 5 mm (5000 µm) and 0.05 mm (50 µm).

2 glass fiber types are particularly preferred: I. Long glass fibers having a mean fiber length of 6000 µm, a diameter of 15 µm, and a powder content (less than 50 µm) of approx. 1% by weight and II. ground short glass fibers having a medium fiber length of 230 µm, a diameter of 13 µm and a powder content (less than 50 µm) of 5% by weight.

As a glass material, the alkali-free aluminum boron - silicate glass ("E-glass") or the alkali-containing "C-glass" is applicable. As suitable erasers, those known in the literature can be used. Particularly suitable for polycarbonate masses are the water wetting agents known for short glass fibers (cf. German Publication No. 1,203 * 991).

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With regard to the technical application of sheets of fiberglass-filled thermoplastic plastics, it has hitherto been used to use them either as electrical insulating materials, cf. DE-publication publication no. 2,437,508, or, for fiberglass contents of up to 5% by weight, as transparent articles for lighting purposes, cf. GB Patent No. 1,162,227.

Light scattering discs are used e.g. for signal elements in single and multiple control instruments or current generators. Light scattering discs must be uniformly bright over their total surface. They can be colored differently or printed with transparent colors. Light scattering discs have so far been made from etched glass or frosted plastic foils. Matted 15 plastic foils are preferred over etched glass because of the greater security, the simpler fabrication of the formats and the better printability. In any case, the matting of such plastic sheets suitable for the manufacture of light scattering discs 20 must be particularly good. Irregularities of the frosting, when radiated, lead to a uniform brightness. The matting of plastic foils, which generally have a depth of glass between 0.2 µm and 2 µm, is admittedly very delicate to mechanical damage that may occur in the manufacture and further processing of the foils. These disadvantages can be avoided when light scattering is not achieved on the matting surface of the plastic film, but in the interior of the plastic film, ie when using foils which, instead of or in addition to a matting, e.g.

has a pigment content. With the known dispersion pigments, e.g. barium sulphate, titanium dioxide, carbon black or silicon dioxide, a light permeability of e.g. 30% first, at foil thicknesses greater than 2 mm, a sufficient scattering effect is obtained, whereby a strong intrinsic staining, e.g. causes the back of a red-transparent plate printed on one side to be orange by radiation.

Surprisingly, it has now been found that sheets 5 of fiberglass-filled, thermoplastic plastics achieve a sufficient scattering effect already at approx. 0.1 mm layer thickness at a glass fiber content of 40% by weight. The spreading effect of these films is independent of the nature 10 of their surface. Thus, the films can be handled significantly more simply, stored, wound, pressed or stamped. In addition, the surface of the sheets of fiberglass-filled thermoplastic plastics can be embossed, scarred or provided with a special form of relief, without having to interfere with the light scattering effect of the sheets.

The invention accordingly relates to the use of foils having a thickness of from 30 µm to 100 µm of glass fiber filled thermoplastic cellulose esters, polycarbonates. polyarylsulfones, poly (2,6-dialkyl-1,4-phenylene oxides) or polyalkylene terephthalates having a glass fiber content between 20% and 30% by weight, relative to the total weight, for the production of light scattering discs.

The present invention has solved the object of providing light scattering discs which can be manufactured in a technically simple manner that can be used in many different fields and which have a sharpness sufficient to reproduce e.g. characters.

From the prior art, it was not expected that films with 20% by weight of glass fibers having a length of e.g. 6000 µm (6 mm) would be suitable for such use in optics.

In particular, it is surprising that with such foils 4

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at a distance of 25 cm, the same spreading effect is obtained as with foils according to GB patent specification 1,162,227 at a distance of at least 200 cm, cf. the following comparative examples.

Cellulose esters useful in the present invention are prepared in the usual manner by esterification of cellulose with aliphatic monocarboxylic anhydrides, preferably acetic and butyric or acetic and propionic anhydrides.

The hydrolysis to be carried out in the crude solution is controlled by a small excess of water so as to obtain a low hydroxyl content (OH number 4-25). The oxidative bleaching of the cellulose ester isolated from the solution must be carried out so that no oxidizing agent can be detected in the final product. Optionally, a post-treatment with reducing agents should be performed.

To determine the OH number, the free hydroxyl groups in the cellulose ester are esterified with acetic anhydride in pyridine, the excess of anhydride is reacted with water and back titrated [Regulation: C.J. Mahn, L. B. Genung, and R. F. Williams, Analysis of Cellulose Derivatives, Industrial and Engineering Chemistry, Vol.

14, No. 12, 935-940 (1942)].

The viscosity of the cellulose ester should be 25 0.3-0.5 poise, measured as a 20% by weight solution in acetone. Preferred cellulose esters used in the case of acetobutyrate have an acetic acid content of 17-23 wt% and a butyric acid content of 45-50 wt%, in the case of acetopropionate a propionic acid content of 61-69 wt% and an acetic acid content of 2-7 wt%. The OH numbers are usually between 4 and 25. The weight average Mw is between 10,000 and 1,000,000, preferably between 100,000 and 500,000.

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Suitable polycarbonates are considered by reaction of aromatic dihydroxy compounds, especially dihydroxy diarylalkanes, with phosgene or diesters of carboxylic acid prepared polycondensates, whereby, in addition to the unsubstituted dihydroxydiarylalkanes, they are also suitable if aryl groups or position relative to the hydroxyl group carries methyl groups or halogen atoms. Branched polycarbonates are also suitable.

The polycarbonates to be stabilized have weight averages Mw between 10,000 and 100,000, preferably 10 between 20,000 and 40,000, which are determined by measuring the viscosity fraction in CH2 Cl2 at 20 ° C and a concentration of 0.5% by weight.

Suitable aromatic dihydroxy compounds are e.g. hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis-15 - (dihydroxyphenyl) alkanes, e.g. C 1 -C 8 alkylene or C 2 -C 6 alkylidene bisphenols, bis (hydroxyphenyl) cycloalkanes, e.g. Cg-C ^ g cycloalkylene or C,-C ^ cycloalkylidene bisphenols, bis (hydroxyphenyl) sulfides, ethers, ketones, sulfoxides or sulfones. In addition, 20 α, α'-bis (hydroxyphenyl) diisopropylbenzene and the corresponding core alkylated or core halogenated compounds. Preferred are polycarbonates based on bis- (4-hydroxy-phenyl) -propane-2,2 (Bisphenol A), bis- (4-hydroxy-3,5-dichloro-phenyl) -propane-2,2 (Tetrachlorbisphenol) A), bis - (- hydroxy-3,5-dibromo-phenyl) -propane-2,2 (tetrabromobisphenol A), bis - (4-hydroxy-3,5-dimethyl-phenyl) -propan-2, 2 (Tetra-methylbisphenol A), bis- (4-hydroxy-phenyl) -cyclohexane-1,1 (Bisphenol Z) and on the basis of three-core bisphenols such as α, α'-bis- (4-hydroxyphenyl) - p-diisopropylbenzene.

Further aromatic dihydroxy aromatic compounds suitable for the preparation of polycarbonates are disclosed in U.S. Patent Nos. 2,970,131, 2,991,273, 2,999,835, 2,999,846, 3,014,891, 3,028,365, 3,062,781, 3,148,172, 35,271. 367, 3,271,368, 3,280,078.

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As poly (2,6-dialkyl-1,4-phenylene oxides) for use in the invention, such are suitable if the weight average Mw weight (measured by the light scattering method in chloroform) is between 2000 and 100,000, preferably between 5,000 and 60,000, and is obtained in the known manner by oxidative condensation of 2,6-dialkylphenols with oxygen in the presence of catalyst combinations of copper salts and tertiary amines (see, for example, German Publication No.

No. 2,126,434 and U.S. Patent No. 3,306,875).

Suitable poly (2,6-dialkyl-1,4-phenylene oxides) are e.g. poly- [2,6-di- (C 1 -C 4 alkyl) ~ 1/4-phenylene oxides], e.g. poly (2,6-dimethyl-l, 4-phenylene oxide).

Suitable 2,6-dialkylphenols are especially those with C 1 -C 4 alkyl substituents, e.g. 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol , 2-methyl-6-butylphenol and 2,6-di-n-propylphenol.

Suitable catalyst combinations are in particular copper (I) -20 chloride and triethylamine, copper (I) sulfate and tributylamine, copper (I) sulfate and tributylamine, copper (I) acetate and N-methylmorpholine and copper (I) - chloride and pyridine.

A suitable process for preparing poly-25- (2,6-dialkyl-1,4-phenylene oxides) is e.g. using copper (X) chloride / pyridine as a catalyst combination according to German publication no.

2,126,434 as follows:

A 2,6-dialkyl-phenol is dissolved in a mixture of 30 n-butanol and toluene, and in the presence of the copper (I) -chloride / pyridine complex, oxidative-dehydrogenating is condensed during oxygen supply. The precipitated polyphenylene oxide is then precipitated from chloroform / methanol.

Suitable polyarylsulfones for use in the invention 35 have a weight average number of Mw (measured according to the light scattering method in chloroform) between 1000 and 200,000, preferably between 7,000 and 60,000. Examples are the polyarylsulfones prepared in known manner from 4,41-dichloro-diphenylsulfone and a bisphenol, e.g. 2,2-bis - (4-hydroxyphenyl) propane, with an average weight of 5 (Mw) of 2000-200,000.

Particularly suitable polyarylsulfones are. branched polyaryl ether sulfones prepared by reacting approximately equimolar amounts of at least one aromatic dialkyl bis hydroxylate and at least one bis (4-10 halogenaryl) compound whose aryl nuclei are joined by at least one sulfonyl group, using about 0.01 mole percent to approx. 2 mole percent, preferably from ca. 0.05 mole percent to approx. 1.5 mole percent, attributed to the bishydroxylate or to the bishalogenaryl compound, of at least one branching agent, i.e., an alkali metal salt of an aromatic compound containing three or more than three hydroxyl groups, and / or a halogenaryl compound having three or more under the reaction conditions of polyaryl ether sulfone substitutable aryl-linked halogen substituents.

Optionally, as a chain switch, e.g. while using a C ^-C ^ monoalkyl halide and / or monophenol in amounts of 0.001 to ca. 5 mole percent attributed to bishydroxylate or bishalogenarylate compound in the preparation of the branched aromatic polyaryl ether sulfones.

The degree of branching of these polyaryl ether sulfones is, of course, dependent on the amount and nature of the branching agent used, i.e. of the aromatic compound containing 3 or more than 3 hydroxyl groups, 30 and / or of it three or more times than 3 under the conditions of the polyarylethersulfone substitutable halogen substituent halogen aromat. In this way, high molecular weight thermoplastic, in the usual solvents, did not form completely soluble to 35 branched polyaryl ether sulfones whose viscosity fractions, measured in solutions of 0.5 g of product in 100 ml of methylene chloride at 35 ° C, are between 1.15 and about, 1.80, and whose number average weights measured by light scattering are between ca. 20,000 and approx.

120,000.

Suitable bis (4-halogenaryl) compounds for

preparation of the branched polyaryl ester sulfones, whose aryl cores are joined by at least one sulfone group, are e.g. monosulfones such as 4,4 '- dichlorodiphenylsulfone or 4,4'-difluorodiphenylsulfone 10 (Formula I, n = O), and dihalogenediaryldisulfonaryls of the general Formula I

Hal ~ CZVSQ2 'Arl' SO2 -O-Hal (n = 0 or 1) in which n = 1, Hal means chlorine or fluoro, and Ar represents a biphenylene or oxybisphenylene group,

These compounds are known from the literature.

Suitable dialkali metal bis hydroxylates (dialkali metal bisphenolates) for the preparation of the branched polyaryl ether sulfones are obtained from diphenols such as hydroquinone or resorcinol, however, preferably from compounds of the general formula 25 HQ - which R is a divalent C 1 -C 2 alkylene - or C2-C12 alkylidene group, C1-C12 cycloalkylene or C5-C15 cycloalkylidene group, a C1-C12 alkylene or aralkylidene group, or a C8 -C1 alkylaryl bisalkyl; -the9ruPPe or the groups -O-, -S-, -SO-, -SO2 ~, -CO-, or a single bond. Examples of formula II diphenols include: Bis- (4-hydroxyphenyl) -methane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, bis- (4-hydroxyphenyl) -phenylmethane, 4.4 ' -dihydroxy-d iphenyl ether,

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-sulfide, -sulfoxide, -benzophenone, especially 2,2-bis - (4-hydroxyphenyl) -propane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl and a, a'-bis- (4-hydroxyphenyl) ) - p-diisopropylbenzene. As branching components of the type three or more than three hydroxyl group-containing aromatic compounds for the preparation of the branched polyaryl ether sulfones, e.g. Mention is made of: Phloroglucine, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2 (= trimer isopropenylphenol), 4,6-dimethyl-2,4,6-10-tri- ( 4-hydroxyphenyl) -heptane (= hydrogenated trimer isopropenylphenol), 1,3,5-tri- (4-hydroxyphenol) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane and -propane, - (4-hydroxyphenyl) -methane, 1,4-bis- ((4 ',' 4 '-dihydroxy-triphenyl) -methyl] -benzene (cf. DE Publication No. 15,113,347) and 2,2-bis - [4,41-bis- (4-hydroxyphenyl) -cyclohexyl] -propane As branching components in the preparation of the branched polyaryl ether sulfones, halogenaryl compounds suitable for three or more than three, under the reaction conditions of the polyaryl ether sulfone preparation are substituted aryl bonded substituents for example, such are mentioned if halogen substituents are activated by an electron attracting group: 1,3,5-tri- (4-chlorophenylsulfonyl) benzene and 2,4,4'-trichloro-diphenylsulfone, 1-chloro-2, 6-25-bis- (4-chlorophenylsulfonyl) -benzene The activation of halo the gene substituents may additionally be effected by the sulfonyl group and also by other electron attracting groups, i.e. those having a positive sigma value (cf. Chem. Rev. 49 (1951), page 273 et seq.

30 and Quart. Rev. 12 (1958) 1 ff). Substituents whose sigma value is greater than +1 are preferred.

From alkali metal hydroxylates derived from the aromatic compounds containing two, three or more than three hydroxyl groups, e.g. the corresponding sodium hydroxylates or potassium hydroxylates are mentioned. Of suitable polar organic solvents for the preparation of the branched polyaryl ether sulfones, e.g. mention is made of diethylsulfoxide, dimethylsulfone, diethylsulfone, diisopropylsulfone and tetramethylene sulfone, preferably, however, dimethylsulfoxide. They are used in amounts of approx. 1 liter to 5 liters, attributed to 1 mole of the dialkali metal bis hydroxylates used.

The preparation of the branched polyaryl ether sulfons is described in detail in German Publication No. 2,305,413.

Thus, the present branched-branched aromatic polyaryl ether sulfones have two-member structural elements of formula 15 [- _ (i) -O-Zo- <r ^ -SO 2 - Ar 1 -SO 2 -Q> - 20 in which Ar 1 is as defined above. n is 0 or 1, Z is a p-phenylene group, m-phenylene group or a divalent group of the formula -oo- where R is as defined above, and X is an integer between ca. 10 and approx. 120. The branched aromatic polyaryl ether sulfones additionally contain 30 in amounts between 0.01 mole percent and 2 mole percent from the introduction of the branching components resulting in trishydroxylate residues or hydroxylate residues having more than three hydroxylate groups and / or aryl branching residues having three or more than three bonds resulting from 35 containing three or more than three substitutable aryl bonded halogen substituents under the reaction conditions of the poly-aryl ether sulfone preparation.

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The polyalkylene glycol terephthalates for use in the invention are, for example, those based on ethylene glycol, propanediol-1,3, butanediol-1,4, hexanediol-1,6, and 1,4-bis-hydroxymethylcyclohexane. The molecular weight (Mw) of these polyalkylene glycol terephthalates is between 10,000 and 80,000. The polyalkylene glycol terephthalates may be prepared in known manner, e.g. from terephthalic acid dialkyl esters and the corresponding diol by re-esterification (cf., for example, U.S. Patent Nos. 2,647,885, 2,643,989, 2,534,028, 2,578,660, 2,742,494, 2,901,466),

One goes for example. from a lower alkyl ester of terephthalic acid, preferably the methyl ester, and esterify it with an excess of diol in the presence of suitable catalysts for the bishydroxyalkyl ester of terephthalic acid. This increases the temperature from 140 ° C to 210-220 ° C. The released alcohol is distilled off.

The condensation is then carried out at temperatures of 210-280 ° C, and the pressure is thereby gradually reduced to less than 1 mm Hg, with excess diol distilled off.

Starting materials for the plastic films used according to the invention are the corresponding fiberglass filled plastics. These are known or can be prepared by known methods (cf., for example, German Patent Specification No. 1,454,802, U.S. Patent Nos. 2,877,501 and 3,453,356 and German Patent Specification No. 1,454,789).

The content of glass fibers in the thermoplastic plastics suitable according to the invention and from the films made according to the invention suitable for the invention, between 20% and 30% by weight, attributed to the total weight, can be adjusted in known manner, taking into account in detail the thickness of the films produced and the desired spreading effect.

The production of the films from suitable glass fiber filled thermoplastic plastics, i.e. glass fiber filled cellulose esters, polycarbonates, polyarylene sulfones, poly (2,6-dialkyl-1,4-phenylene oxides) and polyalkylene terephthalates can be carried out according to the usual technique, e.g. . by extruding onto a commercially available extruder, preferably with a degassing zone connected over an adapter to a wide slotted nozzle. After withdrawing the still plastic foils from the nozzle, these are allowed to run on a cooling grid, a chill rolling system or a three-roll chair, thereby lowering the temperature below the softening point of the polymer concerned. In this way, the foils solidify and can be wound up (cf., for example, German publication publication no.

2,437,508).

The sheets of fiberglass-filled thermoplastic plastics suitable according to the invention can be used as light scattering discs, for example, in single or multiple control instruments or in combination vehicles in motor vehicles. The foils of this invention may be printed with suitable signal colors or may be embossed with symbols (e.g.

20 characters or letters).

In the films suitable for use in the invention, the thermoplastic plastics may contain dyes or pigments, so that the films are obtained correspondingly colored or pigmented. Suitable are usual dyes or usual pigments in the usual amounts.

The films suitable for use in the invention can be formed by thermoforming methods without losing their spreading effect, which is not possible with the use of frosted films, as their frosting is destroyed due to the necessary melting.

The spreading effect of the glass fiber-filled thermoplastic synthetic films suitable for use in the invention can be varied over a wider range, e.g.

35 by changing the film thickness and / or changing the glass fiber content of the film. The spreading effect is measured e.g. with a spectral photometer equipped with an Ulbricht sphere kit.

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In this way, the portion deviated from the approach direction is measured by the light flow (transmission) within the visible light.

A sufficient scattering effect of the films referred to herein exists when the proportion of the light passing directly through the sample can no longer be perceived with the above measuring apparatus.

In experiments, a sufficient scattering effect was found when there was a 10 linear increase in the transmission of the deflected proportion between 350 nm and 700 nm. Thus, e.g. for suitable films at 350 nm a transmission of the deflected light fraction of 15% and at 700 nm a transmission of 30%.

15 Another very simple assessment of the spreading effect can be done visually, with the spreading disc being placed 4 cm from a filament lamp with a piston diameter of 20 mm and a output of 30 watts.

An observer can, by sufficient spreading effect from a distance of 25 cm from the foil, no longer recognize the rear incandescent coil in the inserted incandescent lamp.

Manufacture of the starting products.

25 A, Preparation Specification for a Polycarbonate

Ca. 454 parts of 4,4'-dihydroxyphenyl-2,2-propane and 9.5 parts of p-tert.butylphenyl are suspended in 1.5 liters of water. In a three-neck flask equipped with a stirrer and a gas supply tube, oxygen is removed from the reaction mixture by stirring for 15 minutes with stirring. of nitrogen through the reaction mixture. Then 355 parts of 451 sodium hydroxide solution and 1000 parts of methylene chloride are added. The mixture is cooled to 25 ° C.

While maintaining this temperature under cooling 35, 237 parts of phosgene are added over 120 minutes.

An additional amount of 75 parts of a 45% sodium

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Hydroxide solution is added after 15-20 minutes, or after the phosgene uptake has begun. To the resulting solution is added 1.6 parts of triethylamine and the mixture is stirred for a further 15 minutes. A high viscous solution is obtained, the viscosity of which is controlled by the addition of methylene chloride. The anhydrous phase is separated.

The organic phase is washed salt-free and alkaline-free with water. The polycarbonate is isolated from the washed solution and dried. The polycarbonate has a viscosity fraction 10 of 1.29-1.30, measured in a 0/5% solution of methylene chloride at 20 ° C. This is roughly equivalent to a molecular weight of 32,000. The polycarbonate thus obtained is extruded and granulated.

B. Preparation for a polyarylsulfone (trisphenol addition 1 mole percent) - 57.075 g (0.25 mole) of 2,2-bis (4-hydroxyphenyl) propane and 0.871 g (0.0025 mole) of 2,6-bis ( Weigh 2'-hydroxy-5'-methyl-benzyl-4-methyl-phenol into a metal container and dissolve in 500 ml of dimethyl sulfoxide. The vessel is equipped with a gas supply pipe, an agitator, a thermometer, a reflux condenser and a toluene-filled water capture apparatus. Then a slow stream of nitrogen is passed through the apparatus to provide an inert gas atmosphere.

25.03 g (0.5 + 0.0075 mole) of sodium hydroxide in solid form or as a concentrated solution are added and after dissolving the sodium hydroxide 150 ml of toluene are added. The reaction mixture thus obtained is heated for 6 hours to a temperature of 140-150 ° C, whereby the water contained in the reaction mixture and the water formed by the phenolate formation is continuously distilled with the toluene as an azeotrope into the water collection apparatus and separated there while the toluene again runs. back to the reaction mixture. When all water is removed from the reaction system, the water collection apparatus is emptied, the toluene is distilled off

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And at a temperature of 120-140 ° C, a solution of 72.882 g (0.25 + 0.00375 mole) of 4,4 '- dichlorodiphenylsulfone is added in 100 ml of anhydrous dimethylsulfoxide. Then, with stirring, it is heated slightly after 5 to a temperature of 150 ° C. At this temperature, the reaction mixture is left for 6 hours, whereby the sodium chloride formed during the condensation is rapidly separated. After completion of the reaction, the cooled polymer solution is added to rapidly stirred water, whereby the resulting polyaryl ether sulfone is solidified. It is separated by suction, washed thoroughly and dried in vacuo. For purification, the resulting polyarylsulfone is dissolved in methylene chloride and filtered and poured into an excess of rapidly stirred methanol.

Hereby the polyarylsulfone is excreted as white lilacs. They are separated by suction and dried.

C. Preparation Specification for a Cellulose Ester 500 g of cellulose are added to a mixture of 1.8 kg of 20 acetic anhydride, 2 kg of glacial acetic acid and 17 g of concentrated sulfuric acid and left for 24 hours to form a clear, viscous solution from which the chloroform-soluble primary acetate can is separated by addition of water after dilution with some 25 vinegar. To obtain the acetone-soluble secondary acetate, add 350 g of water and 350 g of glacial acetic acid and so much sodium acetate to the acetylation mixture to transfer the sulfuric acid into the bisulfate and leave the mixture for 3-5 days at 65-70 ° C until a sample of 30 is precipitated with water. turns out to be acetone soluble (Ost, Zeitschr, Angew, Chem, 32, 69 (1919)).

D. Preparation Specification for a Poly (2,6-Dialkyl-1,4-Phenylene Oxide) Poly (2,6-Dimethyl-1,4-Phenylene Oxide) Manufactured in accordance with German Publication No. 2,126,434: 16 146776

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8 kg of 2,6-dimethylphenol are dissolved in a solution of 30 liters of n-butanol, 10 liters of toluene, 4 kg of pyridine and 100 g of copper X-chloride. When supplying 50 liters of oxygen / min. over 6 hours, 2,6-5 -diroethylphenol is oxidatively dehydrogenating to poly- (2,6-dimethyl-1,4-phenylene oxide). At the beginning of the oxygen supply, the temperature rises sharply. When cooling during the first reaction phase, a temperature rise above 55 ° C is avoided. After 2-3 hours, the polyphenylene oxide begins to precipitate. After further oxygenation for approx. For 3 hours, PPO is separated by suction, washed pyridin-free with hydrochloric acid methanol and subjected to chloroform / methanol. You get a pale yellow colored powder. The viscosity fraction (measured at 25 ° C in 15 methylene chloride at a concentration of 5 g / liter) is 1.2 and the molecular weight Mw is 60,000.

E. Preparation for a polyalkylene glycol terephthalate, namely for polyethylene glycol terephthalate: 97 parts of terephthalic acid dimethyl ester. 71 parts of ethylene glycol, 0.15 parts of anhydrous calcium acetate and 0.4 parts of antimony trioxide are placed in a round bottom flask equipped with a distillation kit, air cooler and 25 gas supply capillaries. Evacuation and filling with nitrogen removes the air from the appliance. The components are melted by heating to 170 ° C. Through the capillaries a weak flow of nitrogen is conducted. The methanol 30 formed by the immediate initiation of the esterification is distilled off. After approx. For one hour, the methanol decomposition stops and the temperature is increased for 2 hours to 200 ° C, thereby removing the remaining methanol.

Then excess ethylene oxide is distilled off at 220 ° C and the temperature is increased to 280 ° C. At this temperature, the apparatus is evacuated slightly to approx. 0.3 mm Hg. After another 3 hours

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The reaction is complete. The resulting polyethylene terephthalate has a viscosity of 2.10 measured in a 1% solution in a solvent mixture of equal parts phenol and tetrachloroethane at 25 ° C. This is roughly equivalent to a 5 molecular weight of 28,000.

From the thermoplastic plastics AE, by incorporating the glass fibers suitable for use in the invention in the desired amounts according to the methods described in German Patent Specification No. 1,454,802 or U.S. Patent No. 2,877,501 or U.S. Patent No. 3,435 .356, the corresponding fiberglass-filled plastics are manufactured.

Preparation of films for use in the invention: Example 1

Bisphenol A polycarbonate based on a viscosity fraction of 1.32 (measured at 25 ° C and 0.5 g in 100 ml) with a glass fiber content of 20% short glass fiber with water plain (cf. German submission 20 to 1,201,991) is melted in an extruder with a three-zone screw exhibiting a compression ratio of 1: 3. The cylinder temperature is set in the addition zone of 260 ° C, in the compression and measurement zone of 280 ° C. The temperature of the wide slotted nozzle 25 used is adjusted over the total nozzle width of 280 ° C.

At a screw speed of 60 rpm. per minute, the pull-out speed of the three-wheelchair is adjusted to obtain a 0.4 mm thick film. This foil has a smooth surface on both sides. For visual assessment 30 of the spreading effect of the film thus produced, this is placed 4 cm from an incandescent lamp with a piston diameter of 20 mm and a output of 30 watts.

An observer can no longer recognize the rear incandescent coil 35 in the inserted incandescent lamp from a distance of 25 cm and beyond. When measuring the light transmittance of the foil, it appears that a uniform spread is obtained over the total waveband. The transmission is at 350 nm 10% and at 700 nm 22%.

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Comparative Example A

Example 1 is repeated with the one difference that 2% by weight glass fiber is used instead of 20% by weight. For visual assessment of the scattering effect of the 0.4 mm thick film thus produced, the film should be placed more than 400 cm in front of the incandescent lamp used in Example 1 so that an observer at a distance from the film of 25 cm or more could no longer recognize ® the rear incandescent coil in the inserted 10 incandescent lamp.

Comparative Example · B

Example 1 is repeated with the one difference that 5% by weight of glass fiber is used instead of 15% by weight. To visualize the scattering effect of the 0.4 mm thick foil thus produced, the foil had to be placed more 200 cm in front of the incandescent lamp used in Example 1 so that an observer at a distance from the foil of 25 cm or more could no longer recognize it. rear incandescent coil in the inserted incandescent lamp.

Example 2

Similar to Example 1, a polymeric cellulose propionate whose acetic acid content is 5% and whose propionic acid content is 59%, and whose plasticizer content is 10%, has a glass fiber content of 20% by weight of short glass fibers. The processing temperature is set in comparison with Example 1 in all temperature zones 50 ° C 30 lower. From this material, a 0.1 mm thick film is made. When visually assessing the scattering effect, similar to the experimental device described in Example 1, the incandescent coil in the incandescent lamp placed behind can only be recognized very weakly. The light transmittance 35 (transmission) is at 350 nm 30% and at 700 nm 56%.

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Example 3

Similar to Example 1, a polymer is used as a polyarylsulfone prepared from bisphenol A and 4,4-dichlorodiphenylsulfone (Mw 40,000) with 20% by weight of 5% glass fiber content. The processing temperature is set at 20 ° C higher than in Example 1. The foil is pulled over a chill roller plant, the roller temperature in the trigger is set to 150 ° C. From the 0.4 mm thick film thus produced, 10 is made by a thermoforming method bullets having a diameter of 10 mm and a height of 5 mm. From a signal lamp located at a distance of 1 cm behind this shaped foil and having a output of 12 watts, the incandescent coil can no longer be recognized. The transmission is at 350 nm 15 20% and at 700 nm 40%.

Further foils can be made, varying so as to Example 1, that instead of polycarbonate, the other thermoplastic resins mentioned are used, and that the glass fiber content is further varied within the specified range.