DE1769402A1 - Colored molded bodies made of hydrophobic polyesters - Google Patents

Description

Cologne, May 16, 1968

Mr / reu

EI du Pont de iiemours & Company, Wilmington 19 898, Del. United States of America

colored moldings made of hydrophobic polyesters

The invention relates to colored polyester-based moldings, in particular fibers and films. ™

Fibers and films made from hydrophobic polyester are very difficult to dye. Usually, such polyester fibers are placed in an aqueous dye bath and dyeing is effected in this way at an elevated temperature in the course of more than an hour. Shorter staining times can be achieved by increasing the temperature of the dye bath. Here, too, still werbvolle residence time is lost, also, higher temperatures affect in a degradation of the dye, because the proposed moisten dyes at temperatures of 130 to 200 ⁰ C are not stable. These known methods are described in the USA-Potontschriften 3 098 691 and 3 107 968 (

rub. It is also known to disperse a dye or a pigment in a polyethylene terephthalate after polymerization by removing the polyethylene terephthalate and then melting it together in the presence of a dye as described in US Pat. No. 2½ '/ 1,319. However, the dyes proposed so far are unstable at temperatures above 270 ° if they are left at this temperature for more than 2 hours.

Has the use of very insoluble pigments; Disadvantages as they are never difficult to disperse and are often photographically active. They are mixtures of pigments and paints

009843/1911

required to produce a beautiful blue tint, either incorporating the mixtures into a special layer or adding them to the emulsion.

The dyes used hitherto generally give unsatisfactory results because they have colors that are suitable for unsatisfactory silver halide film photographic materials. In addition, these dyes often contribute to a breakdown of the polymer, making it unusable for photographic purposes will.

The invention is based on the problem of those indicated Difficulties to overcome and perfectly colored moldings made of hydrophobic polyesters.

The invention is based on molded articles made of hydrophobic polyesters, for example from polyesters with at least an aromatic dicarboxylic acid and at least one dihydric alcohol as an ester component. As distinctive these articles are considered to be colored or tinted with an N, N'-diaryldiamine anthraquinone dye, which carries at least three substituting alkyl radicals on each aryl ring.

The polyester-based moldings are produced by (a) either adding the dye to the polyester-forming body Components dispersed, for example in the dicarboxylic acid, their esters or their acid halide and the dihydric alcohol and then the components under formation condense the colored polyester. Another way (b) one arrives at a similar result, by introducing the dye into the molten polyester after polyester formation and from the melt produces a shaped body. Shall photographic carrier films are generated, the film can be biaxially 'before or after the application of a hydrophobic polymeric adhesive be molecularly oriented.

009843/1918

-5-

It has also been found that dyes of the genus ^ ", - li'-diaryldiaminoquinones with three or more alkyl radicals have 1 to 5 carbon atoms, for example methyl, iithyl, propyl, isopropyl, η-butyl, tort. Butyl and n-pentyl radicals, which substitute on each of the aryl rings, can be mixed with the polyester monomers, which then at the high temperatures and under the high vacuum of the information in UrfA-P ^ teiitschriften 2 071 250, 2 465 319 or 2,905,707 condensed i / ground. These particular dyes can be mixed also mitden molten polymer and the Hischung into articles molding. Sum tinting and coloring Polyesterfolieii, fibers and other molded Gebil- λ the required about 0.088 mm .; Mr 2, 2 g dye per kg polyester.

The expression "avei-valent alcohol" includes all alcohols two functional hydroxyl groups, for example glycols including ethyl glycol, 1,5-propanediol and cyclohexane-1,4-dimeth anol.

According to a preferred embodiment of the invention, dimethyl terephthalate is reacted with iithyl englycol in the presence of a suitable catalyst. Such a way of working is described in Sorensen and Campbell , Preparative Methods of Polymer Chemistry, Interscience Lee York, 1961, p. 113 ”. (Correspondingly, the esterification product of dimethyl terephthalate and ethyl glycol, preferably bis (2-hydro: xyethyl) terephthalate, can be added to a 1-1 reaction kettle equipped with three attachments, the one with a stirrer in the middle attachment, one nitrogen -Transmission pipe in one of the other attachments and a condenser connected to a vacuum pump in the third attachment. The antlirachinone dye, for example 1,4- (dipentamethylaniline) anthraquinone, is added to this vessel in quantities of 0.11 to 0.22 g per kg of dimethyl terephthalate. However, amounts as small as 0.01 g and up to 100 g or more of dye can be added, depending on the shade desired in the end product.

such as zinc acetate dihydrate, added to the mixture. Suitable catalysts and associated amounts are listed below. The mixture is gradually heated in a silicone oil bath while a slow stream of nitrogen is passed through the apparatus. At about 220 to 240 ^° C., the monomer is completely melted and the stirrer is turned on. Ethyl eiiglykol now begins to distill and the vacuum is carefully applied very slowly. At a temperature of 230 to 240 ^° C., the nitrogen flow is switched off and the vacuum is slowly but continuously increased. When a temperature between 285 and 290 ° is reached, a full vacuum of, for example, 1 to 2 mm Hg is applied and the polymerization is continued under these conditions for 1 to 1 1/2 hours. During this time you have to adjust the stirrer to the rapid increase in viscosity of the mixture. At the end of the reaction, the nitrogen is reintroduced and the vacuum is gradually released. The cooled polymer particles of blue color are preferably placed between highly polished, 1.27 mm thick, resinous plates made of chrome steel which have been treated with a conventional mold release agent, for example a silicone wax. These. The arrangement is brought between the plates of a conventional melt press preheated to 275 ° C. and pressed together under a pressure of up to 351.5 kg / cm. The composite panels are then removed from the press and directly quenched in cold water. In this way, the desired, blue-tinted polyester film is obtained, which can be molecularly oriented in width and length by stretching by 2 to 5 times.

Many common methods of making good polyester infrago come into practice in the practice of the invention. Here include polyesters which have been prepared by polyesterification of a dicarboxylic acid with dihydric alcohol dnem according to the instructions of the US Patent 2 79 ') ^{(5 <1} j4; Kondeusationsprodukt the dimethyl terephthalate or terephthalic acid and propylene

00984371918, wdorkjinm. "^"

glycol, diethylene glycol, iPetr am ethyl glycol or cyclohexane-1,4-dimethanol or mixed polyesters of any polyethylene terephthalate and ethylene isophthalates according to the information given British Patent 766 290 and the Cayadian Patent 562 6 '/ 2.

In general, the high polymer products will be used accordingly of the invention by adding glycols of the general formula HÜ (CHp) OiI, uorin "n" a number from 2 to 10 means with l'erephthalic acid or its esters or with other I'erephthalic acid derivatives, which are capable of reacting with the mentioned G-lycoles with the formation of G-glycol esters ren, heated. The reaction products are then in the present a K rfcalysators heated to temperatures above their melting point OC until high polymer esters are obtained.

If a transesterification reaction is used, the low molecular weight polymeric polymethylene or polyethylene terephthalates can be converted into the high polymer products by heating them at temperatures above the boiling point of the corresponding glycol under conditions which cause the glycol to be removed. De-i. * Pressure can be reduced in successive stages in such a way that (as heating begins at normal pressure and at a vacuum of (

1 to 20 ram Hg is continued. The ale candidate catalysts can also be present in this Heaktionsstufe.

Conventional catalysts are suitable for the process of the invention, this includes compounds of lithium, sodium, Potassium, calcium, beryllium, magnesium, cadmium, aluminum. Molybdenum, manganese, iron, cobalt, nickel, copper, tin, lead, zinc, bismuth, antimony and other catalysts accordingly the disclosures of U.S. Patents 2,905,707 and

2 465 319 · Also have combinations of metal compounds proven, for example a combination of lithium hydride and ßleimonoxyd, PbO; Zinc acetate, lithium hydride and

009843/1918 bad ~ ⁶ ~

Antimony trioxide; Zinc acetate and tetraisopropyl titanate; Manganese acetate and antimony trioxide and others. In general, the catalysts are present in amounts of about 84 to 210 parts of metal in the catalytic compound per 1,000,000 parts by weight of alkyl terephthalate, in particular amounts of 120 to 130 parts per million parts (ppm) are used. If a combination of catalysts is used, larger or smaller amounts of each catalyst may be required, depending on the combination used. The catalyst can be introduced in the form of powders, chips, pieces, ribbons, as a solution in glycol and in other conventional forms.

In order to produce the tinted polyester moldings for the purposes of the invention, it is necessary to use a dye apply, which is thermally stable for several hours at temperatures above 270 °. Accordingly, the dye should be soluble in the polyester melt and preferably under the polymerization conditions taking place under high vacuum, for example a vacuum of 1 mm Hg, do not sublime. In addition, the dye should be insoluble in water, so that the color does not leach from the film during treatment. Those belonging to the genus of the W, W'-diaryldiaminoanthraquinones belonging dyes have the following ring:

WHAr

MIAr

As used herein, Ar means an aryl group having at least three substituting alkyl radicals on each aryl group. The dyes listed below are particularly suitable for the preparation of the products of the invention:

0 0 9 8 4 37 191g ^BAD

1.) 1,4-di- (2 ', 4', 6'-trimethylaniline) anthraquinone,

2.) l, 4 ~ di- (2 ', 4', 6 ^! -Triethylaniline) -anthraquinone,

3.) l, 4-di- (4'-t-butyl-2 ', ö'-dimethylaniline ^ anthraquinone,

4.) 1,4-di- (2 ', 3'> 5 ', 6'-tetramethylaniliii) -antlirachinon,

5.) 1,4-Β1- (4 · -ϊ> γοπι-2 ', 3', 5 ', 6 ^l -tetramethylaniline) -anthraquinone,

6.) 1,4-di (pentamethylaniline) anthraquinone.

The dye 6 represents a new type of dye and is prepared as described below. In order to obtain a blue dye it is necessary that at least zv / ei of the alkyl radicals are ortho to the amino group are located.

Although the trialkyl-substituted dyes are heat-stable they showed when working at temperatures of 285 up to 290 minor signs of sublimation after long treatment times, as reflected in the blue color of the glycol that appeared during the manufacturing process was carried out. However, these dyes led to satisfactory blue-tinted structures.

Depending on the shade desired for the product, different Amounts of dye are added to the reaction mixture, in general 0.11 to 0.22 g of dye are added per kg of terephthalate in order to set the desired color shade for the purposes of medical X-ray films.

The dyes formulated above have the advantage that they are soluble in the polyester melt and insoluble in water are. Therefore, they cannot be leached from the photographic films during further processing leached the hitherto proposed tinting dyes if mnn; j1o brought 'itinochichteii' into gel

009843/1918

To prepare the dyes formulated above, 1,4-diaminoanthraquinone is condensed with a suitable organic bromide. The condensation can be carried out in nitrobenzene at 185 "to 195 ° using copper (I) chloride and copper (II) acetate as catalysts. Anhydrous potassium carbonate is used as the acid eak 2; ept or, while the reaction is normally 15" to 16 hours required. A second manufacturing process consists in mixing the amine and the bromide with copper (II) acetate and black lead and then refluxing them in o-dichlorobenzene for 15 hours. This procedure is described in Leete et al. "Linear Indathrone and Related Phenazines", J. Org. Chem., Pi , p. 3734 (1966).

Organic bromides suitable for the condensation process are: 1,4-dibromo-2, ~ j , 5 ₅ 6-tetramethylbenzene, bromodurol, bromomesitylene and bromotriethylbenzene, all commercially available substances. The bromopentamethylbenzene required for the synthesis of the dye 6 can be obtained by bromination of pentamethylbenzene in chloroform in the presence of a trace of iodine or by bromination of pentamethylbenzene in 90% acetic acid. It is readily apparent to the person skilled in the art that other suitable bromoalkyl-substituted benzene compounds which have the listed alkyl radicals can be used to prepare the dyes described.

The 1,4-diaminoanthraquinone can be prepared by condensing quinizarin with aqueous ammonia and sodium hydrosulfite under pressure with subsequent oxidation of the leuco-1,4-diaminoanthraquinone in a mixture of o-dichlorobenzene and nitrobenzene.

In the context of the invention it is possible to obtain dyes whose shade differs from the 6 dyes listed there . For example, you can use a blue-violet color

- 9 ORIGINAL BATHROOM

009843/1918

substance, 1,4-di- (pentamethylaniline) -2-methoxyanthraquinone, obtained by condensation of 1,4-diamino ^ -methoxy-anthraquinone with ßrompentamethyl "benzene. In a similar way it is possible to produce a series from blue to Separate out red-purple tinted dyes by adding bromodurol or bromopentamethylbenzene or 1,4-dibromo-2, -j> , 5 »6-tetramethylbenzene with 1,5-diaminoanthraquinone or 1,4 (or 1,5) -diamino-2 -methoxyanthraquinone or 1,4 (or 1,5) -diamino-2, j> -dimethylanthraquinone condensed.

In addition to the satisfactory results, which were input ä arbeituiig of the dyes listed above in the polyester reaction condition, different shades of color and I ^'1 xbabwandlungen can be achieved by mixing other heat-stable dyes having the above-mentioned 6 dyes or entering into the latter. For example, a violet shade can be formed by combining any of the blue dyes described with a hot violet dye, such as i! , ιί'-l, ^ - Anthraquinonylenedianthranilic acid and alizarin Hubine H (CI. 68 215) mixed. The abbreviation QI represents; a reference to the Color Index, 2nd Edition, I ¹ IIe Society of Dyes and Colourists, Dean House Picadilly, Bradford Yorkshire, England, 1956, and the American Association of 'textile Chemists and Colorists, Lov / ell l'echnologi- " cal Institute, Lov / ell, Mass., USA.

In addition to the incorporation of the dyes into the polyester before the polymerization, it is possible to use the polyester to polymerize and vdeder to melt and then the Disperse dye in the melt.

The sensitive emulsion can be a silver halide emulsion be of the following types: silver bromide iodide, silver bromochlorine Ld, pure silver chloride or pure silver bromide. In dio emulsion one works then usual emulsion :; additive, i / i ο llürtemifctol, surface-active substances, chemical onnmibi-

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009843/1918 ⁵ ^ OmG

lizing agents, optical sensitizers and antifoggants, a. The emulsion can also be used to prevent wear Coatings are protected, for example those made of gelatine, in which matting substances such as starch, SiO ^ particles and polymeric latices were incorporated.

As a binding agent for the emulsion gelatine or? other natural or synthetic, organic colloidal binding agents inirage. Suitable binders include water permeable or water soluble polyvinyl alcohol and its derivatives, for example partially hydrolyzed Polyvinyl ac et ate and Polyvinyläthei *. Other suitable Colloids are described in U.S. Patents 2,276,322, 2,276,323, 2,495,918, and 2,833,650.

By incorporating the dye in the carrier film, it becomes possible to increase the sensitivity of the photosensitive emulsion by 10 to 20 % , since most emulsions tend to lose speed when dyes are incorporated directly into them. In addition, the dyes described do not show any absorption peaks in the range from 350 to 500 m / rev and allow maximum permeability for irradiation of fluorescent screens, as used in the customary Höntgen processes.

In addition to the batch preparation, as shown above, satisfactory results can also be achieved by using conventional autoclave processes for the preparation of the polyester terephthalate, with the exception that a suitable amount of the dyes described is dispersed in ethylene glycol and added to the autoclave, before the reaction of terephthalic acid or dimethyl terephthalate and ethylene glycol takes place. In the manner described Wei3e a f arbgetöntes product of Polyathylenterephthalat allowed gain, which can be extrusion into a sheet or a film or squeeze.

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009843/1918 bad original

- li -

The products of the invention can also be prepared by mixing the dyes described and in Ethylene glycol dispersed with bis (2-hydroxyethyl) terephthalate (See also that described in U.S. Patent 2,905,707 Procedure). The monomer of this procedure is v; ird in the presence of the dye at the usual high temperatures and condensed under high vacuum to form a color tinted polymer obtained by casting or extrusion using that described in U.S. Patent 2,627,088 Device can be deformed.

The structures of the invention have the further advantage that the colored base films during further processing does not lose color, ce the dye does not come from the base film is leached. It is also convenient to use a single dye.

The polyesters produced according to the invention provide a uniform color tinted polymer for use in the photographic field. By using blue tinted carrier films With radiographic films, the hadiograph is easier to read, which improves the quality of the diagnosis will.

The colored polyesters can preferably be used for the production of polyester fibers and polyester films. Furthermore, colored packaging films can be obtained according to the invention. The colored films can also be used as Supports for other photosensitive materials can be used, for example photopolymerizable materials or in other areas of application, such as the graphic industry, for relief printing plates or colored products. The blue dyes used in the context of the invention can also be incorporated into the carrier film as a masking shade vi ground.

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009843/1918

The following examples illustrate the invention. Unless otherwise stated, all quantities are Weight is given.

example 1

A three-headed 1 liter flask was placed in a silicone oil bath. A nitrogen rotameter cleaner was attached to one of the attachments. A stainless steel stirrer operated by an air motor was installed in the center attachment. A cooler was placed on the third attachment. Then the cooler was connected to a glycol receiver and also to a vacuum pump via a dry dryer and an acetone / carbon dioxide trap. 4-54 g of the transesterification product of dimethyl terephthalate and ethylene glycol, for example bis (2-hydroxyethyl) terephthalate, which has been produced according to Sorenson and Cambell , Pi> eparative Methods of Polymer Chemistry, Interscience New lork (1961), p. 113 » was then placed in the flask and a conventional catalyst of the type described above was added to the product of the ester reaction.

Wunmehr the dye was added 1,4-di- (2 ', 3''5 ^1, ö'-tetramethyl aniline) -anthrachiiion g in an amount of 0.2 of the mixture and this _t then heated in silicone oil bath while a slower A stream of nitrogen is passed through the apparatus

became. After reaching a temperature of 220 to 24-0 °, the esterification product had melted and the stirrer was set up. As glycol started abzudestiHLeren, mrde slowly created a vacuum on the apparatus. At 210 to 24-0 ° the nitrogen flow was interrupted and the vacuum was increased slowly, but continuously. When the temperature reached 300 °, a complete vacuum of 1.5 mm Hg was obtained and the reaction was continued under these conditions for 1.75 hours .

0098Α3 / 19Ί8

During this time it was necessary to adjust the stirrer to the viscosity increase in the mixture. At the end of The 1.75 hour reaction time was the passage of nitrogen started again, the vacuum slowly released and the reaction products cooled.

The cooled, colored pieces of polymer were then crushed and placed between 1.27 mm thick plates made of chrome steel, which had been treated as follows: The plates had a highly polished surface and were coated with a common oil-like release agent for synthetic resin molds, for example silicone resin , and were heated in an oven at 275 ° for 1 to 2 hours. The layer structure was placed in a standard, preheated laboratory melt press. Size of the plates: 20.3 x 25.4 cm j the base plate was mounted on a punch 10.16 cm in diameter, which had a vertical passage of 11.4 cm. The plates were heated to 275 ° for 1 minute. As shown by the measuring display of the press, they were exposed to a pressure of 6803.9 kg at 275 ° for 1 minute. The compressed film was immediately removed from the press together with the plates and the entire layer structure consisting of plates and film was quenched in cold water. The resulting colored film was a deep blue color that was uniformly dispersed throughout the film. neither color nor polymer was degraded in any way.

Examples 2 to 71

The procedure of Example 1 was followed for Examples 2 to 7 repeated with the exception that other dyes were used in the various examples · In Example 7 a combination of the dyes according to Table I was used. Reaction conditions and results are in Table I. reproduced.

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009843/1918 ^ßADORiG W

Panel I.

At- dye amount vacuum polymer- processing

game g mm Hg sat ionization worki

time temp. (Hour) 2 £ L

2 1,4-di- (2 ', 3', 5 ', 6'-tetra- 0.1 2.0 2 280

methylaniline) anthraquinone

ρentamethylaniline) anthraquinone 0.1 2.5 2.5 290

) 4 l, 4-di- (4 ^l -bromo-2 ', 3 ^l , 5 ¹ ,

6'-tetramethylaniline) anthraquinone 0.1 1.5 2 305

5 l, 4-di- (2 ', 4', 6'-trimethyl-

aniline) anthraquinone 0.15 1 »3 1» 5 285

6 l, 4-di- (4 ^t -_b-butyl-2 ', 6 ^l dimethyl aniline) -anthraquinone 0.2 1.6 1.5 290

7 l, 4-di- (pentamethylaniline) -anthraquinone and 0.035 N, N '-1,5-anthraquinonylene-

dianthranilic acid 0.035 3 2.75 300

The colored polymers of Examples 2 to 6 were not as strongly colored as in Example 1, but each sample was tinted uniformly blue. In Example 7, the colored polymer was purple in color.

Example 8

The compound bis (2-hydroxyethyl) terephthalate was prepared by transesterification as described in Example 1 of US Pat. No. 2,905,707. The dye of Example 1 was in ethylene glycol in an amount of

- 15 009843/1918

0.0018 g / 4-54 g of dimethyl terephthalate dispersed. Dimethyl terephthalate and ethylene glycol were in the presence of a conventional catalyst as described in the example U.S. Patent .2 905 70? implemented. Analogous to the in The method described in Example 1 was the colored bis (2-hydroxyethyl) terephthalate in the presence of a conventional catalyst with increasing temperatures, decreasing Print and polymerize with stirring. The resulting colored polyester was then prepared according to that in Example 1 of the United States patent 2 779 684 are cast, extruded and stretched. A uniform, blue-colored, stretched film that works well as a carrier film ™ suitable for the photographic sector.

Example 9

Both surfaces of the polyester film of Example 8 were coated before the hedge with an undercoat based on vinylidene chloride / methyl methacrylate / itaconic acid and ethyl acrylate, as indicated in Example 1 of British Patent 1,091,834. A customary light-sensitive, dye-free emulsion for X-ray purposes, which contained silver bromoiodide grains containing 1.2 % AgI and 98.8 % AgBr and 105 g gelatin / 1.5 moles silver halide, was then applied to the applied lower layers of the colored carrier film. A comparative sample was prepared for this emulsion with the exception that the comparative emulsion was a

Mixture of a pigment, namely Pigment Blue 15 (CI. 74-160) with a dye containing Vat Violet I (CI. 60 010). The emulsion was also applied to each surface applied non-colored carrier made of polyethylene terephthalate, as described above with an underlayer had been coated. The dye and pigment were added to the emulsion to make it blue in color upon treatment Forming the subsurface, roughly equivalent in density and color

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009843/1918

the color of the test material. The films were exposed at 70 KVÜ », 4 ma. And 5 sec. Through a pair of fluorescent screens through an n2 aluminum step wedge, developed in a conventional developer suitable for x-ray images at 20 ° for 3 minutes and then fixed and washed. Sensitometric examinations carried out on the films showed an increase in sensitivity of about 20 % for the film with the colored carrier film. The results are as follows:

Relative sensitivity

veil

Comparative sample colored carrier film

100

119

0.06 0.06

009843/1918

Claims (5)

PATENT ADVOCATE DR.-ING. BY KREISLER DR.-INO. SCHÖNWALD DRYING. TH.MEYER DR. FUES ι · ι it «ι« f ι · f i «.j. ; 11 COLOGNE 1, DEICHMANNHAUS, 16 # Hal 19 * 1 Mr / Breu Pat 1.) Shaped bodies made of hydrophobic polyesters, in particular films, characterized in that they are colored with a NjN'-diaryldiaminoanthraquinone dye are colored or tinted, which bears at least 3 substituting alkyl radicals on each aryl ring. 2.) Shaped body according to claim 1, characterized in that that there is at least one photosensitive layer of a colloidal silver halide emulsion on them. 3.) Shaped body according to claim 1 and 2, characterized in that the dye is N, N ⁴ -1,4-diaryldiaminoanthraquinone. 4.) Shaped body according to claim 1 and 2, characterized in that the dye l, 4-di- (pentamethylaniline) -anthraquinone, l, 4-di- (2 ', 4', 6 ^l -triethylaniline) -anthraquinone or l , 4-di- (2 ', 3', 5 ', e'-tetramethylanili ^ -anthraquinone is. 5.) FormÄrper according to claim 1 to 4, characterized in that that the polyester is polyethylene terephthalate. 0091 * 3/1918 ORIGINAL INSPECTH)