DE1494135A1 - Pigments - Google Patents

Description

UK Application Priorities No. 21103/61 of June 12, 1961 and 18. May 1962 are used.

The present invention relates to pigments and the use of pigments for coloring organic media with high molecular weight.

Antrachinonbisthiachromone of formula I and II are known compounds, which · "of the German Chemical OwlHohaft Report *" 19II B.nd Kk have been ₀ · Since 3130 and 3131 ben beeohrie of Ulleann in what dl · «rater · in the D "Usch" n patent specification Mr. 238 983 b * eohri "btn is.

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II

It has now been found that compounds of formula I or II in

finely divided form are valuable as pigments for coloring high molecular weight organic products.

According to the invention, pigments and pigment-like compositions of matter are proposed which are composed of one or more of the compounds anthraquinone- / i, 2-bj5,6-bi? -And- ^ 1, 2-bj 8,7-b27-bis-

thiachromon with a surface area of at least 10 m / g

or contain them.

The pigments of the invention can be prepared from the known crystalline Anthraquinone- / 1,2-b; 5,6-bj [7- and "^ I, 2bj 8,7-bjT- bisthiachromones are obtained by methods * such as those in the prior art for the production of finely divided pigments, for example by acidic Pastries and salt grind are known · Other substances which

• ι · ■

Be present in the PigaentstoffsusaMNmNmsungen der Brf induhrorhand may include other pigments, resins and surfactants « such as pine oil and disodium dinaphthobyl kethaii-B-disulfonate.

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The invention also relates to the use of anthachinone * / 1,2-b; 5 »6-b27- and - / i.S-b ^ SjT-b ^ -bisthiachrofflonen old one Surface of at least 10 m / g as pigments for coloring high molecular weight organic products.

The expression ^ organic products with a high molecular weight ¹¹ can be coating compounds, for example paints, varnishes, varnishes and printing inks, plastic compounds, for example polyvinyl chloride, polystyrene, cellulose acetate and polyethylene and fiber-forming substances, for example viscous, polyesters such as polyethylene terephthalate, polyamides such as polyhexamethylene adipamide and Polyolefins such as polypropylene include. The raw materials used in such products are synthetic polymers imQ. Copolymer All such substances can be colored in the mass by incorporating the finely divided anthrachlnon bis-thiaehromine according to the methods known for the incorporation of pigments. The material colored in the mass can then be transferred to its end face. For example, a colored coating mass can be applied to a surface by brushing, dipping or spraying followed by hardening * a colored fiber-forming material composition can be spun into threads and a colored plastic material can be molded, cast or pressed into solid objects.

When such dyes are used, the pigments of the invention have very good fastness properties, for example with respect to solvents and heat, and in particular excellent lightfastness and , in particular, excellent resistance to light

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Change due to weather conditions. Anthraquinones ^ »2-bs 5» 6-b27-i5isthiaehromon gives bright yellowish-red shades of larger Beauty and clarity - the suggestion of this material "so far one academic curiosity, in pigment-like form, makes one valuable contribution to dyeing technology.

The invention is illustrated by the following examples, without to limit them, parts are by weight.

Example 1 .

A ball mill is charged with 80 parts of steel balls, 80 parts of iron nails, 30 parts of dried sodium chloride and 2 parts of anthraquinone- / i »2-bj 5,6-b ^ 7-disthiachromone. The mill is allowed to run at about 120 revolutions per minute for 48 hours. The 0 _e mixture is separated from the balls and hail »^ O with parts of water and 15 parts of concentrated sulfuric acid was stirred and the suspension is heated for half an hour to dissolve iron traces to 90 to 95 ° C. Then the suspension is filtered and the figment with cold. Water washed free of acid. The wet filter cake is mixed with 0.2 part of pine oil and 0.1 part of aqueous. Ammonia (specific gravity 0.83) largely mixed and dried at 40 ° C. A luminous yellowish-red pigment with a surface area of 20 m ² / g is obtained, as is done by J ^ aet's Stlckstoffahsorptionsverfahren.

Bas Pigment is suitable for incorporation into paints, lacquers, varnishes, stove enamels and printing inks and gives surface coatings

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of bright red shades with exceptionally good resistance * celts against solvents, heat and light. The paints containing the pigment have an extraordinarily good resistance against fading when the effects of the weather on · The pigment is also e.g. dyeing of polyvinyl chloride, polystyrene, polyethylene and Cellulose acetate suitable «

Example g

Instead of 2 parts AnthraoMnon ^, 2-fe; 5f6-b ^ 7-bistMaohroeön fm Example 1, 2 parts »ABthrftohinori- ^ t, a-bi8» 7-b'-7bie ~ tbiachrceoo are used. The red pigment obtained in this way is blue! * Is a shade of color than the pigment of Example 1 and has a tla of about 50 m / g, measured according to the Stioketoffab * orptione method; The pigment is sum green · ». Suitable for budding, t * okej tins, oven enamels and printed colors and gives upper * t l "chen3ber" Üie von bllylichrot "!" Color with awsÖ "iwl" nUiQh good resistance to! ^ "Ungseittel, Wtrm and light, Di" The paint containing the pigment has extremely good resistance to fading due to the effects of the weather. The pigment is also suitable for coloring polyvinyl chloride, polystyrene, polyethylene and cellulose acetate.

Parts

fellen Konsentrto ^ «rSoäi ** felsilur * fÄlCsly« a! al « lätma% vtv4 under sehasll · · lühr maus all su ·% ** 400 fiU «ft aüaesetst at 60 to 80 ° C. Di · separation aird * bfiltered and Sturfreig «wasoh« n _{ uwi of the filter bags («about 50 CN> w.-part ·)

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Stirred with 30 to 40 parts of cyclohexanone for 4 hours at 140 ° C., the water being distilled off through a fractionating column. At this stage, microscopic examination shows that the pigment is extremely small. It is filtered off, washed with ethanol and dried. A bright red powder is thus obtained. The specific surface area measured by argon absorption is 44 m 2 / g. When used in paints, lacquers and other surface coating compounds , this pigment gives bright red shades with excellent resistance to solvents, Wime wm laughs * and to the effects of weathering Polystyrene as well as for the dyeing of artificial fibers, such as polyethylene terephthalate and polyhexamethylene adipaside,

2 parts AntbTÄChinon / I ^ -biS ^ -by-biathiachroaon wii * d with 50 parts of steel balls, 80 parts of HXgeln and 30 parts of dry sodium chloride as described in Example 1, ground. The salt pigment is then separated from the balls and nails and kept at room temperature for 24 hours with 40 parts of xylene. The mixture is then added to water and the xylene is removed with steam. As in Example 1, the pigment is removed from slsetispiiren and dried. It becomes _: a ^ -

Pigment m $ t> similar den.in B * obtained ispiel l erhalteneiii However, elevated Leuelillkraft. _{r ^}

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^ ^f ^ -; ■ U9413-.5

j -

The following examples illustrate the coloring of organic products with high molecular weight with the prodUcts of Examples 1 to 4 ". . .... ·. * ··

Example 5 - '

A furnace enamel is produced by grinding in a ball mill 0.6 "parts of the pigment from Example 1 for 2 hours with 5» 4 "bearings of a 16.5% solution of a urea-formaldehyde resin in a mixture of xylene-butanol (4 * 1)» 10 A medium which is obtained by mixing 963 parts of a 5% solution with an oil medium made from non-drying oil, which has been modified from alkyd resin, in xylene with 493 parts of a 53% solution of a urea-fonaaldehyde resin containing xylene-butanol {4x1) then added and. zub Mixing the Beetanäteil «continue to grind, Wb enamel is then reduced in color by adding a white urea-poraaldehyde eaaille of the following

Rütil-aa.ten € 103qrd 333

Urea Porjaaldchyd Resin ( $ 100} 313 Parts ...

(oleediunitait alkyd resin "Modified non-drying ul" 370

Sylol & S2 ! Peile

'Butancl. -. 90 pieces

. ■ ■

■ The Sssaill "wisd" uaf the su fäpbenö "Fllobe aufesprUlit, 15 Kinu

th long «nd« r lAtft getrocäeaet vea & «ehli« filich 30 f§ist »ten ^{treated at 12O 0} 0 I« oven.

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a -

Thus, a coating yon bright red mittlarim Wmgfaksfä he keep up with ausgezeicJiräetsr BeatSndJglelt geg 'n WWMM * Ueht uric} _f solvent and against Vittwungselnnflsee *

how

itfeaaa 0.6 feile * 3 * ss / isi example S beselwlebea «obtained instead of before 0.6 fellen de» Pi-pseiifcs an »the Beiä ^ iei 1 fcelsen examples ®uge» raaclt nettden, ao becomes-a J ^ sill « which covers from j3lMallc5irot © in ikr% to »iPi * Fsetlgkielt. to LBeungsoltteln »^ l ^ i ^ isukI- Meii ^ soie via WittenaBgiseiiiflil ^ sea delivers ·" ■ · - ,.

Example 6

Sine gefli »t> te Polyvinjldilorldetaer imi $ mm®n & iitzn: n & nlwu represents tfureb 2 ^ tmwleji long processing» v <m "0.5 flW.1 ·» vc »3i example! 1» fö Vellen F © lj ¥ iiß | rldtJlorl <äli®i? 35 # J% IvIten , 6,2 Hellet * eines * teslsdben BleHfiii? iNMSÄtpi ^ fc # with a content of 5 * ^ parts basic in lead carbonate and 0,, S parts

i333d l _# 0 Ivllen Yitandloigrd «wf

at ISO ⁰ C. E "is a lenichtena seiiarlaGhrote B1p &ffmsmmm> ßetzung get ^ WEJ. else% 'r Beipstellimg vo "Flg.tt" £ ts? M counter Standen or awr ¥ @ f% ^ g Fanäi as t $ & erz.n £ sma & mi feei

gße% $ ß®% Imt » Me ffei-ibe Mutet at BeröJirwsjg with the

nlent s «© mtf beeltsMt au · * ·

ziclmete consistency jgegeju Wti-jRe scwi *

example

becomes a plastic one

50, © Hellen graffliMerte® F © ijSI; S ^ rl «a on 90980-6 / 1079. *.

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₄ H94135

2-roll mill for heavy load (one roll operating at 8O ⁰ C and the other at 120 ⁰ C) until the complete distribution. The plate obtained in this way is molded under pressure at 140 ° C. The product has a bright pink shade with very good warmth and lightfastness. If the titanium dioxide is omitted, a luminous “pure scarlet color of equally good authenticity is obtained”.

The polyethylene can in this example by the same amount Polypropylene can be replaced · It becomes a bright pink or purely pearled body (with or without titanium dioxide) with very good fastness to heat and! eight

Example B.

100 part »granulated» polystyrene wördan am -i * r Ot ^ srflKch * über * r-

15 minutes long
pulled through / Ati ^ bririsirm von Uber * t? iß Laokiertroffisaeln mm 0.1 part of the pigment of Example 1 \ ma 0.5 part-η titanium dioxide. Then there is Geffliedh as Ötab darch a t & * m at 100 ° C gsipr ^ a *. The staff wiräerbröe * ^ n \ & M b ^ i I5Ö <? Formed under pressure in a template 'The' product obtained in this way would have a slightly pinkish shade old, very good WMüäi «suM lightness. If the titanium dioxide is left out, an object is obtained with a purely luminous color and very good fastness to light and water.

example 9

10 parts ÄnthrÄcMino ^ Iia-bjS. ^ B'T'feistliiÄChroMon »TO parts Water and 7 # 0 teaspoons of oil in jLtS & gen solution of Dinatrituitdi

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Naphthyl methsn-B-disulfonate will gravel _# until at least 90 % of the particles are less than 5 microns in size. the resulting paste is separated from the gravel.

15 parts of the figure dispersion described ob & n _{are shown under;} Stirring continuously to 100 parts of a viscose solution with a content of 7 * 75 % "-" Cellulose sugesetst ^ until a homogeneous mixture is obtained. The mixture is deaerated under vacuum for 5 hours and then through a spinneret using a gear pump with a throughput γοη 0 »6 cm- ^{7 per revolution}

foe $ 5 ®c 60 holes of 0.075 bias diameter each in a spunbond / pressed, which consists of an aqueous solution with a content of 10 $ sulfuric acid * 20% Glauber's salt and 1 $ zinc sulfate, whereby the thread produced in this way is wound onto a roll. The speed of the pressure pump and the take-up reel are adjusted to give thread of 5 denier. P & to is by passing it through a l; desulfurized £ solution of Natriumsülfit at 70 to 80 ⁰ C, by Hindurehielten by an aqueous solution of IMtriumhypochlorit (containing 0.35% available Ciilor) bleached at 20 C, see geiwa well with water and dried ο It is dyed in a red shade with very good fastness to light, washing and perspiration as well as fastness to chemical cleaning agents and bleaching agents »

If necessary, the thread can be desulphurised by guiding it through an ice aqueous solution of sodium sulphide (instead of sulphite) at 70 to 80 ° C.

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14.84135

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Example 10

100 parts Polyäthylenter phthalatspilne are on deip surface by applying coatings to 0.1 part of the pigment des Example 1 covered in the LacktertroBBoel »Then the The coated surface is melted and pressed through a © Spinning nozzle spun “There are pure bright rofce fibers with excellent heat and liquid fastness. ·

If the pigments of Examples 3 are used in Examples 6 to 10 or 4 are used, brighter tones are obtained-through Using the pigment of example g will be bluish red Staining achieved.

Claims

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Claims (1)

149-135 & Claims 1 «) consisting of pigments and pigment-like compositions of matter from or containing one or more of the compounds anthraquinone ^ l, 2-b; 5,6 ~ b27- and - / I, 2-bj8,7-bJ [7bisthiachromon with a Surface of at least 10 m / g » t '■. 2,) Coloring of organic products of higher molecular weight ' nrit a pigment or a pigment-containing substance composition according to claim 1 » J5.) Coloring of coating compounds, plastic and fiber-forming Pot with a pigment or a pigment-containing substance « meeting according to claim 1 » hl) Paints, varnishes, varnishes and printing inks colored with an-'thraquinone ^ I, 2-b; 5 * 6-b ^ 7bisthiachromon. 5 ") polyvinyl chloride !, polystyrene, cellulose acetate, polyethylene _K and polypropylene colored with anthraquinone- / i _i 2-b} 5j6-b ^ 7bisbMaahromon" * ό.) Fibers made from viscose, folj'äthyleneterephthalat, Polyhexamethyleneadipamid and polypropylene colored with Anthraehinon / I, 2-bj5,6-b ^ 7 '<· bisthiachromon · 90 ^ 806/1079 BATH ORIGINAL