DE2037459A1 - Process for the formation of hexagonal crystals of metal-free alpha phthalocyanine - Google Patents

Description

Patent Attorneys Dipt.-Ing. KWbicsmann, 2037459

DiPL.-InG. H.WEICKMANN, DIPL-PHTS. DR. K. FlMCKl DIPL.-ING. RA-WeICKMANN, DIPI ..- CHEM. B. HuBER

I MUNICH K, DEN

POST BOX 160120 '■

MDHLSTRASSE 22, CALL NUMBER 48 3921/22

XEROX CORPORATION, Rochester, Η · ϊ. 14603, Y.St.JU

Process for the formation of hexagonal crystals of metal-free'm alpha-phthalocyan ^ n. \

The invention relates to a method of forming hexagonal Crystals of metal-free alpha phthalocyanine with a Size from about 1 to about 75 microns. *

Phthalocyanine, also called Tetrabenzotetraazaporphin and Tetrabenzoporphyrazine is known as a condensation product are designated by four isoindole groups. Metal-free phthalocyanine has the following structure!

001117/2071

Aufler the

door are lahlreißhe! © ttllfteimte know, at dentn the

of the molecules dircoh Η «1» 1Ιθ of a jeiea group © i® © perledi « see Syetesw ersetit simi · Eb is further

until β β oh «© in the dtr periplior Bemolringen of

and duroh s & hlr «ieh'e erguisehe umi be replaced

Metal-free Ȁt'lialeoyeais
dett three polymorphic JeriaeB, the alpka « _f ü <bt ls) © tG" iiai egg 3MPorm. The X-Porm is a newly discovered pelymorphic form of phthalocyanine, which shows unique electrophotographic properties «It can be seen, for example, in the ien toiti« Patent documents 1 116 §53 and 1 116 554 "beeohriefeen * The different forms of metal-free phthalocyanines can easily be determined by comparing their long-term images and / or infrared spectra, as described in patent specification 1 169 901«

The alpha-perm of phthaleoyanin has some important property · » ■ ohaiten. For example, she becomes comic for Kimstatof " fe, parben and printing inks used «furthermore it is known iai alpha-phthalooyanine «0.1one or together suit the X-Forra Clay phthalooyanine as a conductive material for electrophotography can be used · Furthermore, the alpha por « of phthalooyanin in the] & - should be put in, woiu any suitable milling process, for example ball milling or the sala grinding can be used · Alpha-Phthalooya « nine also find λη application in the diffraction of images during part * chenwanderuag, at »pielsweiae bei 4er fotoelectrophoresis, be« · ■ rub the ears in 4-piece U8 pat * nteohrift 3 384 448 and other pa-

as well as de »Mehreohiohtverftthren, das

009187/20 ?! ,

ORIGINAL INSPECTED

also described in another patent application lit «

In a photoelectrophoretic imaging process who * the variously colored, light-absorbing tiles used in a non-conductive carrier fluid are suspended. This suspension is between brought two electrodes, exposed them to a potential difference and exposed them to an image · When this was carried out Steps find a selective one! «! Ion migration in pictorial form Distribution takes place that creates a visible image on one or both electrodes · An essential component The proceedings are the suspended parties, the inten » must be strongly colored and electrically sensitive to light and apparently a change in their self-charge polarity Exposure to activating radiation duroh interaction with one of the electrodes experience * Colored images are produced produced because mixtures of two or more differently colored Teilohenarten are used, each only for Lioht a certain wavelength or a narrow wavelength band it is sensitive · The particles used must be intensely colored and very sensitive to light

There has already been proposed an imaging method using a multi-layer arrangement interposed between two sheets of an electrically light-sensitive material holds. In this process, the face of the image becomes durable Application of an electrically photosensitive image material formed on a base. In an outline shape The image material holds a light-sensitive material such as alpha-phthalooyanin, diapered in a tough-soft, non-conductive binder · The non-conductive pad is also referred to as a donor sheet · The picture material looks can, if necessary, be made »tough-white · The procedural step This expansion of the image material is called activation and is usually done through

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20374

the formation of the substance layer with a swelling agent, a solvent solvent, partial solvent or exposure to heat «Activation can also be omitted if the Formed substances after their formation on the substrate a solution or fast contains enough residual solvent or is sufficiently viscous to be able to use it Naoh could break through the action of electromagnetic radiation, where normally visible light is used, and an electrical element in an image-wise distribution Upon activation, a receiver sheet is placed on the surface of the image material layer. * The ban becomes electrical field is generated on this multi-layer arrangement, while at the same time exposure is carried out with a light-so-shadow pattern, which corresponds to the image to be reproduced. When the donor sheet is separated from the receiving sheet, the sheet breaks The image fabric is aligned along the lines of the light and shadow pattern defined lines «Part of the image fabric is thereby transferred to one of the sheets while the best on remains on the other sheet, so that a positive image, d «ho a duplicate of the original on which one sheet is present while the other sheet contains a negative image

In the formation of alpha-phthalooyanin for use »in a procedure of the type described above occurs many · «· le difficulties arise · The use of alpha-phthalooyanine in partial migration processes has certain requirements on the crystal size of this material. For example the crystals of alpha-phthalooyanins are said to be largely be pure and a size of about 1 micron to about 75 microns to have·. If hexagonal crystals of this size are used, this also results in a better and more complete color separation

Di · Production of alpha-Phthalooyanin naoh known processes, as for example in "Phthalocyanine Compounds ¹ *

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Ύοη Moser and Thomas, Rheinhold Publishing Cosipany, pages 104-189ι, leads xu crystalline old a size of less than 1 micron · also led to the use of most organic solvents for crystal growth, for example of o-diochlorobenzene or dimethylformamide , see below large crystals of the polymorphic beta form. The beta-phthalooyanine can be converted into the alpha form by dissolving it in 98% sulfuric acid solution and precipitating the solution in bis-water. which are undesirable in a hawking harvesting process. Furthermore, the alpha-phthalooyanine so produced has a particle size of less than 1 micron.

You object of the invention is to alpha-phthalooyanin while avoiding the disadvantages mentioned above and thereby achieving a particle size which is a partial migration process is applicable It should be between approx. 1 and approx. 75 microns the end product is free from sulfuric acid impurities and Be decay products, so it sioh for an improved one photoelectrophoretic ^ imaging process, a multi-layer process and a partial wandering harvesting process with color treads «· suitable

A method of the type mentioned at the beginning is designed according to the invention to achieve this object in such a way that it is metal-free alpha-phthalooyanine and / or metal-free beta-phthalooyanine is mixed with a basic alcoholic solvent · This can also heat up to about take place at the Rüokfluss Temperature, which the Kristallwaohstum favored.

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Any suitable substituted, non-substituted, metal-free Ihthaloeyasiia k
vn metal-free @ s alph &
Phthalooyanin © der Hohungen these? ΐιβϋβΜρ ii @ feeeten results will be »jeiooh ait nrtalljfreiom trrfloht ·

Tiaeiioii · altoholiseii © lißimgesittol k © aa Iböie

good brgeliiiii · aiii

propoxide or MthiumiDatosiS © ris ± 0lt _o Xthanol, propanol or butane oil.

The metal-free Phthalooyanlii ropes as long as possible Keep in mind that Kristall® with ier 0-r3Se v © n ea «1 likr © n 1) 1 "oa" 75 microns are observed "lia © Torsugawaise time lies awiionen ea · 4 and oa »8 sayings, eiirne warming ^ - shorter ones Tents result in aioh when heated at the office temperature

The following examples serve as a further explanation of «* White execution form of the invention "AiitoilQ and Pro" «Devalue pay aioh on the G-e wieirfe, if nothing else specified «

Example I. \

Approx. 30 g met all-free es beta * Phthalooyanin with a! Particle » Sizes of less than 1 micron are incorporated into a solution «. give »the above, 30 g of potassium propoxide in the above« 170 ml of propanol contains · that. Material becomes approximately up to the return flow temperature heated and after a short time 'they result in hexagonal β Crystals of metal-free alpha-phthalooyanes, their öröese between oa · 1 micron and oa. 75 microns lies

Example II
Example I is repeated, with each el οoh instead of the metal

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free beta-phthalocyanines metal-free beta-phthalooyanine is used · The solution is not heated »but ca * Left to stand for 5 saga · Ss result in aioh hexagonalβ Crystals of metal-free alpha-phthalooyanine, the majority of which » se lies between oa 1 micron and oa 75 microns

Examples III and IY

Example I is repeated, where instead of the metal-free beta-phthalooyanins metal-free beta-phthalooyanin used is, and Example II is repeated with the «Under · sohied that instead of the alpha pora the polymorphic beta form is used «In each case they result in crystals metal-free alpha-phthalocyanines with a size of oa 1 micron to oa. 75 microns

Examples Y to * VII

Example I is repeated three times, the solvent being sodium ethoxide in ethanol, potassium propoxide in propanol and Lithium butoxide is used in butanol «The results agree with those from example I. In each of the following Examples YIII - X a suspension is used which contains equal proportions of three colored pigments It is made by dispersing the Pigaentitoffe in Sohio Odorless Solvent 3440 formed, the pigments eight percent by weight mow out the mixture. The mixture can also be referred to as a three-substance mixture. The three-substance mixtures are individually tested by placing them on a HESA glass plate applied as a layer and exposed as in Example I of US Pat. No. 3,384,488, with the under- ' sohied that instead of "Ines Sohwarz-Weiß-DiapositiY" a Kodaohrome-Dispositiv is used · On the ·· width is projects a multicolored image onto each plate as the roller electrode is moved across its surface. One Blocking electrode with baryta paper is used and the roll

009887/2073

has a negative voltage of above _e 2,500 volts. The roller is passed over the plate six times, with "the adhering particles being removed from the barrier electrode after each transition.

Example VIII

The three-component mixture contains metal-free aLpha-phthalocyanine, formed according to Example I ₁ crystal size approx. 1 micron to approx. 75 microns, the yellow pigment Indofast Yellow Toner, Plavanthron, 0 · Ι · Nr.70600, available from Harmon Colors Go., And the magenta pigment Watohung Red B, • Obtainable in barlum salt of 1 "(4'-methyl""5 ^l -ohlorazobenzene * 2-sulfonic acid) -2-hydroxy-3-naphthenic acid, U * I. No. ₀ 15865 Clay EI · duPont de Nemours & Oo * When exposed in the catfish described above, this three-substance mismatch results in a multicolored image that corresponds to the original image and has a very good color, especially a distinctive color separation.

Example ΙΣ

Example VIXX is repeated with a three-substance expression, dl «alpha-phthalooyanine, formed according to Example II, crystal frost o «· 1 micron to about · 75 microns, the yellow pigment stiff H ~ 2 "(1", 3 "Thia» 0l) -8-13-dioxedittaphtfi0 * (1,2-2 »* 3«) - furan-6-oarboxaaid and the magenta pigment Quindo Magenta RV-6803, a ghinaoridone pigment tea, contains lent tone Harmon Oelere, contains · As shown in Example VIII eich auegeeeiohnete tint and color separation inherent *.

Example y

Example VIII is repeatedly old a three-part misehing,

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BATH ORIGINAL

the alpha-phthalooyanin, formed according to Example III, Kristallgröfle oa. 1 micron bia oa. 5 microns, the yellow pigment Algol Yellow GO, 1.2 _t 5,6 ~ Di (O, O ^f -βiphenyl) · - thiazol-anthraohinon, ir. I. ITr. 67300, received Hob. Fön General Dyestuffs, and Bonadur Red B, an insoluble azo dye from Oollway Colors, 0 «I« No. 15865, tnt. As in Example VIII, they produce excellent tinting and color separation properties.

Examples XI ~ HV

A Mehrsohlohtanordnung is prepared as follows: 5 g Sunooo 1290, a microcrystalline Waohs having a melting point of 81 ⁰ C, are dissolved in 100 oom reagent petroleum ether) which is heated to above X 50 ⁰ O, and quenched by the container in kaltββ water is immersed. In this way, small crystals form. 5 g of metal-free alpha phthalooyanine, formed according to Example I (particle size from 1 micron to about 75 microns) are then added to the wax paste and mixed with 284 oom of clean porcelain balls Grinder filled from 568 oom. Ball milling is then carried out in the dark for 3 1/2 hours at 70 rpm, and after milling 20 ecm Sohio Solvent 344-0 are added to the paste. The paste is then made as Sohioht at steamed green Lioht on a Mylar film of 0.05 ma thickness · »ke with a wire-wound Aufetreiohat from Ur.12 on go« * which creates a Sohioht strength of 2.5 microns after opening «The same paste is also applied to three other Mylar- Foils applied, with a spreading stick "No. 8 a thickness of 1.5 microns, a sticking stick ITr« 24 a sticking thickness of 5 microns and a sticking stick Kr «36 a sticking thickness of 7.5 microns · 60 ⁰ G heated in the dark to dry.

009687/2073

10 "« «»

in your case, you see exposed © line - as a smpfan leaf, the end Mylar-Jeli® Y © mO ₉ OS rat strength is then applied to the surface - © iaea Everyone; Spend arblatto-s launched; _e Then, a sheet eahwarseef- © l © ktyia © h leitfähig® is "pier placed on the EepfangsTblatt." vioaaek dl © arrangement is done »Bas Sapfangstelatt ben, and the ihtaaloeyaniB ^ Waehsaehiciht fast Pineelstrieh activatedg \ rnau.

hair pin is used ₉ l @ r with F © tr © l (iömäth ©? saturated ia% · Das Eapfaageiilatt -wiri ü & sm. wioiss ³ aufolsgt

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arrangement slowly led, - to il "b © 2 ° o © ktsi3ig © n IU remove · Do you unite negative © Kltmme?

Ie Ton 8000 Veit is then sent to the black ·, non-permanent electrole

When tension is applied, a -Molit ^ ili is included

Incandescent lamp τοη down duroh iio jiaiert where au a

90 mm _t f 4f5t is used - lie Belichtungestärke is oa »0.108 lux, the lease duration @ a · 3 secu & iexic 33aduroh results in ei oh dine Gtfeaiatentrggi® τοη 2.15- Iwxs« «® Vfaoii der B ·« * liohtung it is the Bmpfangeblattung -Arrangement sucked off ^ whereby the spinning, no oh stopped, Ueibt "The slightly no eh gate hinge ene, petroleum ether Terdui3tat # t iimerhalb one .8 β Kund f naoh Irenauag der llätior" es b Iaidos geieithjiete pictures surüok "what aiii" ^ © la Duplicate dta- Qri «ginftlbAldee 4 on the donor sheet, that ?? and »ro a reversed part of the · original picture« · on the reception desk i et »fben with all animal strengths« ioh οvery good pictures®.

' i Beiapiele IV and XVI

Example XI is repeated aweiaal "with the metal-free alpha-phthalooyanine was used in addition to the cases II and III becomes · In every case aloh pictures result in a more rewarding way Quality. * ■ ■ "■■

Although certain substances and Substance quantities mentioned can also be used in other suitable ways Substances with similar results are used · Further substances can be provided to create a synergists see, improving or otherwise beneficial effect on the properties of the image material to achieve · With · * · For example, various dyes can be used as »spectral sensitizers, complex substances and electrical sensitizers« modification agents such as B · lewis acids can be provided in order to to improve the image generation during partial migration "

Further embodiments and developments of the invention are to the Paehaann after knowledge of the above description Possibly, they are encompassed as a whole by the basic idea of the invention "

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Claims (1)

2037A59 Pat ent claims Process for the formation of hexagonal crystals from metal-free »M ■ al pha-Pht halo oyanin old a size of oa. 1 until oa. 75 microns «daduroh marked that metal-free alpha-phthalooyanin and / or metal-free beta-phthalooyanin mixed with a basic alcoholic solvent 2. Method naoh claim I ₁ daduroh gekennieiohnet that the solvent is mixed with crystals of metal-free alpha-phthalooyanine · 3 · Method according to claim 1 or 2, characterized by that a basic alcoholic solvent is used, its basic properties by a or several of the substances sodium ethoxide, sodium propoxide, Potassium propoxide and lithium butoxide are absorbed 4 · Method according to one of claims 1 to 3, since there · kenniciohnet that a solvent with an alcohol content from one or more dtr substances ethanol, propanol and butanol is used » 5 · The method similar to the ink of claims 1 to 4, because it gtktnnieiohnet, that the Misohung from phthalocyanine and Solvents etc. stored for 4 days to approx. 8 days will. 6 · Procedure naoh tine »dtr claim · 1 to 4» daduroh <· <* Ktnnetiohntt that dl · Misohunf from phthalocyanine and solvent oa. 3 Sage to ea, stored for 8 days will. 7 · Method according to a dtr claim · 1 to 4, because 0 0 9887/2073 ORIGINAL INSPECTED denotes that the mieohung aua phthalocyanine and Solvent up to about the office flow temperature. hitat will θ · Method according to Claim 2, characterized in that » Crystals of metal-free alpha-phthalooyanine used that have a particle size of less than 1 micron to have· 9 · Metal-freeββ alpha-phthalooyanine in hexagonal form Crystals made according to the method according to a of claims 1 to 8 · 10. Using a method according to tinea of the Claims 1 to 8 formed phthalocyanine »in the electrophoresis Image generation: daduroh gelcennaeiohmeli, refers to a bileation containing the phthalocyanine between at least two electrodes, one of which is at least partially thermoset, one electrical PeId and cohesive through the tranaparent electrode; hinduoh a figuratively distributed activating electromagnetism Radiation budget is what is done at least one of the electrodes creates an image from migrated parts 11. Use naoh Anspruoh 10, daduroh marked, daÄ the image suspension a number of finely divided Include at least two different colors in one non-conductive carrier fluid contains that the Teilohen ^ ed he color from a Ii oht sensitive pigment- » substance, whose main ligament absorption band is in the we ~. ■ ent Hohen with his head feeling band auaamaen-> falls and that the parts of a color come from the aetallic alpha-phthalooyanin consist 009887/2073 12 Use according to Claim 11, daduroh marked, that the Bildetoffeuepeneion magenta-colored particles, which are mainly sensitive to green light, contains yellow parts, which are mainly sensitive to blue light and oyan parts, which are mainly sensitive to light, lind that the oyan particles from the polymorphic alpha-form consist of metal-free phthalocyanines. 13. Use of a phthalocyanine formed by the process according to one of Claims 1 to 8 for image generation in a picture of feehioht, thereby identified * ■ eiohnet, dal one iäh ~ white, electrically sensitive to light Image stoff Mhioht awlβohen a donor sheet and an inoculation sheet is provided which contains the metal-free contains alpha-ihthalooyanin, which is attached to the image material rail an electrical field and an image-wise distributed one activating electromagnetic radiation is brewed for exposure and that the bipartisan sheet from the donor * sheet is disconnected when an electrical field is present, where iie lildenoffeehioht in pictorial distribution ■ vomits and a jositif image on one of the leaves, a j legatiTiild adheres to the other leaf j ■ - ■ · ■. ■ ■ r ' 14 · Application Naeh Inepruoh 13, characterized in that aumittdtft the donor sheet and / or the receiver sheet In \ aumindcijlt partially to activating electromagnetic radiation j is permeable · ί 001117/2073