DE1497209A1 - Process for the production of electrostatographic image powder with colored particles - Google Patents

Description

Dr. Expl.

XMSLOl LIMITED 37-41 Hortiner Street, London WI / England

Process for the production of electrostatographic image powder with colored particles

The invention "relates generally to electrostatography and in particular an electrostatoi ^ raphisehes Oil powder (toner) and a process for its production.

Heretofore, these image powders were generally made by thoroughly mixing the heat-softened synthetic resin with the pigment. fabric made. In doing so, these components are only uniform Distribution in a Gtimmi mill or similar Muddled furnishings. Then the material is pulverized, to get small particles. In many cases this was the resin-pigment distribution by jet pulverizing the material "er -". ■

909817/0644

BATH O ^ SIINÄL

U87209

reielrt · Although some very excellent types of image powder were produced by this process, it has certain deficiencies · For example, in general "this process achieves particle sizes which vary over a wide range produced billow powder is generally between 5 and 10 microns *, not infrequently also particles of less than 1 micron "up to 20 microns are obtained. Furthermore, this composition process was slow, expensive, noisy and dusty. In addition, this technique for image powder production causes certain limitations in the selection of the material, since the resin dispersion must be sufficiently finely distributable so that pulverization can be carried out at an economically feasible operating speed This requirement gives rise to the problem that if the resin-pigment mixture is finely enough to be dispersed so that it can be pulverized at high speed, this process can, however, take place over a larger range of different Particle sizes with a relatively high percentage of fine ■ particles is generated. In addition, such very fine. ■ distributable substances are further pulverized or atomized if they are used for image development in xerographic copier !!. All other requirements for xer ο graphic ^: Developer or image powder, such as permanent storage, no clumping , Good triboelectric properties ^1, -for the development, good Bildoualität, no Schichtbildung'oder Verunrelnigung on the xer'ögräphisehen- selenium plate and lower SehffieizpmiM for Hitzefffijfeßerung are the by, this' ^ i Hers1 & l3KjSiijsverfä Forderurigeii

bound. 9O0f17 / O & 4 ^ _B > j5W @ ^ ^L

der "irarlLiegeiiden J) r £ indictng mrd an aeixes .and

SoJÖBe süEii ^ EicIrt ;. The vnaiih. · DieBeja do gymnastics. "te; EIlipi3 ^? Br ihat ^: a gleiciajnäßig Isttgelige! Eaoelieäge & talt, for äie * Ifer ^ namely .feeiiEaBtoSeiiHlfeiiÄ ^^ he ^ -

isii. JaBeaeäem Jsät aidi shown ^: äaB this new ^ ea? - .faäareai sur Hei * s ^ e33aing of. BiiSpilver -the Mi & mg .esdajem iKitei

iSlsiöMöi ^ lg ^ d ^ iiiiil € ie l · diie; Bili
Jfe »der -i & t pa? Ali-btscto. , 3 © äein

BiasGÄliefflJtßJi -d ^ r ö & eit v

l '

± et τβΌη öer ^ ewefle i

Hence τΑτα: _# saMäi feei

one seuo ^ apple ^ ieii JMa * te ,, the Ü

holier JhtflSsuiig Lieferii, ^ SaB sown

see, BilSpalirsr «ntwieteelit will, Oäb i .jg ^ ißßer siaH a3.s Öe Aümxtm & e irjgeaö eteiSB ħölöiÄjgi * teheiie iie« latent Jiiläeß * Das madte dem e ££ iöaffiftgögeiniiße - IS ^ Briisettifae; Sildpulrer is better suited for the production of pictures with high, double aspects. Firstly, particle sizes of picture _{powderB 1} can be achieved.

148.7209-

^ m ^ mM3mS ,: im ^

3i. fat «afc etopte.Bto ^ te.eisM ^ ii * ^ .- ImMc. efera, - afe sSB

geMI *

holding dye includes. The dye used

'can either be water-soluble or water-insoluble * in the first case' it can be added to the resin latex and "dissolved therein, in the second case it can first be converted into an aqueous suspension and then added to the resin latex. Therefore, suitable pigment substances can be used , Color pigments, whatever serious colors, "water-insoluble" colors, or any other common dyes such as powdered metals, are used. Typical .Pigmentstoffen and colors include Monastral Green, Celliton Blue, Victoria Green S, Spirit Blue, IRlT-100 (iron powder) _r Heutral Red, Congo Red, Titanox A-Lo (an anatase titanium dioxide-Plgment), Cadmium Yellow “Antliraquinon Red.

A suitable color or group of colors can be used to color the suspension. Typical acidic colors are e.g. t Anthraquinone CI. Acid Blue 127 "Triphenylmethane-CJ" Acid Blue 103, Azo-CI »Acid Blue 98, Xanthene-CI. Acid Violet 9, nitroso * CI * Acid Green !, Monoazo-CI. Acid Tellow 29, Diazo-C.I. acid Green 20, Xanthene-C.1. Acid Red 92, quinoline CI. Acid Xellow 3, DiSELZo-G »I. Acid Orange 79. ■

Typical basic dyes are thiazole-CI. Basic Tellow t, Ketonimin-CI Basic Yellow 2, Aeridin-Grl Basic Yellow 4 »

The bypic dispersed dyes include ITitroazetaaiin Yellow 2 ItZ-CI * Disperse Yellow 1, Azo-CI. Disperse Orange 3, Azo-Disperse Red 1, Anthraguinon-C.I «Disperse Ylolet Celanthrene

SÖ9817 / 0644

1497203

Red, Amthraquinone-G.1 »Disperse Blue 9, AminOketon-Gil. Disperse Green, -1, Azo-C.1. Disperse Blaok 9, CI »Black 18, 19» 1o _r 1, 7 »12, 24 and 27 as well as Djazo-Cl Food Black 1.

If the shape of the dispersion of dye and resin in the water is maintained and the solids concentration in the final dye latex is controlled, the final particle size of the image powder produced can only be determined by the size of the spray head of the atomizing device! This is possible because the percentage of water in each droplet is the same and, if all the droplets have the same size, the amount of water removed from each droplet during the drying process is the same, which means that a constant proportion of resin and dye remains The number of polymeric particles of the latex in each droplet, and thus in each final toner particle, is relatively large, so that these latex particles form a well-shaped, hard toner particle and the droplets of liquid that are sprayed ", Contained. Encapsulate the dye well ^ whereby the Far Substance "as water-insoluble material in suspension, or if water-insoluble material is present in solution. Therefore, the size of the polymeric particles present in the emulsion is directly dependent on the size of the final toner particles desired. For producing "getter toner particles of smaller dimensions, is' preferable · eine'görln'gere'Gr'oBeÖer polymeric particles it. '' ^ Has Jcif ^ z ^ ^ IGT lkii eiektrostatoferaphischeBildpuiver'für ^ ^'': ''

the ^ iöteä'Z \ iecke are best used when their 'size '"' ^{ÄiMi r} $ ^ W Mkilii ^ egf ,, - being the desired' size ''

80 ^ 817/064 4 BAD OMCSiMAL- 7 -

vest clear E.

l. mifc esteem Gai ^ fe vom ■ .: less ■

se * -Ml ^: maa .die: pßBQt, fc waßBigeax Earfeex s ^ eeääasl &g; · ra &teiE'- uiigeiSte 6 , Q

mijfc: an: IfiirclpesseK am. imtBiceaa 'Söfö- des;:, 0> .§ Taiis, 80: Μ

3! Qiisrr ^ ä3 »-fei3 £ ea :.

dem? jä ^ esc, ni © ase

" im: fen

Äfea; is » Im

MiK at. _fc lie ;: spherical, if one? gijaßfe one; Sfene ^ Partilceits?

<fe

*, 5 ^ teiKÄ3Ä. feat:

-; zm

:.:. ζναε.

Obwoiil. iJigeiiä.: esamir clei? in :: äeir

; siateE tjqs ^ j, & IM- "at, 2S

bath

older-.

3emlgen seoss sem / ö

W®Mm $ & mi ram

Jletea

f Sr

in the

is stirred in, a relatively large number of small monomers distended micelles formed in dei Earalsioii., the Ttfiederumdeselbe large! yesM small polymeric particles "after oil embedment-polymerisation fftoffefi of the difference process form in the EffiulBitfn »

30981770844

-? - ■ 14S7209;

Any suitable natural, modified natural or synthetic resin can be used in the process of the invention. Typical synthetic polymers consist of vinyl ~ 3 olymereri of the following characteristic monomeric structure ^ ^:

These include, for example, the following vinyl monomers. Esters of saturated alcohols with mono- and polybasic unsaturated acids such as alkyl acrylates and methacrylates, 'Haloaerylate, diethyl maleate and mixtures thereof; Vinyl and vinylidene halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene and mixtures thereof; Vinyl esters such as vinyl acetate, unsaturated aromatic compounds such as styrene and various alkyl styrenes, alpha-methylstyrene-paraehlorostyrene, parabromosijyrene, 2,4-dichlorostyrene, vinylnaphthalene, paramethoxystyrene and mixtures thereof; unsaturated amides such as acrylamide, methacrylamide and mixtures thereof; unsaturated nitriles such as aerylonitrile, methacrylonitrile, haloacrylonitrile, phenylacrylonitrile, vinylidenecyanide and mixtures thereof; ! -substituted

unsaturated amides such as!, F-dimethylacrylamide, H-methylacrylamide . :. Isoprene

and mixtures thereof; conjugated butadienes such as butadlene, / and their mixtures; unsaturated beer such as bivinyl ether, biallyl

. Vinyl alkyl ethers. ^

ether, / and mixtures thereof; unsaturated etones such as vinyl ketone, Vinyl alkyl ketone and mixtures thereof ^ - unsaturated aldehydes and aetals such as acrolein and its aetals, methacrolein and its acetals and mixtures of these substances; unsaturated heterocyclic compounds such as vinyl pyridine, vinyl furan, vinyl

90981

* kumaron, B-vinyl carbazql and their mixtures; unsaturated ^: alicyclic compounds such as yynylcyclopentane, tinyljsjüoliexaaa and mixtures thereof; unsaturated oil compounds such as inylthioether; unsaturated hydrocarbons such as ethylene, propylene, ice aron, indene, terpene, polymerisable hydrocarbon components, isobutylene and mixtures thereof; Allyl compounds such as allyl alcohol, allyl esters, diallyl phthalate, triallyleyen arylate and mixtures of these condensation polymers which contain polyesters, such as linear unsaturated allcydis, which are produced by reacting a bifunctional acid or an anhydride such as phthalate -, isophthalic, terphthalic, apple, maleic, lemon, amber, glutaric, ad | pin, tartaric, pimeline, eork, azalaic, sebacic, camphoric acid or anhydride with one Polyol such as "■ glycerine, ethylene glycol, propylene glycol, sorbitol, mannitol, pentaerythritol, diethylene glycol and the like. Polyethylene glycol polycarbonates such as bisphenol esters of carbon dioxide, polyacrylates such as those produced by reacting baths with two-base acids, the diamines containing 2 to 10 carbon atoms and the acids containing 2 to 18 carbon atoms. z, B. prepared by condensing epichlorohydrin with one of the substances bisphenol 'Ä _f resorcinol, Hydroquiiion, - Ithylenglycol, glycerol, or other hydröxys-lhältiger Verbindiaiigenj "· other polyethers, for example, prepared by reacting' produced formaldehyde with plfjanktiohellen glycols ^ Poisftirethane, for example 'by Implementation of a misocyanate such as toluene-2,4-diis © eyana € 7 methylene Ms * A4-phenyiisocyanate), bitolylene diisocyanate, t, 5-faphthalene diisocyanate and hexamethylene diisocyanate with "bucket

- BATHROOM OMGI-NAL - - 11 -

90981 -

lllll

genaiiatmi

iksmaa. ias

aoli;

ircm

ib3.%

ligated

FOSSH RESINS,

At the,

Although most of the #eir in a water pension

Ifeätse-

ίϊϊ

. _s e.g.

organißclieii 3j.

the solution in. Water or duireli ßefrierzerkleizierimg de * Ηατε

dear he & si

latit - .. vests »

-mi * äear Biljäamg; des göIyin & * eK I # -fee3tJfoireäl

the TTe ^ faiireii can be eiitent polymer ei £ Iiaiiex: Ts & gormen , we3lG & © E äSa

s.S. «a:

ise? aaiä

ess T ^ aEseasanlasiEicii ^ set must it? £ ee € eia

h & ±: e

ϊϊ3ϊ ± ηιτ

^ diaJß msh.

aOüiEg fes

aits

to whom ^ νβηι

It

which is added to ^{the latex in 1} lm of an emulsion or suspension, has a lower temperature than the size of the final Ifoner article produced, so that: the deiclucidity of the product is improved. and, the colorant is encapsulated in the final SLoner article. It iiat. far away

BATH

the 'pigment substance with smaller particles a uniform and 'Forms a more stable suspension, and therefore a more uniform one colored toner — particles obtained are not commercially available aqueous suspensions of the desired pigment material obtainable, these can be obtained by mixing the pigment material with Water and a suitable surfactant. Water suspensions of other water-insoluble liquids. Dyes can also be used in this way for later use

" TO-

Addition to the aqueous latex. Are used as dyes water-soluble paints are used. "So these can either be dissolved directly in the aqueous latex or they can be dissolved first in water and then add this solution to the latex.

The spray drying system used in the following examples was the Bowen Läborzerstiiuber from Bowen Engineering Corporation, Horth Branch, Few Jersey. This device is a laboratory standard * conical dryer with on-air flow and has a replaceable spray head that sits near the top of the Drying chamber attached and within the annular drying air manifold is arranged. Any of the known spray arrangements and methods commonly used in spray dryers can be incorporated into the apparatus, such as Centrifugal or swirl pitot tubes, with compressed air or with two liquids operated 'atomization, in which a jet of the liquid to be atomized is atomized by a high speed gas flow' " When it leaves the nozzle, it splits atomization by ultrasound vibrations or atomization due to the impact of the liquid jet on a solid surface. The one in the following examples used atomizer, was one with a "firing disc

ÖföeiNAL

"be," in which the liquid is ^{broken up} by rapidly flowing out of · "δί · - the circumference of a rapidly rotating disc« This atomizer is pre-drawn when solid substances such as pigment are suspended in the liquid, as other atomizers are often worn out during a session at high speed from the friction with these solids. In each of these atomizers, the size of the image powder particles ultimately obtained is a function of the concentration of solids in the droplets. And the size of the droplets formed by the atomizer, although the droplet size formed by the atomizer for each of the different Atomizer depends on various factors, -Is it mainly dependent on the radius xind 'the e-otatioBsgescM / inidigkeit of the centrifugal disk' of the atomizer described above. " Since the sputtering a very intricate and xmvoll st Endig clarified operation is' _t, the best results will likely be through the use of empirical. Values obtained from the examples given below. Unless otherwise stated, the dex atomizer works with a centrifugal disk with a radius of 2.54 cm and an overflow rate of 50,000 per minute. on in the liquid-dependent particle sizes were formed, as given in the examples .; Other methods: can of course show changes in the structure of the Schieuderschelbe, in the speed and in the solids concentration, whereby similar particle sizes are achieved Water is removed by evaporation ^;

- ■■ ig:

H97209

dear Tarö ^ ßsheii ^ sosaia & 2Jd1i. eggs IS32H © dea 33ieZeiifc, wilireiid. derea? ii & s © _: ErSgfckeii: Jn;

: der: "iEcDEdcienliif i; eirtiiskfeHL sinär ,, ictrÄ: ^H: lerwellÄei;" fe ^1P

nxeML S0 Etab ^ i ^ -agin: »,. äa & sie aar -cEenu laiicleii. äer

Commonly _: Sat sicii. geaeigji ?, »& aä inS: 'fea ^ meilssbeai: deoc

mart. eäia® :. deraxiage-! eca ^
iteii £ Xt ^ etaß äääLe Earti ^ eDE the ^ rsipiiJiiMg ^ si ^ adiJeäi ^^ Eemgeratiir τρβζϊ & ΘΒβπ ^. daäegesafe; iifegi: UiEEK Tfe * siKßiaelr- »

sm

of the water; Hsete, äsKE 'eEBfeH ;. Saöasaii® ;: äiem ' 5 & ö die- fealeszieafei- EarlältelL ;: aSfeöEES », Mrfi · aaxs ;, a Hairz: veswendBi ^ welfeEes:" fei
Haue 'deK ZiiaiHe ^ rfceiips ^ rafeEv ISxefeEig; i & feC _t; Εθβεπϊ ;: «se« i,: die -geia? © ie] meffe © EL StoaEeo ^ -IfeirtäilB ^ Germ. lfec3ia © s: etE. dear

: in
Jedioeii. uitgefeSiiiefKEixsii :: imä: ¥ edi

glfe aatsa; dle2r diets ^ . am- E & ü Φ

BAD ORIQiNAL

:: one. % 5 <l

^ " ¹ Ϊ5:

whimsical ice © ;:

: is. one;

ai Sarifeois- & ajcmxi: B ^ M

41

im® .: 251

r; » -. Industrial fair?

IEb: ffliibi © iä; red2ies Μϊ aiicua- zateieeifefc *. Bite dnraafe, Bgimenginig from p

Bte $ 'ieö -9 ^

: " gasstmr- · ^

milt: E

MM ro J Z direct ;,

'pfclfcl

? midfc

^, ä & ßi 'aeair

1 it

an Iireliz.ahX of 21,000 subsidies, which under these conditions--

7 A'0'6 4 L · '

- ¹ - ⁷ - "-U97203L;

The particles produced were 6 "to 8 microns in diameter in the diameter and were well pigmented. When used in a conventional xerographic copier, they gave images of good quality.

example IT

Example III was repeated, but the spray liquid contained 20 $ solids instead of 15 $ and the dry air. temperature was 93 ° C at inlet and 71 ° C at outlet . The conveyed weight was 590 g per minute. Under these conditions, a black, "easily scatterable image powder with a particle diameter of predominantly 5" to 7 microns was produced.

example IT

Example IY was repeated, but the dry air temperature was increased to 116 ° C. on entry. It was "at exit 76 ° C, basing conveyed weight increased to 1133 g per minute. The particles produced in this way had a size of 7 to 11 microns in the present case.

The examples described above III, IY and Y were mixed with a Bowen 213 cm-dec t: \ .. ubungstroclaier lurchgeführt. -:

Example Vi

In this example, an emulsion was prepared and pigmented advantage as described above in Example I, was .However · the diluted a set atomization at 10 · ^ PestkorperkonZe "tion and a Bruckluftzerstäuber at a. -

bad _OmmhSAL -18-

-is- H97209-

speed of 80 milliliters per minute and a nozzle pressure τοη 5.28 at atomized. The, arrangement was made with a Freezing air temperature of 82 C at inlet and 66 C "at Exit operated. There were seven spherical particles a major diameter of about 1 micron »

Example TII

An atomizing liquid containing 102 g of a 65/35 ° styrene-1-butyl methacrylate copolymer at a solids concentration of 12.5% was prepared. Added to this were 11.33 g of Aquablack 15, an aqueous suspension of 30 percent by weight of carbon black with a particle diameter of 20 microns. This liquid was atomized in a centrifugal disk atomizer at a speed of 80 milliliters per minute, a nozzle pressure of 7.04 at and a dry air temperature of 88 C at the inlet and 4-3 ° C at the outlet. The resulting particles were predominantly in size 5 to 7 microns and again an image powder resulted which, when used in a conventional xer © graphic copier, produced good xerographic images. ...

Example ¥ 111

It became an atomizing liquid by mixing 173 milliliters saran latex F-122, which offers SO g solids * with the above-mentioned Aquablack 15 nut suspension, which 10 g 'Contained Pestsfoff produced. The saran latex consists of a polyvinylidene-chloride polymer. This atomizing liquid was used in a centrifugal atomizer at a company

■ speed of 134 milliliters per minute and a nozzle

vort 7 ^ 04- a * t. as well as ei ± ce ^ - ■ 3 & © «3sfett3 ± ^ ? ' C; "at; EiiEtritt-; aast- 66 ° C fei itosteilrt

9,098.1 77064 t BAD

Claims (1)

Ϊ a "be ii t; -aas © -T w -4 Ii ^r & ^ o ^ mim: M mm , monomeric Ji.xi.sgan ^ s ± DÜJjeis! in water : xmn t ^ » - 21 - \ 143720 $;.; 5 * method according to one of claims 1 to 3, characterized thereby "* indicates that the-'addition of the dye to the resin suspension is achieved by dissolving a water-soluble color in the resin suspension. 6. The method according to claim 1, characterized in that the atomizing liquid by adding a dye to. - a polymer latex is formulated so that this atomizing liquid is atomized to such a particle size that the solids contained in each droplet result in the formation of a final solid particle of about 0.5 to about 80 microns, that the atomized droplets In fine distribution are kept in the gas until the water contained in the latex is removed by evaporation and the polymeric particles from the Le, tex coalesce in each droplet around the dye contained therein, and that then the dry image powder thus obtained -Particles are collected, 7 · The method according to claim 6, characterized in that by. the atomization. Droplets of such a size are formed will". äaJS the solids contained in each droplet final image powder particle. with a. Diameter, of approximately Form 0.5 to about 25 microns. 8. The method according to claim 71 germinated, .that for -Zef- - dusting a-polymer latex is used, whose - polymeric particles have a diameter of less than about 6,000 Angstrom units "" _Dan , " - .. ",,.,., ESAU U ™ lijn \ JAL, ^{:; r} -22 -. - 9 ·. Method according to claim 7, characterized in that for atomization a polymer latex: is used-, dessert polymers Particles less than one Angstrom unit in diameter to have" 10. The method naeii claim, δ »daäuröh characterized that öach the haze and coalescence of the polymeric particles one V additional ÄKcalling of the dried particles carried out will. 11. Electrostatographic image powder, made according to the "" · .... Method according to one of Claims 1 to 10, characterized in that that the polymer material contains mostly styrene " 12. Elektrostatographirches image powder according to claim 11 _f, characterized in that öer polymeric substance contains a copolymer of styrene and a methacrylate.