DE1930784A1 - Liquid, electrostatic negative pigment - Google Patents

Description

OR. JUR. DIPL-CHEM. WAITER BEII ALf RED HOEPPENER DR. JUR. DIPL-CHEM. H.-J. WQLFP DR. JUR. HANS CHR. BEIL, MS FIANKFUlT AM MAIN-HQCHST

Our No. 15 '572

SlP Corporation
New York, N, Y. _f VStA.

Liquid, electrostatic negative pigment

dye

The invention relates to a liquid pigment dye mixture (toner) for use in electrostatic printing processes, In particular, it relates to a liquid negative pigment dye (negative-working liquid toner system), which in addition to an electrically conductive carrier liquid contains a pigment or colorant as well as a polymer which gives the pigment mixture the negative signature gives *

In an electrostatic ReproduktionsTerfahren is generally a liquid pigment · used in such an electrostatic process in which a liquid dye is used, is formed - as a result of initially applied negative Oesamtladuag "noraftler ^« ¹ «« a first latent electrostatic image on a light electrically conductive Surface, like zinc oxide. This is followed by a discharge through light induction ^. cleared areas a negative charge remains »To this

-ν-

At this point in time, the liquid pigment pigment substance will wear. In the case of the positive pigment pigments. Bind di lending the pigmentation containing the pigment or colorant!) - ", mixture of substances, positively charged, and; they are therefore directed to the negatively charged areas of the latent image indicated electrostatic reproduction processes in general black-in-wise-Rtprodnk tionen · .- ■: ■ -.-- ■■ -:

In the case of negative pigment dyes, however, the color tint particles, e.g. soot oxer e'ii; Similar free pigment or dye, negatively charged, so they. repelled by the latent electrostatic image and by. attracted any underground areas ... ,, _ '' In the case of a pigment as .Vervieudüng Ttuss thus creates a reverse image of the original, whereby the production: ^rt a ei3s-on-black ^ Druckee is made possible ·

Becomes a pigment like soot in an insulating liquid suspended, in most cases this takes a small amount Micch polarity on. The positive polarity of the dye particles can be intensified without difficulty, ,, that a dispersion or suspension of the pigments or ,,, r Coloring agent in the isolated carrier of the pigment mixed with the substance with various control reagents · »TereetiBt.

The problem is different, however, if for certain - \ Purposes a liquid, electrostatic negative pigment paint » mixture is desired, which is in an electro-static Reproduction process a reverse image or in particular a White-on-black image is able to produce. Here is a liquid pigment mixture required, due to its Components attracted to the underground area of the latent electrostatic image, but at the same time to the latent electrostatic image itself is repelled .. To produce such a liquid, electrostatic negative -

BADORFGLISIAL

ems has a material to be incorporated in the _(f irundpigmentfarbatoff the group consisting of the electrically conductive liquid and the pigment or colorant particles, the "particle after incorporation into such a system on the pigment induces a strong negative polarity so that it while achieving Satisfactory results, for the "production of the negative or reverse image usable"

It is understandable that the development of suitable means converting the positive pigment particles into negative particles able to transform, made much more difficult ale the sheer enhancement of the positive properties of the pigment · Due to the difficulty in the negative pigment system such are those to be developed that will produce a full, clear negative reproduction print Pigment dye systems have not yet been used to any significant extent for certain purposes, despite the strongest power question. As already stated, the Develop a mixture or system that has a clear and complete reproduction print flat streaks and without faded Representation actually represents one of the probes with which the production of negative Pignient colors openly afflicted let.

These slopes! and Unsulängllohkeiten the previous liquid negative PigBentfexbetoffgtaisoh "electrostatic printing process could now erfindungsgemäae by the development of a liquid HegatiT-Pigaentf & rbetoffsystem · da · Au · an electrically insulating carrier liquid bit a pigment or colorant and a polymeric material * is _β da · the liquid Farbstoffgem! sch the negative signatures can be essentially eliminated

This means that a fluid is now available for electrostatic printing processes. Own Regatlv pigment dye system provided in which the deficiencies and disadvantages inherent in the state of the art are practically eliminated

^{/ 15} ν *, BADOR _1Q , NAL

The liquid, electrostatic negative pigment dye according to the invention consists of an electrically insulating liquid containing a pigment or colorant, such as Carbon black, and a polymeric material that makes up the dye mixture which gives negative properties and that preferably from an alkylated polymer of a heterocyclic N-vinyl monomers.

Thus, the liquid pigment dye mixture or system according to the invention has one of the conventional, electrically insulating carrier liquids as the base liquid, as are generally used in liquid developer and pigment dye mixtures. Such electrically insulating carrier fluids usually consist of hydrocarbon solvents that have the required dielectric constant, e.g. less than 5t and the necessary specific resistance, e.g. over 10 ohm cm, so that they can be used properly in the electrostatic reproduction process. Thus, for example, various hydrocarbon LoaungBmittsl such as toluene, kerosene, and mixtures thereof, and various commercially available hydrocarbon solvents and petroleum-based solvents such as ISOPAR with a boiling range of 149-182 ⁰ C or SOLVESSO 100 with a boiling range of 160-174 ⁰ C, SHELL 14 with such a range from 58 to 70 ⁰ C or SHELL ■ X55 are used having a boiling range 58-140 ° C, effective as an electrically insulating carrier liquid of the liquid · pigment system.

As a pigment or colorant for the liquid, Negative electrostatic pigment mixture can do any Means are used conventionally in the electrostatic Positive or negative pigment dyes are used v / earth. The negative properties of the pigment combine calibrate with the respective polymeric substances that become trapped in the liquid system so that each conventional pigment or colorant can be used to advantage. As a colorant or pigment, for example, Ruse and

0883/1513

BADORlQINAt

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various analogous forms derived from it, such as gas soot, flame soot, lamp soot and other soot substances, color pigments, including phosphotungstate and phosphotungstate and phosphorus molybdate colors, produced in the same way _. Alkali blue and many azo pigments as well as nigrosine ^ arben and triphenylmethane yerbs in particular can be used. Again, these are solitary substances as they are usually used for electrostatic positive and negative pigment mixtures Pigments, dyestuffs, before they are produced in electro-pens without printing, give an excellent black background.

The pigment or colorant, for example Ruas, is used after its suspension in the carrier liquid as a pigment in such an amount that is necessary if the negative properties of the polymeric material also result in the negative properties of the polymeric material due to its surface-active properties acts as a dispersant, is drawn up to be deposited on the substrate to provide the desired negative print "of the copy" Normally the pigment comprises from about 0.001 to 10 % of the pigment system or mixture. For special purposes, slightly smaller or larger quantities can of course also be used.

The negative characteristics of ereieit erfIndungsgemissen liquid Pigmentfärbetoffgemiach · a by the use of certain polymeric material · "As already stated, the assets erseugen the ·· required negative features ga. Such polymeric substances consist, as mentioned, preferably of alkylitrttn polymers of a heterocyclic N-vinyl macro-organic.

Such · substances are obtained by alkylation «in ·· Η ·« ο- od * r Oopolymers of a he * i ^ oycllschen ÜWTlnylmonomer,

wise e tire s N-V iny 1-lae tam — monome r en, especially one> Ic-vinyl-pyrrolidone-monOineren with an α-oil fin with 2 bia -, 2000, preferably 2 to 200, in particular 8 to 42 carbon atoms (This alkylation is in the USA-PaI; step.: 3 417 054 described in more detail) or by simultaneous polymerisation and alkylation of a senisee which is a. heterocyclic s N-vinyl monomeres, a monoäthylaniaeli unsaturated ;, polymerizable monomers and an a-olefin »it 2 Ms 2000 carbon atoms or a Gemisehea of the same or from two different heterocyclic N-vinyl monomers and an α-olefin with 2 to 2000 O atoms (these simultaneous Polymerization and alkylation is in the United States patent 3 423 367).

Below are examples of such heterocyclic H-vinyl monomers which, in addition to the nitrogen atom in desi · ^ίι; heterocyclic portion having a Carbonylfuriktion ünä * ^ΛΕ alkylated polymeric derivatives according to the above overall ""'called USA Patentechrlften 3,417,054 and 3,423,367 ■ prepared are: - -' .- "; _- .-"".

N-Vinyl-succinimid, N-Vinyl-diglycolylimld, N-Vinya-glutarimid, N-Viiiyl-3-morpholinon, NV ^> Inyl-5-methyl ^ 3-morpholl2ion _t ^ ^ N-yinyl-5-äthyl-3- ^ norpholinon, B-vinyl-oxazolidone üew · and in the USA patent 3 231 548, ring-oxygen-containing H-yinyl-lactaee, in particular dl · 5-, 6- and 7-membered N-tinyl-lactams, before especially N-vinyl-pyrrolidonj according to the general formulaί

0-0

CH-CHv

BATH ORIGINAL

in the R and R- hydrogen atoms. " Methyl or ethyl acetate, η an integer 1 to 3 and ο the average molecular weight, determined by all N values indicated · j mean measurements of the relative viscosity. ■ '■■ (

The diversity coefficient K, which is described in detail in MDDBRH PLASTICS, Volume 23 »No. 3, pages 157-161, 212, 214, 216 and 218 (1945), is calculated as follows.

ΐοκη rel and K • 1000K 1 75K ₀ ² C. ^{+ 1} - ^5K oc

where c is the concentration in grams per 100 ml of polymer in solution and the symbol ¹ rel means the ratio of the viscosity of the solution to that of the pure solvent »

The alkylated polymers of comparable monomers of 5- »6- and 7-membered Hf-vinyl-thio-lactams, K-acylpyrrolidone, -piperidone and -caprolaeta», can also be used, N-Aoryloyl-5-Biethyi-pyirrolidon, N-Aeryl "yl-6-" Ethy! -Piperidon and H-Aeryloly-7-niethyloaprolaetaa and their corresponding 5-, 6- and 7-ethyl derivativesj N-taryloxywaethyl-pyrrolidone, -piperidon and -capr # l * ctami N-Mtthacryloxy-ethyl-pyrrelidon, -piperidone and -caprolactamj N-methacryloxy-methyl-S-methylpyrrolidone, -6-methyl-piperidone and "7-ethyl-caprolaota" j N-Methacrylamide-ethyl- ^ H-Methacrylaaii'doäthyl-, N-Methacrylamidopropyl- and H- (N-Phenyl-aerylamidopropyl) -pyrrolidone, -piperidone and -oaprolaetSme.

The homopolymers of the above general formula reproduced N-vinyl-lactams (their alkylated derivatives e.g. in accordance with the aforementioned USA patent 3 4-17 054 can be produced) can be obtained without difficulty by homopolymerization of

80 $ g83 / tS1t

N-vinyl pyrrolidone, N-vinyl-5-methyl * pyrroliaon ₉ N-Yinyl-5-ethyl-pyrrolidone, N-vinyl-5,5-dimethyl »pyrrolidone _N-t Vlnyl-5,5-diethyl-pyrrolidone and N-vinyl-S-methyl ^ -ethyl-pyrrolidone, K-vinyl-piperidone, N-vinyl-6-methyl-piperldon, N-vinyl "-6-ethyl-piperidone, M-vinyl-6, e-dinethyl- plperidon * N «» yinyl-6,6-diethyl-piperidone and N-vinyl-b-methyl-e-ethyl-piperidone, N-yinyl-caprolactam, U-vinyl-T-methyl-caprolaetaxa, N-vinyl-7 , 7-dimethyl-caprolactam, N-vinyl-T-ethyl-caprolactaia, K-Yinyl-7 ₉ 7-diethyl-caprolactara and E-vinyl-7-raethyl-7-ethyl- * caprolactam »

To carry out the invention, alkylated derivatives of HOroopolymers of heterocyclic N-vinyl monomers with a K value of from about 10 to 140, preferably from about 30 to 100, are used. These homopolymers can be easily prepared by conventional processes for homopolymerization of the above-listed _s heterocyclic N-> Yinyl «« iBonomeren _t in the ÜSA Patents 2265450 and 2 317 804 2 335, and many others, in which Ausftihrungsbeiepiele are indicated. :

Copolymers obtained by copolymerization of 5 tie 99 of the aforementioned heterocyclic Jf-yinyl monomers with 1 to 95 mol-4 of a monoätnylenisca unsaturated, polymer! " Eatable monomers are obtained and a K «value τοη about 10 to 140 are easy to use according to the invention Products old the solubility properties dictated by the end use alkyl learning.

To the various, mono-ethylenically unsaturated, polymarl beer bars Monomers that are customary ^ eiae with any of the aforementioned, heterocyclic K-vinyl monomers to form copolymers are copolymerized, which in turn according to the USA patent 3,417,054 easy to use according to the invention, alkylated copolymers include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate,

809883 / 1SU BAOORIGINAL

Vinyl lactate, Vinylcaprsat, Vlnyleaprylat ₉ Vinyloltai and 'stearate, acrylonitrile, vinyl ketones, vinyl cyclohexane, styrene, 2-vinylpyridine, 4-vinyl-py _r Iain, acrylic acid, Aoryleetermonomere the Porm @ l.

CH ₂ -GHCOOR ₂

in which R _{9 is} a straight or branched chain alkyl radical with 1 to 18 carbon atoms or an alkoxyalkyl group, the total number of carbon atoms in the alkyl radicals being 3 to 6.

Examples of such acrylic esters are

Methyl-1-ethyl ° ₉ propyl, isopropyl, butyl, isobutyl, sec-butyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-ethyl-1-butyl , Amyl ~ _f 3-Pentyl ™, 2-methyl-i-pentyl-, 4-methyl-2-pentyl-, Hesyl-, 2-ethylhexyl-, xieptyl-, 2-heptyl-, octyl-, 2 "-Octyl-, Vcmyl-, 5-Ityl- _{2_nO} nyl" _f Deeyl-, 2-Methyl-7 "Ethyl-4-undeeyl" - ₉ Dodecyl-, Tetradecyl- "- Hexa ^ ecyl ^ s, Octadecyl- 2 ~ Methoxyätliyl _"i-2 and 2-Ithosyäthyl Butoxyäthylacrylat, methacrylic monomers wi © methacrylic '' Meihylmethacrylat, Cyelohexyl-iaetiiacrylat _t Isobutjl" -m @ thacryl * t _s iso-amyl-p-iaethaorylatj Sethojsj-äthylintthacrylat uad a- Co-chlorine

Ethylid @ a »ac®tat-» methacrylate and Glyc £ d ^ l «ia®tha © rjlat _e © incl _f Phenyl-aÄchlor-acrylatg a «» jLthylaeryl © äur® ₉ methacrylonitrile, ir-ikl-kyl- 'and li-aryl-substituted © acrylamide wi® II-methy 1-acrylainide, N-Xthylacrylamide, N-propyl-acrylam' id, N ~ n-butylacrylamide, Nn-dodecyi-e.crylatHidj Nn-octadecyl-acrylamide ",. N, N-dimethy-acrylamide, N ^ -diethyl-aerylamide, N, N-« Dl-n-butyl acrylamide , NiH ^ Bi-isobutyl ^ acrylamidj N «« Cyclohe3cyl «? Aerylaaiid _t Njii-Dicyclohexyl-acrylamid, N-Phenyl-acrylamidj Np-Ni.tro-

- -9098 * 3 / 1.5.1!

.Λν-: ^ jAi- BADORlQtNAU

N-p-Naphthyl-acryl-r-:

N-methyl-N-phenyl-aero-amide _f , B-dip] ienyl-erylamide _? N-Benzyl-aorylamide, NN “di-benzyl-acrylainide and grafted monomers of the kind described in US Patents 3,029,219-3,035,009-2,036,033 and the like.

Also, a mixture which consists of 5 "to 99 M0I II-vinyl-eueclnimi & _s N-vinyl-3-ffiorpholinone or the like can be copolymerized and the resulting copolymer can be alkylated for use in accordance with the present invention.

On the basis of numerous, carried out with regard to the invention ^ request has been found to be the configuration of the above mentioned ^ monoethylenically unsaturated monomers eowie of many other such substances is not decisive, »da all of them in the proportions given above with the Eopolymerize heterocyclic K-vinyl monomers and thereby Form copolymers in the organic solvent or the G-emic derived therefrom are soluble and easily let alkylitren »

|. With regard to the a «01efine _t used for the production of the alkylated polymers to be used according to the invention, it should be pointed out right at the beginning that all c-olefins with a molecular weight of about 28 up to about 28,000 are used as alkylating agents for dis alkylated polymers of the various heterocyclic H-vinyl monomers can be used, examples of such a-4) l © fine

ethylene, propylene, 1-butene, 1-pentene, a-2 «methyl-t-pentene _s 1-hexene, 5 _{-methyl-1-he3cene p} 2-methyl-1-pentene _p 3-ethyl-1-pentene, i- ^ epten, 1-octene, 1-2foneB, 2 "t-hexen, 1-becen, 1-dodecene, 1-tetradecen _s 1-H @ xad @ een,

909883 / 1S1I

· ORIGINAL BATHROOM

1-heptadecene, 1-octadecene, 1-nonadecene, 1-sicosen, 1-de "osen, 1-Tetracoeen, 1-Pentacosen and Polybutenes with a molecular weight from 400 to 2,500. "

Although linear alpha-olefins are preferred as energy ia ^ andel available eind, they may yet begun in the alkylation reaction, numerous isomers of a "= 01efinen ₉ with 1-pentene to 1-pentacosene and polybutenes are used. The only requirement in this case is that the isomer is ethylenically unsaturated in the α-position.

Instead of one of the individual α-olefins mentioned above, it is also possible to use a mixture of commercially available linear _{α-olefins 9} obtained by creocating ^ etroleumwaehs or polymerizing lower olefins as. Alkylating agents can be used. Α-Olefins with the following carbon ranges are commercially available and can be used! "Cg" - "C ~ -,

Also a mixture of ffi-olsfins, which contains from 65 to 75 # a-glefins with 20 to 42 G * ° Atwm®n and an average molecular weight of 366 and is used in the AXkylierungsr € action «

Except for the alfcylated which are preferably used as gölyseres material Polyasrea τοη H-Vinyl «« öi & oiaeren and inebeaoader «

gyrrelifion-eenoasereja, any substance can be used advantageously ₉ which can give the liquid pigment dyes the necessary negative effects. For example, the following substances can be used according to the invention; natural coal-free carbon-off polymers, for example Gilepait resins, thermoplastic polymers of unsaturated hydrocarbons from Brd® "l- & racking, for example Pieoop & l-resins and oil-soluble C-alkyl-auocinyl derivatives of polyethyleneimine, for example penta- or tetra-ethyleneimine, its Alkyl group contains 50 or more carbon atoms, for example _e oronite resins such as oronite 1200, as disclosed in U.S. Patents 3,219,666 and 3,163,603 «Alle

909883 / 1S1 3

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these materials have surface-active properties and thus enable the required dispersion of the pigment particles in the liquid pigment system, »More importantly, all of these substances have the peculiarity have the ability to convert the pigment system or mixture into an negative, that in electrostatic pressure. Procedure for adjusting reversal or negative reproductions is usable with success.

Accordingly, the polymeric substances to be used according to the invention, through which the liquid pigment dye mixture acquires the necessary negative properties, are generally alkylated polymers of U-vinyl monomers, e.g. alkylated polymers of IJ-vinyl pyrrolidori monomers, natural hydrocarbon polyicrene, e.g. natural bitumen, ₍ thermoplastic polymers of unsaturated hydrocarbons from petroleum cracking or oil-soluble C-alkylsuecinyl derivatives of polyethyleneimines *

The amount of such material that has negative properties able to give to the liquid pigment mixture is according to the invention for a given amount of pigment or Colorant not critical. This material is merely in the:! close used for achieving the. necessary Negative properties while maintaining a persistent Dye suspension or dispersion of the pigment is required. Generally one uses this Material in an amount 0.01 "to 2 to 3 times" Corresponds to the weight of the pigment or colorant, preferably in an amount of 1 to 100 parts per 100; parts' of the pigment used.

According to the invention is the type of production of the liquid Pigment dye mixture is by no means critical, so this can be represented using conventional, state-of-the-art methods. So it was in this context found that a Bre! roller mill, ball mill, KoHoId-

; ° *: ·; '· ° ^{Χ £} 909883/151 3 · :. <:; --- -'

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with high-speed shear mixers, etc., which can be used for the preparation of the dispersions used in the liquid, electrostatic pigment system according to the invention. Thus, for example ea tiblich ₈ is a concentrate or a color (ink) of the ^ igmentfarbstoffes and material capable of the mixture negative characteristics is _g to verlelhen produce in an insulating ^ rägerflüssigkeit and admit anschlieasend this concentration or color further insulating carrier liquid _s after which the liquid pigment mixture for the electrostatic production process is created,

The following examples serve to further explain the

Example 1 . _:

The following materials were mixed on a three roll mill ^, which is eight times roll mill to achieve 'a uniform dispersion in the form of a heavy color over the three-i led them.

2 grams of soot (Raven No. 15)

1 gram Onea by olefin a.lkyliertes polyvinyl pyrrolidone, wherein the carbon chain of the olefin, a length of an average of 16 OE * »© atom besitzt- and 20 $» residual Vinylpyrrolldon _f (öanex 216)

3 grams of an aliphatic solvent

with a Si © d © berelch from 149 to 182 ^ö 0 (Ieopar H)

The Parb © was added to a further quantity of © ©! © ktrisch iaollerendeif Irfigeriquid on one. Soot content of " 5 i * discontinued 2tis production of the final pigment dye system, 1 liter of additional aliphatic" petroleum-based solvent was replaced with 7 al of the 5% pigment dye.,

908883/1 SU - ORIGINAL BATHROOM

193070-4

The pigment mixture was then in a conventional, electrostatic duplicator used to make a to produce negative, electrostatic reproduction * The with the pigment colorant mixture according to the invention prepared Print showed a clear © reproduction of the original Iia reversal— picture, deh, the background of the reproduction was black while the material printed on the original appeared white. Man received a well-filled (geod filled) and essentially streak-free copy.

Ü-elapiel 2

Example 1 was repeated, instead of dea in it material used, which is the liquid pigment colorant mixture which gives negative properties, now one in weaent— borrowed equivalent amount of the following substances used?

An olefin alkylated polyvinylpyrrolidone, where the carbon chain of the olefin has an average length of 2 carbon atoms and 20 $ residual vinylpyrrolidone (Ganex. 220)

An oil-soluble C-alkyl suecinyl derivative of Peritaäthylenimln with 50 or more carbon atoms in the alkyl chain (Cronit 1200)

A thermoplastic polymer of an unsaturated ^ of petroleum derived »hydrocarbons (Piecopal-Hars)

Gilsonite. Natural hydrocarbon

When using such a substance instead of the alkylated one Polymers of the N-vinyl monomer are obtained in all «» cases essentially equivalent results and a # lTR4 © ««. Static negative pigment dye delivers full, clear Negative prints,

BAO ORIGINAL 909883/1513 ^> ~ ^ "

Claims (1)

PAT E riAliSPRÜCHE ι ( 1 .; Liquid, electrostatic negative pigment dye ₉ ^ characterized by the content. a) a carrier liquid, b) a pigment and e) einee polymer which virtue give the i'arbstoff negative properties 2. Pignient dye according to claim 1, characterized in that that the polymer ■ a) alkylated polymers of heterocyclic N-vinyl monomers, wherein the alkyl radical of the polymer contains from 2 to 2,000 carbon atoms, b) natural hydrocarbon polymers ₉ c) thermoplastic polymers of unsaturated hydrocarbons from petroleum cracking or d) oil-soluble C-alkylsuecinyl derivative © of polyethyleneimine, The alkyl group has at least 50 carbon atoms @ on ₉ means" 3rd Piga «ntfÄTbgt © ff Bach claim 2, characterized in that that the pigment is egg " 4 · pigment according to claim 2, characterized in that the polymer is an alkylated polymer of a heterocyclic N-7ynyl-? Ionomers, where the alkyl radical of the polymer Has 2 to 2,000 carbon atoms »- 5. Pignientfarbstoff na _c h to claim 4, characterized in that dasjs the alkyl group of the polymer contains 8 to 42 carbon atoms. 909883 / 1-513 6. Pinion dye according to claim 5> marked thereby ,, that d: is an alkylated polymer an alkylated polymer of a K-vinyl pyrrolidone monomers. ^ Pur GAF Corporation ° New York, NT, TStA, Lawyer