DE2642826B2 - Electrostatographic suspension developer - Google Patents

Description

The invention relates to an electrostatographic suspension developer. It includes a combination r> of components of developers of the first and second kind.

Developers of the first type are e.g. B. from US-PS 69,886 known. Such development systems contain the following components:

a) a carrier liquid in the form of a paraffinic solvent;

see solvent;

b) a film-forming fixative;

c) a dispersant;

d) a tax substance and

e) a fine electroscopic pigment.

Emwickler or toner of the second type are e.g. B. from DE-OS 21 14 773 (un its corresponding US-PS 53 760 and 39 00 412) known. Such development systems contain a carrier liquid as well as a carrier liquid and a control agent, a toner in the form of an amphipathic polymer, d. H. a graft polymer, whose polymeric backbone chain is soluble in the carrier liquid and whose side chains are polymeric and are thermoplastic and will not be solvated by the carrier liquid. These toners have a Particle size between 25 nm and 25 μm. The toner may contain soluble or dispersible dyes or pigments in the developing system or that Amphipathic polymers contain a corresponding chromophoric group chemically bound. The scaffolding chain of the graft polymer can be from * ■>

Polyauryl methacryl / glycidyl methacrylate /
methacrylic acid) or

Polyfisodezylmethacrylat / Glycidylmethacrylat /

methacrylic acid) or
Polyistearyl methacrylate / glycidyl methacrylate /

methacrylic acid) or
Polvilauryl methacrylate / glycidyl methacrylate /

methacrylic acid / chromophore) or
Polyauryl methacrylate / Nl.lSS-tetramethyl-

butyl methacrylamide / glycidyl methacrylate /

methacrylic acid and
the side chains of

Poly (vinyl acetate / N-vinyl-2-pyrrolidone),
Polyvinyl acetate / crotonic acid),
Polvi vinyl acetate / methyl hydrogen maleate),
Polyvinyl acetate or a polymer with

repeating units of methyl

hydrogen maleate

come.

Both toners have drawbacks, those of the second type toners being less serious and in some Cases, especially in the case of office copiers, are of little consequence. However, they limit its application in the production of planographic or offset printing forms and reproductions for microfiches. Flat printing forms with which a large number of printing pieces, e.g. more than 15,000, can be produced, but have the disadvantage that the destruction of the longer operating times to show an electrostatically built-up image. Such planographic or offset printing forms are generally with a zinc oxide-containing layer as a photoconductor and with an aqueous solution of hexacyanoferrate-II or -III applied as wiping water.

If planographic or offset printing forms were produced with a suspension developer of the first type, so noticeable toner deposits were observed even in non-white areas of appreciable size, whereby there is greater intensity on the circumference than in the middle. In the case of electrostatic microfiche reproduction with the use of a dispersion developer of the second type, the boundaries of the image shift somewhat, and it is not possible to make good re-enlargements of such microfiches. Will such However, reproductions for microfiche made with suspension developers of the first kind, so it comes to Difficulty in fixing, which is particularly true of poly-N-vinylcarbazole as a photoconductor. The fixing is generally done with a developer of the first type by heating. However, the image carrier contains In addition to the photoconductor, a thermoplastic material, which is dimensionally unstable with this heating for fixation becomes, which is unsustainable for the application for microfiche.

The object of the invention is now an electrostatographic suspension developer which is advantageous Properties and can be used in common systems; that goes for office copying, however also for injection printing, for reading out cathode ray screen images and for light printing, and in transmission methods such as pressure transmission, vacuum transmission, and electrostatic transmission.

The electrostatographic suspension developer according to the invention is now characterized by Combination of components

a) insulating carrier liquid;

b) amphipathic polymer with dispersing and fixing molecular parts;

c) fixatives and

d) one or more tax substances,

wherein the amphipathic polymer can optionally also contain a chromophoric part of the molecule. Of the The suspension developer may also contain a pigment and / or a dispersant.

The suspension developer of the present invention is prepared by either having a preformed one First type developer and a preformed second type developer by mixing or by one Developer of the second type in the sense of a developer of the first type nor the fixing agent and, if applicable further dispersant added

The suspension developer according to the invention differs from the two known development systems substantial advantage. With it, a very special problem can be solved, namely a kind "Edge effect," d. H. the sharpness of the developed image is improved This edge effect leads to a certain, especially with larger dark pictures optical impression. This impression can be made with a suspension developer near the edges preserved image appear darker; this is apparently related to the reaction of the Optic nerves on the pictures. It is easy to see that this effect on a large area, which is rather gray, It is harder to see that a large black image that is densely black, however, does not occur Has uniform blackness from edge to edge, does not show this phenomenon. The fact remains, however, that the human eye does not perceive it in this way This impression of an image arises when the edge areas are darker than the central areas. Another advantage of the developers according to the invention is the extension of the service life of a planographic printing form, which with the help of the developer according to the invention has been made. If a planographic printing form is produced with a developer of the first type, its Very short lifespan; Parts of the image come off the surface. If, however, an inventive Applied developer, the life of the planographic printing form is much longer, namely at least as long as that of a planographic printing plate made with a developer of the second type; This is essential because the second type developer is much more expensive than the first type developer, so one endeavors will be to apply less of the former. It is this extension of the service life the planographic printing form of printing forms produced with developers according to the invention but not by one expected effect, because already as little amount of developer of the second kind as 1 part to 20 parts Developer of the first type already leads to a planographic printing form whose service life corresponds to that of with 100% developer of the second type.

Another surprising result can be achieved with the developer according to the invention in the context of electrostatographic production of microfiche. If developers of the first type are used for this, then for the fixation of the microfiche a heating required, namely to a temperature so high that so that the dimensional stability of the base is lost and consequently the copy becomes blotchy. This problem does not occur with a developer of the second kind. On the other hand, there is another problem namely insufficient resolution at the edges of the image. In other words, the edges are not sharp and a little wavy. If these microfiches are now enlarged back to their original size, so this waviness, which because of the thin layer thickness of the microfiche, does not play a role ί of quality-impairing influence.

In contrast, these two problems do not arise with the developers according to the invention.

The developer according to the invention shows yet another advantage in the context of the production of

ίο flat printing forms. Will planographic printing forms made with have been produced by one or the other known developer, have been exposed to an etching agent for too long, z. B. overnight, the hydrophobic image areas become hydrophilic. Is now using an oily printing ink

i "> printed, you get none or a very bad one Image. Surprisingly, this phenomenon does not occur with the developers according to the invention.

From the above it follows that the properties of the suspension developer according to the invention are not the

2 »are the sum of the effects of the two known developers used, but that there must be a synergistic effect.

Suspension developers without dyes or pigments are also used for the production of planographic printing plates

2 ^r ) can be used, but a coloring component is often used in this case too

The insulating carrier liquid should have an electrical resistance of at least about 10 ⁹ Ω · cm. It can be polar or non-polar. Preferred

) »One or more hydrocarbons are used for this purpose) as solvents, in particular "petroleum fractions" from distillation or catalytic cracking as well Polymers of aliphatic monomers obtained synthetically or by distillation or cracking

r> have been received. The petroleum fractions are particularly useful because they evaporate quickly and thus allow quick drying, e.g. B. in 2 s; they are not poisonous and have little or no odor. They will be soluble together with

■ "> film-forming fixatives applied, so volatilize they completely and leave the film tack-free, so that no long drying after the image build-up is necessary *, and the picture appears dry shortly after assembly. They don't lead to one

■ · "> Discharge the electrostatic charge before the Pigment is deposited so that any desired contrast can be obtained, and in addition, they are inexpensive.

The petroleum fraction, d. H. a paraffinic solvent, an evaporation rate of at least

'">" least that of kerosene, but be slower than Hexane. It should also have a lower Kauri-Butanol number, i.e. <35, preferably between 26 and 35. This low KB number reduces the likelihood of that the petroleum fraction is the binder of the

> ^r > attacks the photoconductive layer or the paper size on which the photoconductive layer is located; it should be essentially free of aromatics, ie contain ί 2 wt .-%, since these can easily attack the binders of the photoconductive layer. The electric

W) see resistance must be at least about 10 ⁹ Ω · cm and the dielectric constant <3.5. The flash point in the closed cup according to Tagliabue should be a 38 ° C, preferably 49 to 66 ° C. The carrier liquid should have a low viscosity, e.g. B. 5

^h > to 250 mg / cm · s at room temperature.

Various commercial products can be used as the petroleum fraction for the carrier liquid, such as those in the DE-OS 21 14 773 are described as

5 Start of boiling 26 42 826 6th Aniline point Spec.
Weight ^C. End of boiling Flash point K. B. number C. 15 ( 173 C. C. 84 0.7563 Shell Sol 71 177 203 49.5 26.5 84 0.7571 Isopar H 176 187 50.5 26.9 85 0.7587 Isopar K 188 195 52 26.5 86 0.7674 Isopar L 178 206 63 - 84.8 0.7608 Amsco OMS 190 147 51.5 27.0 64 0.8108 Amsco 460
Solvent Insecticide 190 242 65.5 34.5 80 0.7711 base 193 66.5 26.5

There are already suspension developers based on water known (US-PS 34 25 829). Other In addition to petroleum fractions and water, suitable carrier liquids are alcohols, e.g. B. those with 1 to 6 C atoms (ethylene glycol), ether (ethyl isobutyl ether, methyl isopropyl ether, Ci- d-alkyl monoether of Ethylene glycol and dioxane), ketones (acetone, methyl ethyl ketone, methyl isopropyl ketone, ethyl isobutyl ketone), Esters (ethyl acetate, amyl acetate, butyl propionate and the acetates of mono-Ci-O-alkyl ethers of ethylene glycol) as well as halogenated hydrocarbons (chloroform, ethylene dichloride, monochlorobenzene and fluorinated Hydrocarbons).

The suspension developer of the second type is in principle a "latex developer" because it consists of a continuous liquid phase, in which there is an amphipathic polymer as a disperse phase. An "amphipathic" Substance has an affinity for two different phases, one organic and one aqueous, so that the one polymeric unit of the amphipathic polymer is dissolved or from the phase is solvated (carrier liquid) and the other is not solvated by this, i.e. H. it forms a disperse Phase; As mentioned above, the amphipathic polymer combines the fixative and the Dispersant and optionally also a chromophoric unit. This complex molecule causes a narrow grain size distribution of the unsolvated Particles that ultimately result from the electrostatic development of the image on the recording material to be deposited. It is desirable that 2, preferably 1 grain fraction (s) of the unsolvated Particles are or is present in the suspension developer ("monodisperse").

The selection and in particular the production of the amphipathic molecules is in DE-OS 21 14 773 described in detail. Assuming the carrier liquid is a petroleum fraction, it becomes a framework polymer chosen which is solvarized by the petroleum fraction, such as naturally occurring high polymers, e.g. B. Raw rubber, refined oxidized linseed oil, degraded rubber, as well as synthetic polymers such as alkyd resins, Polyisobutylene, polybutadiene, polyisoprene, polyisobornyl methacrylate, acrylic acid polymers of long chain Esters of acrylic or methacrylic acid, such as stcaryl, lauryl, isodecyl, octyl, 2-ethylhexyl and llexyl; Butyesters of acrylic or methacrylic acid, polymeric vinyl esters of long-chain acids, such as vinykicarai. Vinyl laurate, vinyl palmitate and vinyl myristate. polymeric vinyl alcohol ethers including polyvinyl ethers. Polyvinyl isopropyl ether, Polyvinyl isobutyl ether and polyvinyl n-butyl ether.

From the above examples it can be seen that the polymers have a structure similar to that of the carrier liquid have, d. H. the polymers and the carrier liquid have a similar degree of polarity. As far as this Similar polarity is given, mixed polymers, such as block and graft copolymers, block and Graft polymers, tetrapolymers, or multiple monomer / polymers that are generally backbone have to be applied as

Lauryl methacrylate, tylacrylate,

t-octyl methacrylate butyl methacrylate,

Lauryl methacrylic glycidyl methacrylate,

2-ethylhexyl acrylate / acrylic acid,

Isodecyl methacrylate / diethylaminoethyl meth-

acrylate and
Vinyl toluene / butadiene;
Terpolymers, such as

Lauryl methacrylate / isodecyl methacrylate /

Methyl methacrylate,
Stearyl methacrylate / cyclohexyl acrylate /

Methacrylic acid,

Octyl acrylate / crotonic acid / dodecyl methacrylate,
Glycidyl methacrylate / stearyl methacrylal /

Lauryl methacrylate,
Lauryl methacrylate / octyl methacrylate /

Glycidyl methacrylate and
Isodecyl methacrylate / stearyl methacrylate /

Acrylic acid and
Tetrapolymers, e.g. B.

N-vinyl pyrrolidone / butyl acrylic / lauryl

methacrylate / stearyl methacrylate and
Acrylic acid / stearyl acrylate / methyl methacrylate /

Isodecyl acrylate.

The framework structure can optionally be formed with or without chains in a different solvent when it is ultimately used as a carrier liquid, and is then optionally extracted therefrom.

There is no restriction on the monomers for the preparation of the polymers Components. For example, the following framework polymers are suitable for a system based on white spirit:

(a) Homopolymer of O - Cu-Hster of acrylic or methacrylic acid (Polyhxyl-, Polyisodecyl-, Polylauryl-, Polytetradecyl- and Polystcarylmethacrylal or -acrylat with molecular weight /. between IO ¹

to \ O ^b , preferably at least 10 ⁴ );

(b) Copolymers of homopolymers listed under (a) or with methyl, ethyl, isopropyl and Propyl esters of acrylic or methacrylic acid with the proviso that the unsolvated and the> solvated monomers are kept in appropriate proportions to ultimately produce a To ensure solvation of the copolymer in white spirit;

(c) mixed polymers of the above methacrylic and acrylic acid reester with monomers containing other functional groups, such as acrylic, methacrylic, croton, Maleic, atropic, fumaric, itaconic, citraconic acid, acrylic, methacrylic or maleic anhydride, acryloyl chloride, Methacryloyl chloride, acrylic or methacrylonitrile, acrylic or methacrylamides and their derivatives, hydroxyethyl methacrylate or acrylate, hydroxypropyl methacrylate or acrylate, Dimethylaminomethyl methacrylate or acrylate, dimethylaminomethyl methacrylate or acrylate, Diethylaminomethyl methacrylate or acrylate, diethylaminoethyl methacrylate or acrylate, t-butylaminoethyl methacrylate or acrylate, allyl alcohol and its derivatives, cinnamic acid and its derivatives, styrene and its derivatives, methallyl alcohol and its derivatives, propargyl alcohol and its derivatives, indene and its derivatives. Norbornene and its derivatives, vinyl ethers. Vinyl ester ur.J other vinyl derivatives, glycidyl methacrylate and acrylate. Mono- and dimethyl maleate, in mono- and diethyl maleate, mono-n-butyl maleal, Monobenzyl maleate. Mono-2-ethylhexyl or Mono-n-octyl maleate and finally mono- or dimethyl fumarate and mono- and dietary fumarate:

(d) homopolymeric olefins (butadiene. isoprene, isobuty- π len) and copolymers thereof with monomers listed under (b):

(c) terpolymers and tetrapolymers thereof;
(f) polycarbonates. Polyamides. Polyurethanes and polyepoxides. ■>"

Polymer chains of different polarity than those of the are now attached to the selected framework polymer Carrier liquid attached by graft or block polymerization. Suitable monomers are, for. B. -r. Vinyl acetate. Methyl, ethyl. Propyl, isopropyl. Hydroxyethyl, Hydroxypropyl acrylate or methacrylate. Acrylic or methacrylonitrile. Acrylic or methacrylamide. Acrylic or methacrylic acid or anhydride, monomethyl, Monoethyl. Monobutyl. Monobenzyl, mono- "> i> 2-hexyl-. Mono-n-octyl maleate. Monomethyl-. Monoethyl fumarate. Styrene. Vinyl toluene, maleic acid or anhydride and crotonic acid or anhydride. Mixed polymers, Terpolymers and polymers of greater complexity with appropriate polarity are also suitable. ~ >>

If a graft polymerization is used to produce the amphipathic polymer and there are no ethylenic or other unsaturated bonds available for grafting in the framework polymer, then polymeric chains can be grafted onto the saturated framework polymer by activation, e.g. B. with the help of an initiator or by hanging parts containing ethylenic double bonds or unsaturation are formed, which serve as starting points for the activation of the initiator for an in situ graft polymerization; z. B. a mixed polymer of stearyl methacrylate-glacidyl methacrylate (27 : 1 monomer ratio with a molecular weight of e.g. 10,000-150,000) is reacted with methacrylic acid in the presence of a polymerization inhibitor to ethylenically unsaturated bonds for subsequent activation by esterification and in situ polymerization or To form interpolymerization.

The disperse phase, which is essentially the unsolvated polymeric part of the amphipathic Polymers, optionally also includes ungrafted, unsolvated polymer particles. Even though If these are not particularly desirable because of their unsolvated form, they are permissible and In addition, they can behave electrophoretically in such a way that they are electrostatically different Charged areas can be selectively attracted so that an electrostatographic reproduction can be achieved can be done.

Except for the production of planographic or offset printing forms, the amphipathic polymer still contain a chromophoric part of the molecule, or the developer is given the one for the coloring required pigments or dyes.

It is believed that the dyes or pigment particles are attached to the unsolvated moiety of the amphipathic polymer can only be held by second order forces.

Another possibility is. To chemically bond pigments or dyes to the amphipathic polymer. z. B. to the framework or to the chains before the polymerisation of the chains.

The dyes can be on the amphipathic polymer, especially on the unsolvated part of the molecule, also be held by adsorption; however, the dyes can also be used with the amphipathic Polymers are chemically reacted either after their formation or with the skeleton or the chains.

Examples of this are disperse dyes for polyester and mixed polymers of acrylonitrile and vinyl chloride, such as Latyl Orange 3R (C I. Disperse Orange 26). Calcosperse Yellow GL (C.I. Disperse Yellow 57), Calcosperse Blue B (C.I. Disperse Blue 77), Foron Blue BGL (C.I. Disperse Blue 73); Latyl Brown MS (C. I. Disperse Brown 2) and Laryl Violet BN (C. I. Violet 27) or basic dyes for polyacrylates such as Sevron Blue BGL (C.I. Basic Violet 15). Deorlene Brilliant Red 3B (C. I. Basic Red 26), Caicozine Acrylic Blue G (C. 1. Basic Blue 38), Astrazon yellow-brown GGL (C. I. Basic Orange 30) and Astrazon red 5 BL (C. I. Basic Red 24).

The unsolvated part of the molecule preferably contains of the amphipathic polymer reactive groups with the reactive groups of a chromophore can be implemented, e.g. B. basic groups for reaction with acidic dyes. A terpolymer from Acrylonitrile. 2-methyl-5-vinylpyridine and vinyl acetate can be reaction colored with acidic groups containing dyes, such as Pontacryl Brilliant Blue A (C I. Acid Blue 7), Calcocid Brilliant Blue FFR (C I. Acid Blue 104), Femazo Brown N (C I. Acid Brown 14), Crocein Scarlet N (C I. Red 73), Oxanal Yellow I (C I. Acid Yellow 63), and Benzyl Black 4BN (C I. Black 26A).

Another possibility for producing a trifunctional amphipathic polymer exists in reacting a disperse copolymer containing acid groups with basic dyes, e.g. B. a Mixed polymer of vinyl acetate and maleic acid with dyes containing basic groups such as magenta (C I. Solvent Red 41, C L No. 42510B), Crystal Violet (C L Solvent Violet 9. C I. No. 42555Bl Bismarck Brown

2b 42 826

IO

(C.I. Solvent Brown 12, C.I. No. 21010B), Victoria Blue BA (C.!. Solvent Blue4, C. I. No.44045B), Victoria Blue R (C.I. Solvent Blue 6, C.I. No. 44040R), Victoria Blue 4R (C.I. Solvent Blue 2, C.I. No. 43563B), Copying Black SK (C. I. No. 11975), Janus Green B (C. I. No. 11050), Auramine O (C. I. Solvent Yellow 34, C. I. No. 41000B), Victoria Green (C.I. Solvent Green 1, C.I. No. 42000B) and Rhodamine (C.I. Solvent Red 49, Cl. No. 45170B).

Another method of making trifunctional ones Amphipathic polymer is the chemical reaction of a mixed polymer, which is electron accepting Contains groups, such as maleic · or crotonic acid (Lewis acid), those with dye precursors can react. An example of this is a terpolymer of maleic anhydride, vinyl acetate and Styrene on the solvated framework, reacted with a Dye precursors such as bis (p-dimethylaminophenyl) benzotriazyl methane (deep blue).

For the rest, reference is made to the detailed explanations on the production of chromophoric molecular parts Referred to amphipathic polymers in DE-OS 21 14 773.

The fixing agent is a film-forming substance that holds the developed image on the paper support. It is solid at room temperature and soluble or dispersible in the carrier liquid and provides a tack-free, tough and cohesive film so that the developed image does not smear or fall off, and is said to adhere well to the photoconductive layer. An excellent fixing agent is e.g. B. a thermoplastic acidic rosin that has been polymerized and hydrogenated (softening point from 85 to 93 ⁰ C - according to the Hercules drop method -, an acid number from 145 to 162, a density at 20 ⁰ C of 1.065, a saponification number from 155 to 165 , a hydrogenation level about 90% and an average molecular weight of 360, has about 20% of the resin acids are polymerized) or a thermoplastic petroleum hydrocarbon resin produced by polymerization of 30 to 90Gew .-% of unsaturated hydrocarbon fractions having boiling points between 125 and 25O ⁰ C, density 0 , 9 to 0.95 to 15.6 ° C in the form of 5 to 30% cyclodine dimers (such as dicyclopentadiene, dimethylcyclopentadiene, codimer of cyclopentadiene and methylcyclopentadiene), 5 to 20% indene, 5 to 25% vinyl toluene, 0 to 10 % Styrene, the remainder non-polymerizable paraffins, naphthenes and aromatics with at least 8 carbon atoms with a boiling range of z. B. 125 to 250 ⁰ C, whose properties are as follows: softening point (ring and ball) 100 ° C, average molecular weight (osmotically determined) 800, weight ratio C / H (elemental analysis) 10.5, density at 25 ° C 1, 09, refractive index at 25 ° C 1.602, iodine number 65 and acid number <1.

Other useful fixatives are:

resin Acid number Noise softening Point
C. Glycerine ester from modifi 8th 168 decorated rosin Pentaerythriester of 12th 111 rosin Pentaerythritol esters of poly- 14th 135 merized rosin Modified pentaerythritol 14th 135 esters of rosin

HDTV Acid c / .iihl 1 rueidumiiv punkl
( Pentaerythritol ester of 13th 104 hydrogenated rosin Pentaerythritol ester of 14th 192 resin acids dine Modified pentaerythritol 14th 159 esters of rosin Pentaerythritol ester of 15th 172 dimeric resin acids Glycerine esters of poly- 6th 112 rrierized rosin. Hydrogenated rosin 165 76 Pentaerythritol esters of modes <1 180-190 fized rosin (Mercury method) Fully Held GIv- 9 82

cerin ester of rosin

Inside softened 30

Pentaerythritol ester of

rosin

Dimer resin acids 143

Vinyl toluene / acrylate mixed polymer
Vinyl toluene / n-butyl methacrylate / stearyl methacrylate
(U.S. Patent 3,378,513)

6.1

101

152

47

115 R&K

All of the above fixatives, with the exception of the last two, are solvatable in the carrier liquid and the last two dispersible.

The control substance (s) must be soluble or dispersible in the carrier liquid and effect or improve the charging of the fine pigment particles. Examples are di-2-ethylenehexyl sodium sulfosuccinic acid, ditridecyl sodium sulfosuccinic acid, the aluminum, chromium, zinc and calcium salts of 3,5-dialkylsicylic acid, in which the alkyl group is propyl, isopropyl, butyl, isobutyl, tert-butyl, Amyl, isoamyl and other alkyl groups up to C] ₈ -, or the salts of dialkyl-γ-resorcinic acid, isopropylamine salt of dodecylbenzenesulphonic acid, aluminum, vanadium or tin resinates (the metal resinates are prepared by adding a solution of the metal sulphates to a solution of sodium resinate ), Cobalt, iron, lithium, tin and maganoctoates, a partially imidized polyamine with oil-soluble polyisobutylene chains and free secondary amines (density at 25 ° C API 223 or 0.92 g / cm ³ , flash point - Cleveland open cup - 120 ⁰ C, viscosity at 99 ° C 400 SSU, color according to ASTM D-1500 L55D, nitrogen content 2%, alkalinity - SM-205-15-43-); Soybean lecithin, aluminum salt of a 50:50 mixture of the mono- and di-2-ethylhexyl esters of phosphoric acid, zinc, lead, copper-cadmium, aluminum and iron stearates, zinc and aluminum palmitates, aluminum oleate, copper, manganese and cobalt - and lead linoleate, manganese linol resinate, (1- [2-hydroxylethyl] -2- [mixed pentadecyl and heptadecyl] -2-imidazoline, linol resinates are metal soaps of tall oil.

The dispersant is solvatable or dispersible in the carrier liquid, the former being preferred will. The role of the dispersant is to keep the pigment particles in the non-polar solvent system to keep dispersed. The dispersant must be compatible with the fixative; It is also expedient if the dispersant supports the direction of charge of the pigment particles.

Examples of solid dispersants are polymethacrylate or an oil additive in the form of a terpolymer from a mixture of 50 parts by weight of octadecenyl methacrylate, 10 parts by weight of diethylaminoethyl methacrylate and 40 parts by weight of styrene having an average molecular weight of about 50,000.

Further useful dispersants can be found in US-PS 30 48 544 or 36 69 886, such as alkyl methacrylate maleic anhydride polymer, Maleimide polymer, polymers of the reaction products of alkyl methacrylate, Polyethylene glycol methacrylate and maleic anhydride and polymers from a reaction product of alkyl methacrylate, polyethylene glycol methacrylate and the imine of maleic anhydride and tetraethylene pentamine, polyglycol substituted polyesters (U.S. Patent 3,083,187) and polyglycol substituted polyamides (U.S. Patent 3,083,188).

A pigment usually used for suspension developers is suitable as an additionally used pigment. These are generally fine powders that are opaque in bulk and have a corresponding electrostatic charge be able to accept. They are insoluble in the carrier liquid, like powders of metals (aluminum), Metal oxides (magnetic iron oxides), metal salts (cadmium selenide, lead iodide, lead chromate), cyan blue GT 55-3295 (C. I. 71160 - US-PS 24 86 351), Crocein purple NEX (C. 1.27290), fiber black VF (C. 1.30235), Nigrosine Base 424 (C. I. 50415B), Azosol Fast Quellow GRA (C. I. 13900A), Benzofix Black CW-CF (C. I. 35435), Diamin Black CAP Ex (C. I. 30235), Diamond Black EAN Hi (C. 1.15710), Diamond Black PBBA Ex (C. I. 16505), direct jet black EA Ex CF (C. 1. 30235), Hansa yellow G (C. 1.11680), indanthr black BBK (C. ! 59850), Indocarbon CLGS (C. I. 53295), Katigen deep black NND Hi (C. I. 53190), Palatine Fast Black WANA (C. 1.15711), sulfoncyanine black BA-CF (C. I. 26370), Zambezi Black VD Ex (C. I. 30015), Spirit Nigrosine SSB (C. I. 50415), Methyl Violett T (C. I. 42535), Rubanox Red CP-1495 (C.I. 15630), Victoria Blue molybdates (C. 1.425Γ5).

Examples of suspension developers which can be used according to the invention based on toners of the first type are given in US Pat. No. 3,669,886, in particular an example 2,3 and 5.

The proportions of the various components of the suspension developer of the first and second kind can vary over a wide range, so that an indication of the quantity or a quantity ratio of the components These proportions appear largely insignificant for the suspension developer according to the invention vary with the type of copier, the climate, the machine speed, the type of Paper and the experience of the personnel operating the machine, to name just a few factors. Even in the case of the coloring material there can be large variations with the desired intensity of dye or Pigment or the image occur. Generally speaking, it can be said that the proportions of individual components should be higher or lower together, although this is not a strict one Relationship must be the case. With all of these factors in mind and as a rough guide to making the suspension developer according to the invention should have the following minimum and maximum proportions per liter -, are valid:

Fixing agent in the developer of the first type 0.05 to 5 g;

Dispersant in the developer of the first type 0.025 to

5 g;
in pigment in the developer of the first type 0.025 g to 5 g;

Control substance in the developer of the first type 0.005 g to 0.5 g.

Amphipathic polymer with a chromophoric part of the molecule in the developer of the second type - chemical bound or adsorbed - 0.03-30 g.

Amphpathetic polymer without a chromophoric moiety in the developer of the second type about 0.03 to 30 g;

unbound coloring agent in developer: ii second type 0.03 to 30 g;

Control substance in the developer of the second type 1 χ 10 ^b to 10 g;

Remainder in each case carrier liquid.

Examples of developers of the second type are contained in DE-OS 21 14 773 (see Examples 1 to 29). These second type suspension developers contain only a single color component. If necessary, can but also several coloring agents, preferably

jo two or more, applied to through their Working together to achieve the desired depth of color, such as brown-black, blue-black or purple-black.

The second type of suspension developer can also be used

To produce r> in another way, namely by the amphipathic polymer is made in a solvent in which it is completely solvated, whereupon a further solvent is added, in which one type of the polymeric molecular units

4 "is not solvated. This second solvent must however, it can be mixed with the first one; then you can use all or part of the first solvent remove. An example of this is the anionic polymerization of a block polymer of polyisoprene

4 · -) polystyrene and polyisoprene. For this, see example 30 the DE-OS 21 14 773 referenced.

One of the following two can be used for preparing the dispersion developer of the present invention Applying procedures: one is that

ίο you just use the previously prepared suspension developer first and second type mixes in proportions of 0.5 to 99.5% of one and 99.5 to 0.5% of the other developer. The other method is to use the various ingredients to be introduced into the carrier liquid.

A carrier liquid is preferably used for the suspension developer according to the invention which is suitable for both the first and second type developer, although not absolutely

(> o it is necessary, however, to have two carrier liquids applied so these should be compatible. Preferably - but not necessarily - be for the two suspension developers to be mixed use the same control substances The likelihood that the two developers are incompatible is reduced and the measures taken simplified The suspension developer according to the invention can therefore be produced directly by mixing

and the two developers do not have to be separated first make and then mix. Some taxes show a synergistic effect when used in combination. There are tax substances in the Carrier liquid are solvated. The synergism is not necessarily desirable, more so The influence of the control substance is shown in the curve of density versus concentration of the control substance. Because of of synergism, however, the amounts of control substance can be reduced. However, these quantities must can be determined in the usual simple manner for each new combination of tax substances. The amounts of Control substance also depend on the concentration and type of pigments and color components. In the following Examples are several control substances for a suspension developer according to the invention, taking into account the synergistic effect.

It must also be taken into account that the amphipathic polymer already has a dispersant effect and therefore little or no dispersant needs to be added.

The active components of the developer according to the invention in the carrier liquid can be used within so further limits fluctuate, so that the specification of certain proportions or areas does not make sense appears. The following quantities are to be considered as guide values:

Fixing agent - not bound to the dispersing agent - 0.0025 to 5 g / l.

Dispersant - not bound to the fixative - 0.5 to 5 g / l.

Dispersant - not bound to the fixative - 0.5 to 5 g / l.

Coloring component 0 to 1 g / l.

Control substance 1 χ 10 - ^b to 10 g / l.

Amphipathic polymer 0.05 to 30 g / l.

example 1

4.5 g suspension developer concentrate of the first type and 0.5 g of suspension developer concentrate of the second type Art were diluted with a petroleum fraction as a solvent.

The developer of the first type contained 25 grams of thermoplastic petroleum hydrocarbon resin having aromatic or mainly cyclic moieties - consisting of 30 to 90 wt .-% of unsaturated hydrocarbon fraction with boiling point between 125 and 25O ⁰ C, density 0.9 to 0.95 at 15.6 ° C in the form of 5 to 30% cyclodiene dimers such as dicyclopentadiene, dimethylcyclopentadiene, codimer of cyclopentadiene and methylcyclopentadiene, 5 to 20% indene, 5 to 25% vinyl toluene and 0 to 10% styrene, the remainder non-polymerizable paraffins naphthenes and aromatics with at least 8 carbon atoms with a boiling range of, for example 125 to 250 ⁰ C, the properties of which are as follows: softening point (ring / ball) 100 ⁰ C, average molecular weight (osmotically determined) 800, weight ratio C / H 10, 5, density at 25 ° C 1.09, refractive index at 25 ° C 1.602, iodine number 65, acid number <1-20 g lubricating oil additive, 10 g polymerized castor oil, 15 g carbon black and black dye, 9 g furnace black ~ 33 nm + chrome green, 100 g petroleum fraction as a solvent and 03 g cobalt octoate as a 12% solution in mineral oil.

The second type of developer was obtained as follows:

In a 500 cm ³ reactor equipped with stirrer, thermometer, temperature controller, reflux condenser and cooling coils was added 40 grams of lubricating oil additive, 284 g of petroleum fraction and 2.2 g of benzoyl peroxide (99%) with vigorous stirring for 2 h at 8O ⁰ C maintained, then a mixture of 1 g Crotonic acid and 190 g of vinyl acetate were added all at once, whereupon the reaction mass turned dark brown. Then the temperature was brought back to 80 ° C. Azobisisobutyronitrile was added in portions of 0.5 g at intervals of 10 minutes up to a total of 4.6 g (3 hours 40 minutes) and the reaction mass was then kept at 8012.degree. C. for 2 hours. A white latex with a solids content of 35.7% and a particle size of <74 μm was obtained.

100 g of this latex was placed in a three-necked flask of 50 cm ' with a stirrer, reflux condenser and thermometer and added Victoria Blau Base BA (C. 1.44045B) added, added. The temperature rose to 80 ± 5 ° C. where it was held for 2 hours. The blue latex was cooled and passed through a sieve - mesh size 74 μm - filtered to remove the remaining dyes. 2.5 g of a were then added to the colored latex 1% by weight solution of aluminum S.S-diisopropyl salicylate added in a petroleum fraction to obtain a concentrate.

This developer according to the invention gave dense, black copies with no background coloration.

Example 1 was modified in that 0.5 g of suspension developer concentrate of the first type and 4.5 g of suspension developer concentrate of the second type ^{were diluted with 2000 cm 1 of} petroleum fraction. Here too, dense blue-black copies were obtained.

Example 2

A suspension developer for the production of planographic printing plates was obtained by mixing 8 g of the concentrate of the developer of the second type with 0.04 g of the concentrate of the developer of the first type and diluting it with 2000 cm > petroleum fraction.

The first type of developer consisted of 25 g of hydrogenated rosin, 20 g of oil additive in the form of a Terpolymers, 10 g of polymerized castor oil, 15 g of carbon black and black dye, 9 g furnace black ~ 33 nm + chrome green, 100 g petroleum fraction as solvent and 5 drops of aluminum resinate as a 10% solution in the solvent.

The developer of the second type was produced as follows: In a 50 cm ^ reactor with a stirrer. The thermometer and reflux condenser were 360 g of petroleum fraction, 190 g of vinyl acetate, 30 g of an ester. 10 g of crotonic acid and 4 g of azo-bisisobutyronitrile are kept at 85 ± 2 ° C. for 4 hours and then 2 g of azo-bisisobutyronitrile are added and the mixture is polymerized again for 4 hours at the same temperature. The ester was prepared by in a 1-1 reaction flask equipped with stirrer, thermometer and reflux condenser, 400 g of petroleum ether was maintained (boiling range 90 to 120 ⁰ C) under atmospheric pressure at moderate refluxing boiling. A solution of 194 g of lauryl methacrylate, 6 g of glycidyl methacrylate and 3 g of benzoyl peroxide paste (60% by weight in dioctyl phthalate) was added dropwise over a period of 3 hours. After a further 40 minutes at refluxing, 0.05 g of lauryldimethylamine were added and the mixture was kept at the boil for a further 1 hour. Then 0.1 g of hydroquinone and 3 g of methacrylic acid were introduced and kept at refluxing under a nitrogen purge until about 25% of the glycidyl groups had esterified. This took about 16 hours.

100 g of this white latex were in a

500 cm ³ round bottom flask with stirrer, reflux condenser and thermometer with 1.2 g Victoria Green (C I. 42000B), 2.4 g Bismarck Brown (C I. 2101 OB) and 03 g Rhodamine Base (C 1.45170B) 2 heated to 80 ± 5 ° C h. The black latex was filtered - mesh size 74 μm - and 5 cm ^{3 of} aluminum resin solution (10% by weight) in solvent were added.

Excellent results were obtained with this developer in office offset machines.

Example 3

A suspension developer for the production of microfiche was obtained by mixing 4 g each of concentrate of the developer of the first and second type according to Example 2 and diluting with 2000 cm ^{3 of} petroleum fraction.

Example 4

0.04 g concentrate of the developer of the first type and 8 g of concentrate of the developer of the second type were mixed with 2 l Diluted solvent.

The first type of developer contained 25 grams of hydrogenated rosin. 20 g of oil additive in the form of a Terpolymers, 10 g of polymerized castor oil. 20 g furnace soot - 33 nm + chrome green, 4 g "Cyan Blue GT" (Cl. 71 160), 1 g of aluminum stearate and 100 g of petroleum fraction.

The second type of developer became as follows manufactured:

A mixture of 180 g of petroleum fraction, 100 g of vinyl acetate, 15 g of a solution and 2 g of azo-bisisobutyronitrile were placed in a 500 cm ³ flask with a thermometer, stirrer. The reflux condenser and cooling coil were stirred at 86 ± 2 ° C. for 4 h; The solution was obtained as follows: 2.4 kg of petroleum fraction were heated to 110 ± TC and 1.0357 kg of isodecyl methacrylate, 36 g of glycidyl methacrylate and 18 g of a 50 mm were placed in a 5 l glass flask equipped with heating equipment, stirrer, thermometer, nitrogen passageway and reflux condenser % by weight benzoyl peroxide paste in dioctyl phthalate was added dropwise over the course of 3 h at a constant rate. After the addition had ended, the reaction mass was held at the reaction temperature for a further 30 minutes and then 3 g of lauryldimethylamine were added and left at the reaction temperature for a further 1 hour. 0.6 g of hydroquinone were introduced, nitrogen was passed through during the esterification, then 18 g of methacrylic acid were added and the reaction temperature was maintained until 25% of the glycidyl rings were esterified, which took about 8 hours.

^{5 cm 3 of} a 1% solution of aluminum 33-diisopropyl isalicylate were added to the petroleum fraction to 100 g of this latex with a solids content of 33%.

This developer was ideally suited for forms of revenge printing.

Example 5

100 g of dimeric resin acids, 50 g of vinyl toluene / acrylate copolymer, 60 g of carbon black and black dye and 500 g of solvent were mixed in a ball mill at 37 ° C. for 23 hours, then a further 100 g of solvent were added and the mixture was mixed for a further hour at the same temperature. 60 g of latex in the Si ine of Example 4 and 0.75 g of aluminum stearate were added to 145 g of the above mixture and mixed in a ball mill at 37 ° C. for 18 hours. 5 g of this concentrate according to the invention were then ^{diluted with 2000 cm J} solvent.

With this developer, dense black copies with no background coloration were obtained.

It is not necessary to mix the ingredients in the ball mill at an elevated temperature, instead, mixing by hand or by machine at room temperature is generally sufficient.

Example 6

ίο 20 g of dimeric resin acid, 10 g of vinyl toluene / acrylate copolymer, 8 g of carbon black, 120 g of solvent, Ig aluminum stearate and 30 g of latex in the sense of Example 4 were mixed in the ball mill at 37 ° C for 18 h. 5 g of this concentrate were in 2000 cm ^{3 of} solvent

π dispersed.

Dense black copies with no background coloration were obtained.

Example 7

m 20 g dimer resin acid, 10 g of copolymer from Example 6,15 g of carbon black, 120 g of solvent, 2 g of oil, 1 g Aiuminiumstearat and 30 g latex as defined in Example 4 was mixed "18 h at 37 ° C in the ball mill and 5 g of this concentrate with 2000 cm ³

2) Diluted solvent.

The developer made tight black copies with no background staining.

_vi Example 8

25 grams of hydrogenated rosin. 80 g of latex in the sense of the example 2.12 g of carbon black in the sense of the example 5.3 g of "Spirit Nigrosine SSB" (C I. 50415). 6 g carbon black ~ 25 nm, Ig aluminum stearate, 20 g oil additive in the form of a terpolyr. Mers and 50 g petroleum fraction were mixed for 40 h at room temperature in a ball mill and 4 g of this concentrate were ^{diluted with 2000 cm 3} petroleum fraction.

This gave densely black, background-free 4i) copies.

Example 9

25 g hydrogenated rosin, 6 g latex in the sense of 4 ". Example 2, 12 g carbon black in the sense of example 5, 2 g dye in the sense of the example 8.6 g carbon black ~ 25 nm, 2 g aluminum stearate. 20 g oil additive in In the form of a terpolymer and 50 g of petroleum fraction were mixed for 40 hours at room temperature in a ball mill and 6 g of this concentrate were ^{diluted with 2000 cm J} petroleum fraction.

Dense black background-free copies were obtained from this developer.

Example 10

25 grams of hydrogenated rosin. 80 g latex, colored with Victoria Blue BA Base (4%). 8 g of carbon black from Example 5, 2 g of "Spirit Nigrosine SSB", 4 g of furnace black ~ 33 nm + w) chrome green, 10 g of oil additive and 10 g of polymerized castor oil were mixed in a ball mill at 37 ° C. for 39 h and then 0.75 g aluminum stearate, 10 g polymerized castor oil and 50 g solvent were added and mixed for a further hour, after which 3 g of this concentrate were diluted ^{with 2000 cm 3 of solvent.}

The latex was made as follows:

In a 500 cm ³ reactor with a stirrer, thermometer

130 128/126

and reflux killer were 360 g of solvent, 185 g Vinyl acetate and 30 g of a solution as well as 15 g of methyl hydrogen maleate and 4 g of azo-bisisobutyronitrile for 4 h Maintained 85 ± 2 ° C. Then a further 2 g of azo-bisisobutyronitrile were added and the polymerization started Reaction temperature felt for a further 4 h. Particle size of the latex 0.04-0.2 µm.

The solution corresponded to that of Example 2, but 52% of the glycidyl groups were esterified.

With this developer, densely black background-free copies were obtained.

Example 11

950 g colored latex according to Example 10, 20 g hydrogenated rosin, 8 g carbon black and black dye, 2 g "Spirit Nigrosine SSB", 4 g carbon black ~ 25 nm, 8 g oil additive and 8 g polymerized castor oil were heated at 37 ° C Mixed in the ball mill for 40 h and mixed with 25 g of this concentrate with 2000 cm ^{3 of} solvent and 10 drops of a 1% solution of the aluminum salt of 3,5-diisopropylsalicylic acid in the solvent

Excellent planographic printing forms were obtained.

Claims (5)

Claims: IO 1. Elektrostatographijcher suspension developer characterized by the combination of Components a) insulating carrier liquid, b) amphipathic polymer with dispersing and fixing molecular parts, c) fixatives and d) one or more tax substances. 2. Suspension developer according to claim 1, characterized in that the amphipathic Polymer additionally contains a chromophoric part of the molecule. 3. Suspension developer according to claim 1 or 2, characterized in that it also has a Contains pigment 4. Suspension developer according to one of claims 1 to 3, that it also contains a dispersant contains. 5. suspension developer according to one of claims 1 to 4, characterized in that the Amphipathic polymer is made up of a framework polymer and polymers grafted onto it Divide, the amphipathic polymer consisting of two polymeric units, one of which at least one is thermoplastic, one unit solvating in the solvent and the other unit is insoluble in the solvent system. «> 20th