DE2642826C3 - Electrostatographic suspension developer - Google Patents

Description

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

Developers of the first type are known, for example, from US Pat. No. 69,886. 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

Developers or toners of the second type are e.g. B. from the DE-OS 21 14 773 (and the corresponding US-PSs 53 760 and 39 00 412) known such development systems contain a carrier liquid in addition to and a control substance, a toner in the form of an amphipathic polymer, i.e. a graft polymer, whose polymeric backbone chain is soluble in the carrier liquid and whose side chains are polymeric and are thermoplastic and are not solvated by the carrier liquid. These toners have a Particle size between 25 nm and 25 μm. The toner may contain dyes or pigments soluble or dispersible in the developing system, or the like Amphipathic polymers contain a corresponding chromophoric group chemically bound. The skeletal chain of the graft polymer can be from

Polyilauryl methacryl / glycidyl methacrylate / methacrylic acid) or

Polyisodecyl methacrylate / glycidyl methacrylate /

methacrylic acid) or Polyistearyl methacrylate / glycidyl methacrylate /

methacrylic acid) or Polyauryl methacrylate / glycidyl methacrylate /

methacrylic acid / chromophore) or Polvilauryl methacrylate / N-l.l ^ ß-tetramethyl-

butyl methacrylamide / glycidyl methacrylate /

methacrylic acid and ίο the side chains of

Poly (vinyl acetate / N-vinyl-2-pyrrolidoneX Polyvinyl acetate / crotonic acid), Poly (vinyl acetate / methyl hydrogen maleate), Polyvinyl acetate or a polymer with repeating units of methyl

hydrogen maleate

come.

Both toners have disadvantages, being that of the toner

of the second type are less serious and in some Cases, especially in the case of office copiers, are of little consequence. However, they limit its use in the manufacture of planographic or flat printing Offset printing forms and reproductions for micro fiche. Flat printing forms with which, although a high Number of pressure 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

Flat printing or offset printing forms are generally used with a zinc oxide-containing layer as the photoconductor and with an aqueous solution of hexacyanoferrate-II or -III as the wiping water Were flat or offset printing forms with

J5 produced a suspension developer of the first type, see above 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 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 Reproductions for microfiche, however, 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. 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, v. As with this heating for fixation becomes dimensionally unstable, which is important for the application for microfiches is intolerable The object of the invention is now an electrostatograph heavy suspension developer, which leads to 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

M) for transmission methods such as pressure transmission, Vacuum transfer and electrostatic transfer. 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 has significant advantages over the two known development systems. It enables a very special problem to be solved, namely a kind of "edge effect", ie. the sharpness of the developed image is improved. This edge effect leads to a certain optical impression, especially with larger, dark images. This impression makes an image obtained with a suspension developer appear darker near the edges; this is apparently related to the reaction of the optic nerves to the images. It is easy to see that this effect does not occur with a large area that is more gray. It is more difficult to see that a large black image that is dense black but has uniform blackness from edge to edge does not exhibit this fact it remains, however, that the human eye perceives this n ± A \ t in this way. This impression of an image arises when the edge areas are darker than the central areas. A further advantage of the developers according to the invention is the lengthening of the service life of a planographic printing form which has been produced with the aid of the developer according to the invention. If a planographic printing form is produced with a developer of the first type, its service life is very short; Parts of the image come off the surface. If, on the other hand, a developer according to the invention is used, the service life of the planographic printing form is significantly longer, namely at least as long as that of a planographic printing form which has been produced with a developer of the second type; this is essential because the developer of the second type is much more expensive than the developer of the first type so that one will strive to use less of the former. This extension of the service life of the planographic printing form of printing forms produced with developers according to the invention is not an expected effect, because even a small amount of developer of the second type as 1 part to 20 parts of developer of the first type already leads to a planographic printing form whose Lifetime corresponds to that obtained with 100% developer of the second type

Another surprising result is achieved with the developer according to the invention in the context of the electrostatographic production of microfiches. 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, this is how this waviness, which does not play a role in the microfiche due to the low layer thickness, now becomes 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 one or the other known developer has been exposed to an etchant for too long z. B. overnight, the hydrophobic image areas become hydrophilic. Is now using an oily printing ink printed so you get no or a very bad picture. This phenomenon occurs surprisingly the developers according to the invention do not.

From the above it follows that the properties of the suspension developer according to the invention not the Sum of the effects of the two applied known developers, but that there must be a synergistic effect.

For the production of planographic printing forms are also available Suspension developer without dyes or pigments useful, however, in this case too, a coloring component applied

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

jo are one or more hydrocarbons) as solvents, in particular "petroleum fractions" from distillation or catalytic cracking as well Polymers of aliphatic monomers obtained synthetically or by distillation or cracking have been received. The petroleum fractions are particularly useful because they evaporate quickly and allow quick drying, e.g. B. in 2 s; they are not poisonous and have none or one low odor. They will be soluble together with

■ ίο 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 already appears dry shortly after construction. They do not lead to one Discharge the electrostatic charge before the pigment is deposited so that any desired contrast can be achieved and, moreover, they are inexpensive.

The petroleum fraction, d. H. a paraffinic solvent, an evaporation rate of at least at least that of kerosene, but 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 that the petroleum fraction will be the binder of the the photoconductive layer or the paper size on which the photoconductive layer is located; she should be essentially free of aromatics, i.e. contain ^ 2% by weight, since these easily remove the binding agents of the can attack photoconductive layer. The electric

M) see resistance must be at least about 10Ώ · cm and the dielectric constant must be <3.5. The flash point in the closed cup according to Tagliabue should > 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

Beginning of boiling End of boiling Flash point K. B. Number C c C

Aniline point apez. Weight C " 15 C 84 0.75o3 84 0.7571 85 0.7587 86 0.7674 84.8 0.7608 64 0.8108

Shell Sol 71 Isopar H Isopar K Isopar L Amsco OMS Amsco 460 Solvent Insecticide base

173
177
176
188
178
190

190

203
187
195
206
147
242

193

49.5

50.5

52

63

51.5

65.5

66.5

26.5 26.9 26.5

27.0 34.5

26.5

0.7711

There are already suspension developers based on water known (US-PS 34 25 829). Other useful carrier liquids besides petroleum fractions and water are alcohols, e.g. B. those with 1 to 6 carbon atoms (ethylene glycol), ether (ethyl esobutyl ether, methyl isopropyl ether, QQ-alkyl monoether of ethylene glycol and dioxane), ketones (acetone, methyl ethyl ketone, methyl isopropyl ketone, ethyl isobutyl acetate, butyl acetate, butyl acetate), esters (ethyl acetate and butyl acetate Mono-Ci — C ₄ alky lather of ethylene glycol) and 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 exists, in which a disperse phase is one amphipathic polymer is located An "amphipathic" substance has an affinity for two different phases, namely one organic and one aqueous, so that the one polymeric unit of the amphipathic polymer is dissolved from the phase or is solvated (carrier liquid) and the other is not solvated by this, i.e. 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 be present in the suspension developer or is present (»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 solvarized from the petroleum fraction will, like naturally occurring high polymers, e.g. B. Raw rubber, refined oxidized linseed oil, degraded Rubber and 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 stearyl, Lauryl, isodecyl, octyl, 2-ethylhexyl and hexyl; Butyl esters of acrylic or methacrylic acid, polymeric Vinyl esters of long-chain acids, such as vinyl stea.'at, Vinyl laurate. Vinyl imitation and vinyl myristate, polymeric vinyl alcohol ethers including polyvinyl ether, polyvi nylisapropylether, polyvinylisobutylether and polyvi- nyl-n-butyl ether.

From the examples above, m? α 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 one 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 butyl acrylate, t-octyl methacrylate butyl methacrylate, Lauryl methacrylate glycidyl methacrylate, 2-ethylhexyl acrylate / acrylic acid, j5 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 methacrylate / Lauryl methacrylate,

Lauryl methacrylate / octyl methacrylate /

Glycidyl methacrylate and Isodecyl methacrylate / stearyl methacrylate /

Acrylic acid and so tetrapolymers, e.g. B.

N-vinylpyrrolidone / butyl acrylate / 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 on Batis of white spirit:

(a) Homopolynier νυη C «—C22 esters of acrylic or methacrylic acid (polyhexyl, polyisodecyl, polylauryl, polytetradecyl and polystearyl methacrylate or acrylate with a molecular weight between 10 ³

until IO ^h . preferably at least IO ^J );

(b) Copolymers of the homo listed under (a) polymeric 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 mixed polymer in test samples;

(c) Mixed polymers of the above methaoryl and AcryKiiii- "' reesler with monomers containing other functional Groups such as acrylic, methacrylic. Crolon-, maleic-, atropine ·. Fumaric, itaconic, citraconic acids. Acrylic, methacrylic or maleic anhydride. Acr \ - loyl chloride. Methacryloyl chloride. Acrylic or methacrylonitrile, acrylic or methacrylamides and their derivatives. Hvdroxyäthylmethacrylai or Acryiai, Hyutuxypiupyinicil'idCiyiäi uuci -.urviai. Dimethylaminomethyl methacrylate or acrylate. Dimethylaminomethyl methacrylal or acrylate. . ' Diethylamipomethyl 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. Metalvlal-: · alcohol and its derivatives. Propargyl alcohol and its derivatives. Indene and its derivatives. Norbornene and its derivatives. Vinyl ether. Vinyl esters and other vinyl derivatives. Glycidyl methacrylate and acrylate. Mono- and dimethyl maleal. > " Mono- and diethyl maleate, mono-n-butyl maleate. Monobenzyl maleate. Mono-2-ethyihex \ l- or mono-n-octyl maleate and finally mono- or Dimethyl fumarate and mono- and diethyl fumarate:

(d) homopolymeric olefins (butadiene. isoprene, isobutylene) and copolymers thereof with under (b) enumerated monomers;

(e) terpolymers and tetrapolymers thereof;

(f) polycarbonates. Polyamides. Polyurethanes and polyepoxides.

Polymeric chains of a different polarity than that of the carrier liquid are then attached to the selected framework polymer by graft or block polymerization. Suitable monomers are, for. B. 4-, vinyl acetate. Methyl, ethyl, propyk isopropyl. Hydroxyäthyk Hydroxypropyl acrylate or methacrylate. Acrylic or methacrylonitrile. Acrylic or methacrylamide. Acrylic or methacrylic acid or anhydride. Monomethyl, monoethyl, monobutyl, monobenzyl, monovi 2-hexyl. Mono-n-octyl maleate, monomethyl. Monoät hylfumarat styrene, vinyl toluene, maleic acid or anhydride and crotonic acid or anhydride. Mixed polymers, terpolymers and polymers of greater complexity with a corresponding 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, polymer 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. is a mixed polymer of stearyl methacrylate-glacidyl methacrylate (27: 1 monomer ratio with a molecular weight of z. B 10,000-150,000) reacted with methacrylic acid in the presence of a polymerization inhibitor to ethylenically unsaturated bonds for the subsequent activation by esterification and in situ polymerization or to form interpolymerization.

The disperse phase, which is essentially the is unsolvated polymeric part of the amphipathic polymer. may also include non-grafted, unsolvated polymer particles. Although these are not because of their unsolvated form If they are particularly desirable, they are permissible and, moreover, they can electrophoretically so pass away that they can be selectively attracted to electrostatically differently charged areas, so that it can be used for an electrostatographic reproduction.

Aiiljci 'Itii uic! lci "Sici! Üfig VOm f läCnurUCri- OuCT

For offset printing, the amphipathic polymer should also contain a chromophoric part of the molecule, or the pigments or dyes required for coloring are added to the developer.

Ks is believed to be the dyes or pigment particles on the unsolvated moiety of the amphipathic polymer can only be kept by forces / further order.

Fine ar.-iere possibility is. Pigments or dyes to chemically bond to the amphipathic polymer, e.g. B. to the scaffolding or to the chains in front of the Polymerization of the chains.

The dyes can be applied to the amphipathic polymer, in particular on the unsolvated part of the molecule, also held by adsorption; However the dyes can also with the amphipathic polymer either after its formation or with the Framework or the chains are chemically converted.

Examples of this are disperse dyes for polyester and mixed polymers of acrylonitrile and vinyl chloride, such as Latyl Orange 3R (CI Disperse Orange 26). Calcosperse Yellow GL (CI Disperse Yellow 57). Calcosperse Blue B (CI Disperse Blue 77), Foron Blue BGL (C I. Disperse Blue 73): Latyl Brown MS (CI 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 3 B (C I. Basic Red 26), Calcozine Acrylic Blue G (C. I. 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 of the amphipathic polymer preferably contains reactive groups which can be reacted with the reactive groups of a chromophore, e.g. B. basic groups to react with acidic dyes. A terpolymer of acrylonitrile, 2-methyl-5-vinylpyridine and vinyl acetate can be reaction colored with dyes containing acidic groups, 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 I. No. 42510B), Crystal Violet (C I. Solvent Violet 9, C I. No. 42555B), Bismarck Brown

2b 42 82b

IO

(CI Solvent Brown 12. CI No. 2I0I0B). Victoria Blue BA (CI Solvent Blue 4. CI No. 44O45B). Victoria Blue K (CI Solven • Blue 6th C. i. No. 44040R). Victoria Blue 4R (CI Solvent Blue 2. CI No. 43563B). < opying Black SK (CI No. 11975). Janus Green B (CI No. 11050). Auramine O (CI Solvent Yellow 34. CI No. 41000B), Victoria Green (CI Solvent Green 1. C. I No. 42OOOB) and Rhodamine (CI Solvent Red 49. CI No. 451 70B).

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

Otherwise, reference is made to the detailed explanations for the production of chromophoric parts of the molecule Amphipathic polymers in the DK-CXS 21 14 773 referenced.

The fixing agent is a film-forming substance that holds the developed image on the paper support. Fs 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, for example, a thermoplastic acidic rosin that has been polymerized and hydrogenated (softening point from 85 to 93 "C - according to the Hercules drop method -. An acid number from 145 to 162. a density of '20" C of 1,065, a saponification number of I 55 to 165, a degree of hydrogenation about 90% and an average molecular weight of 360. About 20% of the resin acids are polymerized) or a thermoplastic petroleum hydrocarbon resin, produced by polymerization of 30 to 90% by weight of unsaturated Hydrocarbon fractions with boiling points between 125 and 250C. Density 0.9 to 0.95 to 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 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 ⁼ C. whose properties wi e follows: softening point (ring and ball) 100'C. Average molecular weight (determined osmotically) 800. OH weight ratio (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 Softening* Point
ί Glycerine ester from modifi 8th 168 decorated rosin Pentaerythriester of 12th 111 rosin Peniäerythritolester by poiy- 14th 135 merized rosin Modified Pentaerythne 14th 135 esters of rosin

Pentaerythritol ester of
hydrogenated rosin
Pentaerythritol ester of
resin acids dine

Modified pentaerythritol ester of rosin

Pentaerythritol ester of
resin acids dine
Glycerol ester of polymerized tu rosin
I hydrated rosin

J] Jj ₁ I ₁ ,;. ,, l |, r, lj _S l _e r wjn miwj -

fized rosin

Fully hydrogenated glycerol ester of rosin
Softened inside
Pentaerythritol ester of
rosin
Refine resin acids

\ in>! toluene / \ crylate-

Mixed polymer

\ m> r.oluene / n-butyl rivet

iicrylate / stearyl methacrylate

(I S-PS 3 3 "? S 513)

S.iiiK '/. Ihl I ■ «^ K htm ·. '»
ι * 11 iiK ι
t 13th 104 14th 192 14th JS., 15th Γ2 112 I (.5 - ₍ , <j ((Mercury
method) S2

3 (1

143
6.1

K) I

152

47

15 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 or the control substance (s) must ^r in the Trägei! Uid be soluble or dispersible and charging of the fine pigment particles cause or improve. Examples are di-2-ethylene hexyl sodium sulfosuccinic acid. Ditridecyl sodium sulfosuccinic acid. the aluminum. Chrome-. Zinc and calcium salts of SS dialkylsalicylic acid. wherein the alkyl group is propyl-. Isopropyl, butyl. Isobutyl-. lert.-butyl-. Amyl-. Isoamyl and other alkyl groups up to C <* - are, or the salts of dialkyl-γ-resorcinic acid. Isopropylamine salt of dodecylbenzenesulfonic acid. Aluminum-. Vanadium or tin resinates (the metal resinates are made 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 C API 223 or 052 g / cm ^3. Flash point - Cleveland open cup - 12O 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, cobalt and lead linoleate, Manganlinclresir.at, (1- [2-hydroxylethyl] -2- [mixed pentadecyl and heptadecylfJ-2 -imidazoline, linoleum resinates are metal soaps made from tall oil.

Il

The dispersant is in the triiger liquid solvatable or dispersible. the former being preferred. The task of the dispersant is. the To keep pigment particles dispersed in the non-polar solvent system. The dispersant must be compatible with the fixative; it is also expedient. \ »* Nn the dispersant the direction of charge the pigrient supports.

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, VIaleimide polymer. Polymers of the reaction products of alkyl methacrylate, polyethylene glycol methacrylate and maleic anhydride and polymers made from a reaction product of alkyl methacrylate, polyethylene glycol methacrylate and the imine of maleic anhydride and tetraethylene pentamine, polyglycol-substituted polyesters (US-PS 30 83 187) and polyglycol-substituted polyamides (US-PS 30 83 188).

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 - U.S. Patent 2,486,351). Crocein Purple NEX (C.I. 27290). Fiber black VF (C. I. 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. I. 30235), Hansa yellow G (C. I. 11680), indanthr black BBK (C. I. 59850). Indocarbon CLGS (C.I. 53295). Katigen jet black NND Hi (C.I. 53190), Palatine Fast Black WANA (C. I. 15711), sulfoncyanine black BA-CF (C. I. 26370). Zambezi Black VD Ex (C.I. 30015), Spirit Nigrosine SSB (C.I. 50415). Methyl Violet T (C. I. 42535), Rubanox Red CP-1495 (C.I. 15630). Victoria Blue Molybdates (C. 1.42595).

Examples of suspension developers based on type I toners which can be used according to the invention are shown in the US-PS 36 69 886 indicated, in particular Examples 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 This quantitative proportion appears 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

Ratio of Fz ¹ must be I. Taking into account all these factors and as a rough guide for the preparation of the suspension developer according to the invention, the following minimum and maximum proportions per liter should apply:

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;

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 chromophores!

Part of the molecule in the developer of the second type - chemically bound or adsorbed - 0.03 to 30 g.

Amphpathetic polymer without chromophoretti Molecular part in the developer of the second type about G.03 to 30 g;

unbound coloring agent in the second type, 0.03 to 30 g;

Control substance in the developer of the second type 1x10 'bis log;

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 however, several coloring agents, preferably two or more, can also be used 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 manufacture in another way, namely by preparing the amphipathic polymer in a solvent in which it is completely solvated. whereupon another solvent is added, in which one type of polymeric molecular unit 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 Polystyrene and polyisoprene. Reference is made to Example 30 of DE-OS 21 14 773.

One of the following two can be used for preparing the dispersion developer of the present invention Use procedures: one is to simply use the suspension developer previously prepared first and second type mixes, in proportions of 0.5 to 99.5% of one and 99.5 to 03% of the other developer. The other The method consists in introducing the various components 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 this is not absolute However, if two carrier liquids are used, they should be compatible. Preferably - but not necessarily - are the two suspension developers to be mixed the same control substances applied This increases the likelihood that the two developers will not are compatible, reduced and the measures simplified. So you can use the fulfillment Prepare suspension developer directly by mixing

and does not have to first prepare the two developers separately and then mix them. Some tax materials 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, namely that the amphipstic polymer already has a dispersant effect. 3 and therefore you don't need to add a small amount of dispersant.

The active constituents of the developer according to the invention in the carrier liquid can 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 - 0.002a to 5 g / l.
Dispersing agent - not bound to the fixing agent! - 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 I χ 10 "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 g of thermoplastic petroleum hydrocarbon resin with mainly aromatic or cyclic units - which consists of 30 to 90% by weight unsaturated hydrocarbon fraction with a boiling point between 125 and 250 ° 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, "1 to 20% indene, 5 to 25% vinyltoluene 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, whose properties are as follows: Softening point (ring / ball) IW ⁵ C average molecular weight (osmotically determined) 800, weight ratio C / H 10A 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 04 g of cobalt octoate as a 12% solution ir, mineral oil.

The second type of developer was obtained as follows:

In a 500 cm ³ reactor with a stirrer. Thermometer.

Temperature controller, reflux condenser and cooling coils was added 40 g 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 I 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 to SO ⁰ C again. Azobisisobutyronitrile added in portions of 0.5 g in evenings of 10 min up to a total of 4.6 g (3 h 40 min)

η and the reaction mass then for 2 h at 80 ± 2 ° C held. A white latex with a solids content of 35.7% and a particle size was obtained <74 μm.

100 g of this latex were in a 500-cm ^! -Three-

■ i neck flask with stirrer, reflux condenser and thermometer and added Victoria Blau Base BA (C.I. 44045B) 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 width 74 μm -

μ filtered to remove the remaining dyes. to 2.5 g of a 1% by weight solution of aluminum S.S-diisopropyl salicylate were then added to the colored latex added in a petroleum fraction to obtain a concentrate.

: ~> Received with this developer according to the invention one dense, black copies with no background coloring.

Example 1 was modified in such a way that 0.5 g of suspension developer concentrate of the first type and

were diluted in 4.5 g suspension developer concentrate of the second type with 2000 cm ³ 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 concentrate of the developer of the second type with 0.04 g of concentrate of the developer of the first type and diluting it with 2000 cm ^{3 of} petroleum fraction.

4Ii The developer of the first type consisted of 25 g hydrogenated rosin. 20 g of oil additive in the form of a terpolymer, 10 g of polymerized castor oil. 15 g of carbon black and black dye, 9 g of C must 33 nm + chrome green. 100 g petroleum fraction as a solution

4, medium and 5 drops of 10% aluminum resinate Solution in the solvent.

The developer of the second type was prepared as follows: In a 500 cm ³ reactor with a stirrer. The thermometer and reflux condenser were 360 g of earth.

fraction. 190 g vinyl acetate, 30 g of an ester. 10 g of crotonic acid and 4 g of azobisisobutyronitrile 4 h at 85 ± 2 ^C C held and then 2 g of azobisisobutyronitrile was added and a further 4 h at the same temperature polymerization The ester was prepared by in a 1-1-ReaktionskoIben with stirrer , Thermometer and reflux condenser 400 g of petroleum ether (boiling range 90 to 120 ° C) was kept under normal pressure at a moderate refluxing boil. In 3 h a solution of 194 g of lauryl methacrylate became 6 g of glycidyl methacrylate

to and 3 g of benzoyl peroxide paste (60% by weight in dioctyl phthalate) added dropwise. After a further 40 minutes at refluxing, 0.05 g of lauryldimethylamine were added added and kept boiling for a further 1 h. Then there were 0.1 g of hydroquinone and 3 g of methacrylic acid

egg introduced and under nitrogen purge. g air. backflowers Maintained boiling until about 25% of the glycidyl groups were esterified. This took about 16 hours.

100 ε of this white latex were in one

500 cm ^{3 three-} way round-bottom flask with stirrer, reflux condenser and thermometer with 1.2 g Victoria Green (CI 42000B), 2.4 g Bismarck Brown (CI 21010B) and 0.3 g Rhodamine Base (C. 1.45170B) 2 h heated to 80 ± 5 ° C - the black Latsx was filtered - mesh size 74, ^ Ti - and mixed with 5 cm ³ aluminum resinate solution (10 wt .-%) in solvent

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 of concentrate of the developer of the first type and 8 g of concentral of the developer of the second type were added mil 2 i Diluted solvent.

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

The second type of developer was made as follows:

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 stirred in a 500 cm ³ flask equipped with a thermometer, stirrer, reflux condenser and cooling coil for 4 h at 86 ± 2 ° C .; The solution was obtained as follows: 2.4 kg of petroleum fraction were heated to 110 ± 1 ° C. and 1.0357 kg of isodecyl methacrylate, 36 g of glycidyl methacrylate and 18 g were placed in a 5 l glass flask equipped with a heating mantle, stirrer, thermometer, nitrogen passageway and reflux condenser a 50% strength 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 was introduced, nitrogen was passed through during the esterification, then 18 g of methacrylic acid were added and held at the reaction temperature until 25% of the glycidyl rings had esterified, which took about 8 hours.

^{5 cm 3 of} a 1% solution of aluminum-34-diisopropyl salicylate were added to the petroleum fraction to 100 g of this latex with a solids content of 33%.

This developer was ideally suited for planographic printing plates.

Example 5

100 g of dimeric resin acids, 50 g of vinyltgluene / 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 sense 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 measured at 2000 cm ^! Diluted solvent.

With this developer, dense blacks were obtained Copies with no background coloring.

It is. 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

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

π dispersed.

Dense black copies with no background coloration were obtained.

Example 7

20 g of dimeric resin acid, 10 g of copolymer from: Example 6.15 g of carbon black, 120 g of solvent, 2 g of lubricating oil, 1 g of aluminum stearate and 30 g of latex in the sense of Example 4 were mixed in a ball mill for 18 hours at 37 ° C and 5 g of this 2000 cm concentrate ^:

Diluted solvent.

The developer made tight black copies with no background staining.

Example 8

25 g hydrogenated rosin, 80 g latex in the sense of de! Example 2.12 g of carbon black in the sense of the example 5.3 g of »Spiri Nigrosine SSB «(C I. 50415), 6 g carbon black ~ 25 ηm, 1 f Aluminum stearate, 20 g of oil additive in the form of a terpoly

mers and 50 g petroleum fraction were 40 h Room temperature mixed in the ball mill and 4 g

this concentrate diluted ver with 2000 cm ³ petroleum fraction.

This gave densely black copies with no background.

Example 9

25 g hydrogenated rosin, 6 g latex in the sense of de; Example 2, 12 g of carbon black in the sense of Example 5, 2 <dye in the sense of Example 8.6 g of carbon black ~ 25 nm, 2 j aluminum stearate, 20 g of oil additive in the form of a terpolymer and 50 g of petroleum fraction were 40 h at room temperature in mixed in the ball mill and 6 j of this concentrate ^{diluted ver with 2000 cm 3} petroleum fraction.

This developer gave copies that were densely blacked out with no background.

"Example 10

25 g hydrogenated rosin, 80 g latex, colored mi

Victoria Blue BA Base (4%), 8 g of carbon black from Example 5, 2 | "Spirit Nigrosine SSB", 4 g furnace soot ~ 33 nm -i

Chrome green, 10 g of added oil and 10 g of polymerized castor oil were placed in a ball mill at 37 ° C. for 39 hours mixed and then 0.75 g aluminum stearate, 101 polymerized castor oil and 50 g solvent added and mixed for another hour

h-, whereupon 3 g of this concentrate with 2000cm 'Lö • solvents have been diluted.

The latex was made as follows:

In a 500 cm 'reactor with a stirrer, thermometer

230 210/30:

17 18

and reflux condenser were 360 g of solvent, 185 g -in

Vinyl acetate and 30 g of a solution and 15 g of methylhy- Example π

drug maleate and 4 g of azo-bisisobutyronitrile for 4 hours to 950 g of colored latex in the sense of the example 10.20 g

Maintained 85 ± 2 ° C. Then another 2 g of azo-bisisohydrogenated rosin, 8 g of carbon black and black

butyronitrile added and the polymerization at 5 dyestuff, 2 g "Spirit Nigrosine SSB", 4 g carbon black ~ 25 nm,

The reaction temperature was carried out for a further 4 hours. 8 g of oil and 8 g of polymerized castor oil were added

particle size of the latex 0.04-0.2 µm, mixed in the ball mill at 37 ° C for 40 hours and 25 g

The solution corresponded to that of Example 2, however, this concentrate with 2000 cm ^{3 of} solvent and 10

52% of the glycidyl groups were esterified. Drops of a 1% solution of the aluminum salt of

This developer was mixed with densely black 10 3,5-diisopropylsalicylic acid in the solvent

background free copies. Excellent planographic printing forms were obtained.

Claims (5)

Patent claims: 1. Electrostatographic 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 polymeric parts grafted onto it, the amphipathic polymer being made of two polymeric units, at least one of which is thermoplastic, the one unit solvated in the solvent and the other moiety is insoluble in the solvent system