DE2100917A1 - Coatings for electrographic printing processes - Google Patents

Description

The present invention relates to: (l) a base which has a printing surface suitable for electrographic printing and a continuous, electrically conductive coating on this surface, and which is characterized in that the coating is 0.8 l g / m ² to 4.05 g / m ² (0.5 to 2.5 pounds per 3000 square feet) of the substrate of an electrically conductive, water-dispersible polymer having the formula

OCH ₀ -

CH ■
t

CH ₂

τ, τ +

OH

has, wherein X is chlorine, bromine or iodine , the groups H independently of one another under the groups methyl, ethyl and
(CHO) H, where y is an integer between 1 and 30 and η

109830/1780

an integer from 1-4 uedeates, chosen sir.ei, uu.a m eüie integer between 5 and 2000; and furthermore (2) si ;. Process for generating an electrophotograph.it; cue n recording sheet, which is characterized by the following stages:

A. Coating a base with a dispersion, aie 5 to 50% by weight of a polymer which is dispersible in water with the formula

CH t

CH ₀
N ⁺ - R

OH

contains, wherein X is chlorine, bromine or iodine, uie groups R independently of one another among the groups M-thy 1,. "Itnyl and (CJp 0) H, where y is a whole number between 1 and 30 and η a whole number from 1-4 interpretations, chosen and m is an integer between 3 and 2000, to provide a continuous coating in a quantity form, which corresponds to 0.81 to 4.05 g / m ^ of the paper backing;

B. Drying of the coating from the dispersible in water Polymer;

C. Applying a layer of an extender, welcnes Starch, polyvinyl alcohol, polyethyl acetate or polybutyl styrene can be, and

D. Application of an electrophotographic, photoconductive material that can contain one of the oxides, iodides, selenides, sulphides or tellurides of zinc, antimony, aluminum, bismuth, cadmium, mercury, molybdenum or lead, selenium, arsenic trisulphide, lead chromate or cadmium a ^ senide, to order the finished electrophotography recording ^{sheet: ubllden} f 09830/1780

BAD ORfOiMAL

21Ü0917 _tl

Wood o.ciK ele-ctrison conductive polymer that is dispersed in water uü; "cei'i defined formula I corresponds,

It has ijiüij .υίκι, Jj; - proved to be difficult, paper with a coating aas oino, - electrically, conductive Suostan ^, üie dispersed in water j;,., · Is ^ nα the necessary electrical conductivity ei; ever ; Gci.L.rte ::.-...., f Weis, ^ u üuer ^ e ^ hen. A group of Veroin eyes, ui ·., Ei ca proved to be urc.ucliDai ·, contains a polyme-.ic.-Λ: .αε polyn.t; isiei'ten quaternary vinylben ^ ylammoniumveroinüuüger., as described in US patent specification 3 011 91o v? e] -uo: i. P-ypiüx-, aas i with these connexions over ^ ogen, aaftet jedoa.i ei .: etai-ker, a lot more aininax'tiger odor, the iiUi 'üuüurch vaj'i.iinder-t v; erden kc. nn, unless the pH value is adjusted. 1J..1..r_agei: oi. ^: ; ^ u ei.icni cturl: acidic Bei'eich nerauset .-. t, ..ei many: .e: i- die Γοΐ-i'osicn der · ^ um shift order completed Verricuit-uig jei'ö-oeit wi.- d. VJeitemin these Verbina ^ nts I.oüti _.:: Jieli; ^_:;, Lo-iua ^ nac.i economical as well as ^ ufrieende] ,, c; ic]: ti-ic: i leitfäiiigen polymers searched

Gc-u.lis: cit. te voi; qur.-tcrr.isie-rtei.;, polyepihalohydrin in economic c. _; üc:: .. ui'gci: i'c: geii fourth "can, wooei a product stent, v -.- is ei;:, ei =,. triac ·;, conductive Ooei-fillcne aul'vieist and electrisj3. iv. · Leitrü.:. i; -ieitseigeriscaa.ften üoei · a wide range of »el.-üive ;; 3'e ^; .- activity oesitzt. Papiei-, the inventive: .. iu qu ;. .-t-3i'r: isiv2i-ter :, Polyepihclonydrin üoer ^ ogen is, oesit_t ei :: e · ". ^ pe-ifito.-c-ii Ooerfljicheiiividerstanä ii; i range from etv / a ■ j : · "IC" to i; - ICK O /:"::./^ ':', '"over a range of relative

c -

Ir. de. :: elektric c -. conductive, in water dispei'gieroaren PoIyiO.-i ^; t .'υ., ar. - I ⁷ .7i '.. _; el I denote possibly X chlorine, R i-iet ,, yl unu ..: a g ^ .n.-e Zui; l -jwiscen £ 0 and · "100. This PcIy, .ie.-is . t ILlri.v. _ '..... ..Ui ¹ oi: ifavii: c V / eise äui'-c;in; wesenölic.xe ::

Vv..ll :; "C: ^iv; .li; yl;: ir: s OAER ij2; _o -... ..> ei-nifieru :; j ei.ies Ti-i.. T_-io. Y-

109830/1760

BATH

N 028

make alkylamins rait a polyepihalohydrin. The polyepihalohydrin is preferably polyepichlorohydrin, and this is quaternized with trimethylamine. The polymer is preferred essentially completely quarternized., including to it is understood that the polymer is 00 to 100> a quartex-nare Adducts with the formula

OCHo -

CH-t

N ⁺ - R

-t m

contains, wherein X, R and m are as defined above. Partially quaternized polyhalohydrins were also tested, which showed that the paper lacks the necessary electrical conductivity if the degree of quaternization is below 70 ';' . The polymers should therefore, as indicated above, be 30 to 100 % and preferably 90 to 100% quaternized.

To obtain the quaternary polyepichlorohydrin with the desired molecular weight, namely about 750 to 300,000 and preferably 2,000 to 150000, you have to use a polyepihalohydrin choose suitable molecular weight. Polyepihalohydrins with molecular weights in the range from 450 to 180,000 have been investigated it was found that film coatings containing these polymers can be applied to paper without any difficulty. The epihalohydiin preferably has a molecular weight in the range from about 1200 to 100,000.

The amine is preferably trimethylamine or triethylamine. However, other amines such as methyl diethylamine, ethoxydimethylamine or mixtures of amines can also be used. The alkyl groups are independently selected from among mutiiyl, ethyl and (C _n H _2n O) H, where y is an integer between 1 and

109830/1760

- 5 - ■ N 628

30, η is an integer from 1 to 4 and m is an integer between 5 and 2000 mean.

The method of making an electrographic recording sheet according to the invention comprises the stages A to D given above.

In order to carry out these process steps for the production of a base that has an electrically conductive surface coating, the inventive, electrically conductive Polymers as a continuous film by coating, spraying, dipping, brushing or any other suitable application method can be applied to paper. The quaternized polymer is preferably used as a coating in the form of an aqueous Dispersin or solution applied to paper. The coated paper is then dried, leaving a product with an electrically conductive surface is obtained. Suitable or standard application devices, such as knife application devices, were used, and the coated paper was dried by the radiant energy from heating lamps. The coating

can be applied to the paper in a range from 0.81 to 4.05 g / coating weight per m of paper. Together with the polymer other components can be applied, e.g. clay, starch, pigments, etc.

Paper is preferred as the base, including paper with high wet strength, coated or uncoated and with a thickness of 0.076 to 0.152 mm. Other electrically conductive or semiconducting materials can also be used e.g. plastic films including cellophane, fabric as well as metallic foils, e.g. aluminum and copper foils.

The water-dispersible, quaternized polyepihalohydrin is preferably a polyepichlorohydrin quaternized with trimethylamine. The extender is preferably polyvinyl alcohol, but any extender known in the art can be used wex'den. Under certain conditions the extender can

109830/1780

-O- N

can also be omitted. The electrophot, graphic. Photoconductor is preferably zinc oxide, which is a known extender.

Other particularly suitable photoconductors that exist for d ^ .s Processes that can be used are inorganic products, such as the oxides of antimony, aluminum, bismuth, cadmium, Mercury, molybdenum and lead. However, zinc oxide is preferably used. If. High-grade layers are to be created, the zinc oxide to be used should be as pure as possible, advantageously being a product according to the so-called French process, i.e. by atmospheric oxidation of zinc vapor. The photoconductor should in each case are in finely divided form and preferably have a particle size below 1 micron.

Before the coating is applied to a paper base, other polymers can also contain the quaternized polyepihalohydrin be mixed. A polymer such as starch can be used as a component of the coating formulation to achieve the Prevent penetration of the electrically conductive polymer by keeping the latter on the paper surface will. While the use of a polymer such as starch has very little effect on the electrical conductivity properties of the coated paper can serve the purpose stated above. The coating of starch and the quartzized polyepihalohydrin can be a proportion of strength up to a ratio the stick to the electrically conductive polymer of about 1: 1 contain.

The electrically conductive, water-dispersible polymers can be produced in a simple manner, as by the following Examples is explained.

109830/1760

example 1

5800 parts of Epichlorhydriri are placed in a glass-lined reaction vessel, stirred and examined for the water content. If the water content is too high (above 0.2% ), part of the epichlorohydrin is distilled off, the feed being maintained by adding fresh epichlorohydrin. When the water content is low enough (less than 0.2, "'), the vessel is sealed and cooled under a 5 tick fuel pressure from 0.211 to 0.352 kg / cm ^ to ⁰ CO C.

A nitrogen atmosphere is created during the addition of the Kfcalysators maintained, the boiler being opposed by the cooler is open to the atmosphere.

About 72.5 kg of 25 jiges triisobutylaluminxum in toluene is slowly added with careful observation at 60-70 ° C. until an exothermic reaction occurs. The temperature is allowed to rise to 100 ° C. in a controlled manner with the necessary cooling. When the initial reaction subsides, the temperature is kept at 100-110 ° C by adding a catalyst until no more exothermic reaction can be observed. The temperature is at 80 - 85 ⁰ C lowered.

95 liters of water are added below 05 C. The approach is at a vacuum of 559 mm (minimum) up to a temperature from 100 to remove.

Door torn over from 100 - 110 ° C, with 1 - 2 passages of condensate

The total weight of the contents of the reaction vessel is calculated based on the added and removed materials. The charge in wt .- ^ 'for the following stage is calculated as follows:

26.2 fj contents of the reaction vessel Ij) ₁ O /> 25;, i total, aqueous tri-diethylamine

109830/1760

The trimethylamine is added at a temperature below 80 ° C. The Gufäss is briefly ventilated to make it atmospheric To bring pressure.

The reaction vessel is then closed and heated to a pressure of 7 atmospheres, which should be the case at around 90-100 ° C. It is held at this temperature for 16 hours. Then the temperature is slowly increased while maintaining the pressure of J atü and kept at 110-140 ° C for two hours.

It is cooled to 70 - 80 ° C, and with 1Γ3 - 22b kg ^ O; .- iger, aqueous hydrochloric acid up to a pH value of 5 * 5 - 6 * 5 neutralized.

Example 2

750 parts by weight of epichlorohydrin (containing 0.14 parts of water) were introduced under a nitrogen atmosphere into a reaction vessel equipped with a stirrer and cooling. A solution of 25 ';'> triisobutylaluminum in toluene was added in portions at 60 C, until an exothermic reaction showed. It took 28 parts to start the reaction.

The heat of reaction increased the temperature of the reaction mixture to 115 ° C. in 20 minutes. The temperature was maintained at 100 ° -115 ° C. for 1.5 hours with cooling. During this time there was an increase in the apparent viscosity of the reaction mixture a. After the reaction had subsided to the extent that cooling was no longer required, it became rudimentary Addition of catalyst resumed at 75-100 ° C, and 12 parts were added over a period of 3 hours, the temperature being maintained by the resulting heat of reaction. The temperature became another 1.5 Maintained at 90-100 ° C for hours.

After this time, 25 parts of water were added to the remaining catalyst., u decompose, and the temperature was up

109830/1 760

increased to 150 ° C. over a period of 1.5 hours to remove 106 parts of condensate.

The residue was a pale amber, viscous liquid, which are soluble in toluene and xylene and in isopropyl alcohol insoluble

Example 3

158 parts by weight of the product from Example 2 were introduced into a pressure vessel equipped with a stirrer and heater together with 130 parts of a 3 mol ethylene oxide adduct of dimethylamine and 182 parts of a 25% solution of trimethylamine in water and heated to 100 ° C. for 17 hours heated for a long time, during which time the pressure in the reactor dropped from 3 * 3 atü to a slight vacuum. The reaction mixture was brought to a pH of 5.1 with 23 parts of 30 ^ hydrochloric acid.

A clear, brown, viscous liquid was obtained which was readily soluble in water.

Example 4

93 parts by weight of the product from Example 2 were heated to 140 ° G with stirring, and 177 parts of a 3 mol of ethylene oxide adduct of dimethylamine were added in portions over a period of 1 hour. The reaction mass was increased to 110 ° G cooled and 50 parts v / ater was added. The heater was turned on and the reaction mass was 5 hours held at reflux (112-116 ° C) for a long time, after which 50 parts of water added vmrden and the mixture with 35 parts of 30> j'iger Hydrochloric acid were brought to a pH of about 6.

109830/1760

21 QUO 17

- 10 - N 02s

Example 5

176 parts by weight of the product of Example 2 were heated with stirring to I5O ⁰ C, and 251 parts of a 5 mole ethylene oxide adduct of dimethylamine were added over a period of 1 hour. The temperature was held at 128 ° C. for 4 hours, after which 100 parts of water / water were added and the reaction mixture was brought to a pH of about δ with 29 parts of 30% hydrochloric acid.

Example 6

121 parts by weight of the product of Example 1 are together with 520 parts of 25% trimethylamine in water with stirring for 16 hours heated to 100 C in a pressure vessel for a long time. 5 ^ 9 parts of this Product were with 24 parts of 30 ^ iiger hydrochloric acid on one pH of about 6 brought.

Example 7

42 parts by weight of the product of Example 2 were together with 8l parts of a 7 mol of ethylene oxide adduct of dimethylamine and 59 parts of 25 tigern, aqueous trimethylamine with stirring Heated in a pressure vessel at 100 ° C for 16 hours. 515 Parts of this product were mixed with 51 parts of 30% hydrochloric acid brought to a pH of about 6.

Example 8

70 parts by weight of the product from Example 2 were added with stirring heated to 145 ° C, and 199 parts of a 7 mol ethylene oxide adduct of dimethylamine were added over a period of 30 minutes. The reaction ingested for 4 hours held at 130-140 ° C, and 50 parts of water were added. It was refluxed (112 ° C) for a further 2 hours heated. 50 parts of water were added and the reaction mass

109830/1760

- 11 - N 62ο

was with> 2 parts of 30% hydrochloric acid to a pH of otwu C obeyed.

Example j

Zo parts by weight of the product of Example 2 were added together with 99 parts of an 11 mol ethylene oxide adduct of dimethylamine and 4u parts 25 ^; igem, aqueous tri methyl amine with stirring li; Heated in a pressure vessel at 100 ° C for hours. 526 parts of this product were brought to a pH of about 6 with 39 parts of 30% hydrochloric acid.

Polyepibromhydrin and other amines can also be used to create zn similar products.

Test dex 'electrical conductivity

The coated underlay is specific with regard to its Surface resistance tested according to a standard procedure, which essentially corresponds to that in "Standard Methods of Test for Insulation Resistance of Electrical Insulation Matexdals ", ASTM D257-4o.

To produce a printing surface for an electrographic printing process, the process steps are carried out which have been described above for the process for producing electrophotographic surfaces. A concentration of ¹ IOJ solids of the quaternized polymer of Example 1 in water was used. A potential of 500 volts was applied to a sheet of paper after it had previously been conditioned at relative humidities of 20; J or 50; J for 36 hours. The results are summarized in the following table:

109830/1760

N 623

Used paper

Ps

Surface resistance

(Ohm)

(20 fj rel. Humidity)

Ps

Surface resistance (ohms)

(50>: 'rel. Humidity)

Polymer - About, .ugsgewichtρ g / m

number 1

No. 1 + quaternized polymers

No. 2

No. 2 + quaternized polymers

7.6 χ 10

11

2.2 χ IO 2.1 χ 10

11

4.0 χ 10

χ 10

10

8.1 χ 10

1.8 χ 10

6 10

χ 10

5.05

1.72

The papers used, designated No. 1 and No. 2, were those used in the electrophotographic industry.

/ 2 standard papers. For example, the paper weighs cJO g / m and will from a massively healed paper pulp made of bleached, chemical wood pulp, wood pulp, as well as alumina fillers and Fibers, as well as resin solute precipitated by alumina manufactured.

The table shows that the paper has a significantly lower specific surface resistance and thus a considerably higher one Has conductivity when the quaternized polymer the paper has been applied. The coated with the polymer Paper therefore met the industry standard requirements for use in electrographic printing processes.

Other quaternized polyepihalohydrins of the examples can also be used and give good results as electrically conductive polymers. In a similar way, other supports, for example cellophane, fabric and metal foils, can also be used.

- patent claims -

109830/1760

Claims (1)

Patent claims: Γΐ) Backing with a printing surface suitable for electrographic Printing process is suitable and has a continuous, electrically conductive coating on this surface, characterized in that the coating is 0.8 l to 4.05 g / m the substrate of an electrically conductive, water-dispersible polymer with the formula OCH ₂ -CH-I CH ^ RRR OH contains, where X is chlorine, bromine or iodine, the groups R independently of one another under methyl, ethyl and ( ^c _n ^H 2n ° ^ v ^{Hj where} y is an integer between 1 and 30 and η is an integer from 1 to 4, can be selected and m is an integer between 5 and 2000. 2. Support according to claim 1, characterized in that the support is paper. Support according to claim 1 or 2, characterized in that 109830/1760 N 02ό that X is chlorine, R is methyl and 20 and 100 are. m is an integer between 4. A support according to claim 1, 2 or 3 > characterized in that the water-dispersible polymer is formed by essentially complete quaternization of a polyepihalohydrin with a trialkylamine. 5. Underlay according to one of claims 1-4, characterized in that that the water-dispersible polymer by essentially complete quaternization of polyepichlorohydrin is formed with trimethylamine. 6. Support according to claim 5, characterized in that the water-dispersible polymer contains 80 to 100. ) quaternary adducts. 7. A method for producing an electrophotographic recording sheet, characterized in that the following steps are carried out: A. Coating a substrate with a dispersion containing 5 to 50% by weight of a water-dispersible polymer with the formula _a - OH - N ⁺ - R R R OH contains, in which X is chlorine, bromine or iodine, the groups R independently of one another from methyl, ethyl and (CH ₂ O) H, where y is an integer between 1 and ^ O and η is an integer v..n 1 to 4 mean, r. selected 109830/1760 210Ü917 - 15 - N 623 are, and m is a number between 5 gan ^ e ^nd in 2000, is a continuous coating in an amount to form, which corresponds to 0.1 to 4.05 g / m 2 of the paper; 3. drying the coating made from the water-dispersible polymer; C. Apply a layer of an extender that Starch, polyvinyl alcohol *, polybutyl acetate or polybutyl styrene can be; and D. Scanning coating of an electrophotographic photoconductor, the one of the oxides, iodides, selenides, sulfides or tellurides of zinc, antimony, aluminum, bismuth, ^ Can be cadmium, mercury, molybdenum or lead, selenium, arsenic ™ trisulfide, lead chromate or cadmium arsenide, to form the finished electrophotographic recording sheet. Method according to Claim J, characterized in that the base is paper. -j. Method according to Claim 7 or 3, characterized in that the extender is polyvinyl alcohol. 10. The method according to claim "(, 8 or 9, characterized in, that the photoconductor is zinc oxide. A. 11. The method according to any one of claims 7-10, characterized in that that X is chlorine, R is methyl and m is an integer between 20 and 100. 12. The method according to any one of claims 7-11, characterized in that that the water-dispersible polymer by essentially complete quaternization of a polyepihalohydrin Is formed with a trialkylamine. 13. The method according to claim 12, characterized in that the water-dispersible polymer contains 80-100 ', Ί quarternary adducts. 109830/1760 in 109830/1760