DE2100917C3 - Electrographic or electrophotographic support with an electrically conductive layer - Google Patents

Description

OCH ₄ - CH-

X-

CHj

N +

RRR

OH suitable electrically! hurrying polymers, which in Water dispersible and as a layer on electrograpto or dectrophotographic support can be applied to provide.

The object of the invention is based on an electrographic or elektrophotographischeu support having from 0.81 to 4.05 g / m ^a thick electrically conductive layer of a water-dispersible polymeric quaternary amine and

ίο is characterized in that the conductive layer as a polymeric amine a compound of the formula

OCH ₁ -CH-

X-

CH,

N ⁺

RRR

OH

contains, wherein R is the same or different and ao

equal to a methyl, ethyl or - (CtHgnO ^ H-,...,..

Group in which η 1, 2, 3 or 4 and γ contains a whole, in which R_ is the same or different and the same

a methyl, ethyl or -iC _t H _iB O) "H group, in which η 1, 2, 3 or 4 and γ is an integer between» 5 1 and 30, X is a chlorine, bromine or iodine atom and m is an integer between 5 and 2000.

The polymeric amine can be easily quaternized by essentially complete quaternization

wherein R is equal to a methyl group, X is equal to a 30 of a trialkylamine or trioxyalkylamine with one

Chlorine atom and m is an integer to produce polyepihalohydrin. To the quaternare

One must prepare polyepihalohydrin with the desired molecular weight, namely about 750 to 300,000 and preferably up to 150,000

pp,,, γ g

A number between 1 and 30 denotes, X is a chlorine, bromine or iodine atom and m is an integer between S and 2000.

2. Layer support with an electrically conductive layer according to claim 1, characterized in that that the electrically conductive layer contains a compound of the formula given in claim 1,

whole is between 20 and 100

3. Layer support with an electrically conductive layer according to spoke 1, characterized in that that the electrically conductive layer from 80 to 100% of a compound specified in spoke 1 Formula consists

4. Layer support with an electrically conductive layer according to spoke 1, characterized in that that it contains paper as a layer support.

The invention relates to an electrographic or electrophotographic layer support having a 0.81 to 4.05 g / m * thick electrically conductive layer from a water-dispersible polymeric quaternary amine.

It is known to cover paper with a coating of an electrically conductive compound which is dispersible in water and which has the required electrical conductivity properties. One Group of compounds that has been found to be useful for this purpose consists of polymers of polymerizable quaternary vinylbenzyl ammonium compounds (U.S. Patent 3,011,918).

However, the disadvantage of this is that your paper, the is coated with these compounds, a strong, unpleasant amine-like smell adheres, which only can be reduced by reducing the pH of the coating to the strongly acidic range. However, this causes corrosion of the device used to apply the layer. Also, these are connections expensive.

The object of the invention is economical and

wise 2000 "

Choose polyepihalohydrin of suitable molecular weight. Polyepihalohydrins with molecular weights in the range from 450 to 180,000 were investigated, which showed that layers containing these polymers can be printed on paper without any difficulty

can muster. The epihalohydrin preferably has a molecular weight in the range of about 1200 to 100,000.

The invention achieves that the electrographic or electrophotographic layer support

can be produced with the electrically conductive layer in an economical and simple manner and the Electrically conductive layer has electrical conductivity within a wide range for the relative humidity. Thus, a substrate made of paper has

so with the electrically conductive layer, which contains a compound of the above formula I as the polymeric amine, a specific surface resistance in a range from about 5 · 10 ⁸ to 1 · 10 ⁵ ohm / cm * at a relative humidity of about 8 to 75 %. According to one embodiment of the invention contains

the electrically conductive layer is a compound of the formula I given above, in which R equals a? ¹ methyl group, X is a chlorine atom and m is an integer between 20 and 100.

This polymeric amine can be quaternized by trimethylamine with polyepichlorohydrin produce.

According to a further embodiment of the invention, the electrically conductive layer consists of 80 to 100% a compound of the formula L given above This can be achieved in that in the Preparation of the polymeric amine polyepihalohydrin is essentially completely quaternized, wor-

^ ₁ ζ »means that the polymer 80 to 5 ° / quaternary adducts of the formula

OCH ₂ -CH-

χ-

CHj

N ⁺ -R

holds where X, R and m are those given above

!, Have meaning.

^£ Partially quaternized polyhalohydrins

will. A polymer, such as. B. Strength, can be called Component of the electrically conductive layer used to break down the electrically to prevent conductive polymeric amine by keeping the latter on the surface of the paper. because the use of a polymer such as starch has very little effect on the electrical conductivity properties of the coated paper, it can serve the purpose stated above. The shift out ίο Starch and the polymeric amine can have a share of starch up to a ratio of starch to polymeric amine of about 1: 1. The one provided with the electrically conductive layer

, _H ._ ".,. . _Jm ._ have been coated with regard to its specific

wsm »- which showed that the layer 15 surface resistance according to a standard embossing the emergency procedures are checked with the electrically conductive layer, which essentially "Ultimate electrical conductivity is absent if the degree is as specified in" Standard Methods of Test for

. , .—! ... · - "." ".." * <". τη «· / i;» "t r"; "D" i —-,:,. "♦ - Resistance of Electrical Insulation Materials",

D 257-46, described corresponds to, ao For the production of a printing surface for Electrographic printing will have a tration of 40% solids of the polymeric amine used in Example 1 below in water. The electrical conductivity is checked by a Potential of 500 volts is applied to a sheet of paper after it has previously been at a relative humidity of 20 or 50% has been conditioned for 36 hours. The results are summarized in the following table:

30th

35

Used paper

Surface resistance (Ohm)

(20% relative Humidity)

Surface resistance (ohms)

(50% relative humidity)

Polymeric quaternary layer Amine layer weight

(B / m ¹ )

6.4 x 10 ¹⁰

wemugw ι * »-» ·· ο- , -

the quarternization is below 70%. The polymers Therefore, as stated above, 80 to 100% end preferably 90 to 100% quaternized. According to a further embodiment of the invention, the layer support contains paper. The paper can be coated or uncoated, have a high wet strength and a thickness of 0.076 to 0.152 mm.

Other electrically conductive or semiconducting materials can also be used as layer supports become, such as B. Plastic films, including cellophane sheets, Fabric and metal foils, such as. B. aluminum and copper foils.

The polymeric amine of the above formula I can be obtained as a continuous film by coating, Applied to paper by spraying, dipping, brushing or any other suitable application method will. The polymeric amine is preferably used as a layer in the form of an aqueous dispersion or Solution applied to paper. The coated paper is then dried, leaving a product with an electrically conductive surface is obtained.

Standard application devices such as B. a knife 40 x. ^N 1 7 6 · 10

applicators, were applied, and the ^ Jr "j / miymeres coated paper was dried by the radiant energy of quaternary amine from heating lamps. Along with the ^ _r 2
polymeric amine, other components can be applied to Nr 2 + polymeres, such as clay, starch and pigments. _{45 arternary amine 4> 0} . 10 «The substrate with the electrically conductive layer
of the invention provides one used for electrophotographic die designated Nos. 1 and 2

Printing is a suitable printing surface. Papers were those used in electrophotographic

Standard papers used to make an electrophotographic on-industry. The P ^a P ' ^er drawing sheet, the electrically conductive layer 50 weighs, for example, 80 g / m ² and is made from a paper pulp that is moderately raised from the polymeric amine in a manner known per se, made of bleached, chemical with a layer of an extender, the starch, """-'- ^{ui: tf} -""""T«"" rfrfnil «toflen and polyvinyl alcohol, polybutyl acetate or polybutyl styrene
can be provided and then the extender layer
with a layer of an electrophotographic, 55
photoconductive material, which is one of the oxides, iodides,
Selenides, sulphides or tellurides of zinc, antimony,
Aluminum, bismuth, cadmium, mercury, molybdenum or lead, selenium, arsenic trisulfide, lead chromate or
Cadmium arsenide can be provided. A 60
a particularly suitable photoconductor for this is possible
pure zinc oxide produced by atmospheric oxidation
produced by zinc vapor. The photoconductor

should be in finely divided form and preferably jbuu lenc cpiuiiiuiujrunu «...—. - ~

have a particle size below 1 μm. 6 ₅ lined reaction vessel given, stirred unü

¹ Before applying the layer of the polymer, examined with regard to the water content. If the amine on paper as the support may also have other water content too high (above 0.2%), a polymer is mixed with the polymeric amine. Part of the epichlorohydrin is distilled off, the

2.2
2.1

10 "
■ 10 »

8.1 1.8

• 10 «• 10 ¹⁰

8.3 · 10 ⁷

3.05

1.72

holed paper pulp from gcuiuum .., v ..

Wood pulp, wood pulp and alumina fillers and fibers as well as precipitated aluminum oxide Resin sizing agent made.

The table shows that the paper has a significantly lower surface resistivity and thus has considerably greater conductivity when the polymeric quaternary amine is applied to the paper has been. The paper coated in this way therefore met the standard requirements of the industry for use in electrographic printing processes.

example 1 3800 parts of epichlorohydrin are in a with glass

Charging by adding fresh epichlorohydrin was. The temperature was another 1.5 hours

is maintained. After keeping the water content at 90 to 100 ° C for a long time,

is low enough (less than 0.2%), the vessel is

closed and placed under a nitrogen pressure of 0.211 to decompose the remaining catalyst,

up to 0.352 kg / cm »cooled ^{to 60 ° C.} 5 and the temperature was for a period of time

A nitrogen atmosphere * SDRD during the feed of 1.5 hours at 150 ⁰ C increased to 106 parts

Maintaining the rate of the catalyst, removing the condensate.

Kettle through condenser to atmosphere. The residue was a pale amber colored, visopenic is a cool liquid that is soluble in toluene and xylene and

Erwa 72.5 kg of 25% triisobutyluminum in io was insoluble in isopropyl alcohol.
Toluoy is slowly being watched carefully

at 60 to 70 ⁰ C added until an exothermic example 3
The reaction occurs Temp & ature is in a controlled manner with the necessary cooling to 138 parts by weight of the product from Example 2 100 ⁰ C allowed to rise. When the initial reaction subsides in a stirrer and heater, the temperature is kept at 100 to 110 ° C by adding a pressure vessel equipped with 130 parts of catalyst until none of the 3 mol ethylene oxide adduct of dimethylamine exothermic reaction can be observed . And 182 parts of the 25% solution of trimethylamine temperature is lowered to 80 to 85 ⁰ C. placed in water and at 100 ⁰ C for 17 hours

95 liters of water are additionally heated below 85 ° C., the pressure in the reactor during

given. At a vacuum of 3.3 atmospheres during this time, the batch fell to a slight vacuum.

559 mm (minimum) to a temperature of The reaction mixture was with 23 parts of 30% igei

100 to 110 ⁰ C torn over, brought 1 to 2 barrels of condensate hydrochloric acid to a pH value of 5.1,

to remove sat. A clear, brown, viscous liquid was

One calculates the total weight of the contents as hold, which was readily soluble in water.

of the reaction vessel on the basis of the added _R. . . .

and removed materials. The loading in P

Weight percent for the following stage is 93 weight .viie Jes product from example 2

as follows: were heated to 140 ° C. with stirring, and 177 parts

26.2% content of the reaction ^{vessel, 3} ° ^a * ^{3 Mo1} ethyknoxide adduct of dimethylamine

τι 00 / - «co / · -o · -ι- · ι. 1 · were in shares during a period of

73.8% 25%, saturated, aqueous Tnmeth> lam.n. ™ £ ^ _{added The reaction area was added}

The trimethylamine is cooled at a temperature to 110 ^c C, and 50 parts of water were added zuunterhalb 8O ⁰ C. The vessel is set briefly. The heater was switched on, vented to bring it to atmospheric pressure. 35 and the reaction mass was am for 5 hours

The reaction vessel is then sealed and kept under reflux (112 to 116 ⁰ C), after which 50 parts of heated atm to a pressure of 7, which were added in water and is likely to be about the mixture at 90 to 100 ° C the case. 35 parts of 30% strength hydrochloric acid are kept at this temperature for a long time to a pH value of 16 hours. Then the about 6 were brought.
Temperature while maintaining the pressure of 7 atü 40 B eis ρ ie 1 5

slowly increased and at 130 to 140 ⁰ C for 2 hours
held. 176 parts by weight of the product from Example 2

It is cooled to 70 to 8O ⁰ C and 113 to have been with stirring to 150 ⁰ C is heated, and 251 parts of 226 kg 30% aqueous hydrochloric acid to a 5 mole ethylene oxide adduct of dimethylamine pH of 5, 5 to 6.5 neutralized. 45 were over a period of one hour

added. The temperature was for 4 hours

B e i s ρ i e 1 2 kept at 128 ° C, after which 100 parts of water were added

and the reaction mixture was 29 parts

750 parts by weight of epichlorohydrin (containing 30% strength hydrochloric acid to a pH of about 6 0.64 parts of water) were placed in a reaction vessel that was 50%.
which was equipped with stirrer and cooling, example 6

introduced under a nitrogen atmosphere. One

Solution of 25% triisobutylaluminum in toluene 121 parts by weight of the product from Example 1

was added in portions at 6O ⁰ C until were combined with 520 parts of 25% strength Trimethyleine exothermic reaction showed. It took 28 parts of er-amine in water with stirring for 16 hours to initiate the reaction. ^{heated to 100 °} C. in a pressure vessel. 549 parts of this

The heat of reaction increased the temperature of the product and the reaction mixture with 24 parts of 30% strength hydrochloric acid rose to 115 ° C. in 20 minutes. Which brought to a pH of about 6
The temperature was kept under cooling for 1.5 hours. . , _

held at 100 to 115 ° C. During this time 60 examples /

there was an increase in the apparent viscosity of the 42 parts by weight of the product of Example 2

Reaction mixture a. After the reaction had subsided in were together with 81 parts of a 7 mol Äthylendem degree that cooling was not necessary oxide adduct of dimethylamine and 59 parts more, the batch addition of 25% aqueous trimethylamine with stirring of catalyst at 75 to 100 ° C resumed, 65 for 16 hours in a pressure vessel to 10O ⁰ C and 12 parts were heated over a period of 515 parts of this product were added with 51 parts for 3 hours, the temperature by 30% hydrochloric acid to a pH A value of about 6 maintained the heat of reaction generated.

Example 8

70 parts by weight of the product from Example 2 were heated to 145 ° C. with stirring, and 199 parts of a 7 mol ethylene oxide adduct of dimethylamine were added over a period of 30 minutes. The reaction mass was held for 4 hours at 130 to 14O ⁰ C, and 50 parts of water were added woks. The mixture was refluxed (112 ° C.) for an additional 2 hours. 50 parts of water were added and the reaction mass was brought to a pH of about 6 with 32 parts of 30% hydrochloric acid.

Example 9

35 parts by weight of the product from Example 2

were together with 99 parts of an 11 mol of ethylene

5 oxide adduct of dimethylamine and 46 parts of 25% strength aqueous trimethylamine with stirring Heated in a pressure vessel at 100 ° C for 16 hours. 526 parts of this product were made with 39 parts 30% hydrochloric acid to a pH of about 6

ίο brought.

Polyepibromohydride and other amines can also be used to make similar products produce.

Claims (1)

Patent claims: L Electrographic or electrophotographic layer support with a 0.81 to 4.05 g / m * thick electrically conductive layer made of a water-dispersible polymeric quaternary Amis, characterized in that the conductive layer is a polymeric amine compound of the formula