DE1806414B2 - ELECTROPHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

The invention is called an electopholographic uifzcii / hiuingsmalcnal with a Phoioleiier-Bindenillcl-Schichl, do al-, a mixture of binders vlisch polymerizaten complies with.

It is hekanni. in elektrophoiouraphisehen ΛιιΓ- S 'calibration materials binders aiii for example sihkon-, alkyd-. Styrene buladiene or vinyl base / u to turn. These binders should only ile flour Link photoresist and sensitizer to the support. but also the photoleilende layer an improved electrical system without loss of income Lend chargeability, they shouldn't Weatherproof wedge of the elekliophoiographic Improve recording maicriulicn. The known Binders did not sufficiently meet these requirements. being those with such binders Manufactured clektrophotographic material / information material ·! especially in tropical and subtropical countries with regard to their scorch resistance wedge and climate protection to be desired considerably left over. In addition, they contain nitrogenous Copolymers usually only have a low intrinsic resistance and an inadequate insulating capacity. Therefore, the dark decay of electrophotographic made with such binders is Evidence relatively strong, so they exposed and developed as soon as possible after charging. Even in one of these Traps, however, have been greatly displaced with the known electrophotographic recording material .11 Receive copies of images.

The founding was thus based on the task of a Highly sensitive, e ick troph ot ogniphi sch es recording material to create that compared to the known electrophotographic recording Xs materials has significantly better copying properties, especially for treatment in high-speed copiers suitable and extremely weather-resistant.

The invention is based on the knowledge that the problem posed can be achieved by using novel binders in the photoconductor layer.

(The object of the invention is therefore a clektropholographic recording material with a photoleiler binder layer which contains as a binder a mixture of copolymers, which is characterized by the combination of a copolymer of a vinyl compound and a maximum of 40 mole percent of a Compound of Formula ^ ⁰

CH,

Where R equals a hydrogen or halogen atom or an optionally halogenated methyl. Ethyl or propyl radical and X is equal to one

CN-. CON or CONIICI-I ₂ OR ₁ remainder

in which R ₁ denotes a hydrogen atom, a methyl, ethyl, propyl, phenyl or benzyl radical, in <vli> r a maximum of 40 mol percent of a trialkyl or benzy, ammonium salt, of acrylic or methacrylic acid with a maximum of 5 (1 Percentage by weight of a lerpohmerisal made of acrylic acid hydrolyzic acid or Meihacrylsüureh \ dro \ yäth \ lesier, an acrylic, macroylic, crotonic, maleic or illaconic acid and the vinyl bond used for the first copolymer, with a maximum of 50 percent by weight of an (icium) of an organic acid anhydride and a copolymer of acrylic, mehacrylic, i'rotonic, maleic or liaconic acid and the vinyl compound used for the first copolymer or a maximum of 50 percent by weight of a mixture of an organic acid anhydride and a named terpolymer .

The invention increases the resistance to rolling electrophotographic recording materials better !, by acting as a binder for the photoconductor a copolymer of certain carboxylic acid monomers or a mixture of certain copolymers and acid anhydrides are used will. The loss of the acidic components caused here by an increasing amount of the acidic components photoconductive layer on electrophotographic Sensitivity is taken into account that up to 50 weight: percent of a nitrogenous Copolymer with one of the acidic components mentioned either as monomer units (Polymer I) or polymer containing organic acid anhydride (polymer U) as an additive be combined.

The clektrophotographic recording materials according to the invention also have in addition to their good weather resistance excellent electrostatic chargeability. a lower dark decay and less post-exposure fatigue.

The production of the _{fiction L} .c wet electrophotographic recording materials takes place in a manner known per se by adding a mixture of a Pliotoconductor. z. B. zinc oxide, a sensitizer, ζ B. Broinphenolhlau. Fluorescein. Rose Bengal and the like and a binder of the type described are dispersed in a suitable solvent and the coating solution obtained is applied to a layer support in the form of a metal plate or a paper sheet previously made conductive on the reverse side and dried.

The graph shows the influence of the acidic component on the sensitivity of the photoconductive layer and the weather resistance of the electrophotographic Recording material according to the invention. The term "acidic component" includes both the polymers I and the polymers II. The abscissa shows the content of the Acid component in the total volume of the binder in millimoles per 100 g in the photo'citlahigen Layer contained zinc oxide applied.

Curve 1 shows the change in sensitivity with increasing content of the acid component. To determine this change in sensitivity, the time (in seconds) was measured which was required for the charge to fall to half the value on exposure. Curve 2 shows the change in weather resistance with increasing content of the acid component. The Weather Resistance W - ~ '.' .

where \ 's is the saturation potential. Vo the potential at the time of exposure (Γ. <- Vo ----- dark decay)

mean. I'Milt the Ι-.ηηίίΜιιημ the kunenwciie will reported in Example 1 below.

Has graph shows that 1 mil growing <ichali an acidic component the lmplindlichweil iiacliläßi. the Wilierungsbesläiuligkeii but noticeably better> will.

The following examples bring the | · .ιΤιιηΙιιημ closer spoiled.

A eis ρ ie II ι "

I. Making ties slickslofflialligeii
Mixed polymer

70 parts by weight styrene. 10 (lew ichiseile Acryl- is saurebuty lcster. 15 C ieu ilsleile Acr \ lnilril uiul 5 (iewiditsleile Aer \ lamid were in the usual way in X \ | n | and Buianol as Polymensulionsmetlium mix polymerized.

2. I lcrsldlung of the acid components as Mmw ·

no unity of reverberant interpolymer
50 C iew point styrene. 40 (icwicllsteile Acrylsäuicathyller. 15 (iewiehlsleile Melhaci -ylsiiurc-, .'- liytlrowätln! Ester and 3 (iewiclusieile acrylic acid is polymerized in the usual way in xylene, oluo! And bulaiiol as l'ilyniL-iL-i.

Unless these two binders have been used three coating compositions of the following composition prepared. The coating masses were previously electrical on the rear side in the usual way Apply paper made conductive as a support and / u a photoconductive layer covered.

I Vi

Zinc oxide for electrophoiographic purposes in g ...

Sensitizer in ml · Ί

Toluene in ml '. |

Nitrogen-containing polymer in g j

Copolymer containing acidic monomer units in g;

The sensitizer consisted of a solution of Ι "·» bromophenol blue. 0.5 "» fluorescein and 0.25 ",> Hose Bengal in methanol.

The obtained carbon-pholographic recording materials were once after storage in a normal climate, i.e. at 20 C and 65 ″ relative Humidity, and on the other hand in a tropical climate, d. H. at 30 C and SO to N5 '\> relative humidity, evaluated in the following way for their electrostatic properties :

The saturation potential I 's was reached after 30 seconds of continuous charging by means of corona discharge (- 6000 volts).

The potential at the time of exposure Io became after 30 seconds of continuous storage in Dark measured following charging.

The dark decay was thus Vs - \ Ί>.

100
I.

150
20th

ICl

K) (I.

150

20th

The preexposure potential Vs' was measured like the Sältigimgspotenlial l'.s, but after previous exposure of the individual recording materials for 1 minute to a light source with an intensity of 500 lux.

The susceptibility or the half-life 12 / was determined as the time in seconds in which the potential l'.s of the respective electrophotographis seen Recording material when exposed to light with an intensity of 6 lux to half the value fell off.

The dark decay property thus results as V'hVs. it is the better, the higher this value i., i.

The degree of noise is thus given as Vs'jVs and is also the better Jc is higher this value. is.

The results of these investigations are summarized in the following table I:

Tabel

1-.IcMm-

plu.loui-iiphisclu's
On / eidiniirms-

Normal climate i

(a) Ϊ 500 j 0.85! 3.0

(b) 100 '0.10 I.

(C), 500! 0.S5: 6.5

- = Not mcf.lhiir.

The values in the table show that the Recording materials have significantly better properties than the comparison materials. in which the binder consists either only of the nitrogen-containing copolymer or the acidic one Monomereeinheilcn having copolymer consists. When attempting to copy, the electrophotographic Recording material (b) image copies of low density and with the clcktrophoto-

400 0. Tr ip-jnklim I. 1 : i I ν I S I Λ 40 I .S I.
t 0 0.62 1.75 400 (I. 70 [ 4th 0.41 ) .50 ! 0 0.55 0.75 70

graphic recording material (c) obtained extremely blurred and spotty image copies. With the crfindingsgraften In contrast, photographic recording material was clear and opaque Receive copies of images. The elctrophotographic recording

f> 5 drawing material according to the invention is suitable excellent for use in high-speed copiers.

It is also worth mentioning that the

Coating compound (a), after addition of 0.1 g of phthalic anhydride, gave an electropholographic recording material whose half-life was 1/2 / approximately that of the electrophotographic recording material a) and whose value for the dark decay property VoIVs was 0.80.

Example 2

1. Production of the nitrogen-containing copolymer

75 parts by weight styrene. 10 parts by weight of butyl acrylate, 5 parts by weight of N-methylolacrylamide and 10 parts by weight of acrylonitrile were used in more common Copolymerized in xylene and butanol as the polymerization medium.

Components

2. Production of the acid component as a monomer unit containing copolymer

55 parts by weight of styrene, 30 parts by weight of acrylic acid biityl ester. 10 parts by weight of methacrylic acid, i'-hydroxyethyl ester and 4 parts by weight of maleic anhydride were dissolved in toluene by the usual method and butanol copolymerized as a polymerization medium.

ίο Been using these two binders three coating compositions prepared with the following composition. The coating masses were applied in the usual way to paper that had previously been made electrically conductive on the reverse side as a substrate worn and dried to form a photoconductive layer.

100

IbI! κΐ

iVcrplcichprobe

100

100

150

150
20th

150

Zinc oxide for electrophotographic purposes in g ... j

Sensitizer (as in example I) in ml;

Toluene in ml ^!

Nitrogen-containing copolymer in g j

Mixed pole containing acidic monomer units; ! !

mcrisat in g! 15! \ 20

The individual electrophotographic recording materials were as in Example I after storage

on the one hand in normal and on the other hand in tropical climates on their electrostatic properties and their copying

performance examined. The following results were obtained:

Table II

lilcklro-

photographic cs
Recording material

Normal climate

Is

550
150
500

r.i ι s

0.85
0.27
0.85

1 yr

3.0
1.0
6.0

IY Γ

0.70 0.43 0.75 Tropical climate

l.v

In V-

ι: r
3.0

Vs V

The electrophotographic recording material according to the invention furthermore delivered very clear image copies during a copying attempt and turned out to be for the Ideally suited for use in high-speed copiers.

Example 3

Example 1 was repeated with the following copolymers and coating materials:

1. Manufacture of the nitrogenous
Mixed polymer

70 parts by weight of methyl methacrylate. 15 parts by weight bulvl ester of acerylic acid. 5 parts by weight of Acrvl-

500 0.65! 3.0 0.65

50 ■; j 0.40

450 \ 0.70 i 4.0 S 0.60

nitrile and 5 parts by weight of acrylic acid were used in the usual way in toluene and butanol as the polymerization medium co-polymerized: here enough trimethylamine was added to make the carboxylic acid quaternize.

2. Production of the acid components as a mono-

mixed polymer containing meren unit
5 °

65 parts by weight of styrene. 40 parts by weight of butyl acrylate and 2 parts by weight of methacrylic acid were copolymerized in the usual manner in xylene as the polymerization medium.

3. Coating masses

Besiamlteile

Zinc oxide for electrophotographic purposes in g

Sensitizer (as in Example 1) in ml

Toluene in ml

Nitrogen-containing copolymer in g

Copolymer containing acidic monomer units in g

Phthalic anhydride in e

iVerde

M) (I. 100
1 100
t 1 50 I.
150 I.
150 10 20th 10 20th 0.1 0.1 0.1

The individual coating compositions were each applied to aluminum plates as a substrate and dried.

The individual electropholographic recording materials were as in example I according to position

tion on the one hand in normal and on the other hand in tropical climates on their electrostatic properties and examined their copying performance. Here were the following Get results:

Tabel

Electrical
phniouraphic
On / eielin- ^
material ■ ! 's
450 Nc
I '"'■>
0.X5 'rrnalklinia
'. ι: ί
3.0 IsIx
0.70 I .S
400 Tropei
' n>i',
•
: 0.7S climate
I, - ' I. 0.79 4.0 Cv '1
0.60 fb). ^; 150
400 \ 0.45
0.S5 5.0 0.50 '
0.65 SO
3X0 0.70
0.50 V ';
Κ)

The electrophoretographic recording material according to the invention When attempting to copy, • delivered clearer image copies and proved to be suitable for use Ideally suited in high-speed copiers.

Example 4

Example I was made with the following mixture polymers and coating compounds repeated:

I. Production of the nitrogenous
Mixed polymer

70 parts by weight of styrene. 20 parts by weight of butyl acrylate and 10 parts by weight of acrylonitrile were conventionally used in toluene as polymerization medium copolymerized.

2. Production of the acid component as Monomercncinlicit containing copolymer

50 parts by weight vinyl acetate. 20 parts by weight meth acrylic acid methyl ester. 15 parts by weight of acrylic acid butyl ester. 12 parts by weight of acrylic acid - ^ - hydroxy ethyl ester and 3 parts by weight of acrylic acid were in the usual way in toluene and ethyl acetate: Polymerization medium co-polymerized.

3. Bcschichtune masses

Components

Zinc oxide for photographic purposes in g

Sensitizer (as in Example 1) in ml

Toluene in g

Nitrogen-containing copolymer in g

Copolymer containing acidic monomer units in g

Phthalic anhydride in c

(al p. _S cniä «l iVcrplciv (dl (errindnn 100 100 hsprobc) 00 I. I. 100 I. 150 150 1 150 10 20th 150 10 10 H) 20th

The individual coating compounds were each made electrically conductive on the back Paper applied and dried.

The one photographic recording materials were as in Example 1 after storage on the one hand in normal and on the other hand 1 roper klima is looking for their electrostatic properties and their copying performance. Here were fo iiendc results obtained:

Ta be lie IV

f.lcktr .--

la I ...

IbI. . .

.> (! (I O.S? 3.0 450 0.92 2. ') 150 0.30 O.S. 5 4.5

1, Tn ^ penklima ! I 5 C 0 , 1\ : I: ί • 0.65 450 0 7 p 2.5 0.5S 430 .S3 : 2Λ ι 0.70 50 0 : 0 WI 450 7> 4 0

The clektrophotographischcn according to the invention Recording materials with and without phthalic anhydride even failed to deliver in copying tests tropical climates very clear image copies and proved to be excellent weather resistant.

Claims (1)

Claim: Electrophotographic recording material with a pliotolite binder layer. the contains a mixture of copolymers as a binder, characterized by the Combination of a copolymer of a vinyl compound and a maximum of 40 mol percent a compound of the formula CH ₁ = wherein R equals a hydrogen or halogen atom or optionally halogenates one Methyl-. Ethyl or propyl radical and X is the same 10 one CON - or C () NHCH, OR, -Rcst in which R _{1 is} a water loaf. a methyl. Ethyl-. Propyl. Is phenyl or benzyl radical. or not more than 4 () mol percent of a trialkyl or benzyl ammonium salt of acrylic or methacrylic acid, with not more than 50 percent by weight of a terpolymer of hydroxyethyl acrylate or hydroxyethyl methacrylate. an acrylic. Methacrylic. Crotonic, maleic or itaconic acid and the vinyl compound used for the first copolymer. with a maximum of 50 percent by weight of a mixture of an organic acid anhydride and a copolymer of acrylic, methacrylic. Croton-. Maleic or itaconic acid and the vinyl compound used for the first copolymer or at most 50 percent by weight of a mixture of an organic acid anhydride and a named terpolymer. 1 sheet of drawings