DE2458128C3 - Current sensitive image recording material - Google Patents

Description

The invention relates to a current-sensitive recording material of the type specified in the preamble of claim 1

The recording of electrical image signals for visual information reproduction is becoming increasingly important. Typical examples of this, in image telegraphy, Computer print-out stations, instrument writers, etc.

The most commonly used methods are electrical discharge recording and electrolytic recording.

In discharge recording, a white pigment layer is superimposed on a black, electrically conductive one Layer or an electrically conductive layer, e.g. B. aluminum, applied to the black layer. To the Creation of an image is carried out via a recording stylus one discharge, with the black Layer is exposed imagewise. The surface layer is thus perforated in this process. The discharge creates a pungent odor and the stylus wears out relatively quickly. Of the the resulting perforation dust is also annoying, In addition, the paper is easy to get dirty because the black layer by mechanical action, e.g. B. when bending or under pressure, can be exposed. In the interests of the lightest possible perforation the discharge, the surface layer is made as thin as possible. The black layer will therefore regularly shimmer through, so that the paper has a grayish, poor appearance.

The electrolytic recording process is a wet process, the durability of the Recording paper is therefore small and the image properties are impaired by staining. In addition, the recording paper curls when it dries. These disadvantages are inherent in all wet recording methods.

In JP-PS 22 341/1963 and 29 630/1969 is a described dry current-sensitive recording material, in which metal compounds in one j «insulating resin are dispersed. These metal compounds are reduced with a differentiated power supply to the free metals. There are almost all metal compounds that have relatively high electrical conductivity are colored while those are weak

jo colored metal compounds have a low electrical Have conductivity. In order to make such metal connections sensibly electrically conductive, are therefore additional chemical and / or physical treatments required. However, these treatments stain at the same time the metallic connections, and it increases therefore the basic color. The image-wise differentiated

Power is supplied with the help of an electrical Discharge with all of the disadvantages noted above. Further, JP-PS 5 476/1967 and 13 239/1967

4ί describes a method in which an electrically conductive layer is evaporated onto white or transparent compounds such as silicon dioxide. Then Jen dispersed them in a matrix and a image-wise differentiated power supply exposed. the

"Production of the recording material is fine, however problematic, especially with regard to a satisfactory reproducibility wedge.

A current-sensitive recording material which is known from the state of the art

«Has no disadvantages in principle is the subject of the own older right DE-AS 24 14 201.

The current-sensitive layer of the recording material has at least one electrical layer conductive compound, a color-forming compound and a binder with the peculiarity that the electrical conductive compound is a compound containing zeolithiscrics water, i.e. to the zeolites or Zeolite-like compounds. These compounds (see details below) included

ft ^r > a comparatively large amount of water in varying proportions, but nevertheless feel completely dry and are not hygroscopic. This significantly improves the electrical conductivity. Fs is therefore

possible to obtain a recording material suitable for the color formation reaction only requires low currents and high quality images with good Color tone reproduction provides recording materials with a light, white background and excellent grip achievable. These recording materials are also easy to manufacture and non-toxic, have high shelf life and color fastness of recorded images.

In the case of the current-sensitive recording materials according to the older proposal, the color-forming components are present in comparatively high proportions and is the color-forming reaction not always independent of the type of current (direct current or alternating current) or polarity.

The object of the invention is therefore to provide the current-sensitive recording material according to the older Proposal to the effect that the required concentration of the color-forming component reduced and uniform image quality can be achieved regardless of the type of current or polarity.

The inventive solution to this problem is in characterizing part of claim 1 specified. ·

The image recording material according to the invention therefore contains a color-forming compound together with a color development accelerator. It has been found that the color development accelerator can be used reduce the required proportion of the color-forming compound, for example, by '/ s to Vi. The production of the current-sensitive recording material is therefore correspondingly cheaper. on the other hand can be combined with the color development accelerator with the same proportions of color-forming compound Increase the color tone and thus the contrast. As was further found, the presence of the Color development accelerator ensures that the results are independent of the type of current and polarity. That Recording material can therefore be used in all apparatus.

Preferred color development accelerators are aromatic amines, phenols, iron (III) chloride, copper (II) chloride and stannous chloride.

If, in a further development of the invention, a pH-adjusting compound is added to the recording material all additional further components are added, then possible dark reactions can surely suppress between the color development accelerator and the color-forming compound. The pH-adjusting component prevents both the bleaching of the power supply developed image color due to light irradiation as well as color development without power supply as a result Light exposure. The long-term stability of both an excellent image and the recording material itself is thereby decisively increased.

As the pH adjusting compounds, aliphatic or aromatic carboxylic acids, inorganic ones Acids or imides preferred.

According to a further embodiment of the Aufzeichriurigsmaiefiäls are the electrically conductive, zeolitic water-containing compound in a first layer and the color-forming compound as well the color development accelerator and optionally the pH-adjusting compound in another Layer included. This makes it possible to achieve particularly color-intensive image recordings, since the entire color development takes place in a thin surface layer without affecting the conductivity would be undesirably reduced.

However, regardless of this, it is recommended that

Based on one part by weight of color-forming compound, 0.01 to 5 parts by weight of color development accelerator and / or 0.01 to 5 parts by weight of pH-adjusting compound are present.

The term "compound containing zeolitic water" used here stands for compounds in which meet the following conditions:

1. The compound contains so-called zeolitic water, which is in the "cavities" of the crystal structure is weakly bound Even if the compound contains enough zeolitic water, it is not sticky and does not melt, but remains in a seemingly dry state obtain.

2. Even after the zeolitic water contained in the compound by heating or taking has been completely removed under reduced pressure, no structural degradation occurs.

3. The compound from which the zeolitic water has been completely removed absorbs at

2 ") low moisture immediately water and ninant to return to their original saturated state.

4. The zeolitic water lies at the same time with different types of ions, which the connection

jo contains, before. Therefore the connection has a excellent electrical property.

The compounds containing zeolitic water retain their specific physical properties r> regardless of whether they are dispersed in a binder or in pure form.

Specific examples of these compounds are the natural zeolites. They belong to the group of aluminum silicates and can be represented by the following general formula w :

[M ^: \ (M +) ₂ ] O • AI ₂ O ₃ • / HSiO ₂ • / JH ₂ O (3 <mi 10 ;.

where M ²⁺ and M ^{+ are} monovalent or divalent metal ions, usually Ca ²⁺ , or also Sr ²⁺ , Ba ²⁴ and K ⁺

4 ¹ ) mean that can also be replaced by other cations.

The zeolites contain specific "cavities" in their three-dimensional structure, and those indicated above replaceable cations are in these cavities

w men held together with a water molecule. Other organic solvents and solvents can also be retained in the cavities with a high polarity are selectively absorbed. There are a number of synthetic zeolites, which have practically the same three-dimensional structure as the natural zeolites and with regard to their Basic properties are identical to these. There are also natural or synthetic compounds, which have a completely different chemical composition from the zeolites, although they have the same basic properties as zeolites: d. that is, that they have "cavities" and you "; Structure when absorbing and desorbing water does not change. They are called zeolite-like compounds

hi and can also be used.

The zeolites that can be used here, namely natural and synthetic zeolites and zeolite-like compounds, can be classified as follows:

(11 Analcitgruppo

Anal egg! l'ollucit \ iseit Kchocsit

l2) Sotlalil Influenza: llydrosodalil

S \ nthctiNchor / enlilh \ S \ nihclisclicr / eolilh \ S> ntlietischer / eolith>

i'i Chab.i / iiuriippi. " (h.ib.i / H ' (inielinif I rinnil' le \> nil

i4i Niilriili ^ ruppe N.itroht Meviilil Senleeil I hiiniMinil I (ΙιημΙπηιΙ (iiinnardii

Mouni.iinit (Cs.NiD.MSi.O, ν ll, () (v <K)) C ^- ; i | "N;i.-AI," Si _r J '", (II -.> ,. -, (ll .-. l)), s - Cl. ,,

Nii, (.- \ l, .Si _h () |,) (Oil), Nii _{> (} , Cii, J, \ l, - ,, Si, _; ,, () ·. ,,) 20. "? · N ₁ I ₁ - (AI, .Si ₁ -Oi ₁ INiIAIO.- 2 ') II.-C »Ni- (AI-Sii, O,„) ■ \ HO (v - (O Nii.O AI. O ·.:> (. SiO- ν II-O

(C; i Vi-) AliSi.Oi U HiO INiI-CiHAI-Si ₁ O ;. (ι II.O (Ci Μμ Ni KI MSi, O ■ d HO (.K M-Si ₁ OI (»III)

N; iI M-Si-.O _; ., ι 2 HO Ni-C .Η M, Si, O 's II.O CiI MSiO „ι ■ .-. Il-O ViCi-I M.Si.O- I ('Il-O HH M-Si :() ■.,) -I HO Nu (; i (M.Si, .O - ,, i (i Il -O KN, i (.illl-SiJ) · ι 5 II.O KVi (.iillSi.O-) ■ 5 II-O

I Ι.ΐΓπιηΚιιιιμπίΐ'ρί. · I l.irni 'itiini

I'llllill'Mt

(iii-iinnilit

Hi!

Ui IM _: Si I) -ι 4 Il-O iK \ Vi M M. Si (). Id Il-O (.ii M-Si OI 4 HO N.! Ι M-Si OI ^ HO

ViC .ι ι \ l .Si O ι ■ ■ I ΐ SII-O

D'.iJii.irdit I -j ": -. · '·!

NiK MSiO -ι ϊ HO (Nit .ii -AI ₁ Si-O _1. ■ 12 HO Ni Wm. { \ 1 Si Ol IS HO

UT structure

WKroitin Cu -M-Si-O .ι 6 II-O Ni K Ci ι Ai .. Si -O .1 5 III) ί .K MSiO ι - HO Cu AI ₇ Si.O ι 5 HO (Sr.HiCii AISiJ ) .. - 5 HO C ill AISi-O.) 4 HO CiI M-Si, O j)., HO iK.Cii.Nat- .. llAI.Sii-HO _M ] 6 ¹ WI HO IKNalCii.Mg.Mn )] _: I Al, _M 5i - ,,, O- _: ..I 320 lld LiAISi-O ,, HO

(Si / colilliiihnlkhc connections: (S-I) / lithium-like silicone bag

They “do not earth unlei / OoMtI-- classified, reveal iciloch / eol

W '; is \ er.

Ilen 11

'ordierit

Miliiiil

Osiiniilit

I Iwlrilisierlcr Nepbelin

( .Herewith

Huddmgtomt

(SOi \ other /eolite, similar compounds Il (ierniiiiiiile
lh l'hnsph.ile. \ rsen.tte
Sconidil
l'hiirm.ieiisidenl
Uli u.isserli.illige Mel.illowde

l'silonielan

l \ ι kiiniplewerbinikiiigen
PreulVch Hl.in
Weddellil

AI-He -. [Si "O. | /) HO Mg-AhIAISi.O, O n H «) k (.1-AIUe- [Si - ()., J (1.5 HO (K.Nii. (; Il (Mg.Ie) -I ΛΙ.Ι el _; | (Si.AI) -Ο ·. ,,] · HO KN.il AhSi ₁ O;,.! ■ i / Il-O Ni, (.1,1 AI.Si. (); l (O ■; MO Nil. MSi O. (1.5 Il O

M. | H (ie _; ((ieOii O || ■ 4 MO (M Met.illinni

IcAsO ₁ : iho

k | l e- (OMi _: (\ sO
ι li.iI i Oi-.Mn.O

Iho

M. [l eiCNi I- i: IhO. (M Mn.I e.Cn.Ni./n. (D CiC-Oj ■ \ 2 ■ MlI-O. Ι ν II.5i

The above mentioned explanations are siimilnh; in \ M.nilb; ir. here \ on are indigenous grooves greeni »I iiihli" iiiim "- \ 'oliiinen and lioheni W .issergeruih u ege ¹ -your good l.enfiihiL'kt'ii be \ or / ugi.

The \ erweiulelen l.bbildnerulen \ erbungen are the filgentlen.

I. l'.irhbiMner \ ritr Keilu'Mionsisp

The connections eiit'i.ihen a lelr.i / oliiinisiil / -Li ...-. Ι ...- f. .. ■ ", .. ι

\ N

In the molecule and \ erniogenous a forma / .insicture

- Ν --Ν -C = N-NH-

to be formed by reduction when the ring structure is split up. Examples of such compounds are following:

2.3-Diphenyl-5- (p-diphenyl) tetrazolium chloride 2.5-Diphenyl-3- (p-diphenyl) ietrazolium chloride 2.5-diphenyl-3- (p-snr> lphen \ I tetrazolium chloride

2.3.5-tris (p-diphenyl) tetrazolium chloride 2.3.5-triphenyltetrazolium chloride 2.5-Diphenyi-3 - \ - naphthyitei-azoliumchlond 2- (p-Iodopheny!) - 3- (p-Nitr "phenyl) -5-phenyI-tetrazolium chloride

3- (4.5-Dimeth \ l-2-thm / üi \) - 2.) - diphen>:

tetra / chunibromid ") -l'lien> l ? .i bis (pdiplien \ l) tetrii / ohum-

chloric!

2.3 Hiphen \ I-i- (ni-tols I) IeI rii / oliumel · or id 2.3-1; i (m-nit rtiphony l) iet rii / oliiimperch lor.it i - ((i-nitrophen> l) -5-nieth \ l-2-plien> l-

! etra / oliumehlond 2-Phen> l-3- (p-Ciirho \\ plien \ l) ö-ineth \ l

tctra / oliiimchlornl J- (4.5-dimethiii / oi- (2)) - 5-thi.inil- (2)

2-phenyl-tetrazolium bromide

2 ι [^ irtV..hi. Ι. ^. Ί »Λ.ιι -» »ϊ! Ϊ́Ίί.% \ Nli, Mu I1t .-» tt · -. » / <^! iiim

ehlorid
i- (p-Phen> la / ophen \ l) 2.5-diphen \ l-

tetrazolium chloride

2.3 - Dipheny I-5-h \ dro \ M et ra / oliti in In drowi: 2.3-Diphenyl-5- (p-acet.iminophen \ l) tct r.i-

/ olymic chloride

2.3-Diphen \ l-5- (2 'ui "for \ l) teira / <iliumelilorid 2- (2-P \ nd \ l) -3- (4-chlorophen> l) -5-phcn \ l-

tetra / olium acetate 2.5-diphenyl-3- (p-nit ropheny I (tetrazolium-

fluoroborate
3.3 -dianisole-bis [4.4 - (3.5-diphenyl) tetra-

zolium chloride] 3.3 (3.3 -Dinietho \> - 4.4 -biphenylene) bis-

[2- (p-nitrophenyl) -5-phenyltetrazolium-

chloride]
3.3 (4.4-biphenylene) -bis [2.5-diphenyl-

tetra / olium chloride] 2.2.5.5 -Tetrakis (p-nitropheny!) -

3.3 - (3.3'-dimethox> - ^l M'-biphenylene) di-

tetrazolium chloride 3.3-dimethoxy-4.4 -diphenylene-3 ".3" -bis-

[2-phenyl-5- (2-hydroxyphenyi) tetra-

zolium acetate] 33 - Whore tho \ y-4.4 -diphenylene-3 "J" -bis-

[2-pheny! -5- (2-furfuryl) tetrazolium acetate]

2) Τικι / oliumsal / e

The connections reveal cine Irui / oliuntsal / Structure of the formula.

N ^ C

IK) =

^N (Π

N N / -SO.

- N - N

in their molecule and in the case of A'ilsp.ih ·. η des Ring by reducing the structure

- N ■ = - (■ - (~ N NII

/ U form. Examples of such compounds are following:

> - N - N (I.

IK) S

N N

NN

(Il

N N (

'(Il

N N Ζ Sl),

SO.

· * 'Cn

► - N-- N Cl

N N IiI

Cl

ClI.

-N-N /

V-NN Ur

\
NO-

CH

-N *

N-N Cl

CH

C-H;

-n cor

(Il

N --N

V \

N = N -S '

Br

CH

-N Cl "

Il

NO-

c H = CH —e

. _N -Λ-, J

- NN Cl

NO-

> - ■ N N NO.

ClI-.

II.C

O, N

j 's ■■' ■ _v . ■ ■ '■'

V-N-N Cl

^v \ h

¹ I.

Ν - N I

CII

^; N

V '.

j .i

^N - NN (

N N

NN C

CII

N • (N N U N ShC Il N C- \ _v - C N Cl

O, N

N-N CIO,

NO;

OH

^ M ί'Ν.

CH

^ —N — N Br

CH

CH ₃ -NN ΒΓ

v-N-N Cl

cM -.- e '

/ V-N

-N-

N - N

CH;

CII

CN Br

J- COCH;

N - N CIO7 CH,

CO

he

V-N-N

COCH;

N (CH ₃ ),

In addition, triazolium salts with the ring structure are capable

-N-C

Q

- N = N

in the case of a virtual ring splitting by reduction, likewise the structure

-NH-C = C-N = N-

to build.

Examples of such triazolium salts are as follows:

sor

HO-.S

CIΟΓ

V- N N Ur

3) heterocyclic quartars

Ammonium salts obtained by reduction reaction Can form anhydronium base

These compounds are distinguished by the fact that they have an active methyl group or active methylene group attached to carbon atoms adjacent to nitrogen atoms, which form the heterocycles. Examples of such compounds are the following:

l-MethyI-2-2'.4'-dinitrobenzyIpyridinium-

p-toluenesulfonate

i-methyl-'t-chloroquinaldinium sulfate 1,2-dimethylbenzothiazolium p-loluenesulfonate 1-ethyl quinal dinium iodide 1,2-dimethylbenzoxazolium p-toluenesulfonate 1.233 TetrarnethylindoIenium iodide l-beiicyl-2-methylisoquinium bromide 1-phenyl-23-dimethylquinoxalinium bromide l-ethyl ^^ - dimethyl-T-acethylamido-

1.8-naphthylidinium iodide

When the one obtained by the reduction reaction Anhydroniumbase contains the active methylene group so can a substance which with the active one Methylene group is able to react, can be used as a picture-forming aid. Such substances are sine for example aminobenzaldehyde together with derivatives wis p-dimethylaminobenzaldehyde. Niirosoanilinderivau such as p-nitrosodimethylaniline. Benzoquinonderivaic around Quinoline derivatives.

II. Oxidation type color formers

These color formers are in the form of a colorless or essentially colorless intermediate dye product the dye is formed by an oxidation reaction able. Examples of this are the following:

1) Intermediate product of diphenyl methane dyes Bis (p-dimethylaminophenyl) methane 9.9'-Diä (hyl-6.6'-dichloro-3.J'-dicarb-

azolylmethane (S-Äihyl-e-fflethyl-J-carbazolyO-p-dimethyl-

aniinophenylmethane
Leucoauramine
N-phenyl-leucoaura min
N-amyl-Ieucoauramine
NN diethyl leuconiiramine
Nbis (p-dimethylaminophenyl) nic (hylN.Ncli

niethylpiperaziniuni-melhylsiilfiii
Phcnylsulfonamidobisip-cliniethsliiiiiino

phcnyljmelhan

24 15th 58 128 16 Bis (p-dimethylaminophenyl) benzotriazyl methane 10) hydroxy compounds Bis (p-diethylaminophenyl) morphorynylmethane 4-methoxv-naDhthol Bis (p-dimethylaminophenyl) methanol
Bis (p-diethylaminopnenyl) methoxymethane U-dihydroxynaphthalene
Pyrogallol-! 3-dimethyl ether Intermediate products of triphenylmethane o-aminophenol 2) dyes 2-amino-3J-dimethylphenol Leuco malachite green Oxydibenzofuran
Flavanol SJ'-dicarbazolyl-phenylnieihan-leuko-
crystal violet
9.9'.9 "-triethyI-33 \ 3" -tricarbazolylmethane 3.4-DihydroxyfIavan
Ox> Tcanthydrol
Dioxyindole Bis (3-methyl-4-hydroxy-5-carboxyphenyl) - III 2,6-dichlorophenyl methane 11) Other connections Bis (3-methyl-4-hydroxy-5-carboxyphenyl) - ThioinHrtxvl 4-diethylaminophenyimethane IJl IwII IUUAj I
Indoxvl Tris (p-dimethylaminophenyl) methanol
Tris (p-diethylaminophenyl) methoxymethane Ii 4-hydroxy-isocarbostyryl
4-aminoantipyrine || Intermediate products of xanthene dyes j 3) 3.6-Di (dimethy! Arnino) santhcn UI. Color formers present as pH indicators, see Sect 3.6-Di (diethylamino) -9- (o-carboxyphenyl) - Ji-, if xanthydrol Pentamethyl rosaniline hydrochloride | Intermediate products of acridine dyes 2- (p-Dimethylaminostyryl) -quinoline- |
ethyodide I. 4) 3,6-di (dimethylamino) acridane 2,6-DinitrophenoI U S.ö-Diamino ^ J-dimeihyl-g-phenylacridan 2i Tetrabromophenol sulfonphthalein Ij Intermediate products of azine dyes Tetrabromophenol-tetrabromosulfonphthalein | i
Dibromo-dichloro-phenolsulfonphthalein || 5) 2-lvletbyl-3-amino-7-dimethylamino-5.10-di- Tetrabromo-m-cresolsulfonphthalein || hydrophenazine Dichlorophenolsulfonphihalcin | 9 3.7-diamino-5-phenyl-5.IO-dihydrophenazine JIl Hematoxylin Ji 3.7-Di (dimethylamino) phenoxazine Dibromophenolsulfonphthalein M. 3.7-Di (diethylamino) phcnoihiazine Dibromo-o-CresoIsulfonphthalein 2.8-dimethyl-3.7-diamino-5-o-ιolyl- 1,2-dioxyanthraquinone 5.10-dihydrophenazine Quinoline blue cyanine dibromo thymolsulfone 2-mercaplo-3-hydroxy-7-dimethylamino Π phthalein phcnothiazin Phenolsulfonphthalein Reduced forms of indigo and m-CresoIsulfonphthalein Ij
Ethyl bis (2,4-dinitrophenyl) acetate | 6) Indigonoid dyes S-Oxy-l ^ -dimethylbenzenesulfonphthalein 1 Indigo white 4 (1 p-xylenolsulfonphthalein I. Indigo white disulfate. Sodium set Thymolsulfonphthalein | Tetra-acetyl-indigo scissors Thymolphthalein 1 Lcuko-S.S'-dichloro-thioindigo Rcsorcyl-Azobcnzol-Sodium Sulphonate I Leuco-thioindigo-m-sulfobenzoid. Nairium salt Nairium trinitrobenzoate 1 4Ί Trinitrobenzene 1] Letikophthalocyanine Phenolphthalein || 7) Lcuko-cobalt-phthalocyanine p-Niirophenol i Lcuko-ciscn-ptilalocyanine Cresol benzein | o-cresolphihalein 1 Reduced forms of p-quinone dyes Ml A-Naphiholazobcn / ol-nairiuitisulfonai 1 8th) 2.5-DI {p-chloroanilino) -l.4-hydroquinone-
disulfal. Natrrumsal /
2- (p-chloroanilino) -1.4-hydroxynaphihalin- Alizarin Yellow RI
Alizarin yellow GG 1
Picrynitromethylamine 1 disulfal, nairiiimsal /
Lcuko-Indani gold RS. Nalriiimsalz As color development accelerators, the following |
lowing compounds, listed by way of example. The § Aninrazole yellow V Color development accelerators have reduction accelerators Aromatic amino compounds to like. I. p-aminodiphynylaniine
Diphenvlbcn / idin hf > I. Organic Red Development Accelerators Ken / Klin
p-phenylenediamine I) Aromatic amines Oiphenslamin Phen> llndra / in N.N-fiimclhvl-p-phetnleniliiimm »Λ Ί f lydra / <ibcn / (il 4.4 ¹ -l) iiiniinodipheinlmeihiin 2-1 Ivdrn / ino-ben / ihia / ol Met Ils ldiphetnl.ini in-p - «. Iilfnnsaiirt. · Phcnvllndniwlamin

24 17th α-napthylhydrazine 58 128 18th Diphenylhydrazine 4) Other connections Dihydrazino-diphenyl Dihydroxyacetone Semicarbazide Ascorbic acid Aminoguanidine
p-aminodiphenylamine Furojn 1.2.4-triaminobenzene Hydrogen peroxide
Hydroxylamine p-phenylenediamine
OIL. 1 J "* 1 Hydrazine o-phenylenediamine
4-Amino-2-acetamide-N-diethylaniline 1-phenyl-S-methyM-amino-S-pyrazolone 4-Amino-2J> -dimethyl-N-diethylaniIine 4-HydroxyisocarbostyriI
Indoxvl N-diethy] -p-phenylenediamine in Thioindoxvl N- (4-aminophenyl) -tnorpholine Indandione-1 J.S-chlorocoumaron-S N- (4-aminophenyl) piperidine N-ethyl-oxyindole N- (4-Amino-3-methylphenyl) piperidine 3-PhenylisooxazoIon-5 1 - (4-aminophenyl) pyrrolidine
4-Amino-3-ethoxy-N-diethylaniline Pyrimidazolone 1,4-diaminonaphthalene ι> N-phenyl homophthalimide
Leuco indigo 2) aminophenols Phenazine p-aminopheno!
o-aminophenol 6-amino-1-ethyl-1 -23.4-tetrahydroquinoline p-methylaminophenol
p-aminoxylenol 5-Amino-1 - (j3-methylsulfonamido-ethyl) -
2J-dihydroindoi 2,4-diaminoresorcinol II. Inorganic color development accelerators 2.4.6-triaminophenol Ferric chloride N-hydroxyethyl-p-aminophenol 2> Cuprichloride p-hydroxyphenylamino acetic acid
Sodium 1-amino-2-naphthol-6-sulfonate Stannous chloride p-aminosalicylic acid Sodium dithionate
Iron-ethylenediamine-tetraacetatiChelate) 3) phenols Hydrosulfite Hydroquinone i " Furthermore, the long-term stability of the generated Toluohydroquinone Color image and unused image recording size Chlorohydroquinone terials are still remarkably improved by Bromohydroquinone an addition of various organic and inorganic Dicyanhydroquinone Sl shear acids as pH-adjusting components to the 2-lauryl hydroquinone Color development accelerators. Examples of such N-2- (1,4-dihydroxyphenyl) pyridinium chloride pH adjusting acids are the following: Catechol Chlorine catechm 1) Aliphatic carboxylic acids Catechol-o-carboxylic acid 4 (1 a) monocarboxylic acids Gentisic acid Protocatechuic acid ester acetic acid Protocatechuic acid Formic acid Pyrogallol Lauric acid I pyrogallol monomethyl ether 4Ί Myristic acid 1 pyrogallol-1,3-dimethyl ether Palmitic acid Ι methylpyrogallol monomethyl ether tutyric acid 1 p-acetophenone Stearic acid I tannic acid Behenic acid 1 2,5-dihydroxyacetophenone v> Triethyl acetic acid 1 2,5-dihydroxy-benzophenone Crotonic acid I hexahydroxydiphenyl Tiglic acid 1 dihydroxymesitylene ß- bromopropionic acid I DurohydroGhinon 0, /? - Dibromopropionic acid 1 2.5-di-di-tert-butyl paracresol
I o-cresol '' Bromcroionic acid I Λ-naphthol b) di- and polycarboxylic acids 1 ^ -naphthol Oxalic acid Naphthohydroquinone Malonic acid 4-methyl-1-naphthol W) Amber acid 4-methoxy-1-naphthol Glutaric acid 1.2.3-trihydroxynaphthalene citric acid Anthrahydroquinone Adipic acid 1,5-dihydroxynaphthalene Monochlorosatire Phloroglucine Monomet hy! Succinic acid NaDhtholAS Maleic acid Fumaric acid

19th

Ethylene-dicarboxylic acid Propane-1.Z3-tricarboxylic acid Tartaric acid acetone dicarboxylic acid

2) Aromatic carboxylic acids

a) monocarboxylic acids

Benzoic acid 2,4-dimethylbenzoic acid Paranitro-benzoic acid Parasulfo-benzoic acid Salicylic acid 2,4-dichlorobenzoic acid Cinnamic acid

b) di- and polycarboxylic acids

Phthalic acid 3-hydroxyphthalic acid 4-nitrophthalic acid 3-aminophthalic acid ■ 4-chlorophthalic acid Trimellitic acid 1 ^ -naphthalenedicarboxylic acid Pyromellitic acid Phenol-W.ö-tricarboxylic acid

3) imide

Succinimide phthalimide

4) phenols

Trinitrophenol (picric acid) trichlorophenol

5) Inorganic acids

Boric acid
Pyrophosphoric acid

6) Other acids

Nicotinic acid barbituric acid cyanuric acid hippuric acid

The following are listed as binders:

1) Natural high polymers

gelatin

Casein

strength

2) cellulose derivatives

Cellulose nitrate carboxymethyl cellulose

3) Semi-synthetic high polymers

chlorinated rubber cyclized rubber other plasticized natural rubber products

4) Polymerized synthetic high polymers

Polyisobutylene polystyrene

Terpene resin polyacrylic acid polyacrylic acid ester (polyacrylate)

Polymethacrylic acid ester (polymethacrylate)

Polyacrylonitrile

Polyacrylamide

Polyvinyl acetate
Polyvinyl alcohol

Polyvinyl pyrrolidone

Polyacetal resin

Polyvinyl chloride

Polyvinyl pyridine
in polyvinyl carbazole

Polybutadiene

Poly (styrene butadiene)

Butyl rubber

Polyoxymethylene
π polyethyleneimine

Polyethyleneimene hydrochloride

Poly (2-acryloxyethyl-dimethyl-sulfonium chloride)

_{1 ()} 5) Condensation polymerized synthetic
High polymers

Phenolic resin

Amine resin

Toluene resin
2Ϊ alkyd resin

unsaturated polyester resin

Allyl resin

Polycarbonate

Polyamide resin
κι polyether resin

Silicone resin

Furan resin

Thiocol rubber

j. 6) Addition polymerized resins

Polyurethane
Poly (urea tpoxyd) resin

For the substrate of the image recording material can paper, plastic films, conductive material such as metal or metallized paper, e.g. B. with metal vaporized paper or paper coated with metal powder, or paper treated with carbon, etc. is used will.

i ", The image recording material can be in the following Way to be made.

The compound containing zeolitic water, the color-forming component and the modifying component Additive (color development accelerator, pH value

V) constituting compound) with 0.01 to 5 parts by weight per Part by weight of the colorant of the component may be used together with masking agents and pigment dyes and other additives uniformly dispersed in the intended binder. After that, the dispersed

*) "> Material in the coating or dipping process or after Commonly used in papermaking methods applied to the substrate in the form of a layer.

Special limits for the proportion of the zeolitic The compound containing water does not exist. Usually however, the content is 30 to 98% by weight, based on the total weight of the to be dispersed Components, preferably 50 to 95% by weight, optimally 70 to 90% by weight.

Below is the current sensitive recording

h'i information material based on the drawing in detail described; show it

Fig. I, 2 and 3 schematically the structure of the image recording material together with various

Nen methods for performing image recording by means of selective power supply.

The image recording / calibration material according to fig. I made a current-sensitive recording layer I as top layer, a conductive contact layer 2 and from a substrate 3. The three layers form a uniform composite. The recording layer I has the composition described above.

I i g. 2 shows a modified embodiment. According to this, an image recording element consists of the substrate 1. the conductive contact element 2. an electrical insulation layer 5. which contains no color-forming component and no color development accelerator. These compounds are only contained in the separate color-forming layer b . The electrical conduction layer 5 and the color-forming layer β thus represent the

On / eicniKiitgsMjmCm? läoi "ϊ ig.!.

I ■ i g. I shows the simplest form of image recording material. it consists only of the substrate 5 and the recording layer I.

The recording layer is used for image recording I or 5. 6 with the help of a direct voltage of any polarity or alternating voltage sensing stylus 7 scanned. 13 graver is connected to the associated power source 4 connected. The counter electrode 8 is either on the recording layer I or 5. h placed on the contacting layer 2 connected.

Examples of preferred embodiments are given below given.

Example I.

1 g of 5-l'hen \ l-2.3-bis (p-diphen> l) tetraz () liunichliind ■ ind 0.07 g Hvdrochtnon is added to a mixture of a synthetic / eolite of the I, niiasittxps of the / ole composition N, i; (M; Si..O .. | ν li.-O / χ = h). 10 g Tu am i \ v ti des Tx ps rutile. Ki g Polxxinvlhiitxra! knead (with a PoKmerisanonsgrad · x <m HiM) and 1 ■.)>"g Athar.ol added and the whole Ans.nz: one 4 * hours in a ball mill.

The fine dispersion obtained is brought with a Hook! on a carbon-treated '·! rushing Paper on. The one carried out after drying on LuIt ßildatifzeichen success! with one the paper scanning Wolframstichcl and a DC voltage of sth.! ! 50 volts with the S 'ν being the negative pole.

l> develops in the \ om stylus scanned Controller; of the paper cmc reddish-purple coloring with satisfactory Büdquaiuät. The recording in the dust and odorless.

The same results are also obtained; p <> vm eepoltem or with alternating current Burin.

B <

It will be XMC after example! 1 worked, but with the Exception that mar, the color development accelerator Hydroquinone through other reducing color

The results of the image recording are for the color accelerators used in Table I. put together, wöbet Ir. in all cases the results were the same regardless of the polarity of the Cileichstromcs and for alternating currents.

Table I.

I 'arbenlx * icklunush accelerator With «never (iewichls- I '' arhhildun share * ι Uiphcmlhulrazine 3.0 gul 2-1I) drazinohenzthiazole 0.1 gul Paraphein lcndiamine oil gul 4 -. \ Mino-2.5-dimelli> IN- 0.07 very good di.itln! aniline n-Mcllix l.iminophenol oil very gul i, .. \ nijni.s !! i ': yNi! ur ·: (I S s.'hi i'iil (liloilndrochiiioii 0.2 very good Hren / katccliin 0.3 very gul l '\ rogallol oil very good (ierbs.iurc 0.07 very good 2.5-l) iierlhut> l-parakre-> ol 5.0 easy Effect Phloroglucine 0.05 Well \ nthrahxdioquinone 0.03 easy effect Nscorbiiisjure l'.i> 5 Well 1 iirinn l.o easy effect I -Phein l-3-nielhx l-4-amino- 0.1 gul 5-px razolon 4-ll> drow isiicarboslxrxl oil gul Indaiiilion-1.3 0.01 easy Effective N- \ ihx low inilol 0.03 easy effect IIU ..... Il I G:.:'. 4-metho \ x-l-n, iphihol IN THE UUt (/ -Naphthol I). (IS very good N.iphthol AS oil Well (ι- χ mi no-1 -.ithx I-1.2.3.4-th I ra 0.2 very good in ilroquinoline N.ttnunidithion.it 0.1 Well I isen-.ithxlendi.miintelr.i- 0.1 Well acctal (C hel.itι I am happy 0.1 gul Fcrrioxalate 0.1 gul 'H - / ,, gen, i'jl I (ι.-λιιΙινι, ι!' '-I' ru-nxlO '-hi- .in-iiiphenxlil ! (.! / iiliunichiiirul 1 3

It is worked xx ie according to Example 1, but with de The exception is that 5-phenyl-2,3-bis (p-diphen \ l) tc trazoüumchlorid by other color-forming components replace !. The one for all electricity and pohings The same results of the image recording are for di The color-forming components used in Table I / uammensesteüt:

23

Tabel

I *; t rh hi I c ⁷ L ¹ η (I c component

2.M) ipheny 1-3-14-slyry I phenyl helium oil chloride l-'iirhhiklunu

very cool

3- (4.5-I) imethyl-2-lhia / (> lyl-2.5-dipheiiyl-tetrazoliurn- very good chloride

3.3 '- (4.4'-Hiphenylen) -bis (2.5-diphen>! -Tetrazolium- very good chloride )

.V3'-l) ianisnl-his | 4.4 '- (3. Vdipheny I! Tetrazolium- very κ nt chliiridl

Hikll'iirbc

reddish purple dark purple

dark purple hlüuliclisehwar /

very cheap

OH

N, ■

'r

N ^l "

I [I

N N

Red

ί -Mollu l-2.2! 4-dinitro-ben / \ lp \ ridiiiiuniehr

blue

4-C lilorchinjldm-metho-suirat I 2-Πιπκί! Ι> Iben / olhi.i / iiliuni-p-toliuilsuUbnat '' Λ '-Ι) ιϋΐΐΊ> I- (v (i -dichlor-.v. '-Dic.irha / dlylniclh.in

I euko-mal.ichilgrün . '. fi-ni (ilimeth> hiniino> - \ anihcn .vh - [) i.imino-2. "- dimethyl-9-phen \ lacndan 3.T-I) iidimethyl; iniino) -pheno \; i7in Leuco-cobalt-pht.ilocyanin

2.5 - [) i-p-chlorandino-1.4-hydrochtondisulfate <: tersal / Anthr.isol gclb \ ' p-aminodiphynylamine Diphcnyibjn / idin

Well Nile gin yellow very gul blue Well yellow Well green Well rol Well Red very gul blue Well green very good yellow Well gclb Well purple eut purple

Kirbhildcrule component

I iirbhildiing

Hikll'arbc

4-MiMhoxy-1-naphthol very good blue

2-Vlercapt () - 3-h> dn) xy-7-dimcthvlamino-phenothia / in very good hhui

Indoxyl gul blue

Tetrabromophenol sulfone phthalein good hliiulichpiirpur

1 2-I) ihydroxyanthraquinone good rut

Dibromothymol-sullonphthalein very good blue

Cosolic acid gul red

ihymolphthalein very good blue

Example 4

A mixture of 1 g of 3.3 '(3.5-climethoxy-4.4-bipheny len) -bis [2- (p-nitropheny I)] - 5-phenyl tetrazolium chloride. g 2.5-dihulroxyaeetophenone, 10 g polyvinyl butyral with a degree of polymerization of 1500. 5 g of titanium oxide of the rutile type and 150 g of ethanol are used 30 g each of the zeolitic.es listed below Add water containing compounds, leather seeds / is then kneaded in a ball mill for 48 hours.

The dispersion obtained is applied to the surface of an aluminum-coated paper with a doctor blade and then dried for 5 minutes at 100 ° C. The image is then recorded with negatively polarized burin and a direct voltage of about 150 volts. The results of the Image recordings are shown in Table III:

Table III

Zeolite «containing water I arbhildiing links Synthetic faujasite very good Synthetic zeolite X very good Synthetic zeolite Λ Well Weddellite gul Gismondite Well Chabazit Well Scorodit slight effect recognized Clinoptilotite slight effect recognized Mordenite slight effect recognized Natrolite slight effect recognized Analcite slight effect recognized Psilomelan slight effect recognized Cancrinite slight effect recognized Titanium oxide iRutil-type) * no effect

Example 5

The dispersion liquid is prepared as in Example I, but without the hydroquinone from the recipe of the Example 1. The image is recorded as in Example 1. The color density decreases to about half of example I when the stylus is negatively polarized or applied with alternating current, but only by about 1/4 with positive polarity of the stylus.

Example 6

The following components are mixed and kneaded in a ball mill for 48 hours:

Components lot r>
Synthetic laujasite M) Titanium oxide. Rutile type IO Acrylic resin 20th _{4 (} , mixed solution of toluene and KKI Methyl ethyl ketone (l / l) l.cukn-malachitnrün I. Bromine hydroquinone 0.1

i'i The dispersion obtained is applied with a doctor blade aluminum-coated paper with aluminum deposition applied. After drying, a Image recording was carried out with 150 volts DC voltage and a positively polarized stylus. One receives a

■> '> very excellent green image.

Example 7

An image recording material of the type shown in FIG the type shown. The recording layer ″ is therefore composed of an electrical conduction layer 5 and an image recording layer 6 together.

a. Electrical conduction layer 5

The following components are mixed and kneaded in a ball mill for 48 hours:

Components

lot

*) Comparison test.

Synthetic faujasite

Acrylic resin

Mixed solution of toluene and

Methyl ethyl ketone (1/1)

30 g
! 5g
70 g

The dispersion obtained in this way is applied with a doctor blade an aluminum coated paper is applied and dried.

b. Imaging layer

The following components are mixed and kneaded in a ball mill for 48 hours:

HcsUimltcilc

Mont

0.2 u

IUMg

2.3.5- Iris (p-diphcnyl) - 'etra / oliumehiofid
Dihydroxymesilylene
Synthetic / eolite X

Polyvinyl butyral
(Polymcrisiilinitsgrad 4 (XK))
Ethanol

The dispersion obtained is applied to the electrical conductor layer with a doctor blade and dried. The two layers are partially mixed together.

The image is recorded at 150 full DC voltage and about 2f. mA. An excellent, dark purple picture is obtained.

Example 8

I g 5-phenyl-2.J-bis (p-cliphenyl) tetra / oi'i.imchhrid. 0.07 g hydroquinone and 0.07 g phthalic acid are added to 30 g synthetic Zcolilh v. 10 g titanium oxide rlcs Rutile type. 10 g of polyvinyl butyral (degree of polymerization 1500) and 150 g of ethanol were added. The whole The batch is kneaded in a ball mill for 48 hours.

The dispersion obtained is carbon-treated Conductive paper applied and air dried.

The image is recorded with a positively polarized tungsten stylus at 130 volts DC voltage. A reddish-purple color of satisfactory quality is obtained. The image recording is dust and gCTüchsfrci.

Example 9

It is worked v.ie according to Example 8, but with the The exception is that the phthalic acid used there is replaced by other PI-adjusting components.

The results of the image recordings for the pH-adjusting components used in each case are in Table IV shown:

Table IV I .irhhihhmi! Lichtsiahilii.il apart from pl l-cinstcllcndc component in the bar HiklteiK inadequate Well Well inadequate Butyric acid Well Well Well Palmitic acid Well very good Well if-bromocrotonic acid c very good very good Well Oxalic acid very good very good very with Succinic acid very with very ent lack: ·: '! Prnn: m-1? Vlrir: irhonsiiiire Well Well Well Benzoic acid Well Well very good Cinnamic acid very good very good Well 4-nitrophthalic acid Well very good very good U-naphthalan dicarboxylic acid very good very good Well Pyromellitic acid Well Well Well Succinic acid imide very good very good very good Picric acid very good very good Well Pyrophosphoric acid Well very good inadequate Boric acid Well Well very bad Nicotinic acid very aut very bad No addition

In the table above, "light stability in color development outside the image due to the sun's image part" means no color fading in the image part due to sunlight,
light and "light stability outside the image part" none

example

The procedure is as in Example 8, but with the The exception is that the hydroquinone used there is replaced by other reducing color development accelerators The results of the image recordings for the compounds used are given in the table V shown. They are of the type of polarity and type of current independent.

29

Table V

Color change accelerator

Dipheny! Hydrazine

2-hydrazinobenzothiazole

p-phenylenediamine

4-amino-2,5-dimethyl-N-diethylaniline

p-methylaminophenol

p-aminosalicylic acid

Chlorohydroquinone

Catechol

Pyrogallol

Tannic acid

2.5-Ditert-ButyI-ParacresoI

Phloroglucine
Anthrahydroquinone

Ascorbic acid
Furoin

1-phenyl-3-methyl-4-amino-5-pyrazolone
Hydroxyisocarbostyryl

30th

Color formation

Well
gul
Well

very good very good very good very good very good very good very good

slight effect

Well

slight effect good

slight effect

Well
Well

l-arber transformation accelerator > N-ethyloxyindole Color development lndandion-l .3 easy Phenazine effect in 4-methoxy-1-naphthol easy e-NaphthoI effect Naphthol AS Well 6-amino-1-ethyl-I.2.3.4-tetra- Well _{I5 hydroquinoline} very good Sodium dithionate Well Iron-ethylenediamine-tetraacetate (chelate) very good Ferric chloride , _n ferrioxalate Well Well Well Well

Example 11

The procedure is as in Example 8, but with the dei Exception that the 5-phenyl-2J used there 2ϊ bis (p-diphenyl) tetrazolium chloride by other color images components replaced. The results of the image recordings are for whichever one is used color-forming components shown in Table VI. The results are independent of the type of current and polarity.

Table Vl

! • "color-forming component

Farbbüdung Bildlarbc

2.5-Diphenyl-3- (4-styry! Phenyl Hetrazolium Chloride very good

3- (4.5-Dimethyl-2-thiazolyl-2.5-diphenyl-tctrazolium- very good chloride

3.3 '- (4.4'-Diphenylcn) -bis [2.5-diphynyltctrazolium- very good Chloride)

3.3'-Dianisole bis [4.4 '- (3.5-diphynyl) tclrazolium- very good

chloride)

Cl

very good

pul

reddish purple
dark purple

dark purple
bluish black

yellow

Red

continuation Color-forming component

l-methyl ^ J ^ dinitro-benzylpyridinium p-toluenesulfonate

4-chloroquinine methosulfate 1,2-dimethylbenzothiazolium p-toluenesulfonate ^ '- Diethyl-o.o'-dichlorOJ'-dicarbazoIylmethane

Leuco-auramine Leukö-malachite green

3,6-di (dimethylamino) xanthone

S.o-Diamino- ^ J-dimethyl-ii-phenylacrydane

3.7-di (dimethylamino) phenoxadine

Leuco cobalt phthalocyanine

2.5-di-p-chloroaniline-1,4-hydroquinone disulfate ester salt

Anthrosol yellow V

p-aminodiphenylamine

Diphenylbenzidine

4-methoxy-1-naphthol 2-mercapto-3-hydΓOxy-7-dimethylaminophenothiazine indoxyl

Tetrabromophenol sulfonphthalein

1,2-dihydroxyanthraquinone

Dibrümthimol-sulfophthalein Resolic acid

Thymolphthalein

very good

32

Color formation image color

Red

blue

Well Red Well yellow very good blue Well yellow Well green Well Red Well Red very good blue Well green very good yellow Well yellow Well purple Well purple very good blue very good blue Well blue Well bluish purple Well rol very good blue Well Red very good blue

Example 12

To a mixture of I g

3-3 '- (3J'-Dimethoxy-4.4'-biphenylene) -bi $ t2- (p-nitrophenyl)] - 5-phenyitetrazolium chloride, 0.1 g of 2,5-dihydroxy a so fertilize added. Each batch is then kneaded in a ball mill for 48 hours.

The dispersion obtained is applied to aluminum-coated paper with a doctor blade and 5 Dried for minutes at 100 ° C. The image recording

cetophenon, 10 g polyvinyl butyral (degree of polymerisation 55

1500), 0.1 g oxalic acid, 5 g titanium oxide of the rutile type and about 150 volts DC voltage. the

150 ethanol, 30 g of the image recordings in Table VII are given in Table VII

listed compounds containing zeolitic water:

Table VII

/ Compounds containing eolithic water

l-'iirhbildung Wassergehall (weight .- "/.)

Synthetic Faujasite Synthetic Zeolil X Synthetic zeolite Λ

very good very good. 18 38 28

continuation

Compounds containing zeolite water

Color formation

Water content
(Wt .-%)

Weddellite

Gismondite

Chabazit

Scorodit

Clinoptilotite

Mordenite

Natrolite

Analcite

Psilomelan

Cancrinite

Titanium oxide (rutile type) *)

*) Comparison attempt.

Well 26th Well 21 Well 20th slight effect 16 slight movement 14th slight effect 12th slight effect 9 slight effect 8th slight effect 5 slight effect 4th no effect almost nobody

Example 13

The procedure is as in Example 8, but with the The exception is that the hydroquinone and the proportion of 5-phenyl-23-bis (f> diphenyI) tetrazolium chloride are not used tripled, i.e. to 3 g. An image with the same satisfactory color as in FIG Example 8.

Example 14

It was observed that in the absence of phthalic acid in the dispersion according to Example 8, the color formation in the Image recording material wears off after twelve months of storage in the dark. When using Phthalic acid does not show any change in recordability after twenty months or more.

1 sheet of drawings

Claims (7)

Patent claims: 1. Current-sensitive recording material with a current-sensitive layer which contains an electrically conductive compound containing zeolitic ^ water, a color-forming compound and at least one further component, characterized in that the further component is a color development accelerator. Z recording material according to claim 1, characterized in that aromatic amines, phenols, Iron (III) chloride, copper (II) chloride or tin (IV) chloride are used. is 3. Recording material according to claim 1 or 2, characterized in that an additional Another component is a pH-adjusting compound. 4. Recording material according to claim 3, characterized in that the pH-adjusting compounds are aliphatic or aromatic carboxylic acids, inorganic acids or imides . 5. Recording material according to one of claims 1 to 4, characterized in that the electrically conductive zeolites? Water-containing compound in a first layer and the color-forming compound and the color development accelerator and optionally the pH adjusting compound are contained in a further layer. 6. Recording material according to one of claims 1 to 5, characterized in that based to 1 part by weight of color-forming compound, 0.01 to 5 parts by weight of color development accelerator available. 7. Recording material according to one of claims 1 to 6, characterized in that based to 1 part by weight of color-forming compound 0.01 to 5 parts by weight of pH-adjusting compound available.