DE1597621A1 - Diazotype copy material - Google Patents

Description

Kabushiki Kaisha Kicori

Tokyo. Japan f. * L40 L 19ί

Diazotype copier material

1597671

The invention relates to a particularly high-light:.; Pfiricilichps Diazotype copy material, the copier not oim a ~ uarta ..-; o Contains p-aminobenzene diazoniu ri compound.

Since the emergence of copying technology with auxiliary :? From Di ^ oniLU '/ orbi.idungen there is a demand for hoc hei..pf i ::>' Jliche.:i Kopi ^ r <nat ":> ial or in other words, correspondingly hochli." 2L '"': - ⁱ .. _i "? iridliohnn diazonium compounds. This Torderung has si ^ h ^ ir Yiin ter 2 "5I ⁺ -. Exacerbated seitder ,; you ε.η as Diazütyjiekopisr-Llchtquella place of Quecksilberdampfla.upen not only cheaper, but also vjeniger Gecauitstrahlungsenergie donating Flucres ^ s ^ In order to meet this requirement, various arcs of comparatively high-light sensory p-aminoberi2oldia ^ cniu: .i-7erbrid9n have been introduced up to now.

The invention intends to create new, particularly highly sensitive and easily connectable p-Aninobea'jolcliazoniur.i compounds and such connections from nuti-cnder Dia. ^ ctypiekopieri.iaterialien. , ·

Briefly summarized, the invention consists of a photosensitive Layer that contains a very highly sensitive diaronium salt in Form of N-ethyl, N-hydrocythyl and N-nonzyl derivatives of 4- (N-benzyl) aminium diazonium salts contains.

009826/1688 bathroom

More specifically, the invention consists of one Eia-otypie copy material, the distinguishing feature of which is: daoo its photosensitive copy layer at least one Diazoniuiaverbindunj of the formula

contains j in the

IL benzyl, hydroxyethyl or ethyl, IU a hydrogen octoin, hydroxyl, alkoxy I or

• it "

Y is hydrogenated or halogenated, alkyl, carboxyl,

Hydroxyalkyl, hydroxyalkoxyl, -llCji, -G ^ H ^ II ^ ti or a nitrogen-containing heterocyclic radical, X an anionic acid radical, η an integer between 1 and 5 and with R ^ and Y being Uasserstoffato-i the integer 3 to 5 and / R ¹ and R "are alkyl with a maximum of 4 carbon atoms

mean.

GQ9826 / 16Ö8

bath

The diazonium compounds of the present invention can be incorporated into either one component wet developable or two component dry developable or three component dry developable copier materials. With them, :: ian receives image in a shade that varies between black and blue, depending on the type of coupling component used. The light-sensitive copier layer wi.'d orfiiiiigungSGen.lisn aul 'one. ^r ; r \ ", .. or like paper, coated paper or] iun; j1 --- tci'foli'i,: i>. ei ' at normal slide ^ olypiekopieraa'erlalieK üfclio: ij-, -v.u'. ° -

brings and can i-.ua): still Zu :: üt: e,.:. E. eiiien Verj; ill; u :; ^r >: io -

fabric or stabilizer,

The erfindunr ^ fo. / Iau used;: toii Dia ^ oniuinVerbindun ^ on unrön often in For., The Chloriiir : Λ .: scIcIigk: o "» ⁱ r al .: c3 '^; -. I · Double salti .nit a « Λ MeVallcl-lorid, in: .b'i.: Rnciero Zin!: - cd ·· Cadmiuiiichlorid, '• ■» r. ^ Eatelli ·, ucbnl aboi the A: · * ^ ^ · -. ·: ■: . Diazo'iiuinkation-bound anion .: r.io:.;. I.- oiue Rr.II3.; · 1. · And therefore boinplayed au · '. ^ .- r: .. ic, .: <'.? -: -C: *> \ - Γ " ¹ ·; .- * ..;:. can be.

the various Aocior.en, in α '".' all {to.neineii For: .. ol der · = ?. ■: "! ■ .-

^ emlli-o ·?.: ria :: oniuiwerbindu; if; he. no . .rl,! '-'λ; 1, :-. ■ / I. , Isopropyl «n-Bu '..; - l, tert. Butyl, r.-Ar-c "! Ur.i ~ -Tt. A / 1, 1 .. Ilalosön, Cl lcr, ^ rc: n and Flue-, as Al'icr.y K ^ thc: · :: - ·, · '"'·.";, N-lropoxy, I.-crr.. C :: y, n-butoxy, uA: n: -lo;:; - and tcrt. ';! - :: : -, al.3 Hydro ::: 'all:; - I hydroxymethyl, S ¹ -H: .- Grc ::; - ätI "-l,;' - ::; c .-; :::; - n-propyl, Z ^x -H; v: v: i: 'prcryl, 2 ¹ J ¹ -Di ::; - drcx: T ^ -: vl * -' - ^ "'- --- ^:: " ~ ii? ct "r-vr-'I,' ^{: t} -Ilvorcx ^^ n-butyl ur.ö"'-H ^. "crox" - "- £. ~~ ~, rZ ν

009826/1698

ORIGINAL BATHROOM

~ N ' _r »radical N-methy 1 amino, N-sthylamino, N, N-dimethylamino, N, N-diethylamino, Ν, Ν-n-propylamino, pyrrolidino, piperidino, piperazino, N-methylpiper / izino, N -Kthylpiperazino, N-propylpiperazino and morpholino.

As already stated, the diazonium compounds according to the invention can be incorporated into one-, two- or three-component copying materials. Compounds in which the R 1 -substuent consists of benzyl show increased coupling speed and are therefore suitable for both one-component and two-component copying materials. Compounds with R, equal to hydroxyethyl, because of their excellent water solubility, are particularly useful for two- and three-component copying materials, and those with R ₁ equal to ethyl have sufficient coupling power and can therefore be used well for one- and two-component copying materials.

The manufacturing process for the diazonium compounds according to the invention is described below with reference to the 4-dibenzylainino-2, S-diethoxybenzoldiazonium chloride-zinc chloride double salt described.

72.4 g of 2,5-diethoxyaniline and 110 g of sodium acetate were dissolved in 150 ml of water, the solution was kept at 90 to 100 ° and 105 g of benzyl chloride were added dropwise and with stirring, and the mixture was left to react for 5 hours f efitfernte the oily top layer and distilled in a 4 mm Hg Vakuurn, whereby a ICO g between 2J0 ° and 250 ^0-boiling distillate, ·,

009826 / 16ÖÖ _ _r _

ORlGiNAL

F. 63 * 5 - ^^ * 5 ° * were obtained. This distillate was coupled to p-nitroanilindiazoniumverbindungen to form 125 g of a dye, F. 189-199 ⁰ , and the dye was reduced with hydrogen gas to form amines. Upon reaction with acetic anhydride, N _f N'-diacetyl-p-diaminobenzene was obtained as a precipitate. The acetyl derivative of the other component simultaneously obtained was hydrolyzed and subsequently "ated in a conventional manner to Diazoniumverblndung diazo *, which was converted with zinc chloride to give the double salt. There was thus 93 S yellowed ⁱ f-dibenzylamino-2,5-diäthoxybensoldiazoniumchlorid-zinc chloride double salt,

As a further example, the process steps in the production of the 4- (N-Hydroxyäfchyi-N-benzyl) -amino ^^ - dipropoxybenzene diazonium chloride-cadmium chloride double salt are shown in the formula scheme specified:

OC ₃ HY

3 VA WO,

cj? er

2 '*

0Ü9826 / 16Ö8

BATH ORIGINAL

ρ - A / i tr Λ »i ti *

m>

Then i.u For ::: elsche; aa "also .och die Preparation of the 4- (IM-thyl-N-benzyl> arnino-2-arhoxy-5- (2 'Kiorpholino) ethoxyben3oldiazonium chloride-cadranium chloride double salsa explain:

9826/1698

OH

HBr ^

Α / Ο, »

/ VO,

/ VO,

OCyHj ₁ // O

OC _x H ₁₁ "

- NHCHO

° <l * f

r ~ \

, CHO

/ O

'"ν

009826/1698

BATH ORIGINAL

■ » W-

ic.

\, ίΛ

cw,

CXN ₁

OC _z n _r

Ck,

Ne'-1-.E no. ^r -nr3 v ^ -rrjtr. "ir.f- l-.eiho typical, ■ -_'-- :. ·: · ~. * -. ~ v Ti -: - oniu ... · '-r" -, indun-on auf-o ^ Jihlt, next to which there are ■ • ■ 'rr'i'vüio'r "' ¹ '!! ::"".' ■ • oh" iele other ripe ne ^ ep ^ itat.

640

009826/1698

~ ⁹ ~

N ₂ Cl. 1/2 ZnCl ₂

■ • r.r: -. Fsl 3

<Q-CH

'4 ⁿ 9

OCH

.1 / 2ZnCl ₂

^00Η

OCH,
V- ^ J-IT ₂ ol.

1/2 ZnCl ₂

Ο-ί /

Q-CH

¹ Z ^{2 ZnC1} 2

HpOl · 1 / 2ZnOl ₂

OC ₂ H ₄ N (C ₂ H ₅ ) ₂ .HC1 Cl

OC ₂ H ₄ OC ₂ H ₅

1/2 ZnCl ₂

fr-f \ -K ₂ 01.1 / 2ZnOl ₂

-10 009826/1698

BATH ORIGINAL

ΟΟ, Ηγ

0-ch:

HOCgH ₄

OC ₃ H ₇

-1 / 2ZnCl ₂

CC ₂ H ₄ OH

.N-

HIGH.

N - / ^ V-NgCl · 1 / 2ZnCl ₂

^ - / VN ₉ Cl.

^7th r

HOC ₀ H, OC ₂ H ₅

NgCl'1 / 2ZnCl ₂

OG ₂ H ₄

008826/1698

HOC ₂ H ₄

egg

ο 'τ

HOCgH ₄  C) CH ₂ OH ₄

HOC ₂ H ₄

COOH ..1 / 2ZnCl ₂

OC ₅ H ₇

HOC ₂ H ₄

HOO ₂ H ₄ _ / ^(0H 3 ^{) z} N ₂ Cl.1 / 2ZnCl ₂

OC ₃ H ₇

HOC ₂ H ₄ QCH>

C ₂ H ₄ OH

OC ₅ K ₁₁ BAD ORIGINAL

- It- 009826/1698

or ·.; - il P5

OCgH ₅

Cl.l / 2ZnCl,

OC ₂ H ₄ Ii

N ₀ Cl 1 / 2ZnCl,

OC ₂ H ₄ OH

oh

.
N ₂ Cl.1 / 2ZnCl ₂

OCH, 1/2 ZnCl ₂

OC ₄ H ₉

C ₂ H ₅

OC ₂ H ₄ OC ₂ H ₅ ■ Cl

'2 ⁿ 5

Cl . l / 2ZnCl «

009826/1 698

7ο-V- ^ l 3ϋ

COOH

C ₂ H ₅

OC ₂ H ₅

OC ₂ H ₄ OH
N ₂ Cl.1 / 2ZnCl ₂

For.-nel 31

For.ael 3?

Q-OH

C ₂ H ₅

1/2 ZnCl

OCH,

formula

Formula 3 ^ί!

⁰ ^ yf £ * i

^IH 2 S

.1 / 2ZnCl ₂

OC ₅ H ₁₁

BATH ORIGINAL

- 14 -009826/1698

Below is the hearing charge to HaGd of some examples explained in more detail:

example 1

An intensely white carrier, as he did for Diazofcypie-Iepier · « materials is customary, initially received a prefix a suspension of fine-grain silica and vinyl acetate, was then with a solution of the composition

ft-Dibenzylamino-3- (2 ^f -hydroxy) ethoxy-benzenediaioaium chloride-zinc chloride double salt (according to formula 1)

1 * 3 8

Tartaric acid 0.4 g

Boric acid 0.1 g

Water . 100 ml

coated and finally dried »

An original was placed on this photosensitive copying layer and exposed with the aid of an exposure device equipped with a fluorescent lamp of the latent image was completed in a very short time. The copying layer with the latent image was made with the following developer solution treated with a pH value of about 5 * 9

Thiourea 1 # S S

Phloroglucin © *% g

Benzoic acid

oosiae / teis

Sodium acetate 1 # 5 g

HatriumphoBphat 1.5 g

Water 100 ml

The development went quickly vonstatten and provided a sehwar * "copy in dit semitones same tint as the regions highest image density possessed.

dough game 2

Usual paper carrier for normal diazotype copy materials was with the eleventh effective solution of the following additive Upper class

Zinc chloride double sair; (corresponding

Formula 5) 1.5 g

Tartaric acid 6.0 g

Boric acid 1.0 g

Acetic acid 2.0 g

Water 100.0 ε

Caffeine 0, Z g

Kethyicellulose C, 03 c

Isopropanol 3.0 c ß-ii-hydroxynaphthalene-3- carboxylic acid-c i- (2 ¹ U

hydro3tyethyl) ainid 3.0ε

and thoroughly dried

Pie-b ^ r ^ ugsschicht vr was then loaded similarly as in Example 1

r.io:.- .. ":; ni dr.np.oh: ^ it! icch-- ^: o-: enti," e .: ki '.... crAi' /.?: zc i .: ~ - Yc- ta ',:

009826/1698 ^;

BAD ORiGJNAL

, ^ bracht, v ^ ou-ch oin deep blue colored picture developed ..was.

'".ine Kluili -.'hr;:, a satisfactory copy was obtained if.;:.: ■ r ^^ '-. Ki :.': co A ...... uiiiaks with the following alkaline solution el. .j r ^ twi.jl.l.- · !. ' worked:

^ ₁₁ -O c ab or at 5 g

> oi: -t 2 g

100 g

The following solution was applied to an acetyl cellulose film and dried up:

(^ r.to ^ i - ^. without formula 6) Formic acid Zi - ^ - or.er.o acid ■ "'assor

'', -. .y 1 ο nglykc 1 - monoae t hy 1 ät her Cresylglutaric acid

.l ^ clearing and ENTV / icldung rr.it Amraoniakgas made similar v; ie in Example 2, and there was a yellow copy very well as Zv / ischenverläge suitable because they ultraviolet j-rc Vi '. .ac ho ar ^ o is capable of intensively absorbing radiation.

009826/1698

BATH ORIGINAL

4th G 3 G
D * L. O
G 40 G 20th G 2 G

Example '4

An intensely white support, much like it for Dia ^ otypi ^ roolermacer-ialien is customary, initially received a primer ^ eniUds Example 1, was then with a solution of the

4- (N-HydroxyUt: iyl-N-benzyl) aai

Ethoxyben -: old i aaoniumc hl ο r id -Z luke Mo v id double salary: (according to formula Ij5) 1 * 5 S V / eins äure 0.5 g

Water "100 .iil

coated and finally dried.

A template is placed on top of this light-sensitive copying layer placed and equipped with the help of a fluorescent lamp Exposure device exposed, v / obei the formation of the latent image is completed in a very short time was. The copy layer with the latent image was then treated with the following developer solution with a pH of etv / a 5 * 9:

Thiourea 1.3 S

Phloroglucinol 0, ^ g

Benzoic acid 0.25. £:

Sodium benzoate 1.5 g

Sodium phosphate 1.5 β

Water 100 al

A pure black copy was created in which the halftones

09826/1688 bad origüjal j

- 18 - Ϊ

possessed the same tint as the areas of highest image density.

example

A common carrier for normal diazotype copier materials became! Tilt-, a sensitizing solution with the following composition cleared:

4- (N-Hydroxyethyl-N-benzyl) amino-2-methoxy-5-butoxybenzenediazonium chloride-zinc chloride double salt

(corresponding to For.nel 14) 1.5 g

Tartaric acid 6.0 g

Boric acid 1.0 g

Caffeine. 0.5 g

Methyl cellulose 0.08 g

Isopropane 3.0 ml of 2-hydroxynaphthalene-j5-carboxylic acid ~ di- (2 ¹ -

hydroxyethyl) amide 1.2 g

V / ater 100 ml

The resulting sheet was then made similar to Example 1 exposed and then developed with high percentage ammonia gas, resulting in a beautiful blue picture,

A similarly effective copy was obtained by hiring of A.nrconiaks with the alkaline described in Example 2 Solution worked as a developer,

Example 6

A solution of the composition 009826/1698 ^B ^ o original

4- (N-hydroxyethyl-N-benzyl) amino-2- .1; S. chlorine-5 ~ propo :: ybenzoldiazonium chloride- ml fluoroborate double saloon T
S. S. Formic acid 25th ml citric acid fco i.'l V / ater 20th 1..1 Isopropanol T
O Ethylene glycol monomethyl ether Kresylgliit ars Uure

applied and developed similarly as in Example 2 with A; nmcniakgas, as a result of which a yellow copy was obtained, which was very suitable as an intermediate original, since it was ultraviolet and adjacent Able to absorb radiation intensively.

Example 7

A common carrier for diazotype copy materials was first coated with a primer like Example 1 and above : Λ * - the following reading:

2-Hydroxyethyl-4- (N-hydroxyethyl-N-benzyl) aniincs-amyloxybenzoldiazoniuiijchlorid -zinkchlorid-

Double salt (corresponding to For: .iel IS) - '* j

2,3-dihydroxy-6-sulfonaphthalene ic;

Urea IC g

Ethyl urea 20 g

Sulfamide 10 s

Water 100 ml

5 glycolic acid solution fco ml

Saponin solution 3:;. L

009826/1698

BATH ORIGINAL

and connect! dried. On the photosensitive layer a template was placed and exposed using an exposure device, and then development was carried out by heating at 170 ° for 5 seconds, thereby making a deep blue copy.

Example 8

An intensely white paper carrier, such as that used for diazotype copy material It is customary to first receive a primer consisting of a suspension of fine-grain silica and vinyl acetate then with a solution of the composition

4- (N-Sthyl-N-benzyl) amino-3- (2'-ethoxy) ethoxybenzenediazonium chloride-zinc chloride double salt (according to formula 27). 1.3 g

Tartaric acid 0.5 g

Water 100 ml

coated and finally dried.

An original was placed on this photosensitive layer and exposed with the aid of an exposure device equipped with a fluorescent lamp, the formation of the latent image being completed in a very short time. The copy layer with the latent image was treated with the developer solution described in Example 4 and produced a pure black copy in which the halftones had the same shade as the areas of highest image density.

Example 9

A common carrier for normal diazotype copy materials was made with a? Solution Ηίΐ ****** To% "." * "Nt <?"

009826/1698

8AD ORIGINAL - 21 -

ι, 5 G ml 6, 0 G G ι, 0 G ml ο, 5 G 0, 08 g 3, 0 ι ,; 2 100

4- (N-Ethyl-N-benzyl) amino-3- (2 ^t -morpholino) ethoxyö-ethoxybenzoldiazonium chloride-zinc chloride double salt (according to formula 23)

Tartaric acid boric acid caffeine Methyl cellulose

Isopropanol ■

2-Hydroxynaphthalene-3-carboxylic acid ^{di (2!} - hydroxyethyl) amide

water

and then dried.

The coating layer was then exposed similarly to Example 1 and then brought into contact with high percentage ammonia gas, which developed a beautiful blue copy.

A similar copy was obtained if, instead of ammonia, the alkaline solution described in Example 2 was used as the developer worked.

Example 10

The following solution was applied to an acetyl cellulose film and dried:

^ - (N-Ethyl-N-benzylJamino ^ -chlor-S-ethoxybenzene-

diazonium chloride fluoroborate double salt 4 g

Formic acid 3 ml

Citric acid 3 ß

Water '000826/1600 BAD ORIGINAL 25 ral

Isopropanol 1597621
4o rnl Xethylene glycol monomethyl ether 20 ml Cresylglutaric acid 2 g

Exposure and development with Arnmoniakfsas were carried out similarly to Example 2, and a yellow copy was produced which was well suited as an intermediate document because it was ultraviolet and
to absorb neighboring radiation intensively νornag.

Example 11

A common Fapler door for normal diazotype copies was initially with a primer as in Example 1 and then with a solution of the composition

2u (il-Kthyl-IJ-benzyl) auino-3- (2'morpholino) ethoxyo-ethoxybenzoldiazonium chloride-zinc chloride double salt (according to formula 23) ^ rnl

2,3-Dihydroxy-6-sulfonaphthalene 10 ml

Urea 10 ml

Ethyl urea 20 ml

SuIfamid IO ml

Water ICO ml

2C glycolic acid solution 10 ml

l ^ ige saponin solution 5 inl

covered and then dried. On the photosensitive. The first layer was placed on an original and exposed using an exposure device, and development was then carried out by heating at 170 ° for 5 seconds, creating a deep blue
Copy was received.

009826/1698 ^BAD original

- 23 -

Claims (1)

■ patentans η ν ü c ■> β 1) light-sensitive PIc -pi ^ r..atorial typieverf'-kiv ·. aua aui carrier unc r-uf him aufcetragoncr liclito ^ ipfiiiülijlioi ¹ connection, ducure ': _t j'-i'x: o: inzoichnet, o-.sg dieao connection:; G of the general Pcrr.icl entepricht, in the R, 3 ^: i :: yl, Hydroxj'iithyl or iithyl, R ... ^ in hydrogen atom, hydroxyl, alkoxyl or ; ⁿ ^ r » Y is a hydrogen or halonato: .., alkyl, C & rbcxyl, hydroxyalkyl, hydroxy alkoxyl j -I ^ n * - ^C 2 ^H ^ ^Ii * R " ^or a nitrogen-containing ^ .eterocycliöchen radical, X ^ an anionic acid residue, η is an integer between 1 and 5 and, with R ₂ and Y being hydrogen, the integer 3 to 5 and R ¹ and R "alkyl have a maximum of 4 carbon atoms 211. 009826/1698 BAD ORIG «NAL - 2k - 2) Material according to claim 1, characterized in that that the compound as Rp substituents is an alkoxy radical, namely methoxy, kthoxy, n-propoxy, isopropoxy, n-butoxy, n-amyloxy or ter. Amyloxy. J>) Material according to claim 1, characterized in that the compound as Y-substituent is an alkyl radical, namely methyl, sthyl, n-propyl, isopropyl, η-butyl, tert. Butyl, n-amyl or tert. Ainyl. 4) Material according to claim 1, characterized in that the compound as the Y substituent is a hydroxyalkyl radical, namely hydroxymethyl, 2 ¹ -hydroxyethyl, 2 ¹ -hydroxy-n-propyl * 2'-hydroxypropyl, 2 ^f , 3 ¹ -dihydroxypropyl, 2'-Hydroxyisoprppyl, k '-hydroxy-n-butyl-5' or H-HyCLrOXy-BnIyI having. 5) Material according to claim 1, characterized in that the compound al3 Y substituents a -N ^ n radical, namely N-methylamino, N-ethylamino or N, N-dimethylamino, having. 6) Material according to claim 1, characterized in, that the compound as a Y substituent is a material-containing heterocyclic radical, namely pyrrolidino, piperidino, piperazines N-methylpiperazino, N-ethylpiperazino, N-propylpiperazino or morphclino. 7) Material according to claim 1, characterized in that the compound 4ase has a halogen atom, chlorine, bromine or fluorine as Y-substituent * 509826/169 8