DE1422835A1 - Heat developable diazotype material - Google Patents

Description

■ 1422635

17 * 2.1967

Haywriting

B 39 111 Ha / 57

Jean Jacques DOREL, PAEIS, Lueien Raymond DOitlL. » NEUILLY-3UR-SEINE, Germain LAPLACE, PAIiIS ₁ Robert MICOLIB, BEÜILLY-öUR-SBIME,

Heat-developable mazotype material ^

The discovery relates to that which can be developed by heat Biazotype material with a layer trowel on paper and a photosensitive layer containing a diazo compound and a coupling component »

Some known mazotype processes use two Component papers, namely papers that are exposed to ammonia vapor Other processes can be developed using papers only one component, so-called semi-moist apers the coupling agent supplied in the form of a developer that is alkaline, neutral or slightly acidic.

For papers with »v / ei components, the requirement is of gaseous ammonia because of the smell a problem) In addition, there is nooh the 2wang, a system of diazo-coupling Use ttel to anything that is stabilized in such a way that

BATH ORIGINAL

909 · ββ / 0901

New documents

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it does not engage prematurely "not in one with low ©» laden amounts Ammosiakdämpfen milieu _e as "present fältigungswerkstätten whose Kapplungsvermögen but sufficiently large iat to generate enough kontr & strei ·" in the Verviel chen pictures. " With the semi-moist. Papers, on the other hand, require first of all to prepare solutions «which contain oxidizable» substances; Moreover, the application or the application of these solutions to the diasotype paper is not easy, but requires relatively complicated, hitherto imperfect machines.

Various attempts have been made to create a diazotype " Papers that can be developed without ammonia and without a developer solution are to manufacture. Other development methods were used found, e.g. * those with amines, with water, with ■ "Working with water vapor or with heat»

In particular, the heat developable paper goods The subject of fermentation studies have been numerous Proposals made in this regard and numerous Patents granted. The complex system of developing with Heat has recently led to two French patents in particular »

BATH ORIGINAL

The principle of the first French paient (1 249 913 of January 23, 1959) consists in the most stable possible mixture of a diaphragm body and a coupling agent and a base generator in a proportionately; large · Quantity herii.i share .2 {the tabilisierun £ * vird bev by a small amount of an acid otarken * irkt) j for this 2vcck are proposed urea or a urea derivative "Thioh? RNAi of t or L-erivat of Thiourea. This proposal, however, has proven impractical. Bach the second of the

Patents (1 255 950 from November 23, 1959) separates one

about 100 ° fusible ochieht which contains the Ichichtiäis äen hiaeobodies "of the layer _t which contains the coupling elements"

These newer processes also have considerable disadvantages «Idβ the production of these diazotype materials therefore requires three layers _t wa8 represents a considerable evil» so that the -free, dieeer products are ex-hetlieh firhöhtj on the other hand »because ήετ J> iazo body of the coupling agent is sharply separated »a poorly contoured image is obtained *

So it Achien that eu return to the classic Piazotypie method or stay with them Masate _t ie * a paper dle with a single öchicht on a Baei _"# given fall Yorh" 3P was provided with a VorBchicht _t produce MUA _f as this is the The only possibility is to get a correct, good picture on the one hand and to keep the price of the paper low on the other *

BADORfGJNAL

'. * "" "■ UtttSS

• 'r. * ■

The task of the invention is to address these disadvantages of the previously known Process to avoid the need for ammonia for development and the uncertainty of bringing about the risk of the premature coupling and the inconvenience of applying several Splints «

G-emäss the Frftndun ^ vird this is achieved by a wärmeentwickelbar "s Masotypie-materiai with a v-chiehtträ / rer of paper and a photosensitive layer containing a diazo compound and a coupling component _s as clutch Kümponente a ¥ genetic plication of Formula:

contains where 2 is one of the groups

• CH · C - 0 - QO r

• CH * G O CO

~ GE «C - O - CO ·

- ■ CH * C.
t ι t -ο Ο α σο .GK ₅ C. /
a
χ -CH- - ο - σο mm

909 ^ 670901

- CH »C - S - CO -

° 6 «5

CH-CH- CH, - CO t * *

CH, - CH - X - CO * · «

CH ₂ - O - CO -

X - CO - X - CO -

I t

M-K-C-

CH- CH-XH-C (

C-X-C-X

I t

it in d «n« n I ₁ and * ₂ - H, "ium alkyl-, aryl-. "* * ** AB ~ alkyl-P * * ^ b ₅ , B ₄ , B ₅ - H tin" alkyl, aiyl, aralkylod "r 1βμι K" t "rooyoliBch" n Best 1st.

909806/0901

Sevorsugt is a diazotype material of this kind «that as a Kappiango component
2-ethyl «4 ₉ 5-pyraidione or
2 «n« «Btttyl» 4,6 «» pyrandiQn or
2 «Dimethylaminoäthyl« »4» 6 «» pyrandioii or 2 »Ph.enyl ~ 4 ₉ 6-pyrandione contains«

A diazotype material of this kind is also avoided » that as an idazo connection

4 "Diago" 2,5-dimethoxy "l" morpholino "" bensiöl- "Chlopziilcat or para-diazo-diphenylamine-chlorozincate or 4-I) iazo" 2,5-diethoxy-2 ^f "oarboxy-diphenylamine or 4-13iazo "" l "tliinethylamin © to2" methoxy "5" iBethyl-ben8ol or 4 ~ l) IASO-4 ^f "guesses; .oxy-iiphenylamin contains" vo.rs & agsweiae with a Kuppluniiskomponente after. Claim 2.

L ~ has the advantage of being a JKapplangsmictel ζ α dispose of ₉ dus can be mixed with the dazo-Orper in an aqueous solution containing the usual Jusatz substances, especially if it is related to its action and a coupling ability with the Diaso-Eörper a potential at a .Maximum 'iemperotur has, approximately located in the Mow of 180 °, a temperature _f geatattet a normal drying a ~~ i.izopapiers in its manufacture because the

ORIGINAL

1421835

in the production of piazotypin materlal the evaporation dta VaEsers _t tlae the vehicle of the to be deposited on the papitrtmais. ".. oiTc cars divides" the faster it runs "^ e the higher the temperature ö <n ' in' em froekenrsmm is circulating air, whereby from K "npl" n: ^- R "I" potential at these temperatures and the (i * chvin 'ability' l of decomposition of any bases present in the coating liquid) is very low, 'co daea a useful performance per is obtained time IMT · ^l> orteil Verdc-n y'u: SRIF £ e BeechichtunfXSwPlüssigkeiten verwend ^- et _f l _t about 5 - 2% einee the coupling agent and specified above about 1 _# 5 - 2 f include a diazo component.

The coupling components listed above have a structure die die, xistens in Xeto-Porm and in enol-form gaetattettje according to the conditions alch found.

The dlazo substances that can be used for the process according to the invention are iazo substances with a high degree of decomposition under the influence of light and good stability at the temperatures that prevail during use and development, The idazo-rtoff does not have to be destroyed before coupling. T-Ie Kupplungefähigkeit should significantly be such that · the usual lien ^ e of -Jiazo-substance _f sufficiently high contrast firs in the domes "are obtained so that one is not forced very groaae * enffen the diazo body to Yerwenden wae _f The duration of the light exposure would increase "

9O90O6 / -OÖO1 BAD

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Tetresa body dce

BAO ORIGINAL

ixtmr die »« »Steffen ΐΕβΒΒ * α * n * er * lliaso-ES79« i »will · * ·

Ia the BMoaiaataaesfltts »*** elt eenttfi der kttaatsa 41 · ttbUelM · Sttsmtcateff · gaeB »» la »

like s.B. l, 5

iuurnfttof ?, e- ^ r4r® «7e« ^ l * ilyltMob »r« rtoff use,), Uiafcohlorid, AIuaSaiianslfAt,

SI · W — tMWirWta 1 «aa 4tr v»? Seli £ «d Caapoaltloa d «r leeehiolituttesfltisclgfc ·! * Emtawrm & mm, Ami

aora * l «r V« lo · v «rw« ad «t« i & KesgeE ^ »s? haitsil®ee3a» «1» she Iwi

1 »$ - 2 Ji 4 # r IHe» so-Ko «po3 * © at ·,« t «& 1 * 5 - 2 # iPnypi "f" Tr "tfmwn \ ψ ," tv * 1 - 2 ft "iiwr S ^ atacater ·""tvm 3 - 4 Jt «!» · «AmtiosytfAtIoneeittel * uad * tw» 2.5 - 3 Jt

kOuMMfc d «r KcMipeeltlott geaKS der Erf ireäwa *

Substance ·, β.B. iiarpholttSÄdipet ^ su £ * c «tst this student is not aotwtndi« aaa * can »raptrt« mi «la · * vetteren part Uw Erfladumc represents, because - wi · au veii - the fabric · for dl · Stakllltllt dee

alai.

909808/0901

Is 4 «r tüMmsimteim ttbilehMi D4a * © t ^ 9i @ let

lld »s ^ Swtalg:» @ & g »eispf l> & £ ii * h® Ι1δ« β1 ^ «£ Ί with sit EiIf · «iasr stapfe« ® i ^ ar «se

let you

see p.

da® Fapl®2 * mi% t®I * eis®® © in-

, ve ^ el dl « · The frock feew.

, that the 4 Ußd S 5

the unloading is in a "

so *** $ "? £ & fe.ntsm f®" p "ra door area _e sB

150 and 190 ° eatwick9lt. The optie & le Tesper & tur ll «gt

at IBO ⁰ . At this temperature the paper structure is corroded or attacked and the ksapplarsg ie daa

geachiaht praictiaah aoaentaa. At 150 ° or below b®i & Utigt d & B if η Like no a® asu long "oä-sar but sa enters") part. "A ceremony

9 0 98 Ö _6/0 9 01 BÄD ORIGINAL

1422035

Component a} a relatively low density of the obtained Image is the <* sequence. Above 190 ° the paper becomes very thick freed from moisture and then teniates to tear

The copies obtained according to the invention have excellent and remarkable properties. They are stable in storage due to the stability of the colors themselves; The background is very stable due to the effects of gaseous light; it is uncolored; the density of the dye is excellent and the color shades or shades are extremely rich in contrast. As a result of the very small amount (which can approach Hull and be KuIl) of the substance used in the process under the action of heat bases, the developed paper shows practically no yellowing when exposed to light.

The following examples illustrate without deviating the invention restrict, preferred design shapes,

Example It '909806/0 90 1 BATH 100 al ORIGINAL £ from the following solution is produced i 1.5 S. ftasaer 0.5 G i-Aso-2,5-diaethoxy-l-aorpholino-
beneol chlorine cat 0.5 S. citric acid 5 G i / monoacid 1.5 al Thiourea 2.5 2-ethyl-4,6-pyranediol Glyaerin

This liquid is based on a known method Paper applied to every layer, with the excess by means of a so-called pneumatic knife is removedf the paper is dried in a tunnel with warm air » until the moisture content is $ 4. That way will obtain a paper of good appearance that is very stable and very photosensitive and that after developing by passing through a heating apparatus at 18G ^ a provides a good red-violet image that is very high-contrast.

The 4t6-Dioxo-2 «ethyl-1,4-dihydropyran was because of his great coupling power, its solubility in water, the stability of the dyes obtained, the nature and the quality of the coating and its stability to that Exposure to a normal temperature, as well as the richness of contrast of the tones obtained. The coupling ability this substance is maximal at 180 °, so that the paper during production - how normal can be dried «

Example 2ι

The following lion is produced:

Water 100 ml

p-DiaBO-diphenylamine-chlorocinate 1 g

Tartaric acid Ig

Zinc acetate 2 g

Thiourea 3 g

4f6-Dioxo-2-ethyl-1,4-dihydropyran It5 β

9 0SS06 / 0901

U22835

When this liquid hits, a layer is formed on paper in the usual way, with the excess being removed with the help of a so-called pneumatic knife. The paper is then dried in a tunnel filled with poor air until the moisture in the paper has reached a value of 4 ^a .

In this way, a paper with good appearance is obtained, which is very stable and very sensitive to light and that after developing by passing it through a heating apparatus of 180 °, an image still gives is more violet-blue than the picture according to the previous one Example"

Example 3s

A precoating is first carried out with Ea Help the following liquid:

Water 100 ml

Aeroail 2 g 50% aqueous emulsion

of polyvinyl acetate 2 g

It is dried and then there is a pre-coat on top of this . sensitive solution of the following composition applied! Water 100 ml

"Tartaric acid 1 g

4 — Diazo "2" 5 "diethoxy-2 ^f -carboxydiphenylamine. 1 ₉ 5 g

Morpholine adipate 2 g

Thiourea 3g

Ethylene glycol 3 ml

4 "6 - Dioxo-2-n" -butyl-1 _t 4-dihydrop-oil 1.7 S

This liquid is used in a manner known per se to produce a layer on the paper, the excess being removed with the aid of a so-called pneumatic knife; the paper --rird dtnn. dried in a hot air charged with _tunnel% to the G-ehalt to moisture about 4 ^c p is ,.

On this one receives a paper of good appearance, which is very stable, ₉ which is extremely sensitive to light and which, after being developed by passing through a heating apparatus at 180 °, gives a very strong blue image of very good definition and very strong contrasts "

SÖ '# iöß / 09Q 1 .'BAD'ORIGINAL

- ¹⁵ - 1A22835

The 4t6-dioxo-2-n »butyl-l» 4-dihydro-pyran was chosen because of its great coupling capacity and stability With the dye obtained, the quality of the coating and the great contrast of the obtained Colorations "

Example 4t

On a paper precoated according to Example 3 is a sensitive solution of the following composition upset

Water 100 ml

Lactic acid 2g

Ammonium bisulfet 2 g 4-diazo-l-d ime thylamino-2-methoxy-

5-methylbenzene 2g

Thiourea x 4 g

Diethylene glycol 5 g 4 | 6-Dioxo-2-dimethylamino-ethyl ~ l, 4-

dihydrop ;. ran 1.5 g

Saponin 0.05 g

This liquid will hit the paper according to well-known Methods coated, whereby the excess is removed with the help of a so-called pneumatic knife |

SAT ORIGINAL '900 ^ 06/0

The Pppler is then dried in a tunnel filled with warm air $ until a moisture content of about 4 $ is reached *

The result is a paper of good appearance, very stable, extremely sensitive to light _for the after development by sending through by a Erhitsungs "apparat of 180 ° a good brown red kräftigea picture emerges,

Example 5 «

A solution of the following composition is prepared »

water IGO ml Itaconic acid 2 g 4 "DiaEO-4 * -methoxy-diphenylamine 0.8 g Thiourea 2 g Adipate of tris (hydroxy-methyi) amino «- methane 5 g 1,3,6-trisulfonaphthalene 1.5 g

4t6-Dioxo-2 "-phenyl-1 ₉ 4" dlhydro-thio-pyraii 0.8 g

This fluid is administered according to known methods Layer processed on a paper, with the excess

9Ö9806 / 0901

is removed with the help of a so-called pneumatic knife; the paper is then dried in a tunnel filled with warm ituft to a residual moisture of $ 4 * *

In this way a paper of good appearance is obtained. that is very stable, because it is highly sensitive to light and that after it has been developed by sending it through by means of a heating apparatus at 180 ° a strong »brown-red, violet-tinged image results»

The reason for the use of coupling agents of this type is due to the fact that the room temperature and. ₈ did not go through the normal conditions of use, as set forth above to form a Sappein - not even a Biazo body in Amoniakdämpfen or in the presence of any other base _"f if not low-carbon zugeflihrt outside sirdj in the presence of this is therefore likely that in the At the prevailing temperature, these coupling components are in eto? orm and not in their enol form »ie» in the form capable of coupling »which they only assume at a temperature between 150 and 190 ° * Only at this temperature» the coupling can take place «

These papers have an excellent durability it will be packed in the usual white and delivered on * Wisely kept "

BATH ORIGINAL

Claims (1)

Pa t β n <t a n.-s ρ r U c h β '- Wall-developable diazotype material with a Layer support made of paper and a light-sensitive layer with a diazo compound and a coupling component, characterized in that it is a compound of the formula as the coupling component OC H ₂ C- """contains f where Z is one of the groups s CH, - CH * C- O -CO- ■ - CK- «C- O - GO - '■ CH: * C ■ * 0 »GO In 3 "? 6S * Q * 0 · CO.- —- * 3 ■ * οι «i - ο · co Documents. (Artr7ltAb ^? N> J.Sai23dQsXncierungsges.v.4.9, t3S ^ | 1422335 -CH.Ö-S-CO-. ° 6 ^H 5 CH - CH - OH ₂ - OO ^l 2 COOR R CH- - OH - H - OO - ² I i RR ₁ - O - CO - H-OO-
H -N-OO
I.
^R 5 M-Ns
R. C -
"1 OH -
001TBXH ₂ OH - H C-N-
L. V " in which R, R- and R ₂ H, an alkyl, aryl or aralkyl Reet and R ,, R and R ₅ φ, an alkyl, aryl, aralkyl or heterocyclic radical is * 8AD ORIGINAL 0.90 2, Diasötypieramaterial according to approach l _t gefcennseicimet that it «le coupling component 4 »6-Dioxo-2 ^ thyl ~ l * 4-dihydropyran _f or 4 "6-Dioxo-2 ~ ii-btttyl" -lt4-dlhydro-pjran _t or 4 »6-Dioa: o-2« di3Be ttejlaminoäthy 1-1 ₁ 4-dihydro-pyran, or 4 i 6-dioxo-2-pht njl «l _v 4-dihydrothiopyraa contains « 3 «Dlasotypieaaterial I according to claim ₉ characterized gekennxeichn" t _t it as a slide corner joint Ohloreinkat, or para-Diaso-diphesaylaein-ChlorBiaket, or 4-Dieio-1 "-dinethylaffilno-2-Hiethoxy-" 5-xaethyl "ben" ol # or contain BATH ORI0IHÄL