DE1547961A1 - Process for making improved diazotype materials - Google Patents

Description

DR. LUISE WESSELY
PATENT ADVOCATE

TtLtQKAMMEiWESPATENT 8 MUNICH 19 POiTSCHECKt MÜNCHEN 1 «1i» «MONTENST« ASSEWl

• ANKHAUS H. AUFHAUSE * S7 »S0« TELEPHONE: 573203

P 15 47 961 · 5 Heue registration documents

Docket 16 060

INTERNATIOMAL BUSINESS MACHINES COflFORATION Arroonk, N »Y. 10 504, UcS ₃ A ₀

Process for the production of improved di-

azotype materials

BBSCCSSCCSSBCSKSKSC

The present invention relates to a new method for Improving the properties of diazotype materials, More specifically, it concerns a method of treatment of diazotype materials, especially heat-developable «η Di azo ty piernikrof lines to the resolution or »sharpness and the To improve the density of the images developed with these materials «

Ihenao diazotype compositions and materials are known, including generally diazotype compositions

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to understand which are developed through the application of Wirrao Common diazotype compositions become common by bringing it into contact with an alkaline medium, such as gaseous ammonia or an alkaline solution, developed.

Heat developable diazotype compositions have a wide variety of uses, including the manufacture of hi-film materials useful for window cards or the like are. Are heat developable diazotype additives Also useful in the production of copy papers, tracing papers and in many other areas. I am a particular advantage of dlazotype materials that can be developed separately is that the apparatus and process for generating heat are generally much simpler than those for the or mass development of common diazotype materials • used with alkaline media.

However, it has been found that many of the commonly available heat developable diazotype compositions do not Images with the degree of sharpness or density required for certain applications, in particular for milling purposes • Vines · For example, many of these provide compositions Old low density images that have a resolution of about

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60 to 8θ lines each now (L / rnm), if a strong reduction takes place, »; ie for microfilms, for example Resolutions of this order of magnitude lead to the loss of lines in a drawing or other graphic material that or that is to be copied. In some cases it can blurry and out of focus images. If special requirements are placed on the pictures produced with the copying process and the pictures have certain standards correspond to nuts, images with a relatively low resolution or sharpness may be inadmissible.

01 · present invention! »Therefore meets« in new «processes sur production vco DlasotypeMeteriall old honea resolution ability and good optisottsr height «. In particular, it relates to the production of improved wMree developable OlasotjplealkrofilB materials old higher) resolution and higher optical mounts.

The finished and dried die-fill materials are generally treated at elevated temperatures prior to imaging.

P4. · Invention shall be considered in the following more detailed description of the procedure «in connection with the figures in the drawing. Show Bs »

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Pig. 1 shows a graph of the improved resolution achieved by the <r <"findunersgemKseen method and FIg * 2 graphically shows the improved density achieved according to the invention »

In general, according to the invention, a photosensitive diazotype ' Composition treated for about 5 seconds to about 20 minutes or longer at a temperature of about 40 to 150 * 0. These Heat treatment is and can be done prior to imaging either in a vacuum or at normal atmospheric pressure be carried out with equal success.

In the following, the term "resolution" or "sharpness" means the number of lines per mm in the developed image according to Buokbee-Hears or the National Bureau of Standards Target. The density (^ _04x ) relates to the Durohltaelgkei te factor of the developed image, as it is sat in a densitometer according to ASA Standard PH 2.19 - 1959.

Heat developable photosensitive diazotype compositions of the type used in the process of the invention generally contain the following ingredients in about the amounts indicated:

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component

Amount in g

Uohtea-sensitive diazonium " sals or combination of salts

One or more couplers (optional if a coupler is used will)

SÄireetabilizer (s) (optional)

Zinc chloride stabilizer (optional)

Bin or several base builders (optional)

KLn or several coupler formers (optional)

thioharnetoff (optional)

0.2-4.0

0.2 »5.0
to about 1J> 0 to about 1.0 to about 5.0

to about 6.0 to about 4.0

The liohtea pfindllehen compositions are common In a solution of a resinous film-forming material applied as a layer, or a backing is made with them Impregnated.

Compositions of the type described above are suitable for dissolution in 100 ml of a resin carrier solution. Usually will be about 2.0 to 30.0 weight percent of a soluble film-forming agent

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Resin Dissolved in a sufficient amount of volatile solvent to make 100 ml of solution; then the constituents of the heat developable diazotype composition are dissolved in this carrier solution. The amounts given in g above therefore also represent the approximate Oewlohts percentages of the constituents in the final solution.

The solution is then applied as a layer on a suitable substrate, for example on paper or transparent plastics, in order to form a rail up to a few hundredths to tenths of a millimeter (a few mils; 1 mil ”* 0.0254 mm) thick. If the product is to be used for the production of microfilm, an existing polyethylene terephthalate, or other transparent plastic base is particularly satisfactory.

The material is then usually allowed to dry to remove the volatile solvents evaporate, and the product is then cut into the desired fora and ready for use worth it.

The present invention is also used to improve light • sensitive diazonium materials valuable by impregnation, d. H. by applying a solution

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the diazotype zu Bfcrarnensfafcauog in a flüöhfeigen means on the-'surface- of a Hnte ^ Xage and anscltlieasendea Evaporation of the solvent ^ tvergessslit vierden * Es vrlrd no resin-like carrier used here «The diazotype composition is applied as a coating to the base and impregnated onto it.

The impregnation process is common in the field and can be done by applying the heat-developing bareti photosensitive azotype composition directly to the surface of a substrate. A small amount of acid is usually added to the shredded skin to etch the surface of the base and improve absorption.

A typical recipe for impregnation can be contain the following ingredients:

Component Mange in. G

Light sensitive diazonium «-

salt or combination of

Salts G, 2 -.Α, Ο-

Am or more couplers

(optional if a coupler =

former is used) 0.2 «5.0

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Component ffenge in g

SaurestafaiIisat or (en)

(optional) ^ to about 15 * 0

(optional) up to about 1.0

One or more bases «= ·

educator (optional) up to about § ₉ Q

One or more couplers

educator (optional) up to 6 _f 0

Thiourea (optional) at about 4 _f Q

Corrosive acid (if necessary) up to about 5 * 0

The composition KiHHg is considered to be a suitable remainder volatile solvent "such as methanol or ethanol, added" that about 100 ml of solution is obtained will.

Solutions of the type described above are appropriate Documents such as those made of cellulose or triacetate, upset. After drying, the materials are cut to size.

According to the invention, the deposited on the substrate or in this sucked diazotype composition before

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Image generation for at least about 5 seconds at a?> Wis-ch & n 40 and 150 ³ G tempera bur! Treated. Lower heat treatment is sufficient at higher temperatures within the specified range.

As a result of the pretreatment sseigten films .auvor © in on "resolving power of about 60 L / itus * obsessed * nine improvement to more than 150 L / mni and η in some cases even up to optionIf ·> 00 L / mm. In addition, the improvement in sharpness on au enters a Erhöhimg the density of ■ evhalt & mm image. The most pronounced improvement is observed in films which contain a light-sensitive © diazotype assimilation @ t8 «mg in a resin-like film-filling carrier * - It has also been found that there is an improvement in materials which have been impregnated with the DiaKotype supplementary set.

The introductory results according to the invention are from the following Examples that show certain preferred options Implementation of the invention without the invention to restrict,

example 1

A carrier solution of a resinous material is prepared

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by dissolving 15 wt. ~% of polyvinyl butyral in Methanoi v / ground * 10 ml solution obtained. 1.3 g citraconic acid, 0.2 g thiourea, 0.1 g S, 3-dihydroxynaphthalene-6-sulfonic acid sodium salt, 0.15 g p-diazodimethylaniline zinc chloride salt and 0.2 g zinc chloride are added to this solution. The solution is applied to a transparent polyethylene terephthalate pad to form a layer a few hundredths to tenths of a millimeter (a few rails; 1 mil * 0.0254 mm). This film is then allowed to air dry at room temperature The film material thus produced is then exposed to ultraviolet light 1 ?. Seconds exposed and heat developed for 30 seconds at 15Q ³ C by infrared radiation.

The resolution and density of the image thus obtained are then measured. According to a modified national Bureau of Standard Target measured resolution was 54 L / mm, and the optical density measured with a Welch densitometer with a No. green fliter. 99 measured was 0.32.

Example 2

A heat developable diazo film material is made according to the

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-'Working of. Example 1, but the dried Fllmmaterial before exposure in an oven for 1 minute at 1QO ⁰ C'erhitzt ". The film is then exposed and developed as in Example 1. According to the measurement, it is found that the image obtained has a resolution of 84 L / mm and a density of 0.90.

Example 3

The procedure of Example 2 is repeated, but the PiIm will run for 2 minutes instead of 1 minute at 100 ° C treated. After exposure and development, the image has as was determined «a resolution of 125 L / mm and a density of 1.00.

Example 4

The procedure of Example 2 is repeated, but the treatment of the film at 100 ^° C. is extended to 3 minutes. After exposure and development, the resulting image was found to have a resolution of 150 L / mm and a density of about 0.96.

The extraordinary improvement in the resolution as a result of the Oven treatment described in Examples 2, "3 and 4

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shown graphically in FIG. In Pig. I _3, which thus shows the effect of the pretreatment on the resolution, is plotted on the vertical axis, i.e. the resolution irt h / mm. The time of the treatment at 100 ^° C. in minutes is plotted on the horizontal axis. The measured values for the materials produced according to Examples 1-4 are shown as circles.

Example 5

A resin carrier solution is prepared by adding 15 wt .- # Dissolve polyvinyl butyral 5λ methanol to obtain 100 ml of solution. The following components are then dissolved in this solution:

6.4 grams of citraconic acid
2.0 g thiourea
0.4 g zinc chloride

1.0 g p-Dlazodimethylaniline zinc chloride salt

1.0 g 2,3-dihydroxynaphthalene

6-sulfonic acid, sodium salt

The solution obtained is then applied to a transparent poly-

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äthylenterephthalatunterlage applied layer as and dried in air at room temperature, about 22 to-2.4 ⁰ C, 24 hours. This film is then heat developed by exposing it to infrared radiation at 150 ° C for 5 seconds. The density of the image obtained is then measured using a Welch densitometer; a reading of 0.06 is obtained.

Examples 6-12

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Films are made in the same manner as in Example 5. They are developed with increasing development times. The density of the image obtained is measured for each development period. The results are in the summarized in the following table:

example Development time
in seconds density 6th 10 0.11 7th 15th 0.15 8th 20th 0.21 9 25th 0.28 10 30th 0.36 11 40 0.50 12th 50 0.56

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= 14 -

Examples 1j> - 20

A number of films are made according to Example 5 . but the resulting films for 50 seconds at 150 C ^e of be enbehandelt ". These films are then developed for different lengths of time as in Examples 5 "12 = the density of the images obtained is also measured after each development period. The results obtained in this way are summarized in the following table

example Development time in
Seconds density 13th 5 0.26 T4 10 0.33 15th 15th 0.37 16 20th 0.4? 17th 25th 0.5 18th 30th 0.57 19th 40 0.61 20th 50 0.66

The results of Examples 5-12 and 13 = 20 are compared graphically in FIG

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In Pig. 2, which shows the effect of oven handling and air drying on the density of the image; the vertical axis shows the density readings determined with a Welch densitometer, and the horizontal axis shows the development times in seconds = the Sahion In addition to the circles at the upper curve (Gfenbehandiung, 30 seconds, 150 * 0} and the lower curve ijjxtt drying, 24 hours, 22 to 23 ° C) correspond to the numbers of the examples "from which these data originate"

It can be seen that the oven-treated films show a marked improvement in the optical density of the developed image over the films dried on the LnVz for 2k hours at room temperature, about 22 to 24 "C. Furthermore, SiGh ₁ gives that Eilder with much higher Density can be developed much faster with the oven-treated films than with air-dried films. For example, the optical density of the image obtained with a pre-treated film after 25 seconds of development at roo ^s C is almost twice that of the corresponding untreated FiJ .ms (cf. Fig. 2) «.

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■ "- 16 - - · ■ ■" ■ * · ■:. ■

The above examples © show the extraordinary advantages, according to the invention with regard to resolution and density can be achieved in systems that use resinous supports thaiten <> As is inclined in the following examples, wex'den however, similar, if not as pronounced, advantages are obtained by pretreating materials using impregnation methods are made.

Example 21.

Han prepares a solution of the following composition:

13/6 citraconic acid
$ 2 thiourea

1 % dicyandiamide

■ 1 % 2,3-dihydroxynaphthalene ~ 6-sulfonic acid, sodium salt

2 % p-biazo diethylaniline

1/2 zinc chloride

2% formic acid
Remainder methanol

The solution obtained in this way is applied to the surface of a cellulose trlacetate film and the resulting solution is allowed to dry The film is exposed to a UV light source © for about 15 seconds and developed for 30 seconds. The measured © resolution is 40 L / ranu

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■ ° 17 »

Example 22

A film is produced as in Example 21, but according to Dry first treated for 1 minute at 100®G before exposed and developed. The image obtained has a Resolution of 6§ L / mm.

It can be seen from Examples 21 and 22 that a considerable improvement in the image properties is also achieved by heat pre-treatment of materials produced by suction are achieved.

It should be noted that the benefits of the present invention are not obtained simply by air drying the film, whether or not it is. Vacuum or does not take place in a vacuum, "This is clear from the above data out _o Sur achieve the desired results, it is necessary to film at least about f> seconds at temperatures above 40®C, -Jedoch" cash under the Vorkupplungstemperatur the wärmeenfcwiciEel photosensitive DiasoniiSffisusanimensetEimg treat _s usually about 150- ¹⁹ C, "at higher temperatures lying pretreatment goose liurz karm be, for example, in '! ©« rich-by. fj to 15 seconds are, "If jedoeh low ©

i8 -

Temperature © ** should be used <, are longer '/ o Action-free, and time spans of 20 minutes or more 'can be applied »

Regarding the upper tempera turgi * ense of the pretreatment also pointed to the following «* Some Diasctnium & alse and Coupler is one of the heat-developable types of couplers at relatively low temperatures »and the treatment temperature in the above range should therefore be chosen * that premature coupling reactions are avoided »

For every special DiaEotype system there is an optimal® Pre-treatment time and temperature, which lends due to of the A'rtsitswei-Bßn mentioned in the examples 1 - 20 can definitely be grounded.

Especially gut® results are obtained with a wärmsanfewiekelbaren DlaaotypieausaBimeiisetsisog ^ atv a "0 -?.. 5 weight Jl>CitracsonsUure" Ms ·· to 3% thiourea ,, hm z .: ~ ^r *% zinc chloride, tois in 2.0 % dicyandiamide, about C.5 to Sw #

0.5 to 5 % p "DiaKSOdin" ethylaniliii * = SinkGhloridsa * a tj 2.0 to 30% of an inars & rtigen film-forming Mafcei ^ -i dissolves in about 100 ml of a volatile solution

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Resin, contained This composition is based on an approx 0.05 mm (2 mile) thick underlay, for example made of polyethylene terephthalate, so applied that they are coated with a thickness of about 0.075 mm (O> 0 mils) is formed

Films produced in this way are preferably dried and treated ^{for 2 minutes at about 109 ° C.} Near exposure; de B films by means of a Hegafe.lv and developing for 60 seconds by Erw'Urinen at 150 ⁰ G, images with densities of 2.0-0.2 and resolutions of 150 L / mm are obtained.

The heat treatment of the dlazotype material produced according to the invention can »h & f a great achievement of the Effect density of the subsurface; yet this increase lies not in the order of magnitude of the In dor BiXddlünte Increase. As a result, I will also raise a low improvement " of contrasts achieved. -

In general, each Usual may wUrmeentwickelbare Diazotypiezusainraensetzung be used erfindimgsgemäss _etc. This Zvisammensetzungea a variety feekannten can light "sensitive diazonium and --Kupple included? '"

To some of the photosensitive diazonium compounds. That for use in the lecture "n invention"? Agnsii, ge "

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hear for example p-diazodimethy! aniline, p-diazodiethy! aniline, p-dlazo-M-ethyl-N-hydroxyethylaniline, p-di »azo-N-ethyl-o-toluidine, p ~ diazodla'thyl-m-toluidine, p-Diazo-N-ethyl-N-benzy! aniline, 4 ~ Dia2o ~ 1 ° morpholinobenzQl _# 4-Diazo-1-morpholino- ^ i5-diethoxyijenzol and the like. The stabilizing salts of the diazonium compounds can be any of the commonly used stabilizing salts, such as, for example, zinc chloride, boron fluoride, cadmium chloride, tin chloride and the like.

Some suitable couplers for use in the present invention include, for example, sodium 2j,> »dihydroxynaphthalene sulfonate- (6), T-hydrocy-1,2-naphthimidazpl ,. 2.2 ^p, 4.4 x -Tetrahydroxybiphenyl, 3,3 ', 5,5 * -Tetrahydroxybiphenyl, 3 "5" Resorcylsäureäthanolaraid, 2-hydroxy-jS-naphthoic acid "amide" N-ß-Hydroxyäthy 1 -2-hyöroxynaphthaiin -3 ~ earboxaißid, N, N ° -Kthylen-bie-aeetoaoetamla, Tetramethylendiaiain-bisaoetoaoetamld and the like <..

The geoMss of the present invention used resinous ones Compositions include a wide variety of film-forming plastics and natural polymers and resins, dissolved in volatile solvents. For example besides polyvinyl butyral also other suitable ones

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- ■■■■ ■ ..- .21 - ■ ■ '

resinous film formers * including polyvinyl chloride, polyvinyl acetate, cellulose acetate *, polyacrylates, polyvinyl chloride and the like ₆ "are used"

Su suitable volatile solvents include wise methanol, *. Kthanol, methyl ethyl ketone, -thylene glycol ^ monotethyläfchexv acetone, Kthylaeetat, propanol and the like. "

The compositions usually contain one or more stabilizing acids, e.g. acetic acid, citric acid, tartaric acid and the like. © d @ r pass into anhydrides, - if d <@ z * film heat is exposed during-the - heat development * The dissolution of the acid changes the pH value of the. The system unä tägl * the process of the color-shaping reacfci @ a * Di® wMrmeenfewlGk @ contain common catfish mwah Basebiläner »which" are activated & examples of this "are urea,

tmü like "".

It was "!" Found "that ciferaeonic acid © te fe © ad © rs aweokasassiger component in Biaspiiltamssiissisiiissasetssußgea isfe _fl with those of the Fi 'in the dupßh Wteae odes" dupeh © iae combined

and alkali treatment is to be developed »This acid acts as a stabilizer, becomes, however, slightly in when heated the anhydride transferred * resulting in an increase in the pH of the System.

In the above wärmeentwickelbaran Diaaoniumsysfcensen a Kupplerbildner may be present h- d _{3 e.} One compound * which decomposes when heated to form compounds "which are capable of coupling with the light-sensitive diazonium ala" Cyanguanidine acts on these catfish both as a coupler and as a base generator => Many systems also contain smaller amounts of sink chloride as a stabilizer and Thiourea.

It is further noted that the present invention is also applicable to systems which are developed by a combination of heat and alkali development. Thus, the diazo systems which can be developed can be developed first by infrared radiation and further by using vox's gaseous ammonia or an alkali solution ä © r Ük-llch @ n working method © ritwieke ^ ϋ are _e feafeaänglg by the · Arfe ö © s ^ fi & wiukelns esiillt «naE fesssere results öe =

Mflösimg una grssser © r density »

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Claims (1)

23 - Pa t e η ta ns ρ r U ehe 1c method for improving the resolution and density of ^J for the development of wärmeentwlokelbaren liehtempfindliohen Diazotyplematerialien images obtained, characterized "by treating the finished and dried materials before the image formation at elevated temperature doors. 2. The method according to spoke 1, characterized gekennzeiolmtii; that the treatment is carried out for at least 5 seconds at a * »temperature in the range of 40 to 1§0 ^e C» >. Method according to claim 1 or 2, characterized in that that as a heat-developable diazotype photosensitive material one used in which the photosensitive diazatypie composition as a coating on a Carrier pad is applied. 4ο Method according to claim 3, characterized in that « the Diazot'.ypie composition a resinous film-forming Contains material. 9 0 9881/1220 BAD ORSGlNAt 5. The method according to claim h- _s thereby. characterized _s that the treatment is carried out at a temperature in the range from 80 to 110 ° C. 6. The method naofr claim 1 or 2, characterized in that a heat-developable light-sensitive diazotype material is used * in which the di & zotypezU "sweetening by impregnation on ®% n @ ^? Joterl © ge applied iafc" Τ «Procedure for Hers-elXuiig from wMi. ⁱ f «eeiii; windable light-sensitive diasotypiGni & teriftXien, dadiiroh denoted that one dissolves a heat-developable -light-cup! honest &#8211; diazotype &#39; s solution In a volatile solvent to form a solution or in a stick solution, dissolve a film-forming resinous material in a volatile resinous material for this material -.Applies solution to the surface of a base, the. Volatile solvent evaporates to form a coating on the base and this coating is treated before the image generation -at least 5 seconds at a temperature in the range of 40 to 150 ° C » BAD ORIG " ¹ - 9 09881/1220 8v Veri '^ nren according to''Claim T ₉ ' - characterized by ', gsss ■ one © solution with. a content of sfcvja 1ö to 15 wt. ~ &"Citraconicacid;." bis-ice. 3 $ OSiioharnsboiT., To ε «1;» Ο il zinc- 'a to. g _g 0 ^ Dicyandiamide * ..efcws O ^ Ms ^ o $ ass eiisn DiaaoniwmsalKSSs - about 0 ^, 5 feis $ 5 © inss Couplers'-for- the -Diasoniuiuisals. iiml 'about S ₁₁ O b; is '} Q% ! forms ^ ..which the ■ lia ^ aax'tige i4atarA.aT, in which -solvent. "is soluble, this solution is applied to its base, the volatile solvent ■ with the formation of a solid coating on the IJo. te r lage evaporate & and clsn fe'stsn. üsrsisg in front of the Bildergeygwog Eüai at least about 5 seconds long with a-TsaHpspatwr im: Bar ^ iiM ' from.40' to IgO ⁰ O foehsndelfc » 90988 1/1220 ' ^l BATH Lee.r side