DE1572227A1 - Method for producing a photosensitive material - Google Patents

Description

WpL-Ihg. H. ZOEPKE 11 MAY 1967 Patent attorney "

• Mtaoh «ill-Ridleretr * Je87 1572227

PHN.

Ti.V. PHILIPS 'GLOEILAMPENFABRIEKEN, EINDHOVEi / HOLLAND

"Method for producing a photosensitive material".

"The invention relates to a method of manufacture of a photosensitive material in which at least * at the Surface electrically non-conductive base layer the actual, one Aroir.atiaehes diazo sulfate-containing, light-sensitive layer attached is received, as well as on then * 1ichteaipfrndliehe material.

The light-sensitive layer can be hydrophilic and can. e.g. by saponification of a surface layer of a cellulose oil and subsequent impregnation with a solution of such Diazosulfonates are obtained. The material can also be preserved thereby v, ground that on a base layer one with 7 / aö "aer non-impregnated Materials a glass-like photosensitive layer by means of a predominantly Aqueous lounges containing the aromatic diazo sulfonate are attached and, if necessary, contains a wetting agent and / or one or more other compounds that allow the layer to dry out in crystalline form impede.

Such a photosensitive material is aur production photogrsphischer images used in the known * method in which it is brought after the exposure with a Merkuroionen wieerigen containing solution into contact, which preferably also enthSlt silver ions, the 3i1inn _t; of a latent nucleus consisting of mercury or a silver aralgam, which is reinforced by physical development to a visible metal image.

When exposed to light, the diazo sulfonate dissociates at least partially a labile isomeric form into a light reaction product which consists of a diazonium ion and a sulfite ion. Serve sulfite ions

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play "in Bolle in the formation of the phyaikaliaoh more developed metals, if the exposed layer is allowed to come into contact with an aqueous solution of the curative salt, which preferably also contains a silver salt. After completion of the light exposure, the Reik ^ rerlluft but ion in the opposite direction, so that the physical Sntwiokelbarkeit the layers gradually more so disappears j * linger time is that lierkuroionen between the end of exposure and InberUh ^ ungbrin _fc s with the bath containing it passes. Piping phenomenon is known bekSmpft under the name degression of the latent image and to zweckmasei ^ e manner in that in the light-sensitive layer contains a compound, a so-called antireflection _b ressionsxittel, is mounted at the same time, which prevents diazosulfonate is reformed from its light reaction product, namely by binding either the sulphite or the diazonium union, or both, in such a way that the sulphite retains the possibility of reacting with the uranium salt with the formation of sugar filters. The most effective antirepression agents include the water-soluble salts with cations which, with sulfite ions, form sulfites that are poorly soluble and / or poorly disassociated, such as Zn ⁺ , Cd *, Pb, Cu ⁺ * and Ag. These cations are no less effective when they are present in the form of salts of the light-sensitive diazosulfonic acids.

An important disadvantage of the known photosensitive iiaterisls, which in addition to an aromatic diazosulfonate is a powerful Contains anti-regression agent, is that this material is a Has less durability than material because it is not an anti-regression agent contains. This is revealed in the fact that this material in the course of

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Time leads to fog formation more quickly and that usually an increase in temperature during drying of the material after soaking with the solution of the photosensitive substance already leads to fog formation. In addition, such a material usually eliminates a characteristic curve, i.e. the curve which represents the blackening (D) as a function of the logarithm of the exposure energy (logl .t), with a lance, that is, the curve does not appear until after dec Traversing a relatively lance log. It section reaches its maximum steepness, which then goes up to relatively high blackening values. remains retained. Diene limited in particular the applicatio _e -smÖ £ friendliness uieses Liaterials in the Llikrophotogrephie, among other things, integrated in the micro documentation and for the production of photomasks for the production and thin film circuits is applied. On the other hand, there is a need to look back on the many times that, for example, the production of photomasks on the same material is exposed one after the other using the same protective agent, with there being a relatively long time between the first and the last exposure , an effective patching of regression is indispensable.

See the method of the present invention for producing a photosensitive Kateriale is characterized by being light-sensitive Layer old with the help of a predominantly aqueous solution is applied, which in addition to an aromatic Diaioeulfonat and at least an anti-regression agent as a water-soluble mercury in one Quantities of at least 10 ** ora equivalent / l and a maximum of 10 ** ora equivalent / l «Nthe'lt, while the diaeosulphonate in a consentration, which is at least ten times the concentration of mercuric acid, is available.

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Pas erfindungsgemaeee method is inebeecnder · wirksaa FSllen in those in which a Antiregreepicneasittel is used, there is one or more soluble salts containing ice cation Zn, Cd, Pb, Cu or Ag possess than ¹ even in those pills. " in which a salt of a diazoaulfonic acid containing one of these ketions is used.

The photosensitive fibers obtained by means of the process according to the invention Material has a greatly improved durability, with a noticeable haze if it is only at room temperature in the absence of air telegtrt occurs at a much later point in time with one in a corresponding manner, however, without using the mercury compound manufactured material. The improved Holtherkeit results can also be derived from the fact that in the dry process a relatively high temperature is used after the application of the photosensitive solution can be. The characteristic curve of the invention obtained material has a very short foot and the Gacnas, i.e. is the tangent of the angle of inclination β αββ straight part of the curve high. It is generally surprising that this material is a better one Resolving power has uni that also the RanaechSrfe the with him obtained images is improved.

Another feature of the Saeen process according to the invention is that it allows him to use other diazosulfonates than those that have hitherto been usable aSglicL has become let. The restriction is caused by the dark equilibrium

1-1-1-SO ₃ "ti ^ H - H - I ⁺ ♦ SO".

The more it shifts to the right, the bigger the xenge Free sulphite ions in the Sohicht, with which the danger of fogging

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r T _r

increases..Biazoaulfonate are now in the material according to the invention can be used, which previously caused an unsightly veil. Sin An example of such a diazosulfonate is p-hydroxybenzene diazosulfonate. Some diazosulfonates are now also available for practical use, which still have considerable light absorption in the verifiable part of the spectrum. This is of particular interest because it means There are no special provisions in the optics with which the material is used more are necessary and you can easily use the commercially available can use photographic equipment. So you can, for example Use diazosulfonates, such as the 4-lorfolino-2,5-diillethoxybenzene diazoeulfonate with a molecular extinction coefficient c

4th
435 ° H ^v at 1 °

The effect of the Mercury salt in the light-sensitive material

is probably based primarily on rendering the

thermally formed sulfites, while it is possible that the Mercury compound also the adverse effect of the lateral diffusion dee through the photochemical reaction formed sulphite partially reversed power. In any case, it is surprising that the Mercury compound in the light-sensitive solution in a rather large excess compared to the minimum concentration that leads to this effect can without this having an unacceptable influence on the photographic Sensitivity after cutting off the pusses. characteristic curve. Senn, if one of the resolution of the Uerkuro connection, with which the layer is treated after exposure instead of being light-sensitive A layer of such amounts of mercury salt is obtained a great negative effect on the photographic sensitivity, and the more negative the greater the concentration mentioned

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is, and BOgar dermasaen, that's it at a concentration of ^ O

GramraSquivelent / l is no longer sensitive.

According to a preferred implementation of the inventive method, the "Merkuriealr" in the effective range ir the aqueous I. Reurg der Hchterapf 1η · Π1 chen connection is indicated by the fact that this one I. Sur.j; a Merkurosalres is added, Ss Is ^ a known that ir. such a solution, which is geecköttelt with metallic mercury, subsequent equilibrium prevailsi Hg _? * ^f ^ l Hg ⁺ * ■ »Hg. Daa Verlalltni * (Hf * ^) AHl ₂ **) ir. such a solution affects about O ₁ Ol. E» e means, deae, * and cause the Mercury effect rxi , the concentration of the Kerkuroeelsee in the «solidified solution of the sensitive connection, Vie sugleicb an ant! regression ··! ttel entLIIt, aindeeten «5 ^x 10 mol / l are twse. The upper limit of the dosage of the Merkuroealtes is determined by the solubility of the Verkuroealces of the Diasosulfonelure used, which is mostly between 0.01 and 0.1 mol / l.

Biese Auaführungefora asked for the special advantage that - Depending on the degree of humidity of the licbtespfir.rilichen Materials - ready partial nucleation can take place immediately, due to the presence of the metal compound providing the wedge pattern the lateral sulphite diffusion can be even less harmful, It is advisable to use a silver compound as an antiregr # for this variant to use, «hurry, it has turned out to be daee this also has a stabilizing effect on the rreugte Feiratild Has. The concentration of silver pre-binding in the aqueous solution the light-sensitive layer is preferably 0.005 to 0.1 col / l

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be. It is notorIich that the littleness of the silver salts Diaxoaulfonfure used should be corrected. One becomes vorugaweiee Use diaeosulfonates, the ingredients of less than »0.01 AoI / l Silver salt tolerated per liter, such as p-methoxybentol dia-sulfonate, o-chloro-p-aMtfaylbenzoldiazosvlfnnat. and o-methyl-p -chlorbenzoldinzo- ■ ulfcnat. The nucleation is completed by the fact that the exposed Vfiterial advises Iinsar or unaittelb & r with the physical Developer is wetted. However, the best results are obtained if the first wetting ri.it a solution that. both «ine Kerkurr- • ls also contains a silver finish.

AusfQbrungsforn piping leads βοwohl aue a Geeichtapunkt the steepness of the curve charakteriatiaohen ale also from the Begreeeionabeklapfuag and dea AuflBsungaveraSgena eu optimum Ergebniaaen _t wJhrend daa liehteaipfindllcbe material still beelitt a Aehr useful Lebenadauer ..

Aa Raad of some Belapiele and some in the drawings The misfinding becomes closer explained.

1 · saponified strips of blue with a depth of 2μΒ Cellular moisture content was then released for 1 minute ■ Were soaked with luscious LSeungea, which contained per liter!

a) 0.1 mole C4-3alc of p-methocybentol diszoaulfonaluret

b) O ₁ I labl Cd ~ Salt of p-methoxybentol diaeulfonic acid and 0.00005 mole of mercurine filtrate

c) 0.1 mol of Cd-salt of p-XcthoxybenroldiazoaulfonsIure and 0.000 ^ ¹ Oi mercury nitrate}

d) 0.1 mol of Cd salt of p-MethoxybenKoldiazoPulfonsIure and 0.005 moles of mercury nitrate.

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Di · strips were dried for 5 minutes in a filtered air flow from ungefltr 30 ⁰ C (lOO liters / minute). The strips were brought up in the dried state in non-genuine plastic bags. , '

After all the strips had been exposed to the same track with the aid of a Seneitoeeter, a germination bed was only introduced for 4 seconds and treated with 0.005 moles of mercuronitrate per liter of water
Contained 0.003 moles of silver nitrate.

The strips were then peeled for a short period of time in deionized water and physically developed for 4 minutes with the aid of a L8eunfc, which contained tfaeeer per liter
0.05 mol perro-avnoniuoisulphate,
0.01 liol ferric nitrate,
0.1 UoI citric acid,
0.01 moles of silver nitrate,
0.2 f "Arnao 12D" and
0.2 ff "Lieeapol 1".

Aratae 1? D i "t predominantly Dod" * jrla "inat * tat and Lieeapol H an alkylated phenol, which condenses with methylene oxide int Rinse in deionized waeeer and dry the film strips Measured with the aid of a densitometer. The preserved characteristics » Curves (labeled a, b, c and d} are on the graph neob Fig. 1 shown.

The characteristic curve is not suitable for the curve b, c and d are suitable for multi-faceted shark photography, like di ··· bei

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the "production of photomasks for the production of integrated and hy- * bridischer DOnnichachalten is applied.

The conductivity of the n-it solution c sensitized film is at least a factor of 2 higher than that of the film sensitized with solution a. If the LSsuQgen b, c and d were combined with mercury lactate, mercury chloride, or the lierkuris salt of the respective diazoeul fonsfiure instead of mercury nitrate, then completely analogous results were obtained.

2; Strips of the superficially saponified carrier material Example 1 were sensitized by exposing them to aqueous for 1 minute Solutions were soaked that contained per liter! a) 0.2 mol of the Cd salt of p-M · thoxybenzoldiazosulphonic acid and 0.05 'Cd-lactate (l r.dmiun to 1 lactic acid)} b ^ 0.2 moles of Cd-SaIs of p-methoxybenzpldiazosulfonic acid, 0.05

Cd lactate and 0.00015 moles of mercury nitrate) o) 0.2 mol of Cd salt of p-MethoiybenzoldiazoeulfoneSure, 0.05

Cd lactate and $ 0.00 mole of mercuronitrate j

d.) 0.2 mol of the Cd salt of p-Methoxybfcnzoldiazosulfoneffure, 0.05 Cd lactate, 0.005 moles of mercury nitrate and 0.01 moles of silver nitrate.

The strips were exposed to a stream of filtered air for 5 minutes dried at about 30 ° C (100 liters / minute). You were after Stored overnight in gcaohlosaensn bags.

The exposure, introduction and physical development of the strips is carried out in the manner described in Example 1. If one ά · η part of the reduction cure * · between D * 0.10 (only the base reduction) and the D, where the curve in a straight line

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passes over, calls the foot of the curve, then this extends in FOl a over a log Lt-B-range 1.03. In cases b, c and d the ·· distance · is up to 0,? . 0.05 shrunk. The Ganme, dos eich relates to the straight part of the Sci.wSrzun £; 8kurve, iut im
Case a 1 8,
Pall b 1 8,
Pall ct 10 and
Case d 1 12.

The strip d differs from a, b uni c durct. a particularly _£ -erin _t -e regression. After a period of five hours between exposure and the germ introduction (the strip was in air vcn 20 ⁰ C and a relative humidity of ¹ JO ^ kept for diener time) can "no Eapfindlichkeitaverluat found" ground. That on the. Stripe d of the dissolution test obtained has the same value as the air passage on the stripe of Examples 1 and it is

interpreting better than the resolving power on the strip a. c / Venn corresponding strips ·, b and β after the sensitization _r 1 minute in a filtered air tube of un _c ; efa "tr 90 ⁰ C (100 liters / minute) dried and then examined in the same way sensito- • etrieeh» - Then the stripe roped a strong formation of soles, while stripes b and 0 show no closures! They showed the same picture in relation to the characteristic curves as strips b and o which were dried cold.

3. strip saponified Trlgermaterisls of Example I were eeneibilisiert characterized as ·· "ie one minute were getrinkt with solutions contained per liter of water, the _f!

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■ ψ

β) 0.2 llol Ht salt of p-Methoiybenzoldiazoeulfonsäure, 0.1 Kol Cd lactate (l cadmium to 1 lactic acid) *

b) «ie a, but auseerdee 0.00005 moles of mercury nitrate

c) wi · a, but also 0.00015 hol mercury nitrate;

d) wi · a, - however auaserdea'0.0005 UoI Kerkurinitratj ·) White, but also 0.0015 carbonate nitrate; f) wi · ·, but also 0.005 VolI mercury nitrate.

The strips were dried for 1 minute in a filtered air stream Ten approximately 90 ^c (100 liters / minute), IHe exposure, seed introduction, physical development and sensitometric processing of the "strips are carried out in the manner described in Example 1. The results are shown in the table below.

Solution Log It- ^ trail de · Fuseea Qacm « ν · 0.70 6.4

t 0,? 0 6.4

«. 0. £ 0. 6.4

4 0.0 «. 6.4

• 0.04 7.0

f 0.03 12

4. Strips of saponified backing material from Example 1 were used This is caused by the fact that you have drunk aqueous solutions were defleaded per liter

0, ft5 mole of Pb-SaI »clay p-methoiy> enzoldiazoaulfon * luref \) » ie a, jedooa. also 0.00015 Mercury entered.

The Troetaiung, Beliohtung, Ceinelnfahrufm and pajreikalieefc ·. _: ; In the meantime, the stripes were made on the catfish described in Example 1. In the eenaitometric processing, the following results were obtained.

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Solution - Log It range of the Fueses Gamma a 0.90 8.5

b 0.16 8.5

If solutions a and b are removed with the Zn salt of P-listhoxybenzene diaxosulfonic acid instead of using the Fb-ScIz, then The results were completely analogous. .

5. Strips of saponified support material of Example 1 were used Sensitized by drinking rai-t aqueous solutions for 1 minute that were delivered per liter

a) 0.1 mol of Ag salt of o-chloro-p-methylbenzoldiazosulfonEluref

b) 0.4 mol of sodium salt of o-methyl-p-otlorbenioldiaiosulfonic acid and

0.05 moles of silver nitrate}
o) 0.4 mol Ia-SeIz of o-chloro-p-ethylbentoldiaEoaulfonalure and 0.05 UoI silver nitratej

a), b) and ο} as for β, b and c, but «usa plus 0.00015 mol of mercury nitrate.

The strips β and * were on the in Example 1 described · Way and the strips b, b, c, c on the '• fcise described in Example 3 dried. After drying, the strips were closed Plastic bags kept, oils were sensitometrically ^ Tests carried out in the manner described in Example 1. The material a showed a strong after 7 days Scalwler formation, while the material a after 6 holes is still full “Was veil-free.

• m material b soaped afterwards. 1 Monnt veil picture, that β «ar still free of throat-leaps after 3 months.

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The material c showed a sole egg formation after 2 contacts, the material ο was still egg-free after 3 months.

Also a strip made with solution c, which is also 0.005 mol Mercury nitrate was added, "nensifcilized", "ar after Months still free of eggs.

6. Strip saponified TrSfermate rials dee example were thereby eensitized by treating them with aqueous solutions for 1 minute which contained per liter!

a) 0.2 mol Cu salt of p-liethoxybenzoldiazoeulfonsffure and C, 1 mol Cd lactate (1 cadmium to 1 lactic acid)}

b) as a, but also 0.00015 mol of mercury nitrate. '

The strips were dried and continued on to those in Example 1 described · * »Tfeiae» enaitoaetfiech checked. This «examination revealed the related obligations

LSsung log It range of the Puss Gamma a 0.65 10

b 0.08 10

7 * strips of a saponified to a depth of 6 μα Celluloseetriacetate sheeting was sensitized by keeping it for 1 minute were drunk with aqueous solutions which contained ι per liter e) 0.2 mol of C-salt of p-hydroxybenzenesulfonic acid and 0.1 mol

Cd-Likt.t (1 Kftdoiu »xu 1 Xilohafur ·))

b) like A | However «υ ···? 4« · 0.00015 M * l M «rkuriAitr» t. . '

9t · strips were dried and further applied to that described in Bei «pl« 2 1-note Way eeneitometry checked. The strip a showed a * very 1 «η £ βη foot, which turned into fogging, the stripe had% a fuae log It · Ο, ΐβ (veil-free).

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8 .. strips of saponified wears. & Terials of example 1 were sensitized by soaking for 1 minute with aqueous solutions which contained per liter!

a) C ₁ I mole of sodium salt of ^ Uorfollno-c ^ -dimethoxytenzoldiazoulfonate and 0.1 mole of Cd-lactate (1 cadmium to 1 lactic acid) j

b) as a, but with the addition of 0.0005 mole of Merkurini; o) like a, but also 0.005 mol of urinitrate.

The strips were dried and further tested sensitometrically in the manner described in Example 1. Stripe a showed strong haze, stripe b a slight haze and stripe c a fuse lot 0.23 (haze-free). The absorption spectra of the p-* MethoxybentoBulfonata (a) and the 4-Morfolino-2,5-dimethoxybanzoldiazosulfonate (b) Bind shown in Fig. 2.

It was found that the ff. It was the last connection eenibilized material has a very useful sensitivity to OlUhlampenlioht possesses this in contrast to the p-liethoi ^ / benzoldiazoeulfcnat-Meterial.

9. strip saponified β carrier material of Example 1 were characterized sensibiliaiart that si x 1 minute old wlaerigen a solution fetrinkt, dia per liter ^ι Λ 0.2 mol Mg 8ala of p> M * tsoxy "ehzoldiazoaulfonseure, 0.1 IbI Ca-Lact »t,
O ₁ I moles of Milehelure,.
0.01 mol of silver nitrate and
0.005 moles of marcuronitrate (which contained 0.00005 moles of Msrkurl nitrate).

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The strips were dried in the manner described in Example 3. Three strips were popularized in the same way using a sensitometer. They were then treated for 4 seconds with an aqueous solution which contained 0.005 per liter and curonitrate
C ₁ oil mole of silver nitrate.

The strips were then rinsed for a short time in deionized water and followed by 2, 3 and 4 minutes, respectively. physically developed in the developer according to Example L. After rinsing in deionized water and drying, the film strips were measured using a deneitometer. The obtained characteristic curves a, b are shown in the _t Taphiaohen representation of FIG. 3 or c. They show a course in Fuaa and a high gamma that has increased over time since development.

x. Si · Lifetime, during which haze-free results were obtained, took about 12 months, while a material made with an appropriate light-sensitive solution that does not contain Mercury © - contained nitrate, had a lifespan of only a few tons.

The photographic material described in this example settled - microphotography under optimal opfctaeh "n conditions and using mono-chromatic light "at one wavelength" determined by 365 β »μ - a dissolution aversion of 2000 line pairs per Millimeter.

10. A book of 300 pages was made page by page in two stages. photographically reduced, the first stage with a 20-fold reductive to "i.gfa-Agtpf-PilB (silver halide), the second stage as well With a 20-fold reduction on the photographic film of the example 9. The whole book can alao on a stick of photographic material ";

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2
can be imaged with a surface of 60 mm. The surface of a

2
400-facb scaled down side was 0.1 mm. Nevertheless, the contents of the book were legible with the aid of a microscope. The photographic reduction on the photo-spherical picture in this example was carried out with a non-automatic apparatus for moving the material in two directions which are perpendicular to one another. The QesamttufnabJM required a few hours, during which time no disturbing regression of the exposed film occurred. Corresponding results were obtained with the aid of "Ines photographic material" da "using a liohteepfindliohen aqueous acidic solution, which was prepared per liter

contained!

O ₁ 2 Hol Cd-Salt of p-Methoiybenaddiezoaulfonalure,

0.02 Hol Cd-UkUt,

0.02 XoI Xilobilur,

O ₁ Ol Hol silver nitrate and

0.005 get xerolnronitrate.

The latter material showed in relation to the regreaaion the exposure is an even more favorable process than in the above this example described «Vnteriel.

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Claims (1)

-17- 'PHN.1636 TATBNTAi DISCLAIMER 1. Process for the production of a photosensitive material, in the case of the one which is electrically non-conductive on the surface Baeisachicht the actual, an aromatic diazosulfonate containing, light-sensitive layer by means of a predominantly aqueous solution that contains the biazosulfonate and at least one anti-regreeeiona contains agent, characterized in that this solution also contains a -4 / Dissolved mercury salt in an amount of at least 10 gram equivalent / 1 and at most 1O ^- QrammMequivalent / l, while the diazosulfonate is present in a concentration that is at least ten times the mercury concentration * 2. The method according to Anapruch 1, characterized in that the is used as an anti-regression agent in salt, so that all cations Zn, Contains Od, Pb, Cu or A *. 3. The method according to Anapruch 1, characterized in that al light-sensitive compound in Zn, Ca, Pb, Cu or Ag salts Diaeopulfonefure is used. 4. The method according to claim 1 to 3, characterized in that the effective amount of Mtrkurisalr is applied to the solution by adding a solution of a Mercurosalees to the solution in such an amount that the finally · con »ent region of Merkurosals ·· Blndvatian · ΙΟ" Graaefequivalent / l amounts to. '- 5 ·' Method according to claim 4, characterized in that the · dl · '\ LSaung & uea «r a Merkuroaele a silver compound in« in «r of »indeftens 0.005 oral equivalent / l and at most 0.1 contains. 6. Light-sensitive material which, according to one of the above Claims has been received. 909882/1517