DE2306353A1 - LIGHT SENSITIVE MATERIAL - Google Patents

Description

PATENT LAWYERS

Dipl.-Ing. P. WIRTH Dr. V. SCHMIED-KOWARZIK Dipl.-Ing. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

281134 6 FRANKFURT AM MAIN

TELEPHONE TO611)

287014 GR. ESCHENHEIMER STRASSE

Docket 71/30
Wd / Sch

HORIZOFS RESEARCH INCORPORATED 23800 Mercantile Road Cleveland, Ohio 44122 USA

light-sensitive material.

3098 3-A / 1045

The present invention relates to a photosensitive Material that works on virtually any surface including metal (copper, aluminum, chrome, etc.) and Non-metal surfaces (G-Ias, synthetic resins including Polyethylene terephthalate or paper, etc.) can be applied by; any known coating process, such as rolling on, dip coating ", spray coating, Spin coating and other known "methods.

When the obtained coating composition is an appropriate dose When exposed to appropriately selected electromagnetic energy, it is converted into a material that is insensitive to acids and alkalis and is particularly suitable for use as a "photoresist". The mate ■ rial is also used as a protective coating for pipelines, other containers or surfaces in-normal use come into contact with corrosive liquids.

In TJ.S. Patent No. 3,04-2,517 one is dry usable composition described, which is based on a combination of vinyl monomers from the group of N-vinyl V compounds, organic halogen compounds and arylamines based, which is dissolved in an organic binder and which when exposed to light and appropriate treated dry produces a color. In U.S. Patents Mr. 3,042,519 and 3,046,125 become similar organic, soluble compositions described that as "photoresists", which with appropriate treatment to produce a color that can be used and that can be used for this purpose with an organic solvent. be treated medium. A large number of U.S. patents relate to compositions sourced from Contain free radicals, which occur either directly after exposure or as a result of heating or a combination of optical development and heating produce colors.

-309834 / 1.045 " ³ "

In general, the color source is a complex, substituted one Amine, which with an activating agent or an initiating agent is combined or coupled. This complex. Amines Bind are described in a large number of U.S. patents e.g. in No. 3 510 304, 3 042 515, 3 042 517, 3 046 125, 3 046 209, 3 056 673, 3 164 467.3 095 303, 3 100 703, 3 102 810, 3 342 603, 3 102 029, 3 106 466, 3 109-736, 3 272 635. 3 284 205, 3 342 595, 3 377 167, 3,285,744 and 3,342,602. A particular class of amines acts in combination with other agents and in the presence of activating agents as color couplers, and these amines are disclosed in U.S. Patent Nos. 3,533,792 and 3,539 has been described. These color coupling systems generally work by means of a certain class of activating agents from the group of complex amines of the bisdiamino group, those with compounds such as pyrazoles, pyrazolones, mercapto and thiol compounds, acetanilides and substituted acetanilides and phenols are combined or coupled or electronic irradiation are disclosed in U.S. Patent Nos. 3,042,515, 3,121,632, 3,121,633, 3 113 024, 3 284 205, 3 HO 948, 3 HO 949, 3 272 635, 3 445 232, 3 285 744, 3 342 595, 3 342 602, 3 342 603, 3,342,604 and 3,359,105.

Compositions containing ethylenically unsaturated monomers from the class of N-vinyl compounds and organic Halogen compounds contain. And those with exposure and under Electronic radiation generating free radicals are described in U.S. Patent No. 3,147,117 as being photosensitive and electron beam sensitive materials have been described.

Compositions based on organic halogen compounds and N-vinyl compounds and the materials

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From the class of aryl compounds containing "certain metals to prevent heat damage" during processing and storage, have been described in US Pat. No. 3,275,443. In TJ.S. Patent Hr.3 330 659 are compositions useful as "potoresists" and various mixtures of. Ethylenically unsaturated monomers, crosslinking agents; !! and the like include., and compositions that include. the manufacture of. lithographic plates and printed circuit boards and include the use of crosslinking agents. Compositions containing a combination of N-vinyl compounds, free radical initiators and various binders are in the TJ. S. -Patentschrift Fr. 3 374 094 ". The last-mentioned patent specification is of importance for the present application insofar as it is necessary in creating the hydrophylene- ^{hydrophobic conditions for the production of a;} printing plate" or lithographic printing plate is possible, as in _; Column 6 of the said patent has been described to omit water emulsions with certain components.

In U.S. Patent No. 3,443,945 there is color formation ability of a combination of N-vinyl compounds and certain organic amines in the event of an exposure and appropriate processing, this description being an extension of the TJ.S. No. 3 042 517 is. In U.S. Patent Mr. 3,486,898 are the color-forming properties of Combinations of N-vinyl compounds and aryl and / or heterocyclic amines in the presence of an initiator on the basis of free radicals has been described in more detail.

In U.S. Patent Fr. 3,525,616 there is a combination of an N-vinyl-carbazole (belonging to the class of the N-vinyl compounds belongs), a light-sensitive halogen _

30 9 8 34/104 5 " ⁵ ~

hydrocarbon has been described as a source of free radicals and a leuco-triaryl methane dye. This composition is usually developed for use as a "photoresist" by using an organic Solvent is washed.

In U.S. Patent No. 3,563,749 is a combination of N-vinyl compounds, dyes from the class of Merocyanine and a halogenated hydrocarbon with a suitable polymeric binder, which in one dissolved organic solvent has been described. After an exposure and appropriate processing will be the plate then developed by wiping it with cold water. The one specified in this patent specification The main application is in the field of printing, with substrates such as paper, aluminum, copper, zinc, magnesium and certain plastic films. It is remarkable that the only solvents disclosed in U.S. Patent No. 3,563,749 are expressly mentioned, petroleum ether and acetone are.

Express reference is made to the disclosure of the above-mentioned previously published patent specifications.

So quite a lot of it already exists Patent literature describing the color formation and / or "resist" reaction, which occurs when combinations of certain complex organic amines and halogenated hydrocarbons exposed in a suitable binder and then processed, has the object.

The ideal "photoresist" composition that can be used for Used in many fields such as lithography, letterpress, printed circuit manufacture, manufacture of electronic miniature components, chemical milling * and other photomechanical applications, an extra-

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neat large number of chemical, physical and mechanical properties "in order to be fully usable for all of these fields of application. None of the above mentioned parts of the literature describes Materials that have this combination of ideal properties when exposed or irradiated with electrons will. Also has no usual combination of! Compositions this combination of ideal properties emerges from this large area. . . "■

It became a partial list of some of the ideal properties put together, and not just to address the shortcomings of the prior art, but also to demonstrate the novelty and step of the present invention

to explain. . "

Among the most desirable properties for one General purpose photoresist include the following:

1) When making exposure, it should have a sensitivity which is sufficient for projection printing *.

This means that the radiation sensitivity ** at full Exposure should be in the range of about 25 millijoules or less. If color formers are present, the photosensitivity is given as the number of milli-joules it takes to achieve a density of Obtain 1.0 units of nebaidem carrier plus veil.

2) In order to get the highest possible resolution for contact printing *, it should be possible to reduce photosensitivity; it should then be in the range of about 50 to. 150 milli-joules. -

3) The spectral sensitivity of the "photoresist" should be be controllable. It's not just the spectral sensitivity to the panchromatic visible range

* or reproduce. - 7 -

** hereinafter referred to simply as "photosensitivity".

desirable, but the composition should also be changeable such that it has no sensitivity at all, for example in the visible range and only in the UV range that can be obtained with cheap light sources can, is sensitive.

4) Regardless of the light sensitivity of the material it should be sensitive to electron beams.

5) One and the same composition should be able to be effective in both positive and negative ways.

6) Before developing with a reagent, whether based on Water or not, that should be done by the light or electron beams The image generated should be clearly visible, so that the exposed or irradiated layer, if it is without. use of a solvent is developed, is permanently and completely fixed and has sufficient color differences in order to be well suited for image reproduction if necessary.

.7) The photoresist composition should be in all forms, whether it is in the form of a solution, in a dried form on a carrier or a substrate or in the form of a free dried film has a shelf life useful for the ribbon; as The shelf life is called sufficient if the product is at least 6 months or can be stored longer at room temperature without a significant deterioration in photosensitivity, the chemical and physical properties occurs.

8th; The material should essentially focus on each type of Surfaces, including metals, alloys, art

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fabrics, paper, wood, fabric and others, can be applied, without any deterioration in its properties or shelf life.

9) The material should be made in the form of a free film i.e. without the support of a substrate.

- ι

10) Regardless of the type of carrier, on which the material is applied \ fird, - it should adhere firmly to the carrier after exposure or irradiation and development and should also retain this adhesion when it is subsequently treated, especially if it is _L exposed to highly corrosive chemicals. '

11) If the material is to be dissolved (organic solvent) in order to be applied to the various surfaces described, it should be completely soluble in a variety of organic solvents so that all the reagents needed to achieve the ideal properties for full application of "photoresist ^11. These solvents can be alcohols, glycols, cellosolves, chlorine-containing solvents, hydrocarbons, amine-type solvents, ethers, ketones, esters, and combinations of these.

12) The photoresist, whether exposed or unexposed, should in various organic solvents such as aliphatic hydrocarbons! high molecular weight; Glycerine, trichlorethylene, kerosene, mineral oils and vegetable oils, which are normal components of lithographic and printing inks are insoluble.

13) Ideally, after exposure or irradiation and develop those who don't carry a picture! '' laugh easily in cold to warm pure water and the developed ones

3098.34 / 10-45. , " ⁹ "

and processed image areas must be soluble in hot, pure water.

14-j Regardless of how the photoresist is on the image surface composed, developed and / or fixed, it should not only be developed with water be soluble in pure hot water, but also in cold ketones and alcohols with a tolerance for Water, such as acetone, methyl alcohol, and ethyl alcohol, can be readily soluble. It is ideal if the picture is through higher boiling solvents are "stripped" in vapor degreasing processes can. Such solvents can be from the class: Isopropyl alcohol, Cellosolve, Dimethylformamide, tert-butanol, butyl acetate and the like are selected. Removing the screen is e.g. necessary in the production of printed circuits in order to prepare them for subsequent operations, such as the soldering of connecting lines.

15) The image should be insoluble in hot or cold water, any dissolved alkali, acidic and / or neutral salts of all kinds in amounts as small as 0.5 % .

16) The exposed or irradiated, developed and fully fixed image areas, which have a coating of a finished and processed photoresist, should be resistant to practically every type of hot, aqueous solution, whether diluted or concentrated. Such hot, aqueous solutions can include strong alkalis such as sodium hydroxide or potassium hydroxide; strong acids such as hydrochloric acid, nitric acid, sulfuric acid, chromic acid, phosphoric acid, hydrogen fluoride and the like, as well as mixtures of these; contain strong acid salts, such as ferric chloride, cupric chloride, acid fluoride, aqua regia, ferricyanide-hydroxide mixtures and the like.

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Overall, the exposed or irradiated and developed "photoresist" must protect against contact with a large number of acids and alkalis in concentrated form for a period of time that sometimes exceeds 2 hours, be resistant without the photoresist surfaces being noticeably attacked, thereby increasing the possibilities created for deep etching and chemical milling * and still to be expanded.

Though not all of the ideal properties in the previous list which the "photoresist" should have for the various types of application listed, it emerges from the description of the previous state of the art that none of the patent specifications mentioned Compositions have been described which meet all of these requirements, and also no combinations these compositions can meet all of these requirements. The compositions of the invention possess on the other hand those listed in the previous list ideal properties and also other properties that are advantageous for the consumer.

There is one on the market right now. Number of ^ir photoresists with negative performance. When these materials are exposed to corrosive materials or reagents, they generally degrade to an extent that is no longer acceptable for many uses. In addition, the known negative working "photoresists" usually have relatively poor resolution properties. Another disadvantage of the known negative-working "photoresists" is that they are extremely insensitive to light, although they are irradiated with light of a wavelength which is equal to the wavelength of the absorption maximum. Negative-working "photoresists" therefore normally have a light-sensitive

P ility of etv / a 500 to -5Q00 "milli-joules per one. -And after all, for negative-working "photoresists"

* "thruput chemical milling" ■ 309834/1045 -11 -

fairly strong reagents or complicated organic ones Materials to develop after exposure or irradiation. As far as the applicant is aware, no one can this "photoresists" with an alcohol odex · with the azeotropic mixture of an alcohol with water can be developed.

The "photoresist" of the present invention does not have any of the foregoing Lack and also has unexpected advantages compared to the well-known negative-working people "Photoresists".

Usually, from a photographic point of view, Use of negative working "photoresists" with the Thickness also increases the sensitivity to light. However, a good resolution in the micro range To achieve this, the "photoresist" must be applied as thinly as possible, whereby the usual negative-working "photoresist" becomes proportionally less sensitive to light. However, the opposite applies to the "photoresist" according to the invention. The thinner that "Photoresist" is (i.e., the higher the level of resolution achieved as a result of thinness), the more the photosensitivity is higher.

Compositions containing two or more of the foregoing ingredients or various combinations of these have been described in many of the U.S. Patents pending by Eugene Uainer et al, including those listed in column 2 of U.S. Patent No. 3,510 and other patents. To the revelations these patents are expressly referred to here. According to the invention, compositions are used which are similar to those already known, except that they contain a certain type of resin binder which, if it is used in appropriately prepared compositions

30983 4/1045

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is essential, is converted into an acid-resistant, alkali-resistant reaction product. :

Me inventive compositions contain at least one part of each of the following groups:

1. Polymerizable Monomers. _ ■ ..

a) N-vinyl-amine (heterocyclic, arylamines or other)

b) N-yinyl-imide and / or H-vinyl-imide

c) Other monomers (as described below).

2. Activating agent

a) Organic halogen compound

b) sulphonyl and sulfenyl halides

c) Mercapto connection.

3. Basic (alkaline) stabilizer

a) phenolic compound

b) Organic amine (other than the polymerizable

Monomers of 1.)

c) Inorganic base.

4. Resin binder

a) polyvinyl butyral

b) polyvinyl alcohol vinyl acetate

c) polyvinyl acetate

d) vinyl chloride-vinyl acetate copolymer

e) polyvinyl propionate

f) polyvinyl butyrate

g) Copolymer of polystyrene and polysulfone h) ketone resin.

_ 13 _ ..... '3 0.9834 / 1045

In addition, the compositions according to the invention can be or contain more of the following:

5. Antifoggants

, a) Triaryl compound of Sb, As, Bi or P.

6. Sensitizers

a) Optical awareness device for the chosen Irradiation.

7. Color forming components

a) Various dyes (v, ^r ie listed below).

8. Crosslinking Agents.

Polymerizable monomers:

At least one ethylenically unsaturated one capable of polymerization Monomer is a necessary component of the composition according to the invention. Suitable N-vinyl amines and TT vinyl araids and imides are, for example, those in the U.S. patent No. 3 042 517 listed as well as the N-vinyl compounds, in which the N atom is bonded to the aryl nucleus or in which it is a member of a heterocyclic nucleus. Other monomers can also be used, such as the following:

a) IT vinyl amines (heterocyclic and aryl amines)

1. N-vinylindole

2. N-vinyl carbazole

3. N-vinylphenyl-tf-naphthylamine

4. N- ^ ynylpyrene

5.N-vinyldiphenylamine (stabilized with 0.1 fo cyclohexylamine)

6. 3,6-Oimethyl-l ⁱ r-vinylcarbazole

7. 3- (2-Hydroxy-1- naphthylazo) -9-vinylcarbazole

309834/1045 -H-

8. 3- (9'-Xanthyl) -9-vinylcarl3azole

9. 9-vinyl- (2'3 ^l : 3.4) -naphthcartiazole

10. 9-vinyl * -3- (p-hydroxyaniline) -car "bazole

11. 3-indole-phenol-9-vinylcarbazole 1 * 2 · 3-

"b) F-vinyl amides and imides ". ·.

1. N-vinyl succinimide

2. N- ^V inylphthalinide

3. N-vinyl pyrrolidone

4. · N-vinyl-IT-phenylaaetamide

5. N-vinyl-F-methylazetaraid

6. N-vinyl diglyl colimide

7. N-tinylimidazole

c) vinyl monomers

1. styrene

2. 50-styrene-50-maleic anhydride

3. p-gyanostyrene * 4. Vinyl naphthalene

5. 9-methylene-fluorene

6. methyl methaorylate

7. methyl acrylate

8. Acrylonitrile * 9. Acrylamide

* 10. Methyl acrylamide

* 11. Ν, Ν-diphenyl aorylamide

12. Vinyl acetate

13. 5O-vinyl acetate-50-maleic anhydride

14. Ethyl methacrylate

15. Ethyl acrylate

16. Butyl methacrylate

* 17.'Methylacrylanilide ·

* 18. N-N "~ diphenylmethyl acrylamide

* 19th N-phenylacrylamide

20. methyl vinyl ketone

* 21. N-IP-methylenebisacrylamide

30983A / 10A5 -15 -

The different classes of monomers require different treatment processes, each of which is due to their nature. Overall, the N-vinylamines listed under a) can easily be used in air, and no special crosslinking agent is required; under these conditions they work with the highest light sensitivity. The N-yinyl compounds listed under Td) have the equivalent photosensitivity, provided that the initial exposure and / or electronic irradiation is carried out in the absence of oxygen. This is easy to do by either performing the exposure in a vacuum frame or by treating the surface with an atmosphere of liquid nitrogen or argon for at least 30 seconds prior to exposure.

If the monomers in the list under c) are part of the basic composition, they work best in Absence of oxygen and also according to the procedures described above. Some of those listed under c) Monomers are liquid at room temperature and, as liquids, become part of the solvent system. The liquid ones Monomers are usually obtained in the form of a dry film in the fully precipitated system, provided that the system is not excessively heated prior to exposure or exposure; in many cases this dry film is obtained simply by keeping the wet "photoresist" solution at room temperature lets dry. In view of the complications of using such liquid monomers, the solid ones become Monomers are preferred, and these are marked with an asterisk in list c).

The monomers listed under c) can be used as complete replacement materials for the N-vinyl compounds shown in the list be used. It must in their use

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However, certain precautionary measures are taken, especially when they are completely replaced by the compounds mentioned in the list. These monomers are highly effective in an oxygen-free atmosphere, especially with regard to photosensitivity. When these monomers are used in an oxygen-containing atmosphere, their photosensitivity is drastically reduced due to an induction time. Although these monomers without any special. Curing agents can be used is also greatly enhanced their activity by the addition of small amounts of crosslinking agents, about 0.5 to 3 ° f the amount of the monomer from the listed under c) type. _l The most effective crosslinking agents for this purpose are given in the following list. In addition - and this applies again in particular in the event that the ethylenically unsaturated compound added to the composition only comprises materials according to list c) - the desired photochemical reaction is accelerated and made more effective if the monomers include an acyloin (according to Table II of US Patent ITr . 3 330 659) is added.

Crosslinking agent: ■

(U.S. Patent No. 3,330,659)

1. Glyceryl trimethacrylate
• 2. Diethyl maleate

3. Allyl anthranilate

4. Neopentyl glycol dimethacrylate

5. ^, N'-HeDtamethylene bisacrylamide

6. UjiT'-methylenebisacrylamide

7. Ethylene dimethacrylate

8. N, K'-diallyl aniline

Activating agent:

Activating agents include 1) organic halogen compounds, in which at least 3 halogen atoms (Cl, Br or I) are bonded to a single carbon atom (as in the Tl.S patent

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Publications No. 3 042 515, 3 042 516, 3 042 517, 3 056 and others), 2) sulfonyl and sulfenyl halides (as described in U.S. Patent No. 3,113,024) and 3) Mercapto compounds (as described in U.S. Patents No. 3,285,744, 3,359,105 and others).

Express reference is made here to the disclosures in these patents relating to these compounds.

The organic ⁿ alogenverbindungen that can be contained in the light-sensitive compositions useful in this invention, are represented by the general formula: ACX, wherein A is halogen (Cl, Br or I), alkyl, substituted alkyl, including halo-substituted alkyl, aryl , substituted aryl, aroyl and aralkyl and each X is a halogen atom, which can be either chlorine, bromine or iodine, although not all X atoms have to be the same. Iodine is preferred as atom X, and preferred compounds are CHJ ^, CJ. and ^C 2 ^J 6 *

The sulfur-containing activating compounds which can be contained in the photosensitive compositions which can be used according to the invention are represented by the formula R ₁ -SH or R ₁ -SSR ₁ , in which R ₁ denotes an aryl or a heterocyclic ring. Suitable compounds are, for example, 2-mercaptobenzothiazole, 5-methoxy-2-raerkaptobenzothiazole and pentachlorothiobenzene.

Activation compounds that contain both halogen and Sulfur are suitable for the present invention and are in the TJ. S. Patent No. 3,113,024 been. Suitable compounds are e.g. 2-4-dinitrobenzene-sulfonyl chloride, p-chlorobenzene-sulfonyl chloride, Pentachlorobenzene sulfenyl chloride.

Stabilizing agent:

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The compositions of the invention also contain an alkaline material which acts as a stabilizer works. It can be either organic or inorganic Base, or the composition can be a mixture of organic and inorganic materials.

Suitable organic amines can, for example, be phenolic compounds as described in U.S. Patent No. 3,351,467 and they can be represented by the general formula:

OI

wherein Q is one or more hydroxyl or amino or alkyl or allyl groups and η is an integer of at least about 1 and at most [5 . If η is greater than 1, then not all Q's have to be the same. For example, p-aminophenol, pyrocatechol, 2,4-di-tert-pentylphenol, 2,5-bis- (1-1-dimethylpropyl) -hydro quinone, 2,6-di-tert-butyl-p-phenol, tert-butyl-hydroxyanisole, etc. be.

Other organic amines or weakly alkaline, inorganic compounds can be used instead of the phenolic compounds mentioned above or used in addition to these.

Resin binder:

The resin binder is preferably a vinyl compound, for example a vinyl ester, a ketone or a keto ester, with solubility in alcohols or in azeotropic mixtures used from alcohols and water.

All resins mentioned on page 12 have one unusual property in common, namely a high degree of solubility in alcohols from the group: methyl, ethyl and propyl alcohol and a limited degree of solubility in azeotropic mixtures

3 09834/1045

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from alcohol and. Water. The solutions are clear and no swelling occurs if the resin dissolves when immersed in such solvents. In other words, these materials dissolve in the same way if crystalline materials, such as sugar, would dissolve in water. To maintain the optical resolution and to ensure the dimensional accuracy of the stencil after exposure, development and etching, it is extremely important that the material does not swell. In addition, all these non-swelling, alcohol-soluble resins in alcohol apparently react with the N-vinylamine - presumably this is a crosslinking process, which makes them resistant to exceptionally strong alkaline or acidic substances, such as them, without swelling normally used for making etching patterns. It is this property of not swelling in the solvent used to remove the unexposed "photoresist" or in the solvent used for etching that makes this special class of resins so unique. If copolymers are used, they have to be real copolymers and cannot simply be mixtures. For example, impure polyvinyl acetate, which was commercially available as normal polyvinyl acetate until about 2-4 years ago, always contained an admixture of partially hydrolyzed vinyl acetate in the form of polyvinyl alcohol, and this material swells when it is treated with alcohol. Palis, however, the material is fully copolymerized, as is the case with vinyl acetate / vinyl alcohol, it does not swell in alcohol. The same is true for all other types of substances. It has surprisingly been found that if the vinyl esters are very pure and do not contain any admixture of other vinyl compounds, in particular polyvinyl alcohol, they then also dissolve in alcohols without swelling. This applies in particular to the vinyl acetate mentioned in Example 1, if it is 100% pure polyvinyl acetate, as well as to the poly

30983 A "/ 1 0 A 5 -20-

vinyl propionate, if it is 100 % pure polyvinyl propionate, and for polysulfone.

The components mentioned on page 12 under 1, 2 and 3 are in a synthetic resin binder with certain Properties, namely in a resin, which in an alcohol or an azeotropic mixture of alcohol and water is soluble, dispersed or dissolved.

In addition, the compositions can have one or more additional compounds to achieve certain properties) contain. The use of such additional components is optional .and only serves to improve the to impart even further advantageous properties to compositions according to the invention.

Antifoggant:

A possibly usable additional component, useful in the composition of the present invention is a traryl compound of Sb, As, Bi or P; preferably triphenyl stilbene is used. Suitable connections are also those described in U.S. Patent No. 3,377,167.

Color forming compounds:

Optionally, a pitting compound can also be added will.

Forming compounds which can be used according to the invention are e.g. in U.S. Patent No. 3,04-2-515 Leuco crystal violet, leuco opal blue, leuco malachite green, Leukoxanthene, leucoanthracene, leukocyanide and v; Lele others Leuco compounds with structures similar to those normally used have a central carbon atom to which 2 or 3

309834 / 1CU 5-

- 21 -

Aryl groups are bound, such as in the di- and tri-aryl methane derivatives, or in which the carbon atom is a part of a heterocyclic ring fused into one Ring connection forms, as for example in Xanthene, Ihioxanthene, Acrylden, Anthraeen and the like.

The term "leuco compound" also includes the alkyl and Allyl ethers of the compounds mentioned in the previous paragraph.

Styrene and cyan in-dye bases for the invention Compositions useful are described in U.S. Patent Nos. 3,100,703, 3,102,810 and 3,095,303 and suitable herocyanine dye bases in U.S. Patent Serial No. 3,109,736.

The color forming compounds give the "photoresist ^{n is} the ability to form contrasting colors during exposure.

Sensitizers:

Sensitizers can be added to prevent the Composition sensitivity to radiation to improve certain wavelengths. Suitable sensitizers are, for example, stirring, rhodanine dyes, Cyanine and merocyanine dyes.

The ratio of the individual components of the compositions according to the invention can preferably be within the following Limits vary:

Components by weight! Peile

1. Polymerizable monomer about 15-150

2. Stabilizer "1-100

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approximately
It
Il 15th
1
1 - 300
- 100
- 100 Il 0.1 - 10 "O , 01 - ¹ O It 1 -25 η 50 - 10,000 It 30th - 3,000

3. Activating agent

Organic halogen

Sulfonyl and sulfenyl halides

Mercapto compounds

4. Triaryl compounds (optional)

5i color forming compound (optional)

6. Sensitizers (optional)

7. Solvent.

8. Binders

Suitable solvents are those in which the binder / and (iie, constituents) dissolve; e.g. customary organic solvents such as toluene and other hydrocarbons. Acetone and other ketones, what also from the above mentioned patents emerges,

The compositions of the invention should consist of pure Starting materials are produced. Commercially available Materials can be further cleaned if necessary. This is purely for the production of many compositions Use of yellow darkroom lamps or Wratten QA darkroom light filters satisfactory. With other compositions however, it is necessary to work in red darkroom lighting or in complete darkness when the composition is correspondingly sensitive.

After the photosensitive solution has been prepared, it is applied to a clean surface by one of the known methods used to apply "photoresist" solutions. The different layer is then applied in air or in an oven at elevated temperatures, e.g. about 70 and 90 ^° C., dried to remove the solvent; the drying time is usually less than about 1 minute. The dried surface is then irradiated in a suitable manner, for example with mercury light or with visible light if the "photoresist solution is used" Sensitizer has been added. After exposure

309834/1045 - 23 -

the sample is heated to bring the polymerization started in the exposed parts of the sample to completion. This is done by brief heating to about 120 to 20O ⁰ C. At a temperature of about 120 ⁰ C, insolubility and complete polymerization of the exposed areas is achieved in about 2 minutes, while with heating to about 200 ⁰ C only about 10 to 15 Seconds (tending to be more than 10) are needed. This heating step not only accelerates the polymerization initiated by the exposure, it also sets the composition in place so that it is no longer sensitive to light.

The exposure is made at a speed of about 5 to

ρ
20 milli-joules per cm if visible light is used and the system has been appropriately sensitized for visible light with the aforementioned sensitizers. If the material does not contain visible light sensitizers and is irradiated with ultraviolet light of wavelengths from about 3000 to 4000 2 , the photosensitivity is generally 3 to 5 times as high as in the case of visible light. It follows that all of the examples cited in the specification which do not contain an optical sensitizer for visible light have a photosensitivity of about 1 to 5 millijoules. These compositions are therefore 1 to 2 orders of magnitude more sensitive than other negative-working "photoresists", or, in precise terms: 10 to 1000 times more sensitive than other "photoresists", with 10 being the lower limit and the actual number being the Usually 100 to 1000 times. Then the sample is developed with methanol or with an azeotropic mixture of η propanol and water. This development removes the non-irradiated material from the sample. After development, the sample can be etched with any solvent to remove the parts of the sample that are not protected by the "photoresist".

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In the case of the previously known "photoresists", at. which one originally Alcohol-soluble binder is used and then made insoluble by exposure and heating and then developed with alcohol, These tend to be in the alcohol or the alcohol / water containing material to swell instead of dissolving. When they dry again, the picture is slightly distorted, and - cracks sometimes appear, especially on the Edges that help maintain the image obtained are particularly important. In the case of the .in accordance with the invention However, with the binder, this type of swelling and dimensional distortion do not occur, and it is obtained an extremely sharp reproduction, regardless of whether the "photoresist" is thick or thin. The thinner there © "photoresist", The reproduction is therefore sharper.

laughs the Itzen, the exposed "photoresist" is through chlorinated solvent on the group? Methylene dichloride, Ethylene dichloride, trichlorethylene, perchlorethylene and Mixtures of these removed from the sample.

Table 1

Example*
1
2

Binder (40 Solvent (760 g)

5
6th

* contains:

Bakelite AYAC (polyvinyl acetate) Aze'ton

Toluene Gel Io sol ve

Bakelite T-24-9 (vinyl alcohol-vinyl acetate copolymer) -

Bakelite XYHL (vinyl butyral-. Poly vinyl alcohol - poly vinyl acetate mixed polymer)

Bakelite VYHF (vinyl chloride-vinyl acetate copolymer)

Bakelite 251 (polyketone resin)

Bakelite SKD 3955 (poly vinjrlke clay-polystyrene copolymer)

22.5 parts by weight of N-vinyl earbazole

15 parts by weight of 2,6-di-tert-butyl-p-cresol

15 parts by weight of iodoform.

3 0 9 8 3 4/1 0% 5

Claims (14)

P ate nt claims J Photosensitive material, characterized in that it contains the following materials in dispersed or dissolved form in a resin binder with a high degree of solubility in an alkanol selected from the group: methanol, ethanol and propanol, and at least a low degree of solubility in the azeotropic mixtures of alkanol and water comprises: 1) at least one polymerizable monomer, 2) at least one activating agent to enhance the effect of a suitable electromagnetic Irradiation on this monomer, this radiation having to be at least sufficient to cause the polymerization initiate the monomer, 3) and an alkaline stabilizer. 2. Material according to claim 1, characterized in that there is also a triaryl compound of an element from the group: Sb, Bi, As and P, 3. Material according to claim 1-2, characterized in that it also contains an optical sensitizer includes. 4. Material according to claims 1-3, characterized in that it additionally comprises a color-forming agent. 5. Material according to claims 1-4, characterized in that the polymerizable monomer is an N-vinyl compound is used. - "" - 26 30 9834/1045 6. Material according to claim 5, characterized in that the polymerizable monomer is an N-vinyl carbazole is used. · 7. 'Material according to claim 1-6, characterized in that an organic halogen compound as an activating agent, in which at least 3 halogen atoms from the group: Cl, Br and J are bonded to a single carbon atom are used. 8 ", material according to claim 7" characterized in that as an activating agent CBr. is used. 9. Material according to claim 1-8, characterized in that that the alkaline stabilizing agent is a substituted phenol of the general formula: OI wherein Q is one or more hydroxyl, amino, alkyl or allyl group (s), which do not all have to be the same, and η denotes an integer from about 1 to about 5, is used. 10. Material according to claim 1 - 9 »characterized in that that the ratio of the components is approximately as follows (in parts by weight): Polymer dispersible monotneres ■ about 15 - 150 Activating Agent ", 1-300 Alkaline Stabilizer "1-100 Resin binder »30 ^ 3000. 309834/1045 - 27 - 11. Material according to claim 10, characterized in that that it is in "up to about 1 * 0,000 parts by weight of a solvent is dissolved. 12. A method for producing a photoresist image using a composition according to claim 1, characterized in characterized in that it comprises the following stages: - Preparing a solution of the composition according to claim 1 in a solvent, - applying the solution on a solid substrate, - drying the coating, - irradiating the layer with a suitable radiation, - heating of the layer in order to achieve complete polymerisation of the "irradiated parts of this layer, and ' . ■. Developing the photoresist obtained with an alcohol or an azeotropic mixture of alcohol and water. 13. The method according to claim 12, characterized in that to develop an alcohol from the group: methyl, ethyl · * · and propyl alcohol is used. 14. The method according to claim 12, characterized in that it concludes the removal of the polymerized Layer by using a chlorine-containing, alkaline Connection includes. 309834/1045