DE2309062C3 - Process for the production of relief images and mixtures and recording materials which can be used therefor - Google Patents

Description

2. The method according to claim 1, characterized in that the by heating after exposure crosslinkable layer in addition to the light-sensitive compound N-methylolacrylamide derivatives of the formula

RO-CH ₂ -NH-CO-CR '=

RO-CH ₂ -NH-CO-CR '= CH ₂

(D

3 °

contains, in which R is a hydrogen atom or an optionally substituted alkyl group with 1 to 4 Carbon atoms and R 'is a hydrogen atom or a methyl group.

3. Photosensitive crosslinkable material suitable for the production of relief images or resist patterns A mixture containing a photosensitive aromatic ortho-nitrocarbinol ester grouping Compound, characterized in that it contains an epoxy resin prepolymer.

4. Photosensitive mixture according to claim 3, characterized in that it is in addition to the photosensitive Compound N-methylolacrylamide derivatives of the formula

40

contains, in which R is a hydrogen atom or an optionally substituted alkyl group with 1 to 4 Carbon atoms and R 'is a hydrogen atom or a methyl group.

5. Photosensitive mixture according to claim 3, characterized in that the photosensitive Compound in the molecule has at least two groups represented by formula (I) and / or (II) be reproduced:

NO,

(H)

CH-O — C — N -

R ² R ³

55

60

('5 where R ¹ , R ² and R ¹ individually represent a hydrogen atom, an alkyl group or an aryl group.

6. Photographic recording material with a crosslinkable one applied to a layer support Layer containing a photosensitive aromatic ortho-nitrocarbinol ester groupings Contains compound, characterized in that

(a) the crosslinkable layer contains an epoxy resin prepolymer and

(b) a protective film is arranged on the crosslinkable layer.

7. Photographic recording material according to claim 6, characterized in that the crosslinkable layer rubbed the photosensitive compound N-methylolacrylamide derivatives of the formula

RO-CH ₂ -NH -C0-CR '= CH ₂

in which R is a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms and R 'is a hydrogen atom or a methyl group and a protective film is arranged on the crosslinkable layer.

A large number of proposals are already known that relate to light-sensitive materials for production from boards or cards, printed circuit boards, etc. These materials include photosensitive Substances and become when exposed to "actinic rays" or chemically effective rays of light insoluble. Examples of such materials include bichromate type photosensitive resin compositions and polyvinyl cinnamate type. These resin materials are usually in the form of solutions sold, which then when used on a base for the resin image or resin pattern formation applied and dried. The coating and drying operations, however, are quite demanding Skill and so bring considerable difficulties for the user of these materials.

As a substitute for the above-mentioned solution type resin materials, film-like ones have been used in recent years Materials have been disseminated. When used, these need film-like dried resin materials only to be stacked or rolled onto a base intended for image generation, so that the troubles associated with the use of conventional solution type resin materials do not occur. However, it is known that the aforementioned new methods and resin materials in in various directions still need to be greatly improved.

One of these properties to be improved is the adhesion of the resin material to that for image formation used pad. The material currently used for the film process is only through Separation of the solvent in a resin material formed by the conventional solution type and therefore necessarily shows - compared to the Order from Harzmateria! in the presence of solvents - only slight adhesion to the substrate. As a result of this inadequate adhesion,

such as lifting or peeling off the resin from the substrate) during development as well as ■> when etching or plating on, leading to significant Interferences in the application of these resin materials; \ * hrt.

Methods have therefore been proposed by which the resin material applied to the substrate is heated before exposure. Nüdi investigations However, according to the applicant, this procedure does not lead to any satisfactory improvement. Stand against it when exposed to chemically active rays over a longer period of time - although the adhesion the resin material on the base is now slightly improved - as a result of excessive exposure other undesirable phenomena: namely, it will be the one to be removed during later development Partly photo-hardened and the image or pattern available with the material no longer corresponds exactly of the mask or cover and is deteriorated in resolution. It also results as Problem that the cost increases due to the extension of the treatment time.

Another property that should be urgently improved at the moment, besides the adhesiveness, is that physical nature of the resin material. Photosensitive substances used so far including photopolymerizable resins that have been used exclusively in film-like resin materials extremely low physico-chemical strengths, and the consumer of such materials different restrictions are imposed: For example, they may be subject to treatment neutral or acidic conditions, but not under alkaline conditions, such as. B. a usual non-electrolytic copper plating. Furthermore, the mechanical strength is insufficient, and users are often bothered by the formation of cracks due to mechanical impact during different operations. In addition, the currently available resin materials are in the cases not useful where resin materials are subjected to etching, plating or similar treatments and then as they are without peeling them off for permanent protection of the resin-covered parts be used.

The object of the invention is therefore a method for the production of relief images or resist patterns with excellent adhesion and high physicochemical strengths as well as materials to carry out the procedure.

This object is achieved by a method for producing relief images or resist patterns Exposure of a crosslinkable layer containing a photosensitive aromatic ortho-nitrocarbinol ester group containing compound, and washing out the unexposed Sohichtteile with dissolved in a solvent, the method being characterized in that

(a) a layer which can be crosslinked by heating after exposure is used, which is next to the light-sensitive Compound containing an epoxy resin prepolymer, and

(b) the exposure latent image after exposure and before solvent development is selectively hardened by a heat treatment of the exposed layer.

One embodiment of the method is characterized in that the by heating after exposure crosslinkable layer next to the light-sensitive compound N-methylolacrylamide derivatives of the formula

R-CH ₂ -NH-CO-CR '= CH ₂

contains, in which R is a hydrogen atom or an optionally substituted alkyl group with 1 to 4 Carbon atoms and R 'is a hydrogen atom or a methyl group.

In the method according to the invention, the procedure is that one of a layer support and a crosslinkable A layer with such properties that a latent image is formed when it is irradiated with chemically active light (Hardening precursor image) is created in which only the latent image parts are exposed during subsequent heating are selectively hardened, formed layer body optionally after removing a protective layer from its surface - coated on or on the surface of a solid used for image generation is rolled; that the crosslinkable layer is then optionally after removal of the support, especially if this is impermeable to the chemically active light rays, in image distribution chemically effective light rays is exposed to form a latent image in the crosslinkable Layer; that the entire surface of the crosslinkable layer for selective hardening of the latent image areas is heated and that the unhardened portion then by using a liquid - if necessary after removal of the transparent substrate, if it has not yet been separated - removed is formed to form a resist pattern on the surface of the solid for image formation. A feature of the present invention is the hardening of the crosslinkable layer to form the Resist pattern by a combination of irradiation with chemically effective light rays and heating. Accordingly, by combining radiation exposure and heating, the objects of the invention can be achieved can be achieved, and it thus differs from the previously customary processes in which the hardening is brought about only by irradiation with chemically active light. The invention is a significant improvement with regard to the problems of the previously practiced technique achieved, which was not expected could be.

The heating according to the invention is not a high-temperature treatment (usually at about 20O ⁰ C), as it is carried out after the development and referred to as "baking", but a heat treatment carried out before the development. As a result of this heating, only the part exposed to the chemically active rays is selectively hardened.

The photographic recording material according to the invention is illustrated schematically by the drawing reproduced and has a crosslinkable layer 2 applied to a layer support 1, which has a light-sensitive aromatic ortho-nitrocarbinol cstergruppierungen containing compound and is characterized in that

(A) the crosslinkable layer 2 contains an epoxy resin prepolymer and

(b) a protective layer on the crosslinkable layer 2 is arranged.

A preferred support is made from a wide range of substances such as paper, tissue and foil

of polyamides, polyolefins, polyesters, vinyl polymers, Cellulose esters and similar high polymers. A particularly preferred support is a polyethylene terephthalate film that has excellent resistance to solvents and Has heat and is therefore particularly suitable for the production of the recording material. Further this film is permeable to chemically effective light and less permeable to oxygen and thus has the The advantage that it does not have to be peeled off at the time of exposure, but unchanged under a mask or aperture can be used.

The use of this support is particularly preferred in the case of a photopolymerization system with a crosslinkable layer that is desensitized by oxygen. However, if a resin composition layer which is not desensitized by oxygen is the presence of the support not required during exposure. It is usually a layer support with a thickness of 4 used up to 50 μm.

The crosslinkable layer 2 used according to the invention has a thickness of 3 to 250 μm, preferably from 10 to 80 μm and is formed from such a resin composition that when heated after irradiation with chemically active light only selective to one in the exposed parts liquid-insoluble state is hardened. That is, if the layer is chemically active rays is exposed, a latent image (hardening precursor image) is created within the layer, which in the subsequent Heating is hardened.

The term »hardening precursor«, as it is used here, denotes a compound that is used in Exposure of the cross-linkable layer to chemically active light rays is formed and during Testing - as it is (i.e., before heating) is not essential for liquid solubility differs from other parts (i.e. non-irradiated parts) or in terms of liquid solubility is not (yet) significantly different. For example, a carboxylic acid compound therefore corresponds to a Amine compound or a linear polymer, which as a result of exposure to chemically active light is formed, the hardening precursor mentioned here (The above explanation is based on the below given examples of resin compositions become more understandable).

The light-sensitive, for the production of relief images or resist patterns suitable crosslinkable mixtures according to the invention contain a photosensitive aromatic ortho-nitrocarbinol ester grouping compound and are characterized in that it is also an epoxy resin prepolymer contain.

An example of a resin composition or a mixture is characterized by a content of (A) an epoxy resin prepolymer; and (B) a photosensitive compound having at least two in the molecule has groups represented by the following formulas (1) and / or (11):

NO,

CH-O — C-

R ¹

in which R ¹ , R ² and R ³ individually represent a hydrogen atom, an alkyl group or an aryl group.

It is generally known that compounds corresponding to the formulas (III) and (IV) given below form carboxylic acids or amines (see formulas a and b) when exposed to light.

(IV)

NO,

CH-O-CR

R ¹

NO

RC0, H

(Formula a)

Il

CH-OCNR R ¹ R ³

(Formol b)

(where R ¹ , R ^J and R ^{3 have} the meanings already given).

The compounds thus form with irradiation Light carboxyl and amino groups and give rise to the three-dimensional hardening of the resin prepolymers (as a result of d < Existence of these groups), The AmIn and / odi formed in the above fur by irradiation with light Carboxylic acids form the above mentioned Htt treatment test course.

The introduction of the groups represented by the formulas (I) and (II) is easy. That is, the jruppe of the formula (I) is obtained by reacting a

Carboxyl group, a carboxylic acid anhydride group or an acid halide group with one through the Formula (V) reproduced alcohol obtained

NO ₂

CHOH R ¹

where R ^{1 has} the meaning already given.

On the other hand, the group of formula (II) is formed by reacting an isocyanate group with ι s an alcohol of the formula (V) obtained or by the Reaction according to the following scheme:

NO,

+ NO ₂

Il

-C-Cl NO,

CH-Ο — C — O

R ¹

NO,

(Formula c)

NO.

NO,

The compound with at least two groups of the formulas (I) and / or (11) in the molecule is given by Use of a polybasic carboxylic acid derivative, a polyfunctional amine derivative or a polyfunctional one Isocyanate derivative synthesized, For example, a compound with 2 groups is the Formula (I) at the two ends by reacting adipic acid chloride with an alcohol of the formula (V) and a compound having 2 groups of the formula (II) at both ends by the reaction of hexamethylcene diisocyanate obtained with an alcohol of formula (V). Alternatively, a connection with many Groups of the formula (I) obtained in the molecule by polymerizing an acrylic acid ester, which by reaction is formed by acrylic acid chloride with an alcohol of the formula (V).

Epoxy resin moldings useful in accordance with the invention Polymers are compounds with at least 2 epoxy groups in one molecule and include epichlorohydrin bisphenol A condensals, Polyolefin epoxides. Novolak type epoxy resins and high polymers of glycidyl · fio esters of unsaturated acids. This epoxy resin prepoly kidneys graze by heating together with carboxyl and amino groups [those by exposure of Compounds having at least 2 groups of the formula (I) and / or (II) in the molecule are formed] smoothly three-dimensionally networked.

Under normal conditions, the formation of carboxyl and amino groups takes place through exposure of CH — O — C — NR + NO ₂

I 1

R ¹ R ³

(Formula d)

Compounds with groups of formula (1) and (II) mil high effectiveness and can be considered practically quantitative, although the amounts of formed Groups vary depending on the type and intensity of the light source used. Accordingly, can the mixing ratio of the compound with groups of the formulas (I) or (II) with the epoxy resin prepolymer and the curing conditions after irradiation with light are selected from the same point of view as in the case where a polyfunctional carboxylic acid or amine compound and a corresponding one common epoxy resin can be used. Usually, the compound with the epoxy resin polymer mixed in such a ratio that the total amount of the groups of formulas (I) and / or (II), based on the amount of epoxy groups in the epoxy resin prepolymer, 0.1 to 0.8 equivalent preferably 0.3 to 0.7 is equivalent,

The photosensitive mixture can contain different fillers. Additives, pigments, colors etc. as auxiliary components contain. It is necessary in view of the photosensitivity of the composition regarding the Lichiclransparent wedge of the same more or more less constraints to face. Preferred catfish wire a synthetic high polymer and a Welchmachei used to control the film properties of the composition.

According to another embodiment of the invention, the photosensitive, vut

709 627/181

Relief images or resist patterns suitable for crosslinking The mixture should be characterized in that it contains, in addition to the light-sensitive compound, N-methylolacrylamide derivatives of the formula (Vl)

Il

RO-CH ₂ -NCC = CH ₂ H R '

(VI)

contains, in which R is a hydrogen atom or a substituted or unsubstituted alkyl group with 1 to 4 carbon atoms and R 'is a hydrogen atom or a methyl group.

The mixture can mainly consist of photopolymerization sensitizers and the specified N-methylolacrylamide derivatives.

The N-methylolacrylamide derivatives have the property that the vinyl groups present in the molecule when irradiated with chemically active light in Polymerize in the presence of photopolymerization sensitizers and when they are heated, the methyl ether groups result in condensation reactions.

Accordingly, the composition becomes chemical exposed to effective rays to form a polymer pattern as a latent image (curing precursor image) and it is then used to harden solely by condensation of the polymeric image parts, i.e. H. the Hardening precursor image parts heated.

Examples of N-methylolacrylamide derivatives used according to the invention are N-methylolacrylamide, N-ethoxymethylaciylamide, N-propoxymethyl- 3} acrylamide, n-butoxymethylacrylamide and methacrylamide homologues of that. These can be used either individually or in the form of a mixture. the Amount of N-methylolacrylamide derivatives used is 10 to 80% by weight (based on the weight of the resin composition).

The other essential component are photopolymerization sensitizers, which has an initiator and promoter effect on the polymerization of vinyl groups exercise when the composition is irradiated with chemically active light. For examples for sensitizers include compounds of the anthracnquinone type such as i.-butylnthruchinone; links of the acyloin type such as benzoin and alkyl group derivatives thereof; Ketones such as benzophynone and Michlcr's ketone; as well as D1 kütuuu like Diucctyl. These can be cntwedci can be used individually or in the form of a mixture.

The amount of the sensitizer used is 0.1 to 50% by weight, preferably 0.5 to 20% by weight (based on the weight of the photosensitive mixture).

Further auxiliary components for the photosensitive mixture include thermal polymerization inhibitors, binders and plasticizers for imparting and controlling the film properties, as well as colors and pigments.

The outer layer 2 is produced by applying a solution of the above composition to the substrate 1 and then drying it. The (> 5 school / film 3 is coated onto the crosslinkable layer 2 formed in this way. A preferred protective film is selected from the support given above Properties is widely used. The thickness of the protective film is usually from 4 to 50 μm.

The resist pattern forming process according to the invention can be extremely easily carried out practically without any sophisticated technique. The film is applied in layers to the surface of an image-forming solid with removal of the protective film. Typically, one chooses a procedure by which the layer order is carried out under pressure with a hot roll at 40 to 15O ⁰ C.

The surface of the solid is preferably cleaned before the layer is applied or subjected to a pretreatment to increase the adhesion of the crosslinkable layer. In particular, the pre-heating (usually at 50 to 15O ⁰ C) the solid surface provides favorable results. A heat treatment before exposure to chemically active rays after the layer has been applied is not essential, but sometimes brings favorable results. The exposure to chemically active radiation is usually carried out for a short period of time, which, however, varies depending on the type and intensity of the light source used and the type of photosensitive mixture.

Any low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, carbon arc lamp or xenon lamp can be used as the light source for chemically active radiation. High-pressure mercury lamps and ultra-high-pressure mercury lamps are particularly preferred. It is usually sufficient if a resin composition layer of 40 μm thickness is irradiated for 0.5 to 20 minutes with a high-pressure or ultra-high-pressure mercury lamp with an intensity of 500 nW / cm ² (on the irradiated surface). After exposure to chemically active radiation, the crosslinkable layer is heated without any treatment. The heating is carried out to a temperature of 25 to 250 ^° C., preferably 60 to 200 ^° C. Usually, heating takes place over a period of 20 minutes.

Then before crosslinkable layer is from Layer carrier exempted if one is (still) present is and then developed. The liquid wedge to be used for development is a compound found in the Is able to remove uncured parts of the resin composition layer to remove and is usually formed by a halogenated hydrocarbon. In the case of dali for example a water-soluble polymer as a binding If the medium was used in the networked layer, a watery, weakly alkaline solution or elr Alcohol bciuit / t.

After the development, the layer can continue a heat treatment for reinforcement or fesli The relief image thus obtained possesses or protects Sufficient strength, there (read relief or reverse during the etching. Plating * or staining Treatments do not cause any harm (like a sealer or take off) and it will be successful for you the production of boards for printed circuits, in front of offset printing plates as well as for precision machining used in metals.

The invention is described in detail below Hand of examples e'Itlmert.

example 1
(A) Laminate or laminate production

A resin composition was prepared using the following compounds:

Bis (o-nitrodiphenylmethyl) adipate

Epoxy resin

Phenoxy resin

chloroform

Parts by weight

5.68
40.00
60.00
20.00

The resin composition produced in this way was applied to a polyethylene terephthalate film with a thickness of 25 μm and dried to form a crosslinkable layer with a thickness of 30 μm. Subsequently was a polyethylene film of 30 μm thickness as a protective film said crosslinkable layer is applied with the completion of the laminate.

(B) relief imaging

A sheet covered with a copper foil was cleaned in a conventional manner. On the copper foil of the web material, the crosslinkable layer of the laminated body prepared by (A) using two to 100 ⁰ C heated rollers after stripping off the polyethylene film was coated. The resulting product was exposed for 3 minutes through a mask with a 3 kW mercury ultra-high pressure lamp at a distance of 70 cm. Immediately thereafter, the sandwich construction was heated for 5 minutes at 160 ⁰ C, allowed to cool to room temperature and then using a 1: 1 mixed solution of 1.1,2-trichlorethylene and 1,1,1-trichloroethane while achieving a mask exactly corresponding relief image developed. The image thus obtained could be successfully etched by conventional methods and then plated with gold. Further, the image was so no occasion / u Quellerschcinungcn, cracking, even when it was immersed for 10 hours in aqueous sodium hydroxide (pH 12) by 60 'C ^1. It was thus clear that the relief image could successfully serve as a resin resist, even in an alkaline metal treating agent.

H e i s ρ i e I 2

(A) Laminated body manufacture
l "iinc I iiir / composite was using

the following connections made;

N.N'-bis-fo-nilrodiphenyl-methyloxy

ea-'bonylj-hexamethylenediamine

(Formula VII see below)

Epoxy resin

Phenoxy resin

chloroform

Gcwlclmtellc

16.00

20.00

20.00

150.00

CH O-C N- (CHA-N-C-O-CH \ H H A

The resin composition was then treated in the same manner as in Example 1 to produce a Laminate or laminated body.

(B) relief imaging

The laminate produced according to (A) was in

treated in the same way as in Example 1, whereby an accurate, the mask corresponding relief image on the

ίο layer arrangement covered with copper foil obtained would.

Example 3

5 A mixture of 5.0 g of o-nitrobenzyl acrylate, 3.0 g of glycidyl methacrylate, 10.0 g of methyl methacrylate, 0.2 g of azobisisobutyronitrile and 40 ml of methyl ethyl ketone was polymerized for 12 hours at 75 ° C to obtain 14, 0 g of a copolymer. The copolymer thus obtained was dissolved in benzene and the resulting solution to 2 aluminum foils or layers applied with clean surfaces, and then for 20 minutes at 8O ⁰ C dried to produce 2 films with 50 μπι thickness.

One of the two films was irradiated for 5 minutes with a 3 kW mercury ultra high ^{pressure lamp with an intensity of 5000 µW / cm 2} (on the exposed surface) and the other film was left unexposed. 3 g each of the exposed and unexposed film were removed and checked for gelation properties on a hot plate. It was found that the exposed film ^{gelled when heated to 140 °} C. for 180 seconds, while the unexposed film itself

.15 not gelled when heated to 140 ° C for one hour.

Using the aforementioned benzene solution of the copolymer, a laminate or Laminated body with a polyethylene film, a crosslinkable layer of 30 μm thickness and a polyethylene terephthalate film prepared in the same way as in Example 1. The laminated body produced in this way was on a layer arrangement covered with copper foil is stacked or applied for 5 minutes exposed through a mask, heat-treated for 10 minutes at 140 ° C. and then in the same manner as in example I developed while achieving a relief image with a resolution that exactly corresponds to the mask of 12.5 lines / mm and a step table number of 7. The Relicfbild obtained in this way had like that according to Example 1

image thus obtained has excellent resist properties.

Example 4

A resin composition was made using the J ₅ following compounds:

Weight partc

Methyl o-nitrodiphenyl aclipate 5.68

Methylmethac ylnt-Glyeiclylmcth
Oo acrylate-n biitylnielline acrylate copolymer

(Ratio of 70:10:20) 30.00
Methyl / ethyl kelon 70.00

The resin composition thus produced was treated in the same way as in Example I, whereby a prll / ises, the image corresponding to the mask on the with Kiipfeifolii · covered circuit arrangement was formed.

Example 5
(A) Laminated body manufacture

A resin composition was made using the following compounds:

Parts by weight Polymethyl methacrylate 60 N-n-butoxymethylacrylamide 35 Benzoin methyl ether 2 Hydroquinone 0.2 Methyl ethyl ketone 100

Gradual number of 4, however, its resolution could could not be determined with the resolution map used and was less than 2 lines / mm found. In this case it was found that even a part that should not be hardened by the excess exposure had been cured.

Example 6

_{| 0} Example 1 was repeated, except that the resin composition was prepared using the following compounds:

The resin composition thus prepared was coated on a polyethylene terephthalate film of 25 thickness and dried μΐη μίτι at 7O ⁰ C to form a crosslinked layer having a thickness of 30th A polyethylene film with a thickness of 30 μm was then applied as a protective film to the crosslinkable layer to produce a laminate or layered body.

(B) relief imaging

A copper foil-covered assembly was cleaned by a conventional method. The crosslinkable layer of the laminate produced according to (A) using two to 100 ⁰ C heated rollers was then applied to the copper foil of the arrangement, wherein the polyethylene film was peeled off from the laminate. The resulting layer arrangement was irradiated for 50 seconds through a step table number 2 and a resolution map with a 3 kW high-pressure mercury lamp placed at a distance of 70 cm from the layer body. Immediately thereafter, the arrangement was ^{heated to 140 °} C. for 3 minutes, allowed to cool to room temperature and then developed using 1,1,1-trichloroethane to obtain a relief image with a step table number of 9 and a resolution of 15 lines / mm. The image thus obtained was resistant to etching treatment by conventional methods and subsequent plating with gold.

For comparison, a relief image was produced in the same way as above, except that the heat treatment was omitted. The image thus obtained had a step table number of 2 and a resolution of 2 Lines / mm (which lines were not clear).

For the purpose of further comparison, a relief image was generated in the same way as above, except that the heat treatment was omitted and the irradiation with chemically active light for 3 minutes was carried out. The image obtained in this way had a methyl methacrylate-Acrylnilril-

Copolymer (weight ratio

from 10: 1)

N-methylol acrylamide

Trimethylol propane triacrylate

t-butyl anthraquinone

p-methoxypheno!

Weight parts

60 30th

0.2

As a result, an excellent relief image was obtained.

Example 7

Example 5 was repeated, except that compounds obtained by reacting N-methylolacrylamide with Ethylene glycol or cellosolve acetate had been obtained in the presence of an acidic catalyst, were used individually in place of the N-n-butoxymethylacrylamide, making excellent relief images could be obtained. It is thus clear that the above-mentioned compounds such as N-n-butoxymethylarylamide also used for the production of resin compositions suitable according to the invention can be.

From the above examples it clearly follows that relief images are simple using the method according to the invention can be generated and that the images thus generated are fixed on the surface of a for image generation Adhere to the solid and in treatments such as etching, plating, etc., sufficient as a resin protection or "Resist" act and for the production of boards of printed circuits, for precision machining of metals and the manufacture of offset printing plates are useful.

In particular, the epoxy resin composition used according to the invention has an excellent one Alkali resistance, and hence it is useful as a resist material which is subjected to metal treatment for which known film-like resist materials cannot be used.

1 sheet of drawings

Claims (1)

Patent claims: 1. Process for the production of relief images or resist patterns by exposure of a crosslinkable Layer containing a photosensitive aromatic ortho-nitrocarbinol ester groupings Contains compound, and washing out the unexposed parts of the layer with a solvent, . characterized in that (a) a layer which can be crosslinked by heating after exposure is used, which is next to the light-sensitive Compound containing an epoxy resin prepolymer, and (b) caused by exposure latent image after exposure and prior to solution ^'5 medium development is selectively hardened by a heat treatment of the exposed layer.