Ciba-geigy Corporation

Christopher G Demmer

Edward Irving

Kurt Dietliker

Godwin Berner

Werner Rutsch

Max Hunziker

Christopher P Banks

Christopher M Andrews

Ewald Losert

Christopher H Bull

William M Rolfe

Derek James Massy

Edward W Garnish

Roderick D Hathaway

Jane Wilkerson

Roger Francombe

A process for the formation of an image comprises

Process for the formation of positive images utilizing electrodeposition

Process for the formation of an image

Curable epoxide resin compositions

An electrodepositable photosensitive resin which is a phenolic novolak resin having

Photosensitive and electrodepositable phenolic resin with quinone

The present invention provides a method for making a metallic pattern on a substrate having a surface comprising bare metal in predetermined areas and metal coated by a resist in remaining areas which comprises (i) protecting the bare metal by electrodepositing a resin thereon, (ii) while leaving the electrodeposited resin substantially uncured, removing the resist from said remaining areas using a solvent which will not remove the electrodeposited resin, thereby exposing metal in said remaining areas, (iii) etching the metal exposed in (ii) using an etchant which does not remove the electrodeposited resin, and (iv) removing the electrodeposited resin with a suitable solvent.

Method for making metallic patterns

Oxime sulfonates of formula I ##STR1## wherein Y is a polymerizable unsaturated group or epoxide group or an --OH, --NHR.sup.5, --COOH, COOR.sup.6, --COCl, --CH.sub.2 Hal, --SO.sub.2 Cl or --NCO group, Z is an (x+y)-valent connecting member, R.sup.1 and R.sup.2 are monovalent organic radicals, m is 0 or 1, x is 1 or 2 and y is 1 or 2, can be converted into polymers which can be thermally or photochemically dissociated to form free sulfonic acid groups. Said polymers can therefore be used as photoresists which can be developed with aqueous alkalis.

Oxime sulfonates containing reactive groups

An electrodepositable photosensitive modified phenolic novolak resin of general formula ##STR1## where Ar.sup.1 represents a divalent aromatic group linked through aromatic carbon atoms to the indicated groups --OR.sup.2 and --CH(R.sup.1)--,

Modified quinone-diazide group-containing phenolic novolak resins

A positive photoresist is electrodeposited onto a substrate, exposed to actinic radiation in a predetermined pattern, and then exposed areas are removed by contact with a developer. When the substrate is a metal-faced laminate, the exposed metal surface may be etched and the residual electrodeposited layer removed by contact with a suitable solvent, optionally after a second, general, exposure to actinic radiation. Suitable electrodepositable positive photoresists include o-nitrocarbinol esters and o-nitrophenyl acetals, their polyesters and end-capped derivatives and quinone diazide sulphonyl esters of phenolic novolaks, having salt-forming groups in the molecule, especially carboxylic acid and amine groups. The process is suitable for the production of printing plates and printed circuits, especially circuits on both sides of a liminate sheet linked conductively through metal-lined holes in the sheet.

Process for the production of images after electrodeposition of positive

Positive images are produced by (i) exposing to actinic radiation in a predetermined pattern a composition supported on a substrate, which composition comprises a film-forming organic material and a substance which releases a sulphonic acid on exposure to actinic radiation, thereby rendering the composition more soluble in the developer in the exposed areas than the unexposed areas, and (ii) treating the composition with the aqueous base developer to remove the unexposed areas. The image-forming process may be used in the production of printing plates and electrical circuits.

Process for production of positive images using sulfonic acid precursors

Water-dilutable resinous products are obtained by reacting

Preparation of resinous products

Water-soluble or water-dispersible resinous salts are prepared by `tipping` an epoxy resin with a phenol, then carrying out a Mannich reaction with an aldehyde (usually formaldehyde) and an aminosulfonic or aminophosphonic acid, followed by salt formation on the free acid groups, preferably using an aliphatic amino alcohol, e.g., 2-dimethylaminopropan-1-ol. Such salts may be crosslinked by heating in the presence of an aminoplast, a phenol-formaldehyde resin or a blocked polyisocyanate or, when the salts contain free methylol groups, by heating alone. They can be used for preparing coating compositions.

Water-soluble or water-dispersible resinous sulphur or phosphorus

Resinous salts, prepared by thioalkylation or sulfoalkylation of a phenol obtained by advancement of a polyepoxide, followed by at least partial neutralization, have the general formula ##STR1## where R.sup.- represents a group of formula --S--R.sup.1 --COO.sup.- or a group of formula --SO.sub.3.sup.- ; R.sup.1 represents an aliphatic, aromatic or araliphatic divalent group which may contain a further group --COO.sup.- M.sup.+ ; R.sup.2 represents --H or alkyl; one of R.sup.3 and R.sub.1.sup.3 represents a hydroxyl group and the other represents --H, halogen, alkyl, or alkenyl; each R.sup.4 represents --H, halogen, alkyl, or alkenyl; R.sup.5 represents --H, halogen, alkyl, alkenyl, or a group --CH(R.sup.2)OH, --CH(R.sup.2)OR.sup.8, or --CHR.sup.2 --R.sup.- M.sup.+ ; R.sup.6 represents the residue of a polyepoxide, preferably of average mol. wt. 1000-5000; each of the groups R.sup.7, which may be the same or different, represents --H or a covalent bond linked to the group R.sup.6 ; R.sup.8 represents alkyl or alkoxyalkyl; R.sup.9 denotes the residue of an optional terminating group; m represents 1, 2, 3, or 4; n and p represent zero or 1, X represents alkylene, carbonyl, sulfonyl, oxygen, sulfur, or a valence bond; and M.sup.+ represents a hydrogen ion or a cation derived from an alkali metal, ammonia, an amine or one valence of a polyvalent cation, at least 25% of the ions being a said cation. Composition comprising these salts and, if required, a phenoplast, an aminoplast, or a blocked polyisocyanate, are stable when dispersed in water, usually with the aid of a minor amount of an organic solvent, and may be used to form protective films, especially for metal containers.

Resinous salts, their preparations, and their use in coatings

Aqueous dispersions of a phenolic resole and a thermoplastics polymeric material or a rubber, suitable for use as adhesives, are prepared by (a) dissolving a solid thermoplastics polymeric material, such as a polyvinyl acetal or a nylon polyamide, or rubber in a phenol, (b) adding a nonionic or anionic surface active agent and/or protective colloid, (c) adjusting the mixture to a pH above 7 by addition of a base, (d) adding aqueous formaldehyde solution, or a formaldehyde donor, to a molar ratio of phenol to formaldehyde within the range 1:1 to 1:3, (e) if necessary, adding water, and (f) heating the mixture to form a phenolic resole.

Process for the preparation of phenolic resin-containing dispersions and

Carboxylate salts, prepared by a Mannich reaction and useful in the preparation of water-borne coatings, have the general formula ##STR1## where R.sup.1 represents an aliphatic, aromatic, or araliphatic divalent group which may contain a further --COO.sup.- M.sup.+ ; R.sup.2 represents --H, --CH(R.sup.3)N(R.sup.10)R.sup.1 COO.sup.- M.sup.+, or alkyl which may be substituted by --COO.sup.- M.sup.+, --CH(R.sup.3)OH, or --CH(R.sup.3)OR.sup.8, R.sup.1 and R.sup.2 containing together not more than one --COO.sup.- M.sup.+ ; R.sup.3 represents --H or alkyl; each R.sup.4 represents --H, halogen, alkyl, or alkenyl; R.sup.5 represents --H, halogen, alkyl, alkenyl, or a group --CH(R.sup.3)OH, --CH(R.sup.3)OR.sup.8, or --CHR.sup.3 --NR.sup.2 --R.sup.1 --COO.sup.- M.sup.+ ; either R.sup.6 represents --H and R.sup.7 represents the residue of a polyepoxide, preferably of average mol. wt. 1000-5000, or R.sup.6 represents a covalent bond linked to the group R.sup.7, and R.sup.7, together with the indicated hydroxyethylene group, forms a cycloaliphatic ring; R.sup.8 represents alkyl or alkoxyalkyl; R.sup.9 denotes the residue of an optional terminating group; R.sup.10 denotes --H, --COO.sup.- M.sup.+, or an alkyl group which may be substituted by --COO.sup.- M.sup.+, --CH(R.sup.3)OH, or --OCH(R.sup.3)OR.sup.8 ; m represents 1, 2, 3, or 4; n and p represent zero or 1, X represents alkylene, carbonyl, sulfonyl, oxygen, sulfur, or a valence bond; and M.sup.+ represents a hydrogen ion or a monovalent cation derived from an alkali metal, ammonia, or an amine, at least 25% of the ions being a said monovalent cation. Compositions comprising these salts and, if required, a phenoplast, an aminoplast, or blocked polyisocyanate, are stable when dispersed in water, usually with the aid of a minor amount of an organic solvent, and may be used to form protective films, especially for metal containers.

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Cambridge, United Kingdom

Christopher G Demmer