CA1336047C - Method of forming images - Google Patents
Method of forming imagesInfo
- Publication number
- CA1336047C CA1336047C CA000549805A CA549805A CA1336047C CA 1336047 C CA1336047 C CA 1336047C CA 000549805 A CA000549805 A CA 000549805A CA 549805 A CA549805 A CA 549805A CA 1336047 C CA1336047 C CA 1336047C
- Authority
- CA
- Canada
- Prior art keywords
- methacrylate
- monomers
- acrylate
- copolymer
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/164—Coating processes; Apparatus therefor using electric, electrostatic or magnetic means; powder coating
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
Abstract
A process for the formation of an image comprises (i) electrodepositing on a conductive surface a photosensitive film from an aqueous composition which is a solution or dispersion comprising a mixture of (A) a photosensitive o-quinone diazide such as an o-naphthoquinone diazide sulfonyl ester of a phenol, and (B) an electrodepositable film-forming resin such as a reaction product of a novolak resin, formaldehyde and diethanol-amine in (C) an aqueous medium, the composition being substantially free from a resin having both a quinone diazide residue and a carboxyl, phosphonic or sulfonic acid group or amino group in the same molecule, (ii) subjecting the electro-deposited film to radiation in a predetermined pattern, such that exposed areas of the film become more soluble in aqueous base than unexposed areas, and (iii) removing the exposed areas by treatment with an aqueous base. The process is useful in the production of printing plates and printed circuits.
Description
EM/K-16142/1+2/+/ARL 375 .. .. . . . .. .. .
Method of Formin~ Images This invention relates to a method of forming images which is useful in the production of printing plates and printed circuits.
In European Patent Publications Nos. 0 155 231, 0 184 553 and 0 196 999 the electro-deposition of resinous quinone diazide-containing positive photoresists is described. These photoresists are phenolic resins modified by introducing into the resin molecule a carboxyl, phosphonic or sulphonic acid group or amino group and by reacting phenolic hydroxyl groups on the resin with an esterifying derivative of a quinone diazide sulphonic acid. Although these photoresists give good films on electrodeposition and good images on imagewise irradiation, their preparation is difficult and timeconsuming. The reactions involved in the synthesis of the modified phenolic resins, which required elevated temperatures, have to be carefully controlled to avoid decomposition of the quinone diazide residue, otherwise the degree of photosensitivity of the electrodeposited film will be lower than expected. Furthermore, it is not possible to modify the photosensitivity or electrodepositability of the modified phenolic resins without repeating the synthetic reaction sequence.
It has now been found, surprisingly, that good photosensitive films can be electrodeposited from an aqueous composition containing a mixture of an electrodepositable resin and a compound having a quinone diazide residue without the need to prepare a resin having both a quinone diazide residue and a carboxyl, phosphonic or sulphonic acid group or amino group in the molecule. The electrodepositable resin and the quinone diazide can be materials which are readily available commercially. The use of such a mixture permits considerable latitude in formulation. The degree of photosensitivity of the electrodeposited film can be readily varied to meet a particular requirement simply by adjusting the ratio of the amounts of the components of the mixture.
Accordingly, the present invention provides a process for the formation of an image on a conductive substrate which comprises (i) electrodepositing on a conductive surface a photosensitive film from an aqueous composition which is a solution or dispersion comprising a mixture of (A) a photo-sensitive o-benzoquinone diazide sulphonyl ester or amide or o-naphthoquinone diazide sulphonyl ester or amide and (B) an electrodepositable film-forming resin, in (C) an 1) - 2 13360 4~
aqueous medium, said composition being substantially free from a resin having both a quinone diazide residue and a carboxyl, phosphonic or sulphonic acid group or amino group in the same molecule, in which step the electrodeposition is carried out by immersing the substrate on which the image is to be formed as an electrode in the aqueous composition, immersing a conductive material as another electrode and passing an electric current through the aqueous composition to deposit a photosensitive film of the required thickness on the substrate, (ii) subjecting the electrodeposited film to radiation in a predetermined pattern, such that exposed areas of the film become more soluble in aqueous base than unexposed areas, and (iii) removing the exposed areas by treatment with an aqueous base, and with the proviso that, when compound (A) is a o-benzo- or o-naphtho-quinone diazide sulfonyl ester compound and compound (B) is an acrylate compound, then the compound (B) is a) a reaction product of an epoxide resin with a primary or secondary monoamine or a secondary diamine, or b) a cationic or cationic/anionic phenolic resin which is a reaction product of a novolak resin, an aldehyde and a primary or secondary amine or an aminocarboxylic acid; or c) a cationic copolymer of a dialkylaminoalkyl acrylate or methacrylate with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers:
or d) an anionic copolymer of acrylic or methacrylic acid with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more vinyl monomers; or e) an anionic copolymer of a vinyl group-containing sulphonic acid with an acrylate or methacrylate ester and, optionally, one or more other vinyl monomers: or f) a cationic/anionic copolymer or a dialkylaminoalkyl acrylate or methacrylate with acrylic acid or methacrylic acid, an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers, with the proviso that the copolymers c), d), e) and f) do not contain an acrylate or methacrylate copolymer component being a 3-acryloyloxy-2-hydroxylpropyl or 3-methacryloyloxy-2-hydroxy-propyl ester of an hydroxybenzoic acid.
The present invention also provides an aqueous composition suitable for use in the image-forming process of the invention which is a solution or dispersion comprising a mixture of (A) a photosensitive o-quinone diazide as defined above and (B) an electrode-positable film-forming resin as defined above, in (C) an aqueous medium, said com-position being substantially free from a resin having both a quinone diazide residue and a , ....
~ 3 13360~7 carboxyl, phosphonic or sulphonic acid or amino group in the same molecule.
Photosensitve o-benzoquinone diazide sulphonyl ester or amides and o-naphtoquinone diazide sulphonyl esters or amides are well known. Examples include o-benzoquinone diazide sulphonyl or o-naphthoquinone diazide sulphonyl esters or amides of compounds, particularly aromatic compounds, having a hydroxy group or amino group respectively.
Preferred o-quinone diazides are o-benzoquinone diazide sulphonyl esters and o-naphtho-quinone diazide sulphonyl esters of phenols, including monohydric phenols and, particularly, polyhydric phenols such as 2,2-bis(hydroxyphenyl)propanes, dihydroxy-diphenyls, di- and tri-hydroxy-substituted benzophenones, and phenolic resins, including phenol-aldehyde resins and polymers of phenols having polymerisable unsaturated substituents. Suitable phenol-aldehyde resins from which the esters may be derived include novolak resins prepared from phenol itself, an alkyl-substituted phenol such as o-, m- or p-cresol, o-, m or p-tert.butylphenol, o-, m- or p-octylphenol, or a bisphenol such as 2,2-bis(4-hydroxyphenyl)propane, or a mixture of two or more of such phenols, and an aldehyde such as acetaldehyde, benzaldehyde, glyoxylic acid or, preferably, formalde-hyde. Suitable polymers of unsaturated phenols from which the esters may be derived include homopolymers and copolymers of p-vinyl phenol and p-isopropenyl phenol.
Preferred o-quinone diazide sulphonyl esters of phenols are o-naphthoquinone diazide sulphonyl esters of polyhydroxybenzophenones or novolak resins derived from formalde-hyde and an alkyl-substituted phenol or a mixture thereof with phenol. Particularly .. . .... . . ..... .. .. . . . . . . .. . . . . .. . ..... . . . ..
preferred esters are 1,2-naphthoquinone-2-diazide-5-sulphonyl esters of dihydroxybenzo-phenones, trihydroxybenzophenones, novolaks derived from formaldehyde and either a mixture of o-, m- and p-cresols or a mixture of phenol and p-tert.butylphenol.
The photosensitive quinone diazides hereinbefore described are either commercially available or may be prepared by conventional methods, for example by reacting a phenol with an esterifying derivative of an o-quinone diazide sulphonic acid, usually the sulphonyl chloride thereof, under conventional conditions.
Electrodepositable film-forming resins as mentioned hereinbefore are also well known.
They may be cationic resins containing basic groups such as amino groups, anionic resins containing acidic groups such as carboxylic, sulphonic or phosphonic acid groups or resins having both basic and acidic groups.
~' In order for the above electrodepositable resin to be electrodepositable, it is present in the aqueous composition in at least partially inoised form. For cationic resins this is usually achieved by at least partial neutralisation of the basic groups with an acid. For anionic resins, this is usually achieved by at least partial neutralisation with a base. For resins containing both basic and acidic groups, at least partial neutralisation can be accomplished with an acid or a base.
Examples of cationic electrodepositable resins are reaction products of an epoxide resin with a primary or secondary monoamine or secondary diamine, particularly a reaction product of an epoxy resin, such as a diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), with an alkanolamine such as ethanolamine, diethanolamine or propanol-amine; and reaction products of a phenolic hydroxyl group-containing resin, such as a novolak resin, a polymer of an ethylenically unsaturated phenol or a phenolic hydroxyl-terminated adduct of an epoxide resin and a bisphenol, with an aldehyde and a primary or secondary amine, for example reaction products of a novolak resin or a poly(vinyl)phenol with an aldehyde such as acetaldehyde, benzaldehyde or, preferably, formaldehyde, and an amine such as a dialkylamine, an alkylenediamine or an alkanolamine; polymers of basic group-containing acrylic materials such as homopolymers of dialkylaminoalkyl acrylates or methacrylates and copolymers thereof, including copolymers with other vinyl mono-mers, such as alkyl acrylates or methacrylates, and graft copolymers with acrylate or methacrylate group-containing resins such as esters of epoxide resins with acrylic or meth-acrylic acid; and Michael addition reaction products of acrylate or methacrylate group-containing resins with a primary or secondary amine such as ethanolamine, diethanol-amine or morpholine.
Examples of anionic electrodepositable resins are carboxyl-terminated diene polymers such as carboxyl terrnin~çd homopolymers and copolymers of butadiene; polymers of ethylenically unsaturated carboxylic, sulphonic or phosphonic acids, particularly homopolymers and copolymers of acrylic or methacrylic acid; carboxyl-terminated poly-esters; reaction products of hydroxyl group-containing resins, such as hydroxyl group-containing epoxide resins, with polycarboxylic acid anhydrides; and carboxyl group-containing reaction products of epoxide resins with mercaptocarboxylic acids.
Examples of electrodepositable resins containing both cationic and anionic groups are reaction products of epoxide resins with an aminocarboxylic acid, an aminosulphonic acid or an aminophosphonic acid; reaction products of a phenolic hydroxyl group-containing ~, ~ , ~
~ . .. .
. .
~5~ 13~6047 resin, such as a novolak resin, a polymer of an ethylenically unsaturated phenol or a phenolic hyroxyl-termin~tç~l adduct of an epoxide resin and a bisphenol, with an aldehyde, such as acetaldehyde, benzaldehyde or, preferably, formaldehyde, and an aminocar-boxylic, aminosulphonic or aminophosphonic acid; copolymers of an ethylenically unsaturated acid, such as acrylic or methacrylic acid, with an ethylenically unsaturated amine such as a dialkylaminoalkyl acrylate or methacrylate, and optionally one or more further ethylenically unsaturated monomers; and graft copolymers of such an unsaturated acid and unsaturated amine with acrylate or methacrylate group-containing resins such as esters of epoxide resins with acrylic or methacrylic acid.
Preferred electrodepositable resins to be used in the present invention are those containing amino carboxylic or sulphonic acid groups, present in the aqueous composition in at least partially ionised form. Further preferred are cationic or cationic/anionic phenolic resins which are reaction products of a novolak resin, an aldehyde and a primary or secondary amine or an aminocarboxylic acid; cationic copolymers of a dialkylaminoalkyl acrylate or methacrylate with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers; anionic copolymers of acrylic acid or methacrylic acid with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers; anionic copolymers of a vinyl group containing sulphonic acid with an acrylate or methacrylate ester and, optionally, one or more other vinyl monomers; and cationic/anionic copolymers of a dialkylaminoalkyl acrylate or methacrylate, acrylic acid or methacrylic acid, an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers.
Preferred cationic and cationic/anionic phenolic resins are reaction products of (a) a novolak resin derived from phenol, or an alkyl-substituted phenol such as o-, m- or p-cresol, o-, m- or p-tert.butylphenol, o-, m- or p-octylphenol, or a mixture of two or more such phenols, and formaldehyde, acetaldehyde or benzaldehyde, (b) formaldehyde, acetaldehyde or benzaldehyde and (c) an alkanolamine, such as ethanolamine, diethanol-amine, propanolamine or butanolamine, or an aminocarboxylic acid such as sarcosine, glycine, aspartic acid, glutamic acid, iminodiacetic acid, anthranilic acid or p-amino-benzoic acid. Particularly preferred amongst these resins are those where (a) is a novolak resin derived from formaldehyde and either a mixture of o-, m- and p-cresols or a mixture of phenol and p-tert.butylphenol, (b) is formaldehyde and (c) is diethanolamine, sarcosine or glycine. The cationic and cationic/anionic phenolic resins can be prepared by subjecting 1~360-4~
the reactants to conventional Mannich reaction conditions.
Preferred cationic copolymers are copolymers of dimethyl aminoethyl acrylate or meth-acrylate with a Cl to Cl2 alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers. Particularly preferred amongst such copolymers are those of dimethylaminoethyl methacrylate with 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate and styrene.
Anionic copolymers which are preferred are copolymers of acrylic acid or methacrylic acid with a Cl to Cl2 alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers. Particularly plefell~d amongst these copolymers are those of methacrylate acid with methyl methacrylate and 2-hydroxyethyl methacrylate and those of methacrylic acid with methyl methacrylate, 2-ethylhexyl methacrylate and 2-hydroxy-ethyl methacrylate.
Other pl~fellcd anionic copolymers are copolymers of an acrylamide containing a sulphonic acid group with a 3-acryloyloxy-2-hydroxypropyl or 3-methacryloyloxy-2-hydroxypropyl ester of a hydroxybenzoic acid and an alkyl acrylate or methacrylate.
Particularly pler~ d amongst such copolymers is a copolymer of 2-acrylamido-2-methyl-l-propanesulphonic acid, 3-methacryloyloxy-2-hydroxypropyl salicylate, methyl methacrylate and n-butyl acrylate.
. . . .. .. .. . . . . . . . . . . . .~ . . . ................ . .
Preferred cationic/anionic copolymers are those of a diaLkylaminoalkyl acrylate or meth-acrylate with acrylic or methacrylic acid, a Cl to Cl2 alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers. Particularly preferred such copolymers are those of dimethylaminoethyl methacrylate with methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate.
When compound (A) is a o-benzo- or o-naphtho-quinone diazide sulfonyl ester compound, examples of electrodepositable resins are the same resins as already described hereabove and correspond to the definitions given for the acrylate compounds in the proviso in question. The same comments also apply to the corresponding preferred resins andcopolymers respectively.
As already indicated, the electrodepositable resin to be used in the present invention is present in the aqueous composition in at least partially ionised form. Acids suitable for D
-~7~ 1336047 addition to the resin to effect at least partial neutralisation thereof include organic acids such as acetic, propionic, lactic, maleic, p-toluenesulphonic and glycolic acids and inorganic acids such as hydrochloric and sulphuric acids. Bases suitable for addition to the resin to effect at least partial neutralisation thereof include organic bases such as triethyl-amine, triethanolamine, benzyldimethylamine, morpholine and 2-(dimethylamino)ethanol and inorganic bases such as sodium or potassium hydroxide or carbonate and ammonia.
The resin is usually at least 5 %, preferably 20 to 100 %, neutralised. In especially preferred processes, the resin is completely neutralised.
Minor amounts, compared with the volume of water, of an organic solvent such as a ketone, alcohol, ether or ester may be included in the aqueous composition. Suitable organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol, 2-methoxyethanol, 2-ethoxyethanol, 2-n-butoxyethanol, diethylene glycol monbutyl ether, 2-methoxypropyl acetate, 2-ethoxyethyl acetate (oxitol acetate) and mixtures of two or more thereof. Photosensitisers such as Michler's ketone, benzoin ethers, benzil ketals and thioxanthones may also be incorporated in the aqueous com-position.
The o-quinone diazide (A) and the electrodepositable resin (B) are generally used in amounts such that the aqueous composition contains, by weight, at least 0.05 part of (A) per part of (B). Where the above component (A) is itself resinous, it is conveniently present in an amount of 0.5 to 1.5 parts, preferably 0.75 to 1.25 parts, per part by weight of (B). When (A) is not resinous, it is conveniently present in an amount of 0.05 to 0.5 part, preferably 0.1 to 0.3 part, per part by weight of (B).
In preparing the aqueous composition, the quinone diazide (A) and the above electro-depositable resin (B), together with any other optional ingredients, are usually dissolved in the organic solvent and the resulting mixture is diluted with water to give an aqueous com-position suitable for use as and electrodeposition medium. The aqueous composition, which can be a solution but is usually a disperison, generally has a solids content of 2 to 40 %, preferably 5 to 20 % by weight.
Electrodeposition of the photosensitive film from the aqueous composition may be carried out using conventional electrodeposition procedures for resinous materials. Thus, the substrate on which the image is to be formed is immersed as an electrode in the aqueous composition, either as cathode or anode according to the nature of the electrodepositable -' 1336~47 resin and its partial neutralisation, another conductive material such as a metal sheet is immersed as the other electrode and an electric current is passed through the aqueous composition to deposit a photosensitive film of the required thickness on the substrate which is to have the image formed thereon. Voltages up to 200 volts for periods of up to 5 minutes are generally used, but the precise conditions for particular resins, substrates and desired thicknesses may be readily determined by those skilled in the art of electro-depositing resinous materials. After electrodeposition, the substrate bearing the photo-sensitive film is removed from the aqueous composition and is usually rinsed and the heated at a temperature up to 90C to dry the photosensitive film.
The substrate on which the photosensitive film is deposited may be of an electrically conductive plastics material, for example a thermoset resin containing electrically conductive particles distributed therein. Preferably, it is of a metal such as copper or aluminium, either as a solid metal sheet or as a metal-clad l~min:~e which may have metal-lined through-holes or vias. Thus the process of the invention is useful in the production of printing plates and printed circuits.
Subjection of the electrodeposited film to radiation in a predetermined pattern may be achieved by exposure through a mask, i.e. an image-bearing transparency consisting of substantially opaque and substantially transparent areas, or by means of a computer-controlled laser beam. Electromagnetic radiation having a wavelength of 200-600 nm is generally used, and suitable sources include carbon arcs, mercury vapour arcs, fluorescent - . . . . . . ~ . . . . . ....................... . .. . . ... . .. .. - . .
Iamps with phosphors emitting ultra violet light, argon and xenon glow lamps, tungssten lamps, and photographic flood lamps; of these, mercury vapour arcs and metal halide lamps are the most suitable. The exposure time required depends on such factors as the nature of the quinone diazide and electrodepositable resin, the thickness of the electro-deposited film, the type of radiation source, and its distance from the film. Suitable exposure times can readily be found by routine experimentation.
After irradiation, areas of the film exposed to radiation are removed by treating the f1lm with an aqueous base as developer. Suitable developers are aqueous solutions containing 0.5 to 5 % by weight of sodium or potassium hydroxide or carbonate, which may contain small amounts of surfactant and water-miscible organic solvent to aid development.
The image obtained on development consists of areas of the surface of the substrate (which have been exposed by development) and areas of residual photosensitive film, corresponding to the areas not exposed in the imagewise irradiation, overlying the rem~in(ler of the substrate. When the surface of the substrate is metallic, the metal exposed by development may be etched, either to remove metal or to encrease the depth of the image and hence increase its differentiation, the residual photosensitve film in the remaining (non-exposed) areas protecting the underlying substrate from attack. Such etching procedures, for example, using ferric chloride or ammonium persulphate solutions on copper substrates, are well known. The residual photosensitive film can then be removed by, for example, subjection to a further, non-imagewise, irradiation followed by treatment with an aqueous base. Alternatively, the residual film can be removed by treatment with a more powerful solvent than that used for image development, forexample a more concentrated solution of the same base, or by treatment with the same solution as used for development but under more severe conditions, for instance with longer contact between the film and the solution. Suitable filmremoving agents include aqueous solutions containing 1-10 % by weight of sodium or potassium hydroxide or carbonate and organic solvents such as acetone, methyl ethyl ketone, 2-ethoxyethanol, 2-n-butoxyethanol, 2-ethoxyethyl acetate, toluene, or mixtures of two or more thereof.
When the substrate is a metal-clad plastics l~min:~tç, removal of the residual film produces an image, in metal, on the plastics l~min~te The process of the invention is useful in the production of printed circuit boards with buried via holes, that is multilayer boards made using metal-clad plastics laminates having through hole-plated via holes which interconnect the conductive tracking on their two .. ... . . . . . . . . . . . . . . ..................... ... .sides. When such l~min~t~s are used in the process of the invention, the electrodeposited photosensitive film is imagewise irradiated so that the parts of the film coating the via holes are not exposed to the radiation, for example by aligning the via holes with opaque areas of an image-bearing mask.
The invention is illustrated by the following Examples, in which all parts and percentages are by weight unless stated otherwise.
The resins used in the Examples are prepared as follows:
Resin I
A novolak (40 g), prepared from a commercial mixture of cresols ( 1 mol) and formaldehyde (0.75 mol), is dissolved in 2-n-butoxyethanol (80 g) and heated to 80C. A
solution containing diethanolamine (8.4 g), paraformaldehyde (5.28 g; 91 % (HCHO)x), :
.
lactic acid (11.52 g; 75 %) and 2-n-butoxyethanol (10 g) is added and the mixture maintained at 80C for 3 hours. The mixture is diluted with water (200 g), cooled to room temperature and poured slowly into stirred O.OS N sodium hydroxide solution (1.8 litres) at 40C. The buff coloured precipitate formed is filtered off, washed with water and dried in a vacuum oven at 45C to give 41.6 g of Resin I.
Resin II
A novolak (50 g), prepared from phenol (2.25 mols), p-tert.butyl phenol (0.75 mol) and formaldehyde (2.7 mols) is dissolved in 2-n-butoxyethanol and heated to 80C. A solution containing diethanolamine (21 g), formalin (31 g; 38.8 % HCHO) and 2-n-butoxyethanol (10 g) is added and the mixture maintained at 80C for 2 hours. Lactic acid (24 g; 75 %) is added and the mixture reacted at 80C 1 hour. The reaction mixture is then diluted with water (250 g), cooled to room temperature and poured slowly into stirred 0.12 N sodium hydroxide solution (1660 ml). The resulting buff coloured precipitate is filtered off, washed with water and dried in a vacuum oven at 45C to give 65.6 g of Resin II.
Resin III
A novolak (40 g), prepared from phenol (2.25 mols), p-tert.butylphenol (0.75 mol) and formaldehyde (2.7 mols), is dissolved in 2-n-butoxyethanol (80 g) and heated to 80 C. A
solution containing diethanolamine (8.4 g), paraformaldehyde (5.28 g; 91 % (HCHO)X,), lactic acid (11.52 g; 75 %) and 2-n-butoxyethanol (10 g) is added and the mixture maintained at 80C for 3 hours. The reaction mixture is diluted with water (200 g), cooled . .
to room temperature and poured slowly into stirred O.OS N sodium hydroxide solution (1.8 litres) at 40C. The buff coloured precipitate which forms is filtered off, washed with water and dried in a vacuum oven at 45C to give 27 g of Resin III.
Resin IV
A novolak (lS0 g), prepared from phenol (2.25 mols), p-tert.butylphenol (0.75 mol) and formaldehyde (2.7 mols), is dissolved in 2-n-butoxyethanol (250 g) and heated to 80C. A
solution containing sarcosine (10.02 g), paraformaldehyde (7.4 g; 91 %), aqueous 20 %
sodium hydroxide (22.5 g) and 2-n-butoxyethanol (25 g) is added and the mixture maintained at 80C for 3 hours. The reaction mixture is diluted with water (1.600 ml) containing aqueous 20 % sodium hydroxide (18 g), cooled to room temperature and poured slowly into stirred 0.1 N hydrochloric acid (4 litres). The resulting buff coloured precipitate is filtered off, washed with water and dried in a vacuum oven at 45C to give Resin IV.
L) Resin V
A novolak (100 g), prepared from phenol (2.25 mols), p-tert.butylphenol (0.75 mols) and forrn;~l-lehyde (2.7 mols), is dissolved in 2-n-butoxyethanol (220 g) and heated to 80C. A
solution containing glycine (5.6 g), paraformaldehyde (5.0 g; 91 %), aqueous 20 % sodium hydroxide (15.0 g) and 2-n-butoxyethanol (20 g) is added and the ~ Lult; iS maintained at 80C for 4 hours.
The reaction mixture is diluted with water (500 g) containig aqueous 20 % sodiumhydroxide (12 g), cooled to room temperature and poured slowly into stirred 0.04 N
hydrochloric acid (4 litres). The buff coloured precipitate obtained is filtered off, washed with water and dried in a vaccum oven at 45C to give lOS g of Resin V.
Resin VI
A novolak (60 g), prepared from a commercial mixture of cresols (1 mol) and formaldehyde (0.75 mol), is dissolved in 2-n-butoxyethanol (120 g) and heated to 80C. A
solution containing sarcosine (3.2 g), paraformaldehyde (2.38 g; 91 %), aqueous 20 %
sodium hydroxide (7.2 g) and 2-n-butoxyethanol (10 g) is added and the mixture reacted for 5 hours at 80C. The reaction mixture is diluted with water (300 g), vooled to room temperature and poured slowly into stirred 0.03 N hydrochloric acid (2.7 litres). The buff coloured precipitate which forms is filtered off, washed with water and dried in a vacuum oven at 45C, to give Resin VI.
- . .............. . ... . .. . . . . .................. . .. . . .
Resin VII
Methyl methacrylate (50 g), methacrylic acid (10 g), 2-hydroxyethyl methacrylate (40 g), and tert.dodecylmercaptan (0.03 g) are heated to reflux temperature in tetrahydrofuran (350 g). Azobis(isobutyronitrile) (AIBN) (1.5 g) is added and the mixture maintained at the reflux temperature for S hours. The reaction mixture is then cooled to room temperature and poured slowly into stirred hexane (900 ml). The white precipitate formed is filtered off, washed with further hexane and dried in a vacuum oven at 45C to give 89 g of a copolymer having an acid volue of 1.06 equivs/kg.
Resin VIII
Methyl methacrylate 15 g), methacrylic acid (3.8 g), 2-ethylhexyl methacrylate (15 g), 2-hydroxyethyl methacrylate (16.2 g) and tert.dodecyl mercaptan (0.015 g) are heated to reflux temperature in tetrahydrofuran (160 g). AIBN (0.75 g) is added and the mixture is i .
.
m~int~ined under reflux for S hours, cooled to room temperature and poured slowly into stirred hexane (450 ml). The white precipitate formed is filtered off, washed with hexane and dried in a vacuum oven at 45C to give 40 g of a copolymer having an acid value of 0.90 equiv./kg.
Resin IX
Methyl methacrylate (45 g), 2-hydroxyethyl methacrylate (40 g), methacrylic acid (10 g), dimethylarninoethyl methacrylate (5 g) and tert.dodecylmercaptan (0.03 g) are heated to reflux temperature in tetrahydrofuran (350 g). AIBN (l.S g) is added and the mixture m~int~ined under reflux for 5 hours. The reaction mixture is cooled to room temperature and added slowly to stirred hexane (900 ml). The resulting white precipitate is filtered off, washed with further hexane and dried in a vacuum oven at 45C to give 80 g of a copolymer having an amine value of 0.36 equiv/kg.
Resin X
A mixture of styrene (40 g), 2-ethylhexyl acrylate (32.5 g), 2-hydroxyethyl methacrylate (20 g), dimethylaminoethyl methacrylate (7.5 g) and AIBN (1.5 g) is added dropwise over 2 hours to stirred 2-n-butoxyethanol at 100C. The reaction mixture is maintained at 100C for a further hour and a further charge of AIBN (0.5 g) and 2-n-butoxyethanol (5.5 g) is added. This procedure is repeated twice more and the reaction mixture is then maintained at 100C for a further hour before cooling. The resulting solution has an amine value of 0.28 equiv./kg.
.
Resin XI
This denotes a resin made by reacting a novolak prepared from 3 moles phenol, 1 mol of p-tert.butyl phenol, and formaldehyde with 1,2-naphthoquinone-2-diazide-5-sulphonyl chloride so as to esterify about 12 % of the phenolic hydroxyl groups. The resins has an average molecular weight of about 1450.
Example 1: Resin I (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (6.0 g), oxitol acetate (0.5 g) and 2,4-di(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (0.5 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 % solids content. A copper-clad laminate and a stainless steel sheet are immersed in the dispersion as cathode and anode respectively. An electric current is passed through the dispersion at 20 volts for I minute to deposit a resinous film on the laminate. The laminate is removed from the dispersion, rinsed in a mixture of water and butoxyethanol (volume ratio 9:1) and dried at 90C for S minutes, after which the electrodeposited film is a tack-free solid layer having a thickness of 7 micrometers. The dried film is irradiated through a mask for 30 seconds using a 5000 w metal halide lamp at a distance of 75 cm. Development of the irradiated film by immersion in aqueous 3 % sodium hydroxide solution containing 0.01 % of a non-ionic fluorocarbon surfactant (used as a 1 % solution in 2-butoxyethanol) gives a clear positive image of the mask.
The copper exposed by development is removed by etching in an aqueous 40 % solution of ferric chloride at 30C, after which the l~min~te is washed, dried and irradiated again using the 5000 w lamp for 60 seconds without the mask. Immersion of the re-irradiated l~min~tP in aqueous 3 % sodium hydroxid completely removes the residual resin to give a clear image of the mask, in copper, on the l~min~te.
Example 2: Resin I (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (5.0 g), and an ester of 1 mol of 2,3,4-trihydroxybenzophenone with 2.5 mols of 1,2-naphthoquinone-2-diazide-5-sulphonyl chloride (0.5 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 %
solids content. A resinous film is electrodeposited from the dispersion onto a copper-clad l~min~te as described in Example 1, but passing the current at 40 volts for 1 minute. The film is rinsed, dried (to give a thickness of 7 micrometers) and irradiated through a mask as described in Example 1, but i~radiating for l minute. Development as described in .. . . . .......... .. . , . . . . . . . . . . ~ . . Example 1 gives a clear postive image of the mask on the l~min~tt .
Example 3: Example 2 is repeated replacing Resin I with an equal amount of Resin II, passing the current at 20 volts for 1 minute, irradiating through the mask for 30 seconds and developing in an aqueous 1 % sodium hydroxide solution containing 0.01 % of the non-ionic fluorocarbon surfactant (use~l as a 1 % solution in 2-butoxyethanol). A clear positive image of the mask is obtained on the copper-clad laminte.
The copper exposed on development is removed by etching as in Example 1 and the residual resin is completely removed by re-irradiation as described in Example 1 and immersion in aqueous 1 % sodium hydroxide solution to give a clear image of the mask, in copper, on the l~min~te.
Example 4: Example 3 is repeated, but using 1.0 g of the quinone diazide sulphonyl ester.
~, p - --- 13360i7 A clear positive image of the mask is obtained on the copper-clad l~min~te.
Example 5: Resin III (4.0 g is added slowly to a mixture of 2-n-butoxyethanol (S.0 g), oxital acetate (0.5 g), and 2,4-di(1,2-naphthoquinone-2-diazide-S-sulphonyloxy)benzo-phenone (O.S g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a solids content of 10 %. A resinous film is electro-deposited from the dispersion onto a copper-clad l~min~te, rinsed and dried as in Example 1, but passing the cuTrent at lS volts for 1 minute and giving a dried film thick-ness of S micrometers. The dried film is irradiated through a mask and developed as described in Example 3 to give a clear positive image of the mask on the l:~min~te.
Example 6: Resin I (2.0 g) and Resin XI (2.0 g) are added slowly, with stirring, to 2-n-butoxyethanol (6.0 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a solids content of 10 %. A resinous film is electro-deposited from the dispersion onto a copper-clad l~min~te, rinsed and dried as in Example 1, but passing the current at 10 volts for 1 minute and giving a dried film thickness of 6 micrometers. The dried film is irradiated through a mask as described in Example 1 and developed by immersion in aqueous 2 % sodium hydroxide solution con-taining 0.01 % of a fluorocarbon non-ionic surfactant (used as a 1 % solution in2-n-butoxyethanol) to give a clear positive image of the mask on the l~min~tt-.
Example 7: Resin III (2.0 g) and Resin XI (2.0 g) are added slowly, with stirring, to ... . . - . . . . . . .......... .. . . ........ .. . . . . ....... . . .. .
2-n-butoxyethanol (S.0 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 % solids content. A resinous film is electro-deposited from the dispersion onto a copper-clad l;~min~te, rinsed and dried as described in Example 6, but giving a dried film thickness of 8 micrometers. The dried film is irradiated through a mask as described in Example 1 and then developed by immersion in the developer used in Example 3 to give a clear positive image of the mask on the laminate.
The copper exposed by development is removed by etching as described in Example 1.
The residual resin is then removed by re-irradiation as described in Example 1 followed by immersion in aqueous 1 % sodium hydroxide to give a clear image of the mask, in copper, on the l~min~te.
Example 8: Example 7 is repeated, but using 2.5 g of Resin III and l.S g of Resin XI and developing by immersion in the developer used in Example 6. A clear positive image of "
- 15 - 1331i 0 47 the mask is obtained on the l~min:~te.
Example 9: Resin IV (4.0 g) is dissolved in a mixture of 2-n-butoxyethanol (4.0 g), oxitol acetate (0.5 g) and 2,4-di(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (0.5 g). The resulting mixture is neutralised with aqueous 5 % potassium hydroxide and diluted with water to give a dispersion having a 10 % solids content. A copper-clad l~min~te and a stainless steel sheet are immersed in the dispersion as anode and cathode respectively. An electric current is passed through the dispersion at 40 volts for 1 minute to deposit a resinous film on the l~min~te. The l~min~t~ is removed from the dispersion, rinsed in a mixture of water and 2-n-butoxyethanol (volume ratio 9:1) and dried at 90 C
for S minutes, after which the electrodeposited film is s solid, tack-free layer having a thickness of 6 micrometers. The dried film is irradiated through a mask and developed as described in Example 3 to give a clear positive image of the mask on the laminate.
The copper exposed by development is removed by etching as in Example 1 and the residual resin is removed by re-irradiation as in Example 1 followed by immersion in aqueous 1 % sodium hydroxide to give a clear image of the mask, in copper, on the l~min~te.
Example 10: Resin V (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (4.5 g), oxitol acetate (0.5 g) and 2,4-di(1,2-naphthoquinone-2-diazide-5-- sulphonyloxy)benzophenone (O.S;g). The resulting mixture is neutralised with aqueous 5 % potassium hydroxide solution and diluted with water to give a dispersion having a 10 % solids content. A resinous film is electrodeposited from the dispersion onto a copper-clad l~min~te, rinsed and dried as in Example 9, but passing the current at 50 volts for 1 minute. The dried film, 7 micrometers thick, is irradiated through a mask and developed as in Example 3 to give a clear positive image of the mask on the laminate.
Etching of the exposed copper and removal of residual resin as described in Example 9 gives a clear image of the mask, in copper, on the l~min~t~.
Example 11: Example 10 is repeated using 1.0 g of oxitol acetate and 1.0 g of the quinone diazide sulphonyl ester, passing the current at 40 volts for 1 minute giving a dried film thickness of 9 micrometers and developing as in Example 6. A clear positive image of the mask is obtained on the l~min~te.
Example 12: Example 10 is repeated, replacing the mixture used in that Example with a r~
L~
., ,.~
- - 13360~7 -mixture of Resin VI (4.0 g), 2-n-butoxyethanol (4.0 g), oxitol acetate (0.5 g) and 2,4-di-(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (0.5 g), passing the current at 100 volts for 2 seconds giving a dried film thickness of 18 micormeters, and developing by immersion in the developer used in Example 1. A clear positive image of the mask is obtained on the l~min:~te.
Example 13: Resin IV (2.0 g) and Resin XI (2.0 g) are added slowly, with stirring, to 2-n-butoxyethanol (4.5 g). The mixture is neutralised with aqueous 5 % potassiumhydroxide and diluted with water to give a dispersion having a solids content of 10 %. A
resinous film is electrodeposited from the dispersion onto a copper-clad laminate, rinsed, dried, irradiated and developed as in Example 9, but passing the current at 25 volts for 1 minute to give a dried film thickness of 8 micrometers, to give a clear positive image of the mask on the l~min:~te.
Example 14: Example 13 is repeated, replacing Resin IV by Resin V (1.5 g), using 2.5 g of Resin XI and passing the current at 30 volts for 1 minute to give a dried film thickness of 7 micrometers. A clear positive image of the mask is obtained on the laminate.
Example 15: Example 13 is repeated, replacing Resin IV by an equal amount of Resin VI, passing te current at 35 volts for 1 minute to give a dried film thickness of 7 micrometers and developing by immersing in the developer used in Example 6. A clear positive image of the mask is obtained on the l~min~te.
.... . . . ............ . . . . . . . . . .
Example 16: Example 14 is repeated, replacing Resin V by an equal amount of Resin VI
and passing the current at 40 volts for 1 minute to give a dried film thickness of 8 micro-meters. A clear positive image of the mask is obtained on the l~3min~te The copper exposed by development is removed by etching as described in Example 1.
The residual resin is removed by re-irradiation as described in Example 1 followed by immersion in aqueous 1 % sodium hydroxide. A clear image of the mask, in copper, is obtained on the l~min~te.
Example 17: Resin VII (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (5.0 g), oxitol acetate (1.0 g), and 2,4-di(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (1.0 g). The resulting mixture is neutralised with aqueous 5 % potassium hydroxide and diluted with water to give a dispersion having a 10 % solids D
.
- 17- 1~36047 content. A copper-clad l~min~t~ and a stainless steel sheet are immersed in the dispersion as anode and cathode respectively. An electric current is passed through the dispersion at 10 volts for 1 minute to deposit a resinous film on the l~min~te The l:~min~te is removed from the dispersion, rinsed in a mixture of water and 2-n-butoxyethanol (volume ratio 9:1) and dried for 5 minutes at 90C, after which the electrodeposited film is a tack-free solid layer having a thickness of 20 micrometres. The dried film is irradiated through a mask for 60 seconds using a 5000 w metal halide lamp at a distance of 75 cm. Development of the irradiated film by immersion in aqueous 3 % sodium hydroxide solution containing0.01 % of a non-ionic fluorocarbon surfactant (used as a 1 % solution in 2-n-butoxy-ethanol) gives a clear positive image of the mask.
Example 18: Example 17 is repeated, replacing Resin VII by an equal amount of Resin VIII, passing the current at 20 volts for 3 seconds to give a dried film thickness of 10 micrometres and developing by immersion in the developer used in Example 6. A clear positive image of the mask is obtained on the l~min~te The copper exposed by development is removed by etching as in Example 1. The residual resin is then removed by re-irradiation as described in Example 1 followed by immersion in aqueous 2 % sodium hydroxide to give a clear image of the mask, in copper, on the l~min~t~ .
Example 19: Resin VII (1.5 g) and Resin XI (2.5 g) are added slowly, with stirring, to 2-n-butoxyethanol (5.0 g). The resulting mixture is neutralised with aqueous 5 %potassium hydroxide and diluted with water to give a dispersion having a 10 % solids content. A resinous film is electrodeposited from the dispersion onto a copper-clad laminate, rinsed, dried, irradiated and developed as in Example 3, but using the laminate as anode and the steel sheet as cathode, the thickness of the dried electrodeposited film being 10 micrometres. A clear positive image of the mask is obtained on the laminate. The copper exposed by development is removed by etching as in Example 1 and the residual resin is removed by the procedure described in Example 3 to give a clear image of the mask, in copper, on the l:~min~tc.
Example 20: Example 19 is repeated, replacing Resin VII by Resin VIII (2.0 g), using 2.0 g of Resin XI, passing the current at 60 volts for 1 minute to give a dried film thickness of 8 micrometres, and developing as in Example 1. A clear positive image of the mask is obtained on the l~min~te. Etching and removal of residual resin as described in Example 1 gives a clear image of the mask, in copper, on the laminate.
's ~
. ~
Example 21: Resin IX (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (5.0 g), oxitol acetate (5.0 g) and 2,4-di(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (0.5 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 % solids content. A copper-clad I~min~te and a stainless steel sheet are immersed in the dispersion as cathode and anode respectively. An electric current is passed through the dispersion at 10 volts for 1 minute to deposit a resinous film on the l~min:~tf~. The l~min:~te, iS removed from the dispersion, rinsed in a mixture of water and 2-n-butoxyethanol (volume ratio 9:1) and dried for S minutes at 90C, after which the electrodeposited film is a tack-free solid layer having a thickness of 13 micrometres. The dried film is irradiated through a mask for 30 seconds, using a SOOOw metal halide lamp at a distance of 75 cm. Immersion in aqueous 0.5 %
sodium hydroxide containing 0.01 % of a non-ionic fluorocarbon surfactant (used as a 1 %
solution in 2-n-butoxyethanol) gives a clear positive image of the mask on the laminate.
Example 22: Resin IX (2.0 g) and Resin XI (2.0 g) are added slowly, with stirring, to 2-n-butoxyethanol (5.0 g). The mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 % solids content. A resinous film is electrodeposited from the dispersion onto a copper-clad laminate, rinsed, dried, irradiated (but for 1 minute) and developed as in Example 3, the thickness of the dried electrodeposited film being 12 micrometres. A clear positive image of the mask is obtained on the l~min~t~,.
.
The copper exposed on development is removed by etching as in Example 1 and the residual resin is removed by the procedure described in Example 3 to give a clear image of the mask, in copper, on the l;~min~te.
Example 23: Example 22 is repeated, replacing the mixture used in that Example by a mixture of Resin X (3.33 g), Resin XI (2.0 g) and 2-n-butoxyethanol (3.17 g), passing the current at 10 volts for 1 minute to give a dried film thickness of 12 micrometres and developing as in Example 1. A clear image of the mask is obtained on the laminate.
The copper exposed by development and the residual resin are removed by the procedure described in Example 1 to give a clear image of the mask, in copper, on the laminate.
Method of Formin~ Images This invention relates to a method of forming images which is useful in the production of printing plates and printed circuits.
In European Patent Publications Nos. 0 155 231, 0 184 553 and 0 196 999 the electro-deposition of resinous quinone diazide-containing positive photoresists is described. These photoresists are phenolic resins modified by introducing into the resin molecule a carboxyl, phosphonic or sulphonic acid group or amino group and by reacting phenolic hydroxyl groups on the resin with an esterifying derivative of a quinone diazide sulphonic acid. Although these photoresists give good films on electrodeposition and good images on imagewise irradiation, their preparation is difficult and timeconsuming. The reactions involved in the synthesis of the modified phenolic resins, which required elevated temperatures, have to be carefully controlled to avoid decomposition of the quinone diazide residue, otherwise the degree of photosensitivity of the electrodeposited film will be lower than expected. Furthermore, it is not possible to modify the photosensitivity or electrodepositability of the modified phenolic resins without repeating the synthetic reaction sequence.
It has now been found, surprisingly, that good photosensitive films can be electrodeposited from an aqueous composition containing a mixture of an electrodepositable resin and a compound having a quinone diazide residue without the need to prepare a resin having both a quinone diazide residue and a carboxyl, phosphonic or sulphonic acid group or amino group in the molecule. The electrodepositable resin and the quinone diazide can be materials which are readily available commercially. The use of such a mixture permits considerable latitude in formulation. The degree of photosensitivity of the electrodeposited film can be readily varied to meet a particular requirement simply by adjusting the ratio of the amounts of the components of the mixture.
Accordingly, the present invention provides a process for the formation of an image on a conductive substrate which comprises (i) electrodepositing on a conductive surface a photosensitive film from an aqueous composition which is a solution or dispersion comprising a mixture of (A) a photo-sensitive o-benzoquinone diazide sulphonyl ester or amide or o-naphthoquinone diazide sulphonyl ester or amide and (B) an electrodepositable film-forming resin, in (C) an 1) - 2 13360 4~
aqueous medium, said composition being substantially free from a resin having both a quinone diazide residue and a carboxyl, phosphonic or sulphonic acid group or amino group in the same molecule, in which step the electrodeposition is carried out by immersing the substrate on which the image is to be formed as an electrode in the aqueous composition, immersing a conductive material as another electrode and passing an electric current through the aqueous composition to deposit a photosensitive film of the required thickness on the substrate, (ii) subjecting the electrodeposited film to radiation in a predetermined pattern, such that exposed areas of the film become more soluble in aqueous base than unexposed areas, and (iii) removing the exposed areas by treatment with an aqueous base, and with the proviso that, when compound (A) is a o-benzo- or o-naphtho-quinone diazide sulfonyl ester compound and compound (B) is an acrylate compound, then the compound (B) is a) a reaction product of an epoxide resin with a primary or secondary monoamine or a secondary diamine, or b) a cationic or cationic/anionic phenolic resin which is a reaction product of a novolak resin, an aldehyde and a primary or secondary amine or an aminocarboxylic acid; or c) a cationic copolymer of a dialkylaminoalkyl acrylate or methacrylate with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers:
or d) an anionic copolymer of acrylic or methacrylic acid with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more vinyl monomers; or e) an anionic copolymer of a vinyl group-containing sulphonic acid with an acrylate or methacrylate ester and, optionally, one or more other vinyl monomers: or f) a cationic/anionic copolymer or a dialkylaminoalkyl acrylate or methacrylate with acrylic acid or methacrylic acid, an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers, with the proviso that the copolymers c), d), e) and f) do not contain an acrylate or methacrylate copolymer component being a 3-acryloyloxy-2-hydroxylpropyl or 3-methacryloyloxy-2-hydroxy-propyl ester of an hydroxybenzoic acid.
The present invention also provides an aqueous composition suitable for use in the image-forming process of the invention which is a solution or dispersion comprising a mixture of (A) a photosensitive o-quinone diazide as defined above and (B) an electrode-positable film-forming resin as defined above, in (C) an aqueous medium, said com-position being substantially free from a resin having both a quinone diazide residue and a , ....
~ 3 13360~7 carboxyl, phosphonic or sulphonic acid or amino group in the same molecule.
Photosensitve o-benzoquinone diazide sulphonyl ester or amides and o-naphtoquinone diazide sulphonyl esters or amides are well known. Examples include o-benzoquinone diazide sulphonyl or o-naphthoquinone diazide sulphonyl esters or amides of compounds, particularly aromatic compounds, having a hydroxy group or amino group respectively.
Preferred o-quinone diazides are o-benzoquinone diazide sulphonyl esters and o-naphtho-quinone diazide sulphonyl esters of phenols, including monohydric phenols and, particularly, polyhydric phenols such as 2,2-bis(hydroxyphenyl)propanes, dihydroxy-diphenyls, di- and tri-hydroxy-substituted benzophenones, and phenolic resins, including phenol-aldehyde resins and polymers of phenols having polymerisable unsaturated substituents. Suitable phenol-aldehyde resins from which the esters may be derived include novolak resins prepared from phenol itself, an alkyl-substituted phenol such as o-, m- or p-cresol, o-, m or p-tert.butylphenol, o-, m- or p-octylphenol, or a bisphenol such as 2,2-bis(4-hydroxyphenyl)propane, or a mixture of two or more of such phenols, and an aldehyde such as acetaldehyde, benzaldehyde, glyoxylic acid or, preferably, formalde-hyde. Suitable polymers of unsaturated phenols from which the esters may be derived include homopolymers and copolymers of p-vinyl phenol and p-isopropenyl phenol.
Preferred o-quinone diazide sulphonyl esters of phenols are o-naphthoquinone diazide sulphonyl esters of polyhydroxybenzophenones or novolak resins derived from formalde-hyde and an alkyl-substituted phenol or a mixture thereof with phenol. Particularly .. . .... . . ..... .. .. . . . . . . .. . . . . .. . ..... . . . ..
preferred esters are 1,2-naphthoquinone-2-diazide-5-sulphonyl esters of dihydroxybenzo-phenones, trihydroxybenzophenones, novolaks derived from formaldehyde and either a mixture of o-, m- and p-cresols or a mixture of phenol and p-tert.butylphenol.
The photosensitive quinone diazides hereinbefore described are either commercially available or may be prepared by conventional methods, for example by reacting a phenol with an esterifying derivative of an o-quinone diazide sulphonic acid, usually the sulphonyl chloride thereof, under conventional conditions.
Electrodepositable film-forming resins as mentioned hereinbefore are also well known.
They may be cationic resins containing basic groups such as amino groups, anionic resins containing acidic groups such as carboxylic, sulphonic or phosphonic acid groups or resins having both basic and acidic groups.
~' In order for the above electrodepositable resin to be electrodepositable, it is present in the aqueous composition in at least partially inoised form. For cationic resins this is usually achieved by at least partial neutralisation of the basic groups with an acid. For anionic resins, this is usually achieved by at least partial neutralisation with a base. For resins containing both basic and acidic groups, at least partial neutralisation can be accomplished with an acid or a base.
Examples of cationic electrodepositable resins are reaction products of an epoxide resin with a primary or secondary monoamine or secondary diamine, particularly a reaction product of an epoxy resin, such as a diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), with an alkanolamine such as ethanolamine, diethanolamine or propanol-amine; and reaction products of a phenolic hydroxyl group-containing resin, such as a novolak resin, a polymer of an ethylenically unsaturated phenol or a phenolic hydroxyl-terminated adduct of an epoxide resin and a bisphenol, with an aldehyde and a primary or secondary amine, for example reaction products of a novolak resin or a poly(vinyl)phenol with an aldehyde such as acetaldehyde, benzaldehyde or, preferably, formaldehyde, and an amine such as a dialkylamine, an alkylenediamine or an alkanolamine; polymers of basic group-containing acrylic materials such as homopolymers of dialkylaminoalkyl acrylates or methacrylates and copolymers thereof, including copolymers with other vinyl mono-mers, such as alkyl acrylates or methacrylates, and graft copolymers with acrylate or methacrylate group-containing resins such as esters of epoxide resins with acrylic or meth-acrylic acid; and Michael addition reaction products of acrylate or methacrylate group-containing resins with a primary or secondary amine such as ethanolamine, diethanol-amine or morpholine.
Examples of anionic electrodepositable resins are carboxyl-terminated diene polymers such as carboxyl terrnin~çd homopolymers and copolymers of butadiene; polymers of ethylenically unsaturated carboxylic, sulphonic or phosphonic acids, particularly homopolymers and copolymers of acrylic or methacrylic acid; carboxyl-terminated poly-esters; reaction products of hydroxyl group-containing resins, such as hydroxyl group-containing epoxide resins, with polycarboxylic acid anhydrides; and carboxyl group-containing reaction products of epoxide resins with mercaptocarboxylic acids.
Examples of electrodepositable resins containing both cationic and anionic groups are reaction products of epoxide resins with an aminocarboxylic acid, an aminosulphonic acid or an aminophosphonic acid; reaction products of a phenolic hydroxyl group-containing ~, ~ , ~
~ . .. .
. .
~5~ 13~6047 resin, such as a novolak resin, a polymer of an ethylenically unsaturated phenol or a phenolic hyroxyl-termin~tç~l adduct of an epoxide resin and a bisphenol, with an aldehyde, such as acetaldehyde, benzaldehyde or, preferably, formaldehyde, and an aminocar-boxylic, aminosulphonic or aminophosphonic acid; copolymers of an ethylenically unsaturated acid, such as acrylic or methacrylic acid, with an ethylenically unsaturated amine such as a dialkylaminoalkyl acrylate or methacrylate, and optionally one or more further ethylenically unsaturated monomers; and graft copolymers of such an unsaturated acid and unsaturated amine with acrylate or methacrylate group-containing resins such as esters of epoxide resins with acrylic or methacrylic acid.
Preferred electrodepositable resins to be used in the present invention are those containing amino carboxylic or sulphonic acid groups, present in the aqueous composition in at least partially ionised form. Further preferred are cationic or cationic/anionic phenolic resins which are reaction products of a novolak resin, an aldehyde and a primary or secondary amine or an aminocarboxylic acid; cationic copolymers of a dialkylaminoalkyl acrylate or methacrylate with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers; anionic copolymers of acrylic acid or methacrylic acid with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers; anionic copolymers of a vinyl group containing sulphonic acid with an acrylate or methacrylate ester and, optionally, one or more other vinyl monomers; and cationic/anionic copolymers of a dialkylaminoalkyl acrylate or methacrylate, acrylic acid or methacrylic acid, an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers.
Preferred cationic and cationic/anionic phenolic resins are reaction products of (a) a novolak resin derived from phenol, or an alkyl-substituted phenol such as o-, m- or p-cresol, o-, m- or p-tert.butylphenol, o-, m- or p-octylphenol, or a mixture of two or more such phenols, and formaldehyde, acetaldehyde or benzaldehyde, (b) formaldehyde, acetaldehyde or benzaldehyde and (c) an alkanolamine, such as ethanolamine, diethanol-amine, propanolamine or butanolamine, or an aminocarboxylic acid such as sarcosine, glycine, aspartic acid, glutamic acid, iminodiacetic acid, anthranilic acid or p-amino-benzoic acid. Particularly preferred amongst these resins are those where (a) is a novolak resin derived from formaldehyde and either a mixture of o-, m- and p-cresols or a mixture of phenol and p-tert.butylphenol, (b) is formaldehyde and (c) is diethanolamine, sarcosine or glycine. The cationic and cationic/anionic phenolic resins can be prepared by subjecting 1~360-4~
the reactants to conventional Mannich reaction conditions.
Preferred cationic copolymers are copolymers of dimethyl aminoethyl acrylate or meth-acrylate with a Cl to Cl2 alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers. Particularly preferred amongst such copolymers are those of dimethylaminoethyl methacrylate with 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate and styrene.
Anionic copolymers which are preferred are copolymers of acrylic acid or methacrylic acid with a Cl to Cl2 alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers. Particularly plefell~d amongst these copolymers are those of methacrylate acid with methyl methacrylate and 2-hydroxyethyl methacrylate and those of methacrylic acid with methyl methacrylate, 2-ethylhexyl methacrylate and 2-hydroxy-ethyl methacrylate.
Other pl~fellcd anionic copolymers are copolymers of an acrylamide containing a sulphonic acid group with a 3-acryloyloxy-2-hydroxypropyl or 3-methacryloyloxy-2-hydroxypropyl ester of a hydroxybenzoic acid and an alkyl acrylate or methacrylate.
Particularly pler~ d amongst such copolymers is a copolymer of 2-acrylamido-2-methyl-l-propanesulphonic acid, 3-methacryloyloxy-2-hydroxypropyl salicylate, methyl methacrylate and n-butyl acrylate.
. . . .. .. .. . . . . . . . . . . . .~ . . . ................ . .
Preferred cationic/anionic copolymers are those of a diaLkylaminoalkyl acrylate or meth-acrylate with acrylic or methacrylic acid, a Cl to Cl2 alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers. Particularly preferred such copolymers are those of dimethylaminoethyl methacrylate with methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate.
When compound (A) is a o-benzo- or o-naphtho-quinone diazide sulfonyl ester compound, examples of electrodepositable resins are the same resins as already described hereabove and correspond to the definitions given for the acrylate compounds in the proviso in question. The same comments also apply to the corresponding preferred resins andcopolymers respectively.
As already indicated, the electrodepositable resin to be used in the present invention is present in the aqueous composition in at least partially ionised form. Acids suitable for D
-~7~ 1336047 addition to the resin to effect at least partial neutralisation thereof include organic acids such as acetic, propionic, lactic, maleic, p-toluenesulphonic and glycolic acids and inorganic acids such as hydrochloric and sulphuric acids. Bases suitable for addition to the resin to effect at least partial neutralisation thereof include organic bases such as triethyl-amine, triethanolamine, benzyldimethylamine, morpholine and 2-(dimethylamino)ethanol and inorganic bases such as sodium or potassium hydroxide or carbonate and ammonia.
The resin is usually at least 5 %, preferably 20 to 100 %, neutralised. In especially preferred processes, the resin is completely neutralised.
Minor amounts, compared with the volume of water, of an organic solvent such as a ketone, alcohol, ether or ester may be included in the aqueous composition. Suitable organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol, 2-methoxyethanol, 2-ethoxyethanol, 2-n-butoxyethanol, diethylene glycol monbutyl ether, 2-methoxypropyl acetate, 2-ethoxyethyl acetate (oxitol acetate) and mixtures of two or more thereof. Photosensitisers such as Michler's ketone, benzoin ethers, benzil ketals and thioxanthones may also be incorporated in the aqueous com-position.
The o-quinone diazide (A) and the electrodepositable resin (B) are generally used in amounts such that the aqueous composition contains, by weight, at least 0.05 part of (A) per part of (B). Where the above component (A) is itself resinous, it is conveniently present in an amount of 0.5 to 1.5 parts, preferably 0.75 to 1.25 parts, per part by weight of (B). When (A) is not resinous, it is conveniently present in an amount of 0.05 to 0.5 part, preferably 0.1 to 0.3 part, per part by weight of (B).
In preparing the aqueous composition, the quinone diazide (A) and the above electro-depositable resin (B), together with any other optional ingredients, are usually dissolved in the organic solvent and the resulting mixture is diluted with water to give an aqueous com-position suitable for use as and electrodeposition medium. The aqueous composition, which can be a solution but is usually a disperison, generally has a solids content of 2 to 40 %, preferably 5 to 20 % by weight.
Electrodeposition of the photosensitive film from the aqueous composition may be carried out using conventional electrodeposition procedures for resinous materials. Thus, the substrate on which the image is to be formed is immersed as an electrode in the aqueous composition, either as cathode or anode according to the nature of the electrodepositable -' 1336~47 resin and its partial neutralisation, another conductive material such as a metal sheet is immersed as the other electrode and an electric current is passed through the aqueous composition to deposit a photosensitive film of the required thickness on the substrate which is to have the image formed thereon. Voltages up to 200 volts for periods of up to 5 minutes are generally used, but the precise conditions for particular resins, substrates and desired thicknesses may be readily determined by those skilled in the art of electro-depositing resinous materials. After electrodeposition, the substrate bearing the photo-sensitive film is removed from the aqueous composition and is usually rinsed and the heated at a temperature up to 90C to dry the photosensitive film.
The substrate on which the photosensitive film is deposited may be of an electrically conductive plastics material, for example a thermoset resin containing electrically conductive particles distributed therein. Preferably, it is of a metal such as copper or aluminium, either as a solid metal sheet or as a metal-clad l~min:~e which may have metal-lined through-holes or vias. Thus the process of the invention is useful in the production of printing plates and printed circuits.
Subjection of the electrodeposited film to radiation in a predetermined pattern may be achieved by exposure through a mask, i.e. an image-bearing transparency consisting of substantially opaque and substantially transparent areas, or by means of a computer-controlled laser beam. Electromagnetic radiation having a wavelength of 200-600 nm is generally used, and suitable sources include carbon arcs, mercury vapour arcs, fluorescent - . . . . . . ~ . . . . . ....................... . .. . . ... . .. .. - . .
Iamps with phosphors emitting ultra violet light, argon and xenon glow lamps, tungssten lamps, and photographic flood lamps; of these, mercury vapour arcs and metal halide lamps are the most suitable. The exposure time required depends on such factors as the nature of the quinone diazide and electrodepositable resin, the thickness of the electro-deposited film, the type of radiation source, and its distance from the film. Suitable exposure times can readily be found by routine experimentation.
After irradiation, areas of the film exposed to radiation are removed by treating the f1lm with an aqueous base as developer. Suitable developers are aqueous solutions containing 0.5 to 5 % by weight of sodium or potassium hydroxide or carbonate, which may contain small amounts of surfactant and water-miscible organic solvent to aid development.
The image obtained on development consists of areas of the surface of the substrate (which have been exposed by development) and areas of residual photosensitive film, corresponding to the areas not exposed in the imagewise irradiation, overlying the rem~in(ler of the substrate. When the surface of the substrate is metallic, the metal exposed by development may be etched, either to remove metal or to encrease the depth of the image and hence increase its differentiation, the residual photosensitve film in the remaining (non-exposed) areas protecting the underlying substrate from attack. Such etching procedures, for example, using ferric chloride or ammonium persulphate solutions on copper substrates, are well known. The residual photosensitive film can then be removed by, for example, subjection to a further, non-imagewise, irradiation followed by treatment with an aqueous base. Alternatively, the residual film can be removed by treatment with a more powerful solvent than that used for image development, forexample a more concentrated solution of the same base, or by treatment with the same solution as used for development but under more severe conditions, for instance with longer contact between the film and the solution. Suitable filmremoving agents include aqueous solutions containing 1-10 % by weight of sodium or potassium hydroxide or carbonate and organic solvents such as acetone, methyl ethyl ketone, 2-ethoxyethanol, 2-n-butoxyethanol, 2-ethoxyethyl acetate, toluene, or mixtures of two or more thereof.
When the substrate is a metal-clad plastics l~min:~tç, removal of the residual film produces an image, in metal, on the plastics l~min~te The process of the invention is useful in the production of printed circuit boards with buried via holes, that is multilayer boards made using metal-clad plastics laminates having through hole-plated via holes which interconnect the conductive tracking on their two .. ... . . . . . . . . . . . . . . ..................... ... .sides. When such l~min~t~s are used in the process of the invention, the electrodeposited photosensitive film is imagewise irradiated so that the parts of the film coating the via holes are not exposed to the radiation, for example by aligning the via holes with opaque areas of an image-bearing mask.
The invention is illustrated by the following Examples, in which all parts and percentages are by weight unless stated otherwise.
The resins used in the Examples are prepared as follows:
Resin I
A novolak (40 g), prepared from a commercial mixture of cresols ( 1 mol) and formaldehyde (0.75 mol), is dissolved in 2-n-butoxyethanol (80 g) and heated to 80C. A
solution containing diethanolamine (8.4 g), paraformaldehyde (5.28 g; 91 % (HCHO)x), :
.
lactic acid (11.52 g; 75 %) and 2-n-butoxyethanol (10 g) is added and the mixture maintained at 80C for 3 hours. The mixture is diluted with water (200 g), cooled to room temperature and poured slowly into stirred O.OS N sodium hydroxide solution (1.8 litres) at 40C. The buff coloured precipitate formed is filtered off, washed with water and dried in a vacuum oven at 45C to give 41.6 g of Resin I.
Resin II
A novolak (50 g), prepared from phenol (2.25 mols), p-tert.butyl phenol (0.75 mol) and formaldehyde (2.7 mols) is dissolved in 2-n-butoxyethanol and heated to 80C. A solution containing diethanolamine (21 g), formalin (31 g; 38.8 % HCHO) and 2-n-butoxyethanol (10 g) is added and the mixture maintained at 80C for 2 hours. Lactic acid (24 g; 75 %) is added and the mixture reacted at 80C 1 hour. The reaction mixture is then diluted with water (250 g), cooled to room temperature and poured slowly into stirred 0.12 N sodium hydroxide solution (1660 ml). The resulting buff coloured precipitate is filtered off, washed with water and dried in a vacuum oven at 45C to give 65.6 g of Resin II.
Resin III
A novolak (40 g), prepared from phenol (2.25 mols), p-tert.butylphenol (0.75 mol) and formaldehyde (2.7 mols), is dissolved in 2-n-butoxyethanol (80 g) and heated to 80 C. A
solution containing diethanolamine (8.4 g), paraformaldehyde (5.28 g; 91 % (HCHO)X,), lactic acid (11.52 g; 75 %) and 2-n-butoxyethanol (10 g) is added and the mixture maintained at 80C for 3 hours. The reaction mixture is diluted with water (200 g), cooled . .
to room temperature and poured slowly into stirred O.OS N sodium hydroxide solution (1.8 litres) at 40C. The buff coloured precipitate which forms is filtered off, washed with water and dried in a vacuum oven at 45C to give 27 g of Resin III.
Resin IV
A novolak (lS0 g), prepared from phenol (2.25 mols), p-tert.butylphenol (0.75 mol) and formaldehyde (2.7 mols), is dissolved in 2-n-butoxyethanol (250 g) and heated to 80C. A
solution containing sarcosine (10.02 g), paraformaldehyde (7.4 g; 91 %), aqueous 20 %
sodium hydroxide (22.5 g) and 2-n-butoxyethanol (25 g) is added and the mixture maintained at 80C for 3 hours. The reaction mixture is diluted with water (1.600 ml) containing aqueous 20 % sodium hydroxide (18 g), cooled to room temperature and poured slowly into stirred 0.1 N hydrochloric acid (4 litres). The resulting buff coloured precipitate is filtered off, washed with water and dried in a vacuum oven at 45C to give Resin IV.
L) Resin V
A novolak (100 g), prepared from phenol (2.25 mols), p-tert.butylphenol (0.75 mols) and forrn;~l-lehyde (2.7 mols), is dissolved in 2-n-butoxyethanol (220 g) and heated to 80C. A
solution containing glycine (5.6 g), paraformaldehyde (5.0 g; 91 %), aqueous 20 % sodium hydroxide (15.0 g) and 2-n-butoxyethanol (20 g) is added and the ~ Lult; iS maintained at 80C for 4 hours.
The reaction mixture is diluted with water (500 g) containig aqueous 20 % sodiumhydroxide (12 g), cooled to room temperature and poured slowly into stirred 0.04 N
hydrochloric acid (4 litres). The buff coloured precipitate obtained is filtered off, washed with water and dried in a vaccum oven at 45C to give lOS g of Resin V.
Resin VI
A novolak (60 g), prepared from a commercial mixture of cresols (1 mol) and formaldehyde (0.75 mol), is dissolved in 2-n-butoxyethanol (120 g) and heated to 80C. A
solution containing sarcosine (3.2 g), paraformaldehyde (2.38 g; 91 %), aqueous 20 %
sodium hydroxide (7.2 g) and 2-n-butoxyethanol (10 g) is added and the mixture reacted for 5 hours at 80C. The reaction mixture is diluted with water (300 g), vooled to room temperature and poured slowly into stirred 0.03 N hydrochloric acid (2.7 litres). The buff coloured precipitate which forms is filtered off, washed with water and dried in a vacuum oven at 45C, to give Resin VI.
- . .............. . ... . .. . . . . .................. . .. . . .
Resin VII
Methyl methacrylate (50 g), methacrylic acid (10 g), 2-hydroxyethyl methacrylate (40 g), and tert.dodecylmercaptan (0.03 g) are heated to reflux temperature in tetrahydrofuran (350 g). Azobis(isobutyronitrile) (AIBN) (1.5 g) is added and the mixture maintained at the reflux temperature for S hours. The reaction mixture is then cooled to room temperature and poured slowly into stirred hexane (900 ml). The white precipitate formed is filtered off, washed with further hexane and dried in a vacuum oven at 45C to give 89 g of a copolymer having an acid volue of 1.06 equivs/kg.
Resin VIII
Methyl methacrylate 15 g), methacrylic acid (3.8 g), 2-ethylhexyl methacrylate (15 g), 2-hydroxyethyl methacrylate (16.2 g) and tert.dodecyl mercaptan (0.015 g) are heated to reflux temperature in tetrahydrofuran (160 g). AIBN (0.75 g) is added and the mixture is i .
.
m~int~ined under reflux for S hours, cooled to room temperature and poured slowly into stirred hexane (450 ml). The white precipitate formed is filtered off, washed with hexane and dried in a vacuum oven at 45C to give 40 g of a copolymer having an acid value of 0.90 equiv./kg.
Resin IX
Methyl methacrylate (45 g), 2-hydroxyethyl methacrylate (40 g), methacrylic acid (10 g), dimethylarninoethyl methacrylate (5 g) and tert.dodecylmercaptan (0.03 g) are heated to reflux temperature in tetrahydrofuran (350 g). AIBN (l.S g) is added and the mixture m~int~ined under reflux for 5 hours. The reaction mixture is cooled to room temperature and added slowly to stirred hexane (900 ml). The resulting white precipitate is filtered off, washed with further hexane and dried in a vacuum oven at 45C to give 80 g of a copolymer having an amine value of 0.36 equiv/kg.
Resin X
A mixture of styrene (40 g), 2-ethylhexyl acrylate (32.5 g), 2-hydroxyethyl methacrylate (20 g), dimethylaminoethyl methacrylate (7.5 g) and AIBN (1.5 g) is added dropwise over 2 hours to stirred 2-n-butoxyethanol at 100C. The reaction mixture is maintained at 100C for a further hour and a further charge of AIBN (0.5 g) and 2-n-butoxyethanol (5.5 g) is added. This procedure is repeated twice more and the reaction mixture is then maintained at 100C for a further hour before cooling. The resulting solution has an amine value of 0.28 equiv./kg.
.
Resin XI
This denotes a resin made by reacting a novolak prepared from 3 moles phenol, 1 mol of p-tert.butyl phenol, and formaldehyde with 1,2-naphthoquinone-2-diazide-5-sulphonyl chloride so as to esterify about 12 % of the phenolic hydroxyl groups. The resins has an average molecular weight of about 1450.
Example 1: Resin I (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (6.0 g), oxitol acetate (0.5 g) and 2,4-di(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (0.5 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 % solids content. A copper-clad laminate and a stainless steel sheet are immersed in the dispersion as cathode and anode respectively. An electric current is passed through the dispersion at 20 volts for I minute to deposit a resinous film on the laminate. The laminate is removed from the dispersion, rinsed in a mixture of water and butoxyethanol (volume ratio 9:1) and dried at 90C for S minutes, after which the electrodeposited film is a tack-free solid layer having a thickness of 7 micrometers. The dried film is irradiated through a mask for 30 seconds using a 5000 w metal halide lamp at a distance of 75 cm. Development of the irradiated film by immersion in aqueous 3 % sodium hydroxide solution containing 0.01 % of a non-ionic fluorocarbon surfactant (used as a 1 % solution in 2-butoxyethanol) gives a clear positive image of the mask.
The copper exposed by development is removed by etching in an aqueous 40 % solution of ferric chloride at 30C, after which the l~min~te is washed, dried and irradiated again using the 5000 w lamp for 60 seconds without the mask. Immersion of the re-irradiated l~min~tP in aqueous 3 % sodium hydroxid completely removes the residual resin to give a clear image of the mask, in copper, on the l~min~te.
Example 2: Resin I (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (5.0 g), and an ester of 1 mol of 2,3,4-trihydroxybenzophenone with 2.5 mols of 1,2-naphthoquinone-2-diazide-5-sulphonyl chloride (0.5 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 %
solids content. A resinous film is electrodeposited from the dispersion onto a copper-clad l~min~te as described in Example 1, but passing the current at 40 volts for 1 minute. The film is rinsed, dried (to give a thickness of 7 micrometers) and irradiated through a mask as described in Example 1, but i~radiating for l minute. Development as described in .. . . . .......... .. . , . . . . . . . . . . ~ . . Example 1 gives a clear postive image of the mask on the l~min~tt .
Example 3: Example 2 is repeated replacing Resin I with an equal amount of Resin II, passing the current at 20 volts for 1 minute, irradiating through the mask for 30 seconds and developing in an aqueous 1 % sodium hydroxide solution containing 0.01 % of the non-ionic fluorocarbon surfactant (use~l as a 1 % solution in 2-butoxyethanol). A clear positive image of the mask is obtained on the copper-clad laminte.
The copper exposed on development is removed by etching as in Example 1 and the residual resin is completely removed by re-irradiation as described in Example 1 and immersion in aqueous 1 % sodium hydroxide solution to give a clear image of the mask, in copper, on the l~min~te.
Example 4: Example 3 is repeated, but using 1.0 g of the quinone diazide sulphonyl ester.
~, p - --- 13360i7 A clear positive image of the mask is obtained on the copper-clad l~min~te.
Example 5: Resin III (4.0 g is added slowly to a mixture of 2-n-butoxyethanol (S.0 g), oxital acetate (0.5 g), and 2,4-di(1,2-naphthoquinone-2-diazide-S-sulphonyloxy)benzo-phenone (O.S g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a solids content of 10 %. A resinous film is electro-deposited from the dispersion onto a copper-clad l~min~te, rinsed and dried as in Example 1, but passing the cuTrent at lS volts for 1 minute and giving a dried film thick-ness of S micrometers. The dried film is irradiated through a mask and developed as described in Example 3 to give a clear positive image of the mask on the l:~min~te.
Example 6: Resin I (2.0 g) and Resin XI (2.0 g) are added slowly, with stirring, to 2-n-butoxyethanol (6.0 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a solids content of 10 %. A resinous film is electro-deposited from the dispersion onto a copper-clad l~min~te, rinsed and dried as in Example 1, but passing the current at 10 volts for 1 minute and giving a dried film thickness of 6 micrometers. The dried film is irradiated through a mask as described in Example 1 and developed by immersion in aqueous 2 % sodium hydroxide solution con-taining 0.01 % of a fluorocarbon non-ionic surfactant (used as a 1 % solution in2-n-butoxyethanol) to give a clear positive image of the mask on the l~min~tt-.
Example 7: Resin III (2.0 g) and Resin XI (2.0 g) are added slowly, with stirring, to ... . . - . . . . . . .......... .. . . ........ .. . . . . ....... . . .. .
2-n-butoxyethanol (S.0 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 % solids content. A resinous film is electro-deposited from the dispersion onto a copper-clad l;~min~te, rinsed and dried as described in Example 6, but giving a dried film thickness of 8 micrometers. The dried film is irradiated through a mask as described in Example 1 and then developed by immersion in the developer used in Example 3 to give a clear positive image of the mask on the laminate.
The copper exposed by development is removed by etching as described in Example 1.
The residual resin is then removed by re-irradiation as described in Example 1 followed by immersion in aqueous 1 % sodium hydroxide to give a clear image of the mask, in copper, on the l~min~te.
Example 8: Example 7 is repeated, but using 2.5 g of Resin III and l.S g of Resin XI and developing by immersion in the developer used in Example 6. A clear positive image of "
- 15 - 1331i 0 47 the mask is obtained on the l~min:~te.
Example 9: Resin IV (4.0 g) is dissolved in a mixture of 2-n-butoxyethanol (4.0 g), oxitol acetate (0.5 g) and 2,4-di(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (0.5 g). The resulting mixture is neutralised with aqueous 5 % potassium hydroxide and diluted with water to give a dispersion having a 10 % solids content. A copper-clad l~min~te and a stainless steel sheet are immersed in the dispersion as anode and cathode respectively. An electric current is passed through the dispersion at 40 volts for 1 minute to deposit a resinous film on the l~min~te. The l~min~t~ is removed from the dispersion, rinsed in a mixture of water and 2-n-butoxyethanol (volume ratio 9:1) and dried at 90 C
for S minutes, after which the electrodeposited film is s solid, tack-free layer having a thickness of 6 micrometers. The dried film is irradiated through a mask and developed as described in Example 3 to give a clear positive image of the mask on the laminate.
The copper exposed by development is removed by etching as in Example 1 and the residual resin is removed by re-irradiation as in Example 1 followed by immersion in aqueous 1 % sodium hydroxide to give a clear image of the mask, in copper, on the l~min~te.
Example 10: Resin V (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (4.5 g), oxitol acetate (0.5 g) and 2,4-di(1,2-naphthoquinone-2-diazide-5-- sulphonyloxy)benzophenone (O.S;g). The resulting mixture is neutralised with aqueous 5 % potassium hydroxide solution and diluted with water to give a dispersion having a 10 % solids content. A resinous film is electrodeposited from the dispersion onto a copper-clad l~min~te, rinsed and dried as in Example 9, but passing the current at 50 volts for 1 minute. The dried film, 7 micrometers thick, is irradiated through a mask and developed as in Example 3 to give a clear positive image of the mask on the laminate.
Etching of the exposed copper and removal of residual resin as described in Example 9 gives a clear image of the mask, in copper, on the l~min~t~.
Example 11: Example 10 is repeated using 1.0 g of oxitol acetate and 1.0 g of the quinone diazide sulphonyl ester, passing the current at 40 volts for 1 minute giving a dried film thickness of 9 micrometers and developing as in Example 6. A clear positive image of the mask is obtained on the l~min~te.
Example 12: Example 10 is repeated, replacing the mixture used in that Example with a r~
L~
., ,.~
- - 13360~7 -mixture of Resin VI (4.0 g), 2-n-butoxyethanol (4.0 g), oxitol acetate (0.5 g) and 2,4-di-(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (0.5 g), passing the current at 100 volts for 2 seconds giving a dried film thickness of 18 micormeters, and developing by immersion in the developer used in Example 1. A clear positive image of the mask is obtained on the l~min:~te.
Example 13: Resin IV (2.0 g) and Resin XI (2.0 g) are added slowly, with stirring, to 2-n-butoxyethanol (4.5 g). The mixture is neutralised with aqueous 5 % potassiumhydroxide and diluted with water to give a dispersion having a solids content of 10 %. A
resinous film is electrodeposited from the dispersion onto a copper-clad laminate, rinsed, dried, irradiated and developed as in Example 9, but passing the current at 25 volts for 1 minute to give a dried film thickness of 8 micrometers, to give a clear positive image of the mask on the l~min:~te.
Example 14: Example 13 is repeated, replacing Resin IV by Resin V (1.5 g), using 2.5 g of Resin XI and passing the current at 30 volts for 1 minute to give a dried film thickness of 7 micrometers. A clear positive image of the mask is obtained on the laminate.
Example 15: Example 13 is repeated, replacing Resin IV by an equal amount of Resin VI, passing te current at 35 volts for 1 minute to give a dried film thickness of 7 micrometers and developing by immersing in the developer used in Example 6. A clear positive image of the mask is obtained on the l~min~te.
.... . . . ............ . . . . . . . . . .
Example 16: Example 14 is repeated, replacing Resin V by an equal amount of Resin VI
and passing the current at 40 volts for 1 minute to give a dried film thickness of 8 micro-meters. A clear positive image of the mask is obtained on the l~3min~te The copper exposed by development is removed by etching as described in Example 1.
The residual resin is removed by re-irradiation as described in Example 1 followed by immersion in aqueous 1 % sodium hydroxide. A clear image of the mask, in copper, is obtained on the l~min~te.
Example 17: Resin VII (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (5.0 g), oxitol acetate (1.0 g), and 2,4-di(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (1.0 g). The resulting mixture is neutralised with aqueous 5 % potassium hydroxide and diluted with water to give a dispersion having a 10 % solids D
.
- 17- 1~36047 content. A copper-clad l~min~t~ and a stainless steel sheet are immersed in the dispersion as anode and cathode respectively. An electric current is passed through the dispersion at 10 volts for 1 minute to deposit a resinous film on the l~min~te The l:~min~te is removed from the dispersion, rinsed in a mixture of water and 2-n-butoxyethanol (volume ratio 9:1) and dried for 5 minutes at 90C, after which the electrodeposited film is a tack-free solid layer having a thickness of 20 micrometres. The dried film is irradiated through a mask for 60 seconds using a 5000 w metal halide lamp at a distance of 75 cm. Development of the irradiated film by immersion in aqueous 3 % sodium hydroxide solution containing0.01 % of a non-ionic fluorocarbon surfactant (used as a 1 % solution in 2-n-butoxy-ethanol) gives a clear positive image of the mask.
Example 18: Example 17 is repeated, replacing Resin VII by an equal amount of Resin VIII, passing the current at 20 volts for 3 seconds to give a dried film thickness of 10 micrometres and developing by immersion in the developer used in Example 6. A clear positive image of the mask is obtained on the l~min~te The copper exposed by development is removed by etching as in Example 1. The residual resin is then removed by re-irradiation as described in Example 1 followed by immersion in aqueous 2 % sodium hydroxide to give a clear image of the mask, in copper, on the l~min~t~ .
Example 19: Resin VII (1.5 g) and Resin XI (2.5 g) are added slowly, with stirring, to 2-n-butoxyethanol (5.0 g). The resulting mixture is neutralised with aqueous 5 %potassium hydroxide and diluted with water to give a dispersion having a 10 % solids content. A resinous film is electrodeposited from the dispersion onto a copper-clad laminate, rinsed, dried, irradiated and developed as in Example 3, but using the laminate as anode and the steel sheet as cathode, the thickness of the dried electrodeposited film being 10 micrometres. A clear positive image of the mask is obtained on the laminate. The copper exposed by development is removed by etching as in Example 1 and the residual resin is removed by the procedure described in Example 3 to give a clear image of the mask, in copper, on the l:~min~tc.
Example 20: Example 19 is repeated, replacing Resin VII by Resin VIII (2.0 g), using 2.0 g of Resin XI, passing the current at 60 volts for 1 minute to give a dried film thickness of 8 micrometres, and developing as in Example 1. A clear positive image of the mask is obtained on the l~min~te. Etching and removal of residual resin as described in Example 1 gives a clear image of the mask, in copper, on the laminate.
's ~
. ~
Example 21: Resin IX (4.0 g) is added slowly, with stirring, to a mixture of 2-n-butoxy-ethanol (5.0 g), oxitol acetate (5.0 g) and 2,4-di(1,2-naphthoquinone-2-diazide-5-sulphonyloxy)benzophenone (0.5 g). The resulting mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 % solids content. A copper-clad I~min~te and a stainless steel sheet are immersed in the dispersion as cathode and anode respectively. An electric current is passed through the dispersion at 10 volts for 1 minute to deposit a resinous film on the l~min:~tf~. The l~min:~te, iS removed from the dispersion, rinsed in a mixture of water and 2-n-butoxyethanol (volume ratio 9:1) and dried for S minutes at 90C, after which the electrodeposited film is a tack-free solid layer having a thickness of 13 micrometres. The dried film is irradiated through a mask for 30 seconds, using a SOOOw metal halide lamp at a distance of 75 cm. Immersion in aqueous 0.5 %
sodium hydroxide containing 0.01 % of a non-ionic fluorocarbon surfactant (used as a 1 %
solution in 2-n-butoxyethanol) gives a clear positive image of the mask on the laminate.
Example 22: Resin IX (2.0 g) and Resin XI (2.0 g) are added slowly, with stirring, to 2-n-butoxyethanol (5.0 g). The mixture is neutralised with lactic acid and diluted with water to give a dispersion having a 10 % solids content. A resinous film is electrodeposited from the dispersion onto a copper-clad laminate, rinsed, dried, irradiated (but for 1 minute) and developed as in Example 3, the thickness of the dried electrodeposited film being 12 micrometres. A clear positive image of the mask is obtained on the l~min~t~,.
.
The copper exposed on development is removed by etching as in Example 1 and the residual resin is removed by the procedure described in Example 3 to give a clear image of the mask, in copper, on the l;~min~te.
Example 23: Example 22 is repeated, replacing the mixture used in that Example by a mixture of Resin X (3.33 g), Resin XI (2.0 g) and 2-n-butoxyethanol (3.17 g), passing the current at 10 volts for 1 minute to give a dried film thickness of 12 micrometres and developing as in Example 1. A clear image of the mask is obtained on the laminate.
The copper exposed by development and the residual resin are removed by the procedure described in Example 1 to give a clear image of the mask, in copper, on the laminate.
Claims (18)
1. A process for the formation of an image on a conductive substrate which comprises (i) electrodepositing on a conductive surface a photosensitive film from an aqueous composition which is a solution or dispersion comprising a mixture of (A) a photo-sensitive o-benzoquinone diazide sulphonyl ester or amide or o-naphthoquinone diazide sulphonyl ester or amide and (B) an electrodepositable film-forming resin, in (C) an aqueous medium, said composition being substantially free from a resin having both a quinone diazide residue and a carboxyl, phosphonic or sulphonic acid group or amino group in the same molecule, in which step the electrodeposition is carried out by immersing the substrate on which the image is to be formed as an electrode in the aqueous composition, immersing a conductive material as another electrode and passing an electric current through the aqueous composition to deposit a photosensitive film of the required thickness on the substrate, (ii) subjecting the electrodeposited film to radiation in a predetermined pattern, such that exposed areas of the film become more soluble in aqueous base than unexposed areas, and (iii) removing the exposed areas by treatment with an aqueous base, and with the proviso that, when compound (A) is a o-benzo- or naphtho-quinone diazide sulfonyl ester compound and compound (B) is an acrylate compound, then the compound (B) is a) a reaction product of an epoxide resin with a primary or secondary monoamine or a secondary diamine, or b) a cationic or cationic/anionic phenolic resin which is a reaction product of a novolak resin, an aldehyde and a primary or secondary amine or an aminocarboxylic acid; or c) a cationic copolymer of a dialkylaminoalkyl acrylate or methacrylate with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers:
or d) an anionic copolymer of acrylic or methacrylic acid with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more vinyl monomers; or e) an anionic copolymer of a vinyl group-containing sulphonic acid with an acrylate or methacrylate ester and, optionally, one or more other vinyl monomers: or f) a cationic/anionic copolymer or a dialkylaminoalkyl acrylate or methacrylate with acrylic acid or methacrylic acid, an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers, with the proviso that the copolymers c), d), e) and f) do not contain an acrylate or methacrylate copolymer component being a 3-acryloyloxy-2-hydroxylpropyl or 3-methacryloyloxy-2-hydroxy-propyl ester of an hydroxybenzoic acid.
or d) an anionic copolymer of acrylic or methacrylic acid with an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more vinyl monomers; or e) an anionic copolymer of a vinyl group-containing sulphonic acid with an acrylate or methacrylate ester and, optionally, one or more other vinyl monomers: or f) a cationic/anionic copolymer or a dialkylaminoalkyl acrylate or methacrylate with acrylic acid or methacrylic acid, an alkyl or hydroxyalkyl acrylate or methacrylate and, optionally, one or more other vinyl monomers, with the proviso that the copolymers c), d), e) and f) do not contain an acrylate or methacrylate copolymer component being a 3-acryloyloxy-2-hydroxylpropyl or 3-methacryloyloxy-2-hydroxy-propyl ester of an hydroxybenzoic acid.
2. A process according to claim 1, in which (A) is an o-benzoquinone diazide sulphonyl ester or o-naphthoquinone diazide sulphonyl ester of a phenol.
3. A process according to claim 1, in which (B) is a resin having an amino, carboxyl or sulphonic acid group which is present in the aqueous composition in at least partially ionized form.
4. A process according to claim 1, in which (B) is a cationic or cationic/anionic phenolic resin which is a reaction product of a novolak resin, an aldehyde and a primary or secondary amine or a aminocarboxylic acid, or secondary amine or an aminocarboxylic acid; or a cationic copolymer of two or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate and at least one of said monomers being an alkyl or hydroxyalkyl acrylate or methacrylate; or an anionic copolymer of two or more vinyl monomers, at least one of said monomers being acrylic or methacrylic acid and at least one of said monomers being an alkyl or hydroxyalkyl acrylate or methacrylate;
an anionic copolymer of two or more vinyl monomers, at least one of said monomers being a vinyl group-containing sulfonic acid and at least one of said monomers being n acrylate or methacralte ester; or a cationic/anionic copolymer of three or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate, at least one of said mono-mers being acrylic acid or methacrylic acid and at least one of said monomers being an alkyl or hydroxyalkyl acrylate or methacrylate.
an anionic copolymer of two or more vinyl monomers, at least one of said monomers being a vinyl group-containing sulfonic acid and at least one of said monomers being n acrylate or methacralte ester; or a cationic/anionic copolymer of three or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate, at least one of said mono-mers being acrylic acid or methacrylic acid and at least one of said monomers being an alkyl or hydroxyalkyl acrylate or methacrylate.
5. A process according to claim 1, in which (B) is a reaction product of (a) a novolak resin derived from phenol or an alkyl-substituted phenol, or a mixture of two or more thereof, and formaldehyde, acetaldehyde or benzaldehyde, (b) formaldehyde, acetaldehyde or benzaldehyde, and (c) an alkanolamine or an aminocarboxylic acid; or a copolymer of two or more vinyl monomers, at least one of said monomers being dimethylaminoethyl acrylate or methacrylate and at least one of said monomers being a C1-C12 alkyl or hydroxyalkyl acrylate or methacrylate; or a copolymer of two or more vinyl monomers, at least one of said monomers being acrylic acid or methacrylic acid and at least one of said monomers being a C1-C12 alkyl or hydroxyalkyl acrylate or methacrylate; or a copolymer of three or more vinyl monomers, at least one of said monomers being an acrylamide containing a sulfonic acid group, at least one of said monomers being an alkyl acrylate or methacrylate and at least on of said monomers being a 3-acryloyloxy-2-hydroxypropyl or 3-methacryloyloxy-2-hydroxypropyl ester of a hydroxybenzoic acid; or a copolymer of three or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate, at least one of said monomers being acrylic or methacrylic acid, and at least one of said monomers being a C1-C12alkyl or hydroxyalkyl acrylate or methacrylate.
6. A process according to claim 5, in which (B) is a reaction product of (a) a novolak resin derived from formaldehyde and either a mixture of o-, m- and p-cresols or a mixture of phenol and p-tert.butylphenol, (b) formaldehyde and (c) diethanolamine, sarcosine or glycine, or a copolymer of dimethylaminoethyl methacrylate with 2-ethylhexyl acrylate, 2-hydroxy-ethyl methacrylate and styrene; or a copolymer of methacrylic acid with methyl methacrylate and 2-hydroxyethyl meth-acrylate or a copolymer of methacrylic acid with methyl methacrylate, 2-ethylhexyl meth-acrylate and 2-hydroxyethyl methacrylate; or a copolymer of 2-acrylamido-2-methyl-1-propanesulfonic acid, 3-methacryloyloxy-2-hydroxypropyl salicylate, methyl methacrylate and n-butyl acrylate, or a copolymer of dimethylaminoethyl methacrylate with acrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate.
7. A process according to claim 1, in which a minor amount, compared with the amount of water, of an organic solvent is included in the aqueous composition.
8. A process according to claim 1, in which (A) is resinous and is present in an amount of 0.5 to 1.5 parts per part by weight of (B); or (A) is non-resinous and is present in an amount of 0.05 to 0.5 part per part by weight of (B)
9. A process according to claim 1, in which the aqueous composition has a solids content of 5 to 20 % by weight.
10. A process according to claim 1, in which the conductive surface is metallic and metal exposed by the development stage (iii) is etched, either to remove the metal or to increase the depth of image, and residual photosensitive film is then removed.
11. A process according to claim 10, in which the residual photosensitive film is removed by subjection to a further, non-imagewise, irradiation followed by treatment with an aqueous base.
12. An aqueous composition suitable for use in a process according to claim 1, which is a solution or dispersion comprising a mixture of (A) a photosensitive o-benzoquinone diazide sulphonyl ester or amide or o-naphthoquinone diazide sulphonyl ester or amine and (B) an electrodepositable film-forming resin, in (C) an aqueous medium, saidcomposition being substantially free from a resin having both a quinone diazide residue and a carboxyl, phosphonic or sulphonic acid group or amino group in the same molecule.
13. A composition according to claim 12, in which (A) is an o-benzoquinone diazide sulphonyl ester or o-naphthoquinone diazide sulphonyl ester of a phenol.
14. A composition according to claim 12, in which (B) is a resin having an amino, carboxyl or sulphonic acid group which is present in at least partially ionized form.
15. A composition according to claim 14, in which (B) is a cationic or cationic/anionic phenolic resin which is a reaction product of a novolak resin, an aldehyde and a primary or secondary amine or an aminocarboxylic acid, or a cationic copolymer of two or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate and at least one of said monomers being an alkyl or hydroxyalkyl acrylate or methacrylate; or an anionic copolymer of two or more vinyl monomers, at least one of said monomers being acrylic or methacrylic acid and at least one of said monomers being an alkyl or hydroxyalkyl acrylate or methacrylate;
an anionic copolymer or two or more vinyl monomers, at least one of said monomers being a vinyl group-containing sulfonic acid and at least one of said monomers being an acrylate or methacrylate ester; or a cationic/anionic copolymer of three or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate, at least one of said monomers being acrylic acid or methacrylic acid and at least one of said monomers being an alkyl or hydroxyalkyl acrylate or methacrylate.
an anionic copolymer or two or more vinyl monomers, at least one of said monomers being a vinyl group-containing sulfonic acid and at least one of said monomers being an acrylate or methacrylate ester; or a cationic/anionic copolymer of three or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate, at least one of said monomers being acrylic acid or methacrylic acid and at least one of said monomers being an alkyl or hydroxyalkyl acrylate or methacrylate.
16. A composition according to claim 15, in which (B) is a reaction product of (a) a novolak resin derived from phenol or an alkyl-substituted phenol, or a mixture of two or more thereof, and formaldehyde, acetaldehyde or benzaldehyde.
(b) formaldehyde, acetaldehyde or benzaldehyde, and (c) an alkanolamine or an aminocarboxylic acid, or or (B) is a copolymer of two or more vinyl monomers, at least one of said monomers being dimethylaminoethyl acrylate or methacrylate and at least one of said monomers being a C1-C12 alkyl or hydroxyalkyl acrylate or methacrylate; or a copolymer of two or more vinyl monomers, at least one of said monomers being acrylic acid or methacrylic acid and at least one of said monomers being a C1-C1 alkyl or hydroxyalkyl acrylate or methacrylate; or a copolymer of three or more vinyl monomers, at least one of said monomers being an acrylamide containing a sulfonic acid group, at least one of said monomers being an alkyl acrylate or methacrylate and at least one of said monomers being a 3-acryloyloxy-2-hydroxypropyl or 3-methacryloyloxy-2-hydroxypropyl ester or a hydroxybenzoic acid; or a copolymer of three or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate, at least one of said monomers being acrylic or methacrylic acid and at least one of said monomers being a C1 to C12 alkyl or hydroxyalkyl acrylate or methacrylate.
(b) formaldehyde, acetaldehyde or benzaldehyde, and (c) an alkanolamine or an aminocarboxylic acid, or or (B) is a copolymer of two or more vinyl monomers, at least one of said monomers being dimethylaminoethyl acrylate or methacrylate and at least one of said monomers being a C1-C12 alkyl or hydroxyalkyl acrylate or methacrylate; or a copolymer of two or more vinyl monomers, at least one of said monomers being acrylic acid or methacrylic acid and at least one of said monomers being a C1-C1 alkyl or hydroxyalkyl acrylate or methacrylate; or a copolymer of three or more vinyl monomers, at least one of said monomers being an acrylamide containing a sulfonic acid group, at least one of said monomers being an alkyl acrylate or methacrylate and at least one of said monomers being a 3-acryloyloxy-2-hydroxypropyl or 3-methacryloyloxy-2-hydroxypropyl ester or a hydroxybenzoic acid; or a copolymer of three or more vinyl monomers, at least one of said monomers being a dialkylaminoalkyl acrylate or methacrylate, at least one of said monomers being acrylic or methacrylic acid and at least one of said monomers being a C1 to C12 alkyl or hydroxyalkyl acrylate or methacrylate.
17. A composition according to claim 16, in which (B) is a reaction product of (a) a novolak resin derived from formaldehyde and either a mixture of o-, m- and p-cresols or a mixture of phenol an p-tert.butylphenol, (b) formaldehyde and (c) diethanolamine, sarcosine or glycine, or a copolymer of dimethylaminoethyl methacrylate with 2-ethylhexyl acrylate, 2-hydroxy-ethyl methacrylate and styrene; or a copolymer of methacrylate acid with methyl methacrylate and 2-hydroxyethyl meth-acrylate or a copolymer of methacrylic acid with methyl methacrylate, 2-ethylhexyl meth-acrylate and 2-hydroxyethyl methacrylate; or a copolymer of 2-acrylamido-2-methyl- 1-propanesulfonic acid, 3-methacryloyloxy-2-hydroxypropyl salicylate, methyl methacrylate and n-butyl acrylate; or a copolymer of dimethylaminoethyl methacrylate with acrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate.
18. A composition according to claim 1, which contains a minor amount, compared with the amount of water, of an organic solvent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8625383 | 1986-10-23 | ||
| GB868625383A GB8625383D0 (en) | 1986-10-23 | 1986-10-23 | Forming images |
| GB878704061A GB8704061D0 (en) | 1987-02-20 | 1987-02-20 | Forming images |
| GB8704061 | 1987-02-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1336047C true CA1336047C (en) | 1995-06-27 |
Family
ID=26291447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000549805A Expired - Fee Related CA1336047C (en) | 1986-10-23 | 1987-10-21 | Method of forming images |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5080998A (en) |
| EP (2) | EP0662636A3 (en) |
| JP (1) | JP2704619B2 (en) |
| CA (1) | CA1336047C (en) |
| DE (1) | DE3751598T2 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4939229A (en) * | 1989-05-12 | 1990-07-03 | Rohm And Haas Company | Method for preparing lithographically sensitive branched novolaks using a mannich base intermediate |
| JP2847321B2 (en) * | 1990-08-14 | 1999-01-20 | 日本石油株式会社 | Positive photoresist composition |
| GB9101345D0 (en) * | 1991-01-22 | 1991-03-06 | Ciba Geigy | Electrodeposition method |
| JP2677460B2 (en) * | 1991-02-14 | 1997-11-17 | 日本ペイント株式会社 | Alkali developable photosensitive resin composition |
| JPH04258957A (en) * | 1991-02-14 | 1992-09-14 | Nippon Paint Co Ltd | Positive type photosensitive electrodepositable resin compoition |
| US5223373A (en) * | 1991-04-29 | 1993-06-29 | Industrial Technology Research Institute | Positive working photosensitive composition and photosensitive electrodeposition composition prepared therefrom |
| US5314789A (en) * | 1991-10-01 | 1994-05-24 | Shipley Company Inc. | Method of forming a relief image comprising amphoteric compositions |
| US5242780A (en) * | 1991-10-18 | 1993-09-07 | Industrial Technology Research Institute | Electrophoretic positive working photosensitive composition comprising as the photosensitive ingredient an aliphatic polyester having o-quinone diazide on the side chain and end groups |
| US5384229A (en) * | 1992-05-07 | 1995-01-24 | Shipley Company Inc. | Photoimageable compositions for electrodeposition |
| US5624781A (en) * | 1993-05-28 | 1997-04-29 | Kansai Paint Co., Ltd. | Positive type anionic electrodeposition photo-resist composition and process for pattern formation using said composition |
| DE19530630A1 (en) * | 1995-08-21 | 1997-02-27 | Hoechst Ag | Process for the preparation of methyl-substituted polyalkylidene polyphenols |
| JP3796982B2 (en) * | 1998-06-02 | 2006-07-12 | 住友化学株式会社 | Positive resist composition |
| JP4644330B2 (en) * | 1999-03-10 | 2011-03-02 | 関西ペイント株式会社 | Cationic electrodepositable resin composition |
| US6482943B1 (en) | 1999-04-30 | 2002-11-19 | Slil Biomedical Corporation | Quinones as disease therapies |
| US6649587B1 (en) | 1999-04-30 | 2003-11-18 | Slil Biomedical Corporation | Polyamine analog conjugates and quinone conjugates as therapies for cancers and prostate diseases |
| EP1173223A2 (en) * | 1999-04-30 | 2002-01-23 | Slil Biomedical Corporation | Conjugates as therapies for cancers and prostate diseases |
| US7312244B2 (en) * | 1999-04-30 | 2007-12-25 | Cellgate, Inc. | Polyamine analog-amino acid conjugates useful as anticancer agents |
| DE10112023A1 (en) * | 2001-03-07 | 2002-10-02 | Atotech Deutschland Gmbh | Method of forming a metal pattern on a dielectric substrate |
| DE10337506A1 (en) * | 2003-08-14 | 2005-03-17 | Kodak Polychrome Graphics Gmbh | Heat-sensitive positive-working lithographic printing plate precursor |
| KR102466198B1 (en) | 2017-01-20 | 2022-11-14 | 에보니크 오퍼레이션즈 게엠베하 | Glycerol (meth)acrylate carboxylic acid esters with long shelf life |
| JP7004216B2 (en) * | 2018-04-20 | 2022-02-10 | 日油株式会社 | Copolymer for overcoat material or resist resin |
| EP3611155A1 (en) | 2018-08-16 | 2020-02-19 | Evonik Operations GmbH | Preparation of (meth)acrylic acid esters |
Family Cites Families (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3551154A (en) * | 1966-12-28 | 1970-12-29 | Ferrania Spa | Light sensitive article comprising a quinone diazide and polymeric binder |
| US3890153A (en) * | 1971-03-13 | 1975-06-17 | Philips Corp | Positive-acting napthoquinone diazide photosensitive composition |
| AU4415872A (en) * | 1971-08-11 | 1974-01-10 | Ppg Industries Inc | Electrodepositable micellar dispersion |
| JPS5221526B2 (en) * | 1972-01-10 | 1977-06-11 | ||
| US4129544A (en) * | 1976-04-29 | 1978-12-12 | E. I. Du Pont De Nemours And Company | Aqueous acrylic coating composition for electrical conductors |
| GB1588417A (en) * | 1977-03-15 | 1981-04-23 | Agfa Gevaert | Photoresist materials |
| JPS5498244A (en) * | 1978-01-20 | 1979-08-03 | Toray Industries | Method of forming positive photo resist image |
| JPS555913A (en) * | 1978-06-28 | 1980-01-17 | Toray Ind Inc | Photochemically reactive formed material |
| US4268602A (en) * | 1978-12-05 | 1981-05-19 | Toray Industries, Ltd. | Photosensitive O-quinone diazide containing composition |
| JPS56122031A (en) * | 1980-03-01 | 1981-09-25 | Japan Synthetic Rubber Co Ltd | Positive type photosensitive resin composition |
| US4362853A (en) * | 1980-10-24 | 1982-12-07 | Ciba-Geigy Corporation | Resinous salts, their preparation, and their use in coatings |
| JPS57150844A (en) * | 1981-03-13 | 1982-09-17 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
| JPS57150884A (en) * | 1981-03-14 | 1982-09-17 | Tokyo Shibaura Electric Co | System for depleting picture image |
| JPS57178238A (en) * | 1981-04-27 | 1982-11-02 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
| JPS57192952A (en) * | 1981-05-25 | 1982-11-27 | Konishiroku Photo Ind Co Ltd | Composition of developing solution |
| US4529682A (en) * | 1981-06-22 | 1985-07-16 | Philip A. Hunt Chemical Corporation | Positive photoresist composition with cresol-formaldehyde novolak resins |
| JPS58134631A (en) * | 1982-01-08 | 1983-08-10 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
| US4414311A (en) * | 1982-03-18 | 1983-11-08 | American Hoechst Corporation | Cathodic deposition of light sensitive components |
| JPS59193453A (en) * | 1983-04-18 | 1984-11-02 | Ricoh Co Ltd | Image forming material |
| DE3586263D1 (en) * | 1984-03-07 | 1992-08-06 | Ciba Geigy Ag | METHOD FOR PRODUCING IMAGES. |
| US4592816A (en) * | 1984-09-26 | 1986-06-03 | Rohm And Haas Company | Electrophoretic deposition process |
| US4632891A (en) * | 1984-10-04 | 1986-12-30 | Ciba-Geigy Corporation | Process for the production of images |
| DE3442756A1 (en) * | 1984-11-23 | 1986-05-28 | Hoechst Ag, 6230 Frankfurt | RADIATION-SENSITIVE MIXTURE, RECORDING MATERIAL MADE THEREOF, AND METHOD FOR THE PRODUCTION OF HEAT-RESISTANT RELIEF RECORDINGS |
| GB8505402D0 (en) * | 1985-03-02 | 1985-04-03 | Ciba Geigy Ag | Modified phenolic resins |
| JPS61206293A (en) * | 1985-03-08 | 1986-09-12 | 日本ペイント株式会社 | Manufacture of circuit board |
-
1987
- 1987-10-19 EP EP95104396A patent/EP0662636A3/en not_active Withdrawn
- 1987-10-19 DE DE3751598T patent/DE3751598T2/en not_active Expired - Fee Related
- 1987-10-19 EP EP87810602A patent/EP0265387B1/en not_active Expired - Lifetime
- 1987-10-21 CA CA000549805A patent/CA1336047C/en not_active Expired - Fee Related
- 1987-10-22 JP JP62267615A patent/JP2704619B2/en not_active Expired - Fee Related
-
1990
- 1990-12-17 US US07/629,099 patent/US5080998A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3751598T2 (en) | 1996-04-18 |
| JP2704619B2 (en) | 1998-01-26 |
| US5080998A (en) | 1992-01-14 |
| EP0662636A2 (en) | 1995-07-12 |
| JPS63141048A (en) | 1988-06-13 |
| EP0265387A3 (en) | 1990-02-07 |
| EP0662636A3 (en) | 1995-11-22 |
| EP0265387A2 (en) | 1988-04-27 |
| EP0265387B1 (en) | 1995-11-15 |
| DE3751598D1 (en) | 1995-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1336047C (en) | Method of forming images | |
| US4632900A (en) | Process for the production of images after electrodeposition of positive photoresist on electrically conductive surface | |
| EP0194824B1 (en) | A method for preparing a printed circuit board | |
| EP0354018A2 (en) | An electrodeposition coating composition and image-forming method using the same | |
| US5002858A (en) | Process for the formation of an image | |
| CA2028386A1 (en) | Method for making metallic patterns | |
| KR100286598B1 (en) | Formation method of positive photosensitive resin composition and resist pattern | |
| US5232816A (en) | Positive type photosensitive resinous composition comprising a resin copolymer having at least a phosphoric acid ester monomer | |
| EP0302827B1 (en) | Process for the formation of images | |
| CA1334897C (en) | Electrodeposition coating composition and image-forming method using the same | |
| CA1319776C (en) | Process for the production of images | |
| US5422222A (en) | Electrodeposition coating composition | |
| CA1333578C (en) | Production of metallic patterns | |
| JPS636070A (en) | Positive photosensitive electrodeposition coating | |
| JPH04345164A (en) | Photosensitive quinone diazide compound and positive type photosensitive composition and photosensitive electrodeposition coating composition containing the compound | |
| EP0496554A1 (en) | Electrodeposition method | |
| JPH03281671A (en) | Electrodeposition positive photoresist composition | |
| JPS63221178A (en) | Positive type photosensitive cationic electrodeposition paint composition | |
| JPH05117557A (en) | Positive type photosensitive anion electrodeposition coating resin composition, electrodeposition coating bath using the same, preparation of resist pattern and production of print circuit board and print circuit board | |
| JPH04198372A (en) | Positive type photosensitive anion electrodeposition coating composition | |
| JPH0683048A (en) | Positive photosensitive resin composition | |
| JPH04198370A (en) | Positive type photosensitive cation electrodeposition coating composition | |
| JPS63221177A (en) | Positive type photosensitive anionic electrodeposition paint composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |