GB2299585A - Coating compositions - Google Patents

Coating compositions Download PDF

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Publication number
GB2299585A
GB2299585A GB9507101A GB9507101A GB2299585A GB 2299585 A GB2299585 A GB 2299585A GB 9507101 A GB9507101 A GB 9507101A GB 9507101 A GB9507101 A GB 9507101A GB 2299585 A GB2299585 A GB 2299585A
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GB
United Kingdom
Prior art keywords
coating
composition
ethylenically unsaturated
substrate
carboxylic 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.)
Withdrawn
Application number
GB9507101A
Other versions
GB9507101D0 (en
Inventor
Stephen Anthony Hall
Nicholas Eric Ivory
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coates Brothers and Co Ltd
Original Assignee
Coates Brothers and Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Coates Brothers and Co Ltd filed Critical Coates Brothers and Co Ltd
Priority to GB9507101A priority Critical patent/GB2299585A/en
Publication of GB9507101D0 publication Critical patent/GB9507101D0/en
Priority to US08/930,634 priority patent/US5990189A/en
Priority to DE69605295T priority patent/DE69605295D1/en
Priority to EP96909268A priority patent/EP0819267B1/en
Priority to AU52832/96A priority patent/AU5283296A/en
Priority to PCT/GB1996/000861 priority patent/WO1996031806A1/en
Publication of GB2299585A publication Critical patent/GB2299585A/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer

Abstract

Photopolymerisable material, suitable for use in the production of photopolymerisable coatings or resists on, for example, printed circuit boards, is an ethylenically unsaturated polymerisable reaction product of a polyepoxide and a mixture of (i) a major proportion of an ethylenically unsaturated carboxylic acid and (ii) a minor proportion of a saturated aliphatic or aromatic carboxylic acid; further modified by reaction with a dicarboxylic acid or anhydride thereof.

Description

COATING COMPOSITIONS This invention is concerned with improvements in and relating to coating compositions and more particularly is concerned with coating compositions for the production of photopolymerizable coatings upon substrates.
In order to provide for the attachment of electrical components to a printed circuit board of the type comprising a patterned layer of an electroconductive metal (generally copper) on an electrically non-conductive substrate (generally a plastics impregnated substrate) a patterned layer of a solder resist is applied to the board so as to expose parts of the patterned metal layer and the so-coated board is contacted with molten solder so that the solder adheres to the patterned metal layer at the exposed portions thereof. Generally, before the board is contacted with the solder, the electrical components are placed on the other side of the board (although, of course, not in the case of surface-mounted boards) with conducting elements extending therefrom passing through holes in the board into the exposed portions of the patterned metal layer.
It has now been found, in accordance with the present invention, that a patterned solder resist may be formed from a photopolymerizable composition comprising a modified epoxy resin, as hereinafter defined, by exposing a layer of such a composition to actinic radiation through a suitable transparent substrate bearing an opaque image, and subsequently, in a "development" step, removing unexposed composition with a solvent therefor, namely an aqueous alkaline solution.
According to one embodiment of the invention, therefore, there is provided an ethylenically unsaturated polymerizable reaction product of a polyepoxide and a mixture of (i) a major proportion of an ethylenically unsaturated carboxylic acid and (ii) a minor proporation of a saturated aliphatic or aromatic carboxylic acid, further modified by reaction with a dicarboxylic acid or anhydride thereof.
The invention also provides a coating composition, for the production of a photopolymerizable coating, comprising a modified reaction product as described above together with a photopolymerization initiator for the said polymerizable reaction product and a liquid carrier.
Preferably, the composition also contains an inert inorganic filler, the said filler and the said reaction product suitably being present in a ratio of from 5 to 25 parts by weight of filler to from 95 to 75 parts by weight of the modified reaction product.
The invention also provides a method of forming a photopolymerizable coating upon a substrate which comprises applying a coating of a coating composition as defined above to the substrate and allowing it to dry by evaporation of the liquid carrier.
The modified reaction product of polyepoxide and ethylenically unsaturated carboxylic acid, generally acrylic acid or methacrylic acid, is hereinafter simply referred to as the "modified epoxy acrylate". The modified epoxy acrylate should preferably be solid or semi-solid at ambient temperature, e.g. should preferably have a ring and ball softening point (determined according to British Standard Specification No. 4692 of 1971) of at least 300C, preferably at least 6O0C. The unmodified epoxy acrylate is one derived from the reaction of a polyepoxide and a mixture of an ethylenically unsaturated carboxylic acid or reactive derivative thereof and a saturated aliphatic or aromatic carboxylic acid or reactive derivative thereof. The polyepoxide is preferably an aromatic polyepoxide.
Aromatic polyepoxides are polyepoxides containing phenyl groups (polyphenyl polyepoxides) such as polyepoxides derived from the reaction of bisphenols, especially polynuclear bisphenols such as bisphenol-A, with epichlorohydrin, or epoxidised phenol or cresol novolacs, the latter being especially preferred.
Aromatic polyepoxides are well known materials and are described, for example in "Chemistry of Organic Film Formers", Solomon D.H., 2nd Edition, Krieger Publishing, 1977, at pages 188, 189 and 192.
The polyepoxide is first reacted with a mixture of a major proportion of an ethylenically unsaturated carboxylic acid and a minor proportion of a saturated aliphatic or aromatic carboxylic acid. Suitably the said mixture comprises from 65 to 90 mole% of unsaturated acid, preferably 75 to 85 mole thereof; the balance being saturated acid. Suitable unsaturated acids include monocarboxylic acids such as acrylic and methacrylic acids. Suitable saturated aliphatic acids include aliphatic monocarboxylic acids containing from 2 to 22 carbon atoms, preferably 4 to 16 carbon atoms, such as ethanoic, pentanoic, iso-butyric and stearic acids. Suitable saturated aromatic acids are acids containing from 7 to 9 carbon atoms, such as benzoic, methylbenzoic and ethylbenzoic acids.The use of such saturated acids has been found to improve the toughness and/or flexibility of the acid coating finally formed from the modified epoxy acrylates. The polyepoxide will generally be reacted with the mixture of acids in approximately stoichiometric amounts of carboxylic acid groups to epoxide groups. Thus, the ratio of carboxylic acid groups to epoxy groups is suitably from 0.95:1 to 1:1.
The unmodified epoxy acrylate is subsequently modified by reaction with a dicarboxylic acid generally in the form of an anhydride, suitably to give a product having an acid value of from 30 to 130 mgKOH/g, preferably from 35 to 80 mgKOH/g. A wide variety of anhydrides may be employed to the purpose of modification and examples of these include succinic, didodecylsuccinic itaconic, citraconic, maleic, phthalic, hexahydrophthalic, tetrahydrophthalic, methylnadic and trimellitic anhydrides.
The photopolymerization initiator used in the compositions of the invention serves to induce polymerization of the epoxy acrylate when the composition, after application to a substrate, is subjected to actinic radiation. A wide variety of such photopolymerization initiators are known in the art, such as benzoin ethers and anthraquinone derivatives.
Preferred initiators for use in the compositions of the invention are phenyl ketone initiators such as benzophenone, acetophone or Mischlers ketone or mixtures thereof.
The initiator is suitably present in the composition in an amount of from 1 to 10% by weight, based on the weight of the epoxy acrylate.
The compositions of the invention also contain a liquid carrier. This may, for example, be an organic solvent for the modified epoxy acrylate, with the modified epoxy acrylate dissolved therein, and examples of such solvents include lower carboxylic acid ester of lower alcohols (e.g. isopropyl acetate), lower dialkyl ethers (such as diethyl ether), ketones (such as acetone or methyl ethyl ketone), or, preferably, hydroxyalkyl ethers such as glycol monoethyl ether and ethylene glycol monobutyl ether.
Alternatively the carrier may comprise water with the modified epoxy acrylate dispersed as a solid therein or an organic solvent solution of the modified epoxy resin emulsified therein. Such compositions are described, for example, in EP-A-0536272 and EP-A-0573426.
The amount of carrier present in a coating composition of the invention as applied to a substrate (e.g. a printed circuit board) will, to some extent, depend upon the nature of the method by which the composition is to be applied to the substrate. Thus, where the composition is to be applied to a substrate by, for example, a screen printing process, it may contain up to 30% by weight of carrier whereas if it is to be applied to the substrate by a curtain coating process it may contain up to 50% by weight of carrier.
The compositions of the invention may conveniently be formulated containing a lower amount of carrier than is required in the actual application process, the additional carrier required being added to the composition to dilute it prior to the application process.
The filler, which will be in powdered or finely divided form, serves to improve the resistance of the composition, when used as a solder resist, to heat or thermal shock such as is experienced when the cured composition is brought into contact with molten solder.
The filler should, when the coating composition is employed in the production of a solder resist, not be one which undergoes thermal decomposition when heated by contact with molten solder and examples of suitable fillers include blanc fixed, aluminium hydrate, china clay, calcium carbonate (coated or uncoated) and micronised talc, or mixtures thereof. The weight ratio of filler to modified epoxy acrylate is from 5 - 25 : 95 - 75, preferably from 10 - 20 : 90 - 80, more preferably from 15 - 20 : 85 - 80.
In general, in order to provide a generally tack-free coating from the composition (as is described below), it is preferable, when using less solid modified epoxy acrylates (i.e. those having lower softening temperatures), to employ higher levels of inorganic fillers, but, of course, within the broad range noted above.
The coating compositions of the invention also suitably contain a colorant, for example an organic pigment such as a chlorinated phthalocyanine pigment, in order that the application of the composition to a substrate provides a visible image. Suitably such colorants will be present in amounts of up to 5% by weight, based on the weight of epoxy acrylate, filler and initiator, preferably from 0.5 - 2% by weight thereof. The coating compositions of the invention may also contain antifoaming agents, such as silicone oils, in order to improve their application properties and such antifoaming agents may be present in amounts similar to those given above for the coloring agents.
Whilst the compositions of the invention contain the modified epoxy acrylate as principal photopolymerizable ingredient, other photopolymerizable materials may be present and examples of such include esters of mono- or polyhydric alcohols with ethylenically unsaturated carboxylic acids such as acrylic or methacrylic acid, and liquid epoxy acrylates. Such other photopolymerizable materials are not, however, essential and when used it is preferred that they be employed in minor amounts as compared with the modified epoxy acrylate, e.g. in amounts of less than 25%, preferably less than 10%, of the weight of the modified epoxy acrylate.
A coating composition of the invention is used to form a photopolymerizable coating upon a substrate by applying it to the substrate by an convenient method, such as screen printing, curtain coating, roller coating or spray coating, and then allowing the applied coating to dry to a tack-free condition (i.e. to a condition such that it does not adhere to a surface with which it may come into contact) and generally this drying will be accelerated by heating the applied coating.
The resultant coating may be polymerized by exposure to actinic radiation, for example from a source such as a mercury vapour lamp.
As indicated above, a polymerizable coating obtained from a coating composition of the invention is particularly suitable for use in the production of a solder resist in a process for the manufacture of a printed circuit board. It should, however, be noted that such a polymerizable coating may also be used as to form a patterned etch or plating resist since the coating is acid and alkali resistant (it being possible to later wholly remove the coating by treatment with a hot dilute aqueous alkaline solution such as 5% aqueous sodium hydroxide solution, although such removal may not be necessary when the coating is used in the definition of inner layers in a multilayer construction since it is chemically compatible with adhesives used to bond multilayer constructions).
A further embodiment of the invention provides a method of forming a pattern of solder upon a layer of an electrically conductive metal supported on an electrically non-conductive substrate by providing the metal layer with a patterned resist coating, whereby portions of the metal layer are coated with the solder resist coating and other portions of the metal layer are not so coated, and contacting the metal layer provided with the solder resist coating with molten solder whereby solder adheres to the portions of the metal layer not coated with the solder resist coating, in which the solder resist coating is formed by polymerizing, by exposure to actinic radiation, a photopolymerizable coating obtained by applying a coating composition in accordance with the invention to the metal layer and allowing it to dry.
One such process comprises the steps of: (a) providing a circuit board having a patterned layer of a conductive metal (hereinafter simply referred to as copper) with a coating of a coating composition of the invention, at least over the copper layer, for example by screen printing process, by a curtain coating process or by electrostatic spray deposition, in all cases the coating of the composition will extend over the whole of the surface of the board; (b) allowing the coated composition to dry to a tack-free, i.e. by evaporation of volatile organic solvent therefrom.
(c) exposing the coated board to actinic radiation through a positive for the desired solder pattern (i.e. a transparency, generally a photographic transparency, having light transmitting portions corresponding to the non-solderable portion of the desired solder pattern and non-transmitting portions corresponding to the solderable portions of the desired solder pattern) to cure the exposed portions of the coating, i.e. to photopolymerize the photomerizable material therein; (d) removing the non-exposed portions of the coating by means of aqueous alkaline solution (e.g. sodium carbonate solution); and (e) contacting the board having a patterned coating image with molten solder, e.g. in the form of a so-called "standing wave" of solder, to apply solder to the board in the desired pattern.
This process makes it possible to provide circuit boards with a patterned solder resist of high definition and accuracy since, in general, exposure through a positive to actinic radiation provides for good accuracy and definition which is of importance as the overall size of circuit boards, and hence the size of individual parts of the solder resist pattern, decrease, a tendency which as been noted recently. It is to be noted that in the above process, step (e) follows directly from step (d), that is there is no requirement for a heat-curing step after radiation curing. However, if desired such a heat-curing step may be employed.
In this case the composition applied to the board preferably also contains a thermal curing agent which will assist thermal curing of the modified epoxy acrylate. Suitable thermal curing agents include polyamines, polyamino resins, dicyandiamide, melamine derivatives and blocked isocyanurate materials. Where the composition applied to tne board contains a thermal curing agent it is generally more convenient to put the system up as a two-part system, one part containing the modified epoxy acrylate and the other part containing the curing agent therefor. Suitable two-part systems, employing aqueous carriers are disclosed in WO 93/06350.
The circuit board having a patterned layer of copper thereon used as starting material in step (a) of the process described above may be produced in a number of ways, either by the so-called "subtractive" method or by the so-called "additive" method.
In the subtractive method a laminate comprising a layer of copper on a non-conducting substrate is first provided with a positive patterned image of an acid-resisting coating and the exposed copper is then etched away with a suitable acidic etchant, e.g. acid cupric chloride, the remaining copper then being exposed by removal of the acid-resisting coating. A coating of acid-resistant material may, as is well-known, be applied by a patterned coating method, such as a screen printing method, or by coating the copper with a layer of a photosensitive composition and subsequently exposing this to light through a positive or negative image of the desired copper layer, depending on whether the resist coating is a so-called positive or negative working resist and subsequently removing the developable (i.e. solvent-soluble) portions of the image with a suitable solvent.
The compositions of the invention are, themselves, perfectly suitable for use as negative working resists, i.e. resists the exposed portions of which are cured to give an insoluble coating. Thus, the circuit boards having a patterned layer of copper on the surface thereof may be provided by firstly coating a copper-clad substrate with a coating composition of the invention, allowing the coating to dry, exposing the dried coating to actinic radiation through a positive of the desired copper layer pattern to cure the portion of the coating exposed to radiation, removing the uncured portion of the coating with a solvent there for and subsequently etching the coated board. The cured coating may then be removed by washing with a solvent therefor, e.g. aqueous sodium hydroxide solution. The board may then be provided with a patterned solder coating as described above.
In the additive method for the preparation of the board having a patterned layer of copper, a non-conductive substrate is first coated with an activating material for a so-called electroless copper plating solution, the board is then provided with a negative patterned image of a resist coating, and the board is then immersed in an electroless copper plating solution to form a layer of copper on the exposed portions of the board, i.e. those not covered with the resist. Here again the composition of the invention may be used to form the resist layer, for example by coating the activated board with a layer of the coating composition, allowing it to dry and exposing it to actinic radiation through an appropriate positive of the circuit pattern so that the exposed portion of the coating is photo hardened, the non-exposed portion subsequently being removed with a suitable solvent.
Whilst the compositions of the invention are photosensitive, they are not effectively sensitive to subdued light or light having a wavelength above 420 nanometers. Thus the initial application of.the coating composition to a substrate can be carried out in the light (although of course not light having a high amount of actinic radiation).
In order that the invention may be well understood the following examples are given by way of illustration only. In the examples all parts are by weight unless otherwise stated.
Example 1 A photoimageable resin was produced by reacting an epoxy cresol novolak resin (Quatrex 3410, Dow Chemicals) (40 parts) dissolved in propylene glycol diacetate (30.7 parts), with acrylic acid and benzoic acid (12 parts and 3 parts respectively) in the presence of hydroquinone (0.1 parts) and triphenyl phosphine (0.2). The resulting acrylated resin was then carboxylated with tetrahydrophthalic anhydride (14 parts).This photoreactive resin was then incorporated in the following photoimageable ink formula: Material Parts Photoimageable Resin 58 Tris (2-hydroxy ethyl) 3 isocyanurate triacrylate Irgacure 903 5 (Ciba Geigy) Quantacure ITX 1 (Biosynthetics Inc.) Propylene glycol diacetate 3 Barium sulphate 21 Talc 5 Colour concentrate 3 Byk-OSS (Byk Chemicals) 1 This formulation was printed on to the photocured resist layer using a 32T mesh silk screen and dried at 90C for 15 minutes to give a tack free finish. The resultant film was 30 microns thick. The resist layer was then photoimaged through a suitable art work at an 2 exposure level of 400 mJoules/cm2 and the desired pattern developed using 0.6* w/w sodium carbonate solution at 400C.The resultant film showed good resolution of the phototool design and displayed good resistance to solder at 2300C; once it had been given a further W cure of 2000 mJoules/cm2.
Example 2 A photoimageable resin was produced as described above, but the acids reacted with the epoxy cresol novolak were acrylic acid (14 parts) and stearic acid (10 parts), the other proportions of constituents being altered accordingly. This resin was included in the following ink formulation.
Material Parts Photoimageable Resin 65 Irgacure 903 7 (Ciba Geigy) Quantacure ITX 1 (Biosynthetics Inc.) Pigment Concentrate 6 Flow aid 2 Antifoam 2 Talc 13 Propylene Glycol Diacetate 3 Dicyandiamide 3 A thermal curing agent for the above ink was produced my mixing the following ingredients: Material Parts Epoxy cresol novolak resin 30 Propylene glycol diacetate 25 Tris (2-hydroxy ethyl) 15 isocyanurate triacrylate Talc 30 This thermal curing agent was mixed with the ink above in the ratio of 2 parts ink to 1 part thermal cure agent. The mixed ink was then printed through a 32T silk screen and dried at 900C to produce a dry film thickness of 25 microns. This tack free film was exposed through suitable solder mask artwork and the unexposed areas developed away using a weak solution of sodium carbonate. The imaged film was then given a thermal bake at 1500C for one hour to yield a fully cured film which was resistant to solder at 2300C and showed good resolution of the original artwork pattern.

Claims (4)

CLAIMS:
1. An ethylenically unsaturated material which is an ethylenically unsaturated polymerisable reaction product of a polyepoxide and a mixture of (i) a major proportion of an ethylenically unsaturated carboxylic acid and (ii) a minor proportion of a saturated aliphatic or aromatic carboxylic acid; further modified by reaction with a dicarboxylic acid or anhydride thereof.
2. A coating composition, for the production of a photopolymerisable coating, comprising an ethylenically unsaturated material as claimed in claim 1 together with a photopolymerisation initiator therefor and a liquid carrier.
3. A composition as claimed in claim 2 also containing an inert organic filler.
4. A method of forming a photopolymerisable coating upon a substrate which comprises applying a coating of a coating composition as defined above to the substrate and allowing it to dry by evaporation of the liquid carrier.
GB9507101A 1995-04-06 1995-04-06 Coating compositions Withdrawn GB2299585A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
GB9507101A GB2299585A (en) 1995-04-06 1995-04-06 Coating compositions
US08/930,634 US5990189A (en) 1995-04-06 1996-04-04 Coating compositions
DE69605295T DE69605295D1 (en) 1995-04-06 1996-04-04 COATING COMPOSITIONS
EP96909268A EP0819267B1 (en) 1995-04-06 1996-04-04 Coating compositions
AU52832/96A AU5283296A (en) 1995-04-06 1996-04-04 Coating compositions
PCT/GB1996/000861 WO1996031806A1 (en) 1995-04-06 1996-04-04 Coating compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9507101A GB2299585A (en) 1995-04-06 1995-04-06 Coating compositions

Publications (2)

Publication Number Publication Date
GB9507101D0 GB9507101D0 (en) 1995-05-31
GB2299585A true GB2299585A (en) 1996-10-09

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Family Applications (1)

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GB9507101A Withdrawn GB2299585A (en) 1995-04-06 1995-04-06 Coating compositions

Country Status (6)

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US (1) US5990189A (en)
EP (1) EP0819267B1 (en)
AU (1) AU5283296A (en)
DE (1) DE69605295D1 (en)
GB (1) GB2299585A (en)
WO (1) WO1996031806A1 (en)

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GB2318796A (en) * 1996-10-25 1998-05-06 Coates Brothers Plc Coating compositions
WO1998049214A1 (en) * 1997-04-25 1998-11-05 The Dow Chemical Company Nitrogen-containing epoxy resins for photocurable coating applications
WO2023095783A1 (en) * 2021-11-29 2023-06-01 味の素株式会社 Resin composition containing modified vinyl ester resin

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US6555592B2 (en) * 2001-02-27 2003-04-29 Advance Materials Corporation Photothermosetting composition comprising acrylated epoxy resin
GB0117155D0 (en) * 2001-07-13 2001-09-05 Coates Electrographics Ltd Improvement in or relating to photocurable resist inks
CN1802603A (en) 2003-07-17 2006-07-12 霍尼韦尔国际公司 Planarization films for advanced microelectronic applications and devices and methods of production thereof
KR20110128819A (en) * 2009-02-09 2011-11-30 훈츠만 어드밴스트 머티리얼스(스위처랜드) 게엠베하 Powder coating composition
CN102804066B (en) * 2010-03-22 2015-04-01 株式会社Lg化学 Photocurable and thermocurable resin composition, and dry film solder resist
US10189188B2 (en) * 2016-05-20 2019-01-29 Canon Kabushiki Kaisha Nanoimprint lithography adhesion layer

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EP0819267A1 (en) 1998-01-21
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EP0819267B1 (en) 1999-11-24
WO1996031806A1 (en) 1996-10-10
US5990189A (en) 1999-11-23
GB9507101D0 (en) 1995-05-31

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