TWI356664B - Method for creating curcuit assemblies - Google Patents

Description

IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for manufacturing a circuit assembly. [Prior Art] Electrical components (such as 'resistance thieves, transistors, and capacitors) are usually mounted on circuit boards such as printed circuit boards. Structurally. The circuit panel typically includes a generally planar sheet of dielectric material in which the electrical conductors are disposed on one of the major and flat surfaces of the sheet or on two major surfaces. The conductors are typically formed of a metallic material such as copper and used to interconnect electrical components that are mounted to the board. Where the conductors are disposed on the two major surfaces of the panel, the panel may have through-hole conductors extending through the holes in the dielectric layer (or "via vias") to ± Interconnecting the conductors ^to date a four-layer circuit board assembly has been fabricated that combines a plurality of stacked circuit panels with additional layers of dielectric material that face adjacent panels of the stack The conductors on the surface are separated. Such multi-layer assemblies typically incorporate interconnections extending between conductors on various circuit panels in the stack as needed to provide the desired electrical interconnection. Circuits and cells are fabricated in an incremental scale package stage in a microelectronic circuit package. In general, the smallest scale package level is typically a semiconductor wafer that houses a plurality of microcircuits and/or their components. Such wafers are typically made from ceramics, stone slabs and the like. An intermediate package stage (ie, a "wafer carrier") comprising a multi-layer substrate can have a plurality of J-scale a-chips attached to a plurality of microelectronic circuits attached thereto. Likewise, such intermediate package levels can themselves be attached to Larger scale circuit cards, motherboards and the like. The intermediate package level is used for several purposes throughout the circuit 107369.doc 1356664, including: structural support, small scale microcircuits and circuit transition integration Dissipation to larger scale boards and heat from circuit assembly. Substrates used in conventional intermediate package stages have included a variety of materials 'for example, ceramics, fiberglass reinforced polyepoxides, and polyimine. Although the substrate can provide sufficient rigidity to provide structural support for circuit assembly, it typically has a coefficient of thermal expansion that is very different from the thermal expansion coefficient of the microelectronic wafer attached thereto. As a result, the circuit assembly is reused. The subsequent failure becomes a danger due to the failure of the adhesive joint between the layers of the assembly. Similarly, the dielectric material used on the substrate must be satisfied. Requirements include conformality, flame resistance and compatible thermal expansion properties. Conventional dielectric materials include, for example, polyimine, polyepoxides, phenolics, and fluorocarbons. These polymeric dielectrics typically have A coefficient of thermal expansion that is much higher than the coefficient of thermal expansion of adjacent layers. There has been a growing need for a circuit board structure that provides high density, complex interconnections. Applications in which the circuit layer is placed on top of the other A dielectric material typically separates the circuitized layers. The polymeric dielectric materials typically used in circuit assembly fabrication are thermoplastic or thermoset polymers. Thermoset materials are typically first cured to form a conformal coating. As density and complexity increase, there is an increasing demand for dielectric materials having a gradually decreasing dielectric constant and dielectric loss factor. SUMMARY OF THE INVENTION The present invention is directed to a method for fabricating a circuit assembly. Method 107369.doc 1356664 comprises: (4) applying a curable coating composition to a substrate (8) to cure the coating composition to form on the substrate a coating, and (c) applying a conductive layer to all surfaces. The curable coating composition comprises: (1) one or more ungelatinized active hydrogen-containing resins, (ii) one or more polycuratives and丨(1) Depending on the need, or a plurality of vine transfer catalysts. In a further embodiment, the method also includes: (4) applying a resist to the conductive layer applied in step (4) 'e) treating the anti-surname The agent forms a predetermined pattern of exposed underlying metal, (1) (4) the exposed metal, and (g) strips the remaining _2 抗 胁 1 to form a circuit pattern.

Except in the operating examples, or where otherwise stated, the number used to describe all the components expressed in the patent application, the reaction conditions, etc.; the number should be understood to be in all cases by the term &quot About, heart change. Therefore, unless stated to the contrary, the following description and additions: t Approximate numerical parameters set forth in the patent scope are intended to be determined by the specifics of the present invention. At the very least, and not in an attempt to limit the application of the equivalents, the application of the patents should be interpreted in accordance with the number of significant digits reported and by the application of general rounding techniques. Although the numerical range and parameter of the broad scope of the present invention are closed to the near d value, the numerical values described in the specific real money (4) are reported as accurately as possible. Any numerical value, however, inherently contains certain errors that are necessarily caused by the standard deviation found in the respective test. 〇 ‘ It should be understood that’ any range of numbers stated in the essay is intended to include all sub-scopes of the corpus. For example, the range of "1 to 10" is intended to encompass 107369.doc 1356664 between the stated minimum value 1 and the stated maximum value Η) and includes all subranges of the two, meaning A minimum value equal to or greater than 1 and a maximum value equal to or less than 1 。. As mentioned above, in an embodiment, the present invention is directed to a method for preparing an electrical assembly. The method comprises: (4) Applying a _curable coating composition to the substrate, (8) curing the curable coating composition to form a coating on the substrate, and (c) applying a conductive layer to all surfaces. The curable coating composition comprises (1) one or more ungelatinized active hydrogen-containing resins, (Π)- or a plurality of polyester curing agents, and (iii) optionally one or more transesterification catalysts. Curable in the method of the present invention. The coating composition comprises an ungelatinized active hydrogen-containing resin (1) as a primary film-forming agent. A wide variety of film-forming polymers are well known and can be used in the cured coating compositions of the present invention, with the proviso that they contain activity Hydrogen group, As described by the Zerewitinoff test, it is described in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (Vol. 49, p. 3181 (1927). In one embodiment, the active hydrogen is obtained from a hydroxyl group, a thiol group, a first amine. The base and/or the second amine group. "Ungelatinized" means that the resin is substantially free of cross-linking and has an intrinsic viscosity when dissolved in a suitable solvent, such as (Example 10) according to ASTM-D1795 or ASTM-D4243. The intrinsic viscosity of the reaction product is indicated by one of its molecular weights. On the other hand, since the gelation reaction product has a substantially infinitely high molecular weight, it will have an intrinsic viscosity that is too high to be measured by energy. As used herein, a "substantially non-crosslinked" reaction product refers to a reaction product of a weight average molecular weight (Mw) of less than !, _, _ as determined by gel permeation chromatography on a 107369.doc. Various active hydrogen-containing resin materials are suitable for use in the present invention. Non-limiting examples of suitable resins include: polyepoxide polymers, acrylic polymers, polyester polymers, urethane polymers, shiji polymers, polybond polymers, polyurea polymers , vinyl polymers, polyamine polymers, polyaniline polymers, mixtures thereof and copolymers thereof. As used herein, "dream-based polymer'' means a polymer comprising one or more "Si〇_ units in the backbone. These fluorenyl polymers may include hybrid polymers such as those heteropolymers comprising an organic polymeric block having one or more -SiO units in the backbone. The polymer is typically a water-dispersible, electrodepositable film-forming polymer. The water-dispersible polymer may be ionic in nature; that is, the polymer may comprise an anionic functional group to impart a negative charge or a cationic functional group to impart a positive charge. Most often, the polymer comprises a cationic salt. A group, usually a cationic amine salt group. Non-limiting examples of film-forming resins suitable for use as the polymer of the compositions of the present invention, especially in anionic electrodepositable coating compositions, include alkali solubilizing, carboxylic acid group-containing polymers, a reaction product or adduct such as a drying oil or a semi-dry fatty acid ester with a secondary acid or anhydride, and a reaction product of a fatty acid ester, an unsaturated hydrazine or an anhydride with any additional unsaturated upgrades. The modified material is further reacted with a polyol. Also appropriate

I. An example of an at least partially neutralized interpolymer of a hydroxyalkyl ester of an unsaturated carboxylic acid, an unsaturated carboxylic acid and at least one of its 'thin unsaturated monomers'. Still another suitable I07369.doc • 10 1356664 electrodepositable resin comprises an alkyd amine based plastic vehicle, i.e., a vehicle comprising an alkyd resin and an amine aldehyde resin. Another suitable anionically electrodepositable resin composition comprises a mixed ester of a resinous polyol. Such compositions are described in detail in U.S. Patent No. 3,749,657, No. 9 and No. 10, lines 1 to 13. Other acidic functional polymers known to those skilled in the art, such as phosphatized polyepoxides or squamous acrylic polymers, may also be used. Further, the resin which is suitable for use as a polymer, which comprises one or more pendant urethane functional groups, is exemplified by the resins described in U.S. Patent No. 6,165,338. In a particular embodiment of the invention, 'polymer is a cation, an active hydrogen-depositable resin that is capable of being deposited on a cathode. Non-limiting examples of such cationic film-forming resins include amine salt-containing resins, such as acid-solubilizing reaction products of polyepoxides with a first or second amine, such as those described in U.S. Patent No. 3,663,389. Reaction products of Nos. 3,984,299, 3,947,338 and 3,947,339. In addition to the epoxy-amine reaction product discussed immediately above, the polymer may also be selected from the group consisting of cationic propyl acrylate resins, such as those described in U.S. Patent Nos. 3,455,8,6 and 3,928,157. Resin. A resin containing a quaternary ammonium salt group may be used in addition to the resin containing an amine salt group. Examples of such resins include those which are formed by the reaction of an organic polyepoxide with a tertiary amine salt. Such resins are described in U.S. Patent Nos. 3,962,165, 3,975,346, and 4,001,1,1. Examples of other cationic resins are resins containing a third phosphonium salt group and a resin containing a quaternary phosphonium salt group, such as those described in U.S. Patent Nos. 3,793,278 and 107,369, doc. Further, a film-forming resin such as that described in European Application No. 12463 can be used. Further, a cationic composition prepared from Mannich can be used, such as the cationic composition described in U.S. Patent No. 4,134,932. In one embodiment of the invention, the polymer may comprise one or more positively charged resins comprising a first and/or second amine group. Such resins are described in U.S. Patent Nos. 3,66.3,389, 3,947,339 and 4,116,900. In the U.S. Patent No. 3,947,339, a polyketimine derivative of a polyamine such as di-ethyltriamine or tri-extended ethyltetramine is reacted with a polyoxo oxide. When the reaction product is neutralized by an acid and dispersed in water, a free first amine group is produced. Further, when the polyepoxide is reacted with an excess of a polyamine such as diethyltriamine and triethylamine, an equivalent product is formed, and the excess polyamine is vacuum stripped from the reaction mixture. Such products are described in U.S. Patent Nos. 3,663,389 and 4,116,900. It may also be advantageous to use a mixture of the above ionic resins. In one embodiment of the invention, the polymer has a cationic salt group and is selected from the group consisting of first, second and/or third amine groups (such as those above) Polyepoxide-based polymers of the described amine groups and an acrylic acid polymer having hydroxyl and/or amine functional groups. As previously discussed, in a particular embodiment of the invention, the polymer It has a cationic salt group. In this case, the cationic salt groups are usually formed by solubilizing the resin by using an inorganic or organic acid such as those conventionally used in electrodepositable compositions. Suitable examples of solubilizing acids include, but are not limited to, amine sulfonic acid, acetic acid, chylo and carapace. In an embodiment of the invention, the solubilizing acid comprises amine sulfonic acid and/or lactic acid. In a particular embodiment, the coating composition useful in the method of the present invention comprises one or more components comprising a covalently bonded self-priming atom. It should be understood that for the purposes of the present invention, "covalently bonded self-atomic atoms" means a covalently bonded halogen atom that is opposite to a dentate ion (e.g., a gas ion in an aqueous solution). The coating composition used in the process of the present invention may have a weight of at least 1 weight percent, or at least 2 weight percent, or at least 5 weight percent, or at least 1 weight percent, based on the total weight of the resin solids. Covalently bonded halogen content. Further, the coating composition used in the method of the present invention may have a total of less than or 4 to 50 weight percent, or less than or equal to 3 weight percent, or less than or equal to 25 weight percent, or less than or equal to 2 weight percent. The dentate content of the valence bond "The coating composition can have a covalent bond between any combination of such values (including the stated values). In one embodiment of the invention, the coating composition is an electrodepositable coating composition comprising a resinous phase dispersed in an aqueous medium. The covalently bonded southerene content of the resinous phase of the electrodepositable coating composition can be obtained from a halogen atom covalently bonded to the resin (1). In this case, the covalent bond of the keratin content Attributable to a reactant for forming any of the film-forming resins described above. For example, the resin may be a phenol (for example, a toothed polyphenol such as gasified or brominated bisphenol A) and an epoxy group-containing material (such as those described above with reference to the resin (1)) Reaction product. In the case of a polymer containing an anionic group, it may be followed by solubilization with phosphoric acid. Alternatively, a suitable polymer can be produced by reacting an epoxy group-containing compound with a halogenated acid followed by reacting any remaining epoxy groups with phosphoric acid at 107369.doc -13· 1356664. These acid groups can be used to solubilize with an amine. Similarly, in the case of a polymer containing a cationic salt group, the resin may be the reaction product of an epoxy functional material (such as the materials described above) with a halogenated phenol, followed by reacting any remaining epoxy groups with an amine. . The reaction product can then be solubilized using an acid. In one embodiment of the present invention, the covalently bonded halogen content of the resin (1) can be obtained from a selected functionalized phenol, a halogenated polyepoxide, a functionalized acrylic polymer, a southernized polyolefin, a toothed phosphate. A halogenated compound of at least one of its mixtures. In another embodiment of the present invention, the covalently bonded halogen content of the resin (1) is obtained from a halogenated polyhydric phenol such as chlorinated bisphenol A (such as tetra- bisphenol A) or brominated bisphenol A ( For example, tetrabromobisphenol quinone) β In addition, the covalently bonded halogen content can be obtained from a halogenated epoxy compound, for example, a diglycidyl ether of a dentate. The active hydrogen-containing resin (1) is present in the curable coating of the present invention in an amount of from 10% by weight to 9% by weight, or from 3% by weight to 45% by weight, based on the total weight of the curable coating composition. In the composition. The composition used in the method of the present invention as previously discussed' further comprises one or more polyester curing agents. The polyester curing agent (ii) is a material having one or more ester groups per molecule. The ester groups are present in an amount sufficient to effect cross-linking at an acceptable cure temperature and cure time (e.g., at temperatures up to 250 ° C and cure times of up to 90 minutes). It will be appreciated that the acceptable cure temperature and cure time will depend on the substrate to be coated and its use in the final application of I07369.doc -14 - 1356664. A compound suitable as a polyester curing agent (ϋ) is a polyester of a polycarboxylic acid. Non-limiting examples include: bis(2-hydroxyalkyl) esters of dicarboxylic acids such as bis(2.hydroxybutyl)sebacate and bis(2-hydroxyethyl)terephthalic acid.

Sa, mono(2-ethylhexanyl)benzene trimellitate; and poly(2.hydroxyalkyl)ester of an acid half ester prepared from di-salted liver and alcohol (including polyterpene alcohol). The latter type may be particularly specifically adapted to provide a (four) having a final functional group greater than two. A suitable example includes - a polyfluorene prepared by the following method, first having several equivalents of a dicarboxylic anhydride (for example, succinic anhydride or phthalic anhydride) with a trihydric or tetrahydric alcohol (such as glycerol) , trimethylolpropane or isoamyl alcohol) is reacted at a temperature below 15 〇t, and then the acid is condensed with at least one equivalent of alkylene oxide (such as 1,2-butylene oxide) , ethylene oxide or propylene oxide) reaction. The polyester curing agent (ii) may contain an anhydride. Another suitable vinegar comprises a low 2-hydroxyl-alkyl terminated polyalkylene terephthalate vinegar. φ In a particular embodiment, the polyester comprises at least one ester group per molecule wherein the carbon atom adjacent to the esterified hydroxyl group has a free hydroxyl group. Also suitable polyesters are tetrafunctional polyesters prepared from half ester intermediates prepared by the following process: trimestrienic acid Sf and propylene glycol (mol ratio 2:1) The reaction is followed by reaction of the intermediate with U-butylene oxide and the glycidyl ester of the branched monocarboxylic acid. In a specific embodiment, the polyester curing agent (ii) is substantially free of acid in the case where the active argon-containing resin (1) contains a cationic orphan group. The present invention is substantially free of acid " means an acid having less than 0.2 meq/g. 107369.doc -15· 1356664 For aqueous coating systems (eg for cathodic electrodepositable) coating compositions, 'appropriate polyester curing agents may include self-polycarboxylic anhydrides, one or more ethylene glycols, alcohols, glycols Non-acidic polyester prepared from monoethers, polyols and/or monoepoxides.

Suitable polycarboxylic anhydrides may include dicarboxylic anhydrides such as succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, methylhexahydron-butanol Anhydride, 3,3,,4,4,_benzophenone tetrazoic acid dianhydride and pyromellitic dianhydride. A mixture of anhydrides can be used. Suitable alcohols may include linear alcohols, cyclic alcohols or branched alcohols. The alcohols may be in the form of aliphatic alcohols, aromatic alcohols or araliphatic alcohols. As used herein, the terms ethylene glycol and monoepoxide are intended to include compounds containing no more than two alcohol groups per molecule, which may be at 15 Torr. (: The temperature below the carboxylic acid anhydride function is reversed

Suitable monoepoxides may include the glycidylation of the branched mono (iv). Alternatively, an alkylene oxide such as acetonitrile or propylene oxide can be used. Suitable ethylene glycols may include, for example, ethylene glycol and polyethylene glycol, propylene glycol and polypropylene glycol, and 1,6-hexanediol. A mixture of ethylene glycol can be used. : for example, by reacting the meta-anhydride (TMA) with the branched mono-hectoric glycidyl ester in a molar ratio of 1: i in one or more steps in 50 steps (if necessary, by means of Non-acidic brewing is prepared by a brewing catalyst such as stannous octoate or stupid amine. In addition, partial: formic acid can be combined with 3 molar equivalents of monoethanol (such as 2. ethylene glycol or ethylene glycol or trimellitic acid needles (1 mole) can be first with 107369.doc -16 * 1356664 The monoalkyl ether (such as ethylene glycol monobutyl ether) is reacted at a molar ratio of 1: 5 to 1: i, after which the product is allowed to react with 2 mol of the glycidyl monophosphate of the branched monocarboxylic acid. In addition, polycarboxylates (that is, they contain two or three carboxyl functional anhydrides per molecule) or a mixture of polycarboxylic anhydrides can be simultaneously with ethylene glycol (such as 1,6-hexanediol) and/or Ethylene glycol monoether and monoepoxide are reacted, and then the product can be reacted with a monoepoxide if desired. For aqueous compositions, such non-acidic polyesters can also be used as polyamines (such as The base triamine) is modified to form a guanamine polyester. These "amine modified" polyesters can be incorporated into the above linear or branched amine adducts to form self-curing amine adducts. The non-acidic polyesters of the type described herein are generally soluble in organic solvents and are not difficult to mix with the active hydrogen-containing resin (1) described above. Mixtures suitable for use in aqueous systems or mixtures of such materials are typically dispersible in water in the presence of a resin comprising a cationic or anionic salt group i, such as any of the resins previously described. The transesterification catalyst (iii) may optionally be present in the compositions used in the process of the invention. The catalyst (iii) may be any suitable catalyst known for catalysis of vine transfer reactions. In an embodiment of the invention, the catalyst (iii) comprises a metal oxide, a metal complex or a metal salt. Suitable metal oxides include, for example, oxides of samarium, bismuth and tin, including oxidized dihydrocarbyl groups. Tin, such as dioctyltin oxide or dibutyltin oxide. Alternatively, lead oxide and antimony telluride may be used when dissolved in an acidic aqueous solution (for example, an aqueous solution of an acid). The salt of the field may include oblique, reed, a salt, a lock, an iron, a tin, and a tin salt (for example, an octanoate or a cyclic acid salt), including a dihydrocarbyl tin diacetate. Non-limiting examples of the salt 107369.doc -17* 1356664 include octanoic acid , zinc octoate and formic acid II A suitable example of a metal complex is titanium acetylate pyruvate. Also suitable are salts of alkali metals and alkaline earth metals, salts of lanthanides, and salts of erbium, brocade and chromium (for example, Octanoic acid salt and naphthenate); lead, zinc, money decoration, steel, steel, ethyl sulphonate, sulphonate, sulphate, sulphate, sulphate, sulphate, sulphate Any mixture of materials and/or complexes. The amount of catalyst in view of the available metal oxides, salts or complexes, or variations in their solutions may be by the metals contained in the compositions. The content is indicated. Depending on the total weight of the curable coating composition, a metal content of 3.0% by weight is suitable, or a metal content of 〇3 to 16% by weight may be used. As mentioned above, the method of the present invention comprises: (a) applying any of the above-described curable coating compositions to a substrate '(b) curing the coating composition to form a coating on the substrate' and (c) A conductive layer is applied to all surfaces. The substrate (or "core") can comprise any of a variety of substrates. In one embodiment, the substrate is electrically conductive. "A suitable conductive substrate can comprise: a metal substrate, such as an alloy of iron, aluminum, gold, nickel, copper, magnesium, or any of the foregoing metals; and coated with a conductive material (eg, A substrate coated with a material of conductive carbon). An example of a suitable iron-nickel alloy is INVAR (a trademark owned by Imphy S. A. of 168 Rue de Rivoli, France) which contains approximately 64 weight percent iron and 36 weight percent. This alloy has a low coefficient of thermal expansion which is comparable to the coefficient of thermal expansion of 107369.doc -18-1356664 for tantalum materials used to prepare wafers. This feature is required, for example, to prevent the continuous increase of the wafer scale package or the continuous reduction of the adhesion between the layers of the bond due to thermal cycling during normal use. When a nickel-iron alloy is used as the conductive core, a copper metal layer can be applied to all surfaces of the conductive core to ensure optimum conductivity. The copper metal layer can be applied by conventional means such as electrodeposition or metal vapor deposition. The copper layer typically has a thickness of from 1 to 8 microns. In another embodiment, a circuitized material such as a printed circuit board is suitable for use as a substrate. The coating composition can be applied by various coating techniques well known in the art, for example, by roll coating or Spray coating technology. In such cases, the resinous binder may or may not include solubilized or neutralized acids and amines to form cationic salt groups and anionic salt groups, respectively. The voltage for electrodeposition applied by electrophoretically applying any of the ion-containing compositions previously described to a conductive substrate can vary and can be, for example, as low as 1 volt to as much as several kilovolts, but Usually between 5 〇 and 5 〇〇. The current density is typically between 5 amps per square foot and 5 amps (5 to 5 mA per square centimeter) and tends to decrease during electrodeposition to indicate that an insulating conformal film has been formed at the core. All exposed surfaces. As used herein and in the specification and in the scope of the claims, "conformal, film or coating means a film or coating having a substantially uniform thickness that conforms to the configuration of the substrate, including in any pores that may be present. (but not closed) the surface. After the coating has been applied by a suitable method, such as the methods mentioned above, it is cured. The coating can be cured at ambient temperature or Change from 90 ° C to 30 (the high temperature of TC lasts 5 to 9 minutes to heat 107369.doc 19 1356664 cured to form a dielectric coating on the substrate. The thickness of the dielectric coating can be Only 5 microns, or only 25 microns, or only 20 microns. Those skilled in the art will recognize that the core surface can be pretreated or otherwise prepared to coat the dielectric coating prior to application. Dielectric coating. For example, it is appropriate to 'clean, rinse, and/or use an adhesion promoter before applying the dielectric. After applying the dielectric coating, it can be removed by a predetermined pattern as needed. The surface of the dielectric coating is exposed to portions of the substrate. Excision can be performed using a laser or by other conventional techniques, such as mechanical drilling and chemical or plasma etching techniques. After an optional ablation step, a conductive layer can be applied to all surfaces. It may contain a conductive paste or ink or metal.

Suitable conductive pastes and inks may, for example, include conductive silver coated copper pastes such as DD pASTE SAP 5 10 and c〇nductor Ink P2000, both of which are commercially available from TATSUTA SYSTEM ELECTRONICS CO., LTD. These materials can be coated by a screen printing technique. Suitable metals include copper or any metal or alloy having sufficient electrical conductivity. The electrically conductive material can be applied by electrodeposition or any other suitable method known in the art to provide a uniform electrically conductive layer. Alternatively, the conductive layer can be applied in a predetermined pattern, such as a circuit pattern. The thickness of the conductive layer can vary from 1 micron to 50 microns or from 5 microns to 25 microns. In the case where the dielectric coating is removed prior to application of the conductive layer, conductive or metallized vias are formed. 107369.doc •20- 1356664 ▲In order to enhance the adhesion of the conductive layer to the dielectric polymer, all of the coatings of the conductive layer can be treated with ion beam, corona discharge or plasma bombardment. The surface is bonded to apply an adhesion promoter layer to all surfaces. The thickness of the adhesion promoter layer may vary from 50 angstroms to 5000 angstroms, and may be selected from the group consisting of chrome-titanium, bromine, cobalt, ruthenium, iron, indium, copper, gold, tungsten, and metal or metal oxides.

In a progressive embodiment, the method of the present invention also comprises: (4) applying an anti-money agent to the conductive layer applied in step (4), and (4) treating the anti-synthesis agent to form a -敎 pattern of the underlying conductive layer. (f) (d) the exposed conductive layer, and (g) stripping the remaining second resist to form a circuit pattern 0

A resinous photosensitive layer (eg, "resistance, or "resist") can be applied to the conductive layer after application of the conductive layer. If desired, prior to application of the photoresist The coated substrate can be cleaned and/or pretreated; for example, treated with an acid surrogate to remove the oxidized metal. The resinous photosensitive layer can be a positive or negative photoresist. The thickness of the photoresist layer It can vary from i microns to 5 microns, or from 5 microns to 25 microns, and can be applied by any method known to those skilled in the art of photolithography. The processing method is reduced to produce the desired circuit pattern. Suitable positive photosensitive resins include any positive photosensitive resin known to those skilled in the art. Examples include dinitrobenzyl functional polymers such as those disclosed herein. U.S. Patent No. 5,6, 〇35, Dinitrobenzyl Functional Polymers in Lines 3 to 15 "The resins are highly photosensitive. In one embodiment, the resinous photosensitive layer comprises Dinitrobenzyl functional 10736 9.doc • 21· 1356664 A composition of a polymer which is usually applied by spraying. In a single embodiment, the resinous photosensitive layer comprises an electrodepositable conjugate which contains dinitrate A benzylic functional polyurethane and an epoxy-amine polymer, such as those described in Examples 3 to 6 of U.S. Patent No. 5,600,035. Negative photoresists include liquid or dry film compositions. Any of the liquid compositions described may be applied by spraying, roll coating, spin coating, curtain coating, screen coating, dip coating or electrodeposition coating techniques. Coating the liquid photoresist by electrodeposition, more preferably, coating the liquid photoresist by cationic electrodeposition. The electrodepositable photoresist composition comprises an ionic polymeric material, which may be a cationic or anionic polymeric material, And may be selected from the group consisting of polyesters, polyamino phthalates, acrylic fibers, and polyepoxides. Examples of photoresists coated by anionic electrodeposition are shown in U.S. Patent No. 3.738,835. By cation Electrodeposition coated photoresist is described in US patents Examples of dry film photoresists include dry film photoresists disclosed in U.S. Patent Nos. 3,469,982, 4,378,264, and 4,343,885. Dry film photoresists are typically laminated to surfaces, such as by application. Hot roll. It should be noted that after coating the photosensitive layer, the multilayer substrate can be packaged at this point to allow for transport and processing of any subsequent steps at a remote location. In a separate embodiment of the invention, After the photosensitive layer is applied, a photomask having a desired pattern can be placed over the photosensitive layer and the layered substrate can be exposed to a suitable level of sufficient radiation source, typically 107369.doc -22. 1356664 A source of actinic radiation. As used herein, the term "sufficient level of radiation" refers to the level of radiation that, in the case of a negative resist, polymerizes monomers in the region exposed to the exposure, or It depolymerizes the polymer or makes the polymer more soluble in the case of a positive anti-surname agent, which results in a difference in solubility between the radiation exposed area and the jurisdictional shielded area.

The reticle can be removed after exposure to the source of radiation and the layered substrate developed using conventional development solutions to remove more soluble portions of the photosensitive layer and reveal selected regions of the underlying conductive layer. The conductive layer thus exposed can then be surnamed by a metal etchant that converts the metal to a water soluble metal complex. The soluble complexes can then be removed by spraying water. The photosensitive layer protects the underlying substrate during the etching step. The remaining photosensitive layer, which is impermeable to the surname, can then be removed by a chemical separation process to provide a circuit pattern that is connected by conductive vias. After the circuit pattern on the multilayer substrate is prepared, other circuits can be attached and the pieces are formed to form a circuit assembly. Additional components include (for example) such as half

One or more smaller-scale components of a conductor wafer, an intermediate layer, a larger-scale circuit card or motherboard, and active or passive components. It should be noted that the secondary layer used to prepare the circuit assembly can utilize suitable steps of the process of the present invention to prepare components that can be attached using conventional adhesives, surface mount techniques, wire bonding or flip chip techniques. [Embodiment] The following examples are illustrative of the present invention, and it is not intended to limit the invention to its details. Unless otherwise stated, the following examples and all parts of the entire description are in the form of weights and percentages. 107369.doc -23- 1356664 EXAMPLE The following example illustrates the preparation of an electrodeposited coating and its use in a method for forming a circuit assembly in accordance with the present invention. Example 1: The following example describes the cations used in the electrodeposited coating tank described below

Synthesis of binders. The adhesive is prepared from the following ingredients: Ingredient parts by weight ΜΑΖΟΝ® 165Π 150.0 EPON® 8802 755.3 Tetrabromobisphenol A 694.9 TETRONIC® 150R13 0.2857 Aminopropyl diethanolamine 114.7 Diethanolamine 49.57 2-Butoxy Ethanol 832.4 EPON 880 16.14 Crosslinker 4 1 v · “ a ▲ · —τ:~—————— 1195 A plasticizer available from BASF Corporation. An epoxy resin priced from Hexion Specialty Chemicals. A surfactant active from BASF Corporation.

Prepared according to Example 5 of 4Si9〇iiff_463, and pine butoxyethanol will be MAZON 1651, EPON 880, tetrabromofluorene s August

夭 Bisphenol A and TETRONIC 150R1 were fed into a 4-neck round bottom flask equipped with a stirrer, a temperature probe and a Dean-Stark fat under a nitrogen blanket. The three persons, @, were heated to a temperature of 70 ° C and stirred for 15 minutes. The heat source is then removed and aminopropyldiethanolamine and diethanolamine are added. After about 10 minutes, the reaction mixture was allowed to warm to a maximum temperature of 1 76 °C. The reaction was allowed to cool to a temperature of 13 5 ° C after one gentleman's hour to add 2-butoxyethanol and further marinate. 7 The mixture was cooled to 125 ° C » The mixture was then held from the peak temperature rise at 125 ° C for a total of 107369.doc • 24- 1356664 for two hours. The EPON 880 was fed a second time and a crosslinking agent was added and the solution was stirred at 125 ° C for one hour. The reaction mixture (3428 parts) was poured into a solution of the amine acid (49.5 parts) dissolved in deionized water (1287 parts) under vigorous agitation. After an hour of agitation, an additional amount of deionized water (3970 parts) was slowly added to obtain a dispersion having a non-volatile content of 30.2%. Example 2: This example demonstrates the preparation of an ungelled cationic soap for use in the synthesis of the microgel examples shown below. The cationic soap is prepared from the following ingredients: Component weight β (g) EPON 828 1023 Double A-epoxy Ethylene adduct 365 Bisphenol A 297 2-butoxyethanol 187.2 Benzyl dimethylamine 1.4 Benzene Dimethylamine 3.0 Diketimine 1 2 182.3 N-methylethanolamine 85.2 Acetic acid 105.9 Deionized water 1065.9 Deionized water 735.9 Deionized water 1156.4 Deionized water 867.3 107369.doc •25· 1 1/6 Moer's double An adduct of age A/ethylene oxide derived from a BASF surfactant. A solution of 71% of the reaction product of diethyltriamine and methyl isobutyl ketone in 2 methyl isobutyl ketone. EPON 828, bisphenol A-ethylene oxide adduct, bisphenol A and 2-butoxyethanol were fed into a reaction vessel and heated to a temperature of 125 ° C under a nitrogen atmosphere. Add the first portion of benzyl diamine and allow the reaction to warm to 1356664. 18 ° ° C ° During the temperature rise, when the reaction reaches 16 (TC, start to maintain a small 8 ^. After the temperature rise peak, allow The resin was cooled back to 160. (:, the holding process was continued. After the holding process, the reaction was cooled to 130 C' and a second portion of benzyldimethylamine was added. The reaction was kept at 1070. Extrapolation of the epoxy equivalent. Under the expected epoxy equivalent, the diketimine and N-methylethanolamine are added in succession and the mixture is allowed to warm to about 150 C. At the peak temperature rise, the hold is maintained for one hour to allow the The reaction is cooled to 125 C. After the one hour hold, the resin is dispersed in solution A of acetic acid dissolved in the first portion of deionized water. The second, third, and fourth portions are then used. Ionized water was used to reduce the dispersion. The resulting cationic soap was vacuum stripped until the content of methyl isobutyl ketone was less than 0.05% » Example 3: This example shows the cationic cation of the cationic oxime from Example 2 above. Synthesis of a gel. The gel is prepared from the following ingredients: Parts by weight (g) Ingredient 2517 443 66.4 5.81 337 Cationic urgency of Example 2 - Deionized water EPON 828 (85 〇 / 甲基 in methyl isobutyl ketone) Methyl Deionized water was added to the cationic soap of Example 2, and the mixture was heated to 7 (TC) under a nitrogen blanket. EPON 828 solution was added at 15 minutes (4) by good actuation. Butyl ketone was used as a rinse and the mixture was held under thief 107369.doc -26- 1356664 for 45 minutes. The mixture was then heated to m over 70 minutes and maintained at this temperature for good mixing. 3 hours. Deionized water was then added and the mixture was cooled to give a 18.9% non-volatile content microgel dispersion. Electrodeposition coating tank and coating Example A: This example is shown for the preparation of Preparation of a blend of coating tanks in Example D. The blend was prepared from the following ingredients: Ingredient parts by weight (g) Resin of Example 1 15748 Ethylene glycol monohexyl ether 540 Deionized water 2500 Slowly stirring The electrodeposition resin of Example 1 was placed in a container. Ethylene glycol monohexyl ether was slowly added to the resin under agitation and stirred for 30 minutes. Deionized water was then added to the mixture. Example B: This example shows Preparation of a second blend of coating tanks in Example D described below. The blend was prepared from the following ingredients: Ingredient parts by weight (g) E62781 203.7 Deionized water 203.7 Catalyst slurry, Purchased from PPG industries, Inc. The above ingredients were mixed under low agitation for 30 minutes. Example C: 107369.doc -27- 1356664 This example demonstrates the preparation of a third blend for use in preparing a coating tank of the examples described below. The blend was prepared from the following ingredients: Parts by weight (grams) 3434 3434 Ingredients Addition of Example 2 Deionized water _ Deionized water was slowly added to the addition of Example 2 under agitation. The mixture was mixed for one hour. Example D: The second blend of Example B was added to the blend of Example a under agitation. Deionized water (500 grams) was used to rinse the vessel used in the second blend of Example B into the agitated mixture. To this mixture was added a third blend of Example c followed by two gallons of deionized water. This mixture was filtered through a 3M oil sorbent cloth filter into a large (14 liter) polypropylene bath. Deionized water is added to fill the tank enough. Approximately 7 gallons of permeate was removed from the coating tank via ultrafiltration, where the permeate was replaced by deionized water. The final pH and conductivity of the ultrafiltration paint were 565 and 765 micro-tiles, respectively. The measured solid content (hours at HfCTi) of the tank was 1 〇 25%. Example E: The electrodepositable coating composition of Example D was electrophoresed at 175 volts from an electrodeposition bath at a temperature of 90 °F. Coated to copper foil (Qak, a subsidiary of Mitsui Kinz〇k〇c〇rp〇me Group) - 4 ounces of TOB-111 copper foil supplied by Mitsui) lasted 3 minutes. The electrocoat foil was rinsed with deionized water and heated to a temperature of 240. The coating was cured for 30 minutes to provide a cured dielectric film thickness of about 22 microns. 107369.doc • 28. 1356664 A 25 micron copper layer was deposited on the coating by the following procedure: activation of the coating on the copper foil by oxygen plasma treatment followed by immediate deposition of a chromium deposit in a column Layer and a steel seed layer "Calculate the thickness of copper to approximately 25 microns by standard electrolytic copper electrodeposition" Adhesion test: by test method IPC-TM-650.2.4.9 ("Peel

The 90° peel strength test described in Strength, Flexible Printed Wiring Materials") measures the adhesion of the copper layer to the dielectric. To test the thermal stability of the coating and the subsequent adhesion of the metallized layer to the coating, the metallized coated foil is placed in a forced air oven that is heated to 260 ° C for three hours. Minutes and six minutes. Table 1, which shows the reduction in spalling strength of the metallized layer-to-coating peeling strength β after three minutes and six minutes of exposure to a heated environment and after three minutes of exposure to a heated environment. 'With the increase in time, no further reductions were measured. At any time during the thermal test, no cracking, bursting or blistering defects occurred at the interface of the metallized copper dielectric coating & dielectric coating-steel foil. Table 1: Peeling strength of copper-dielectric interface before hot dew --1----- 3 minutes under Cangzhou rc at 260 ° C for 6 minutes 6.4 5.2 5.2 ------. The specific embodiments of the present invention have been described for purposes of illustration, but it will be understood by those skilled in the art that the details of the invention may be practiced without departing from the invention as defined by the appended claims. change. 107369.doc •29·

Claims (1)

1356664 Do you do January? Japanese repair (^) is replacing the patent application No. 094144936, the Chinese patent application scope replacement (September 1998) X. Patent application scope: • 1· A method for preparing circuit assembly, the method includes: (a) applying a curable coating composition to a substrate. The curable coating composition comprises: (1) one or more active hydrogen-containing resins, (ii) one or more polyester curing agents, and (iii) (b) curing the curable coating composition to form a coating layer on the substrate, as needed; and (c) applying a conductive layer to the cured composition At least a portion of the surface wherein the conductive layer is heated to 260 ° C meets the requirements of ipc-TM-650.2.4.9. 2. The method of claim 1, further comprising: (d) applying a resist to the conductive layer applied in step (c); (e) processing the resist to form an underlying conductive layer (f) etching the exposed conductive layer; and (g) stripping the remaining resist to form a circuit pattern. 3. The method of claim 1 wherein the coating composition comprises a covalently bonded halogen. 4. The method of claim 3, wherein the covalently bonded dentate content is in the range of from 5% by weight to 50% by weight based on the total weight of the resin solids present in the coating composition. 5. The method of claim 1, wherein the active hydrogen-containing resin (i) is obtained from at least one of a polyepoxide polymer and an acrylic polymer. The method of claim 3, wherein the resin (1) has a covalently bonded halogen content obtained from the toothed polyepoxide and/or the halogenated acrylic polymer. 7. The method of claim 6, wherein the covalent bond present in the resin (1) is obtained from the self-chemically diverse. 8. The method of claim 7, wherein the halogenated polyphenol comprises The method of claim 8, wherein the halogenated polyfluorene comprises tetrabromobisphenol a. I 〇. Wherein the active hydrogen-containing resin (1) comprises a cationic salt group II. The method of claim 7, wherein the coating composition is electrodepositable. 12. The method of claim 1, wherein the polyester Ii) a polyacetic acid comprising a poly-sour acid having one or more SB groups per molecule. The method of claim 12 wherein the polyester (丨丨) is substantially free of acid. Wherein the polyester (丨丨) comprises at least one fluorenyl group per molecule, wherein the carbon atom adjacent to the esterified hydroxyl group has a free hydroxyl group. 5. The method of claim 1, wherein the transesterification catalyst comprises a metal An oxide, a metal salt or a metal complex. 16. The method of claim 15 wherein the metal oxide The metal salt and or the metal complex is obtained from a metal selected from the group consisting of tin, antimony and lead. 17' The method of claim 1, wherein the substrate is electrically conductive. The substrate comprises at least one metal selected from the group consisting of copper and an iron-nickel alloy. 19. The method of claim 1 wherein the conductive layer applied in step (c) is copper 0 20_ as claimed in claim 1 The method wherein the coating composition comprises a microgel. 107369-980904.doc