JPS6052089A - Printing circuit - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention includes an ink for a printed circuit device, a circuit transfer method, a printed circuit device and a method of manufacturing the same.

This application is a continuation in part of the following pending U.S. patent applications: U.S. Application No. 508.056.198
Filed on June 24, 2015, U.S. Application No. 516,689.1
Filed on July 25, 1998, U.S. Application No. 516,677
．． Filed on July 25, 1983.

Printed circuits used electrically are often subject to critical demands. That is, the printed circuit should be wettable by solder to ensure good bonding between the circuit and the conductors.

It should also be capable of electroless metal plating to accommodate a variety of product applications.

As such, printed circuits should also have good adhesion to dielectric substrates. In the case of the present invention, adhesiveness is expressed as 1 tensile force and 10 levels. And last but not least, the circuit should have good electrical conductivity.

Many methods of manufacturing printed circuits or printed circuit boards are known. Although a variety of studies have been carried out with known techniques for producing them.

The methods described below often have one or more drawbacks.

U.S. Pat. No. 4,396,666 discloses printing an epoxy mixture containing 65-85% by weight of solderable metal powder onto a substrate, slightly pyrolyzing the cured epoxide, and soldering. Although a method has been described in which the metal is fully exposed for attachment, this method has obvious drawbacks. One is that the resin decomposes irregularly, making the exposed surface of the circuit uneven. Indeed, removing volatile materials from the circuit will result in the formation of sifters, holes, etc., and the uniformity of the circuit will be disturbed. Since pyrolysis affects the uniformity of the film, especially the binder part, the adhesion of the metal particles to the substrate will be questionable.

High temperature pyrolysis, ie at least 2000° C., will cause substantial damage when the substrate is made of thermoplastic material.

Japanese patent application 56.357/73 (January 26, 1981
2435/81) describes printing a circuit pattern on a transfer paper with conductive ink and contacting the printed surface of the transfer paper to a board with a flash heat compression bonding agent. The pattern is formed on the transfer paper by a screen printing method.

This application lists the advantages of this method as follows. Simplicity, accuracy, uniformity, non-contaminating steps, reuse of poorly formed nine boards, flexibility.

If the method of the Japanese patent is attempted, there may be problems with transfer to dielectric surfaces, and the resulting product may lack desirable parameters of conductivity, bonding, or plating ability.

The ink used in the Japanese application contains silver dispersed in a solution containing a thermoplastic copolymer. Example 1 uses a vinyl chloride 9-vinyl acetate copolymer, and Example 2 uses an acrylic resin whose components are not listed. In Example 1, the silver powder contained 89.47% by weight, and in Example 2, it contained 88.09%, resulting in good plating performance, easily soldered circuits, and good adhesion. It is stated that this was done. However, there is no mention of the board used.

Advantageously, the technology of this Japanese application can transfer circuits onto a board, but several drawbacks have been found in this method.

Depending on the amount of thermoplastic resin in the ink, the resin will coat the metal sufficiently, which will adversely affect the wettability of the solder and the electroless plating of the circuit. In addition, the use of thermoplastics limits the ability to effectively solder circuits, thus rendering the soldering technique less than its native method.

Another technique is the dispersion method described in US Pat. No. 4,327,124, issued April 27, 1982.

In this patent, a thermosetting phenolic resin (B stage) is saturated with copper powder, with a loading of 70-75%, and a circuit pattern is formed on the board through a silk screen. Copper powder is then sprinkled onto the wet resin film print. The film is cured and soldered.

In addition to the fact that copper dusting is an inconvenient method that does not allow uniform metal distribution, the use of copper powder itself is a questionable choice due to its tendency to form non-conducting oxides over time. be.

Metal powder of a metal that forms oxides forms oxides more easily simply because the surface area is expanded by the metal powder.

Another technique is to apply ink containing 90% or more silver particles by weight to a certain circuit pattern, as disclosed in U.S. Patent No. 4,264,47, issued on August 28, 1971.
No. 7, but none of the known techniques has the advantages of this invention.

This invention consists of highly supported metal particles in a thermosetting adhesive binder comprising a printing ink; a release layer conveying the path formed by the ink; and a thermosetting adhesive. Printed transfer compositions; the use of transfer compositions in methods of making various components, such as printed circuit boards, and all new products, including printed circuits and devices thereof, having desirable characteristics obtainable using this invention. Consists of products produced by a method.

The present invention relates, in part, to an Al printed circuit as a component of its device, in particular (α) a solid dielectric support surface; (h) a layer or path consisting of a thermosetting resin and electrically conductive metal particles. It consists of

In the arrangement of at least one electrical circuit element, the metal particles are present at about 68% to about 87% by volume based on the dry layer, and the aforementioned electrical circuit element has good plating ability by electroless plating technology.

(C1 layer consisting of thermosetting resin (active adhesive interface between the supporting surface and the lower surface of Al).

Most preferably, the components are soldered to a standard test and/or a standard plating test and/or a surface resistance of 0.5 ohm/square or less, preferably 0.1-0.
A component that meets the requirements for a 1 ohm/square conductive circuit element has parallel layers of electrical paths that are bonded at specific points and separated from other specific sections by an insulator.

The paths lie at angles in the plane and extend from each other and beyond the non-planar supports around the sides of the board base.

The invention relates, however, to a) a print transfer composition, in particular a solid release surface coated thereon with a path of arrangement of an electrical circuit, an original diagram or element of an electrical circuit, and 54 to 87% by volume of electrically conductive metal particles; Made of thermosetting resin. The electrically conductive metal particles 1 used here are (1) a metal component having electrical conductivity, and (2) passing through 100 mesh according to the US sieve standard, which is most preferable. It passes through a 200 mesh sieve and stays on a 350 mesh sieve according to the US Sieving (Sheep) standard.

Furthermore, this invention provides that (C) the cross-linking of the thermosetting resin is
For example, changing from A stage resin to B stage resin,
A preferred embodiment using an advanced resin that also includes a decomposing print transfer composition tBl substantially eliminates tackiness of the coating and preferably has no viscosity at the coating release surface and can be coated without changing the coating. The goal is to break up the cross-links by making it possible to overlap nine surfaces.

This inventor, ii) a printed transfer suitable for transferring a metal particle circuit to a dielectric solid support surface, the surface comprising: (a) a solid release surface; and (a) a solid release surface; The layer is at least in the form of an electrical circuit element, containing 11 thermosetting resin and 11 electrically conductive metal particles, the amount of which in the resin component is such that the soldering satisfies standard tests, and tC1 thermosetting resin composition, and optionally also includes an active adhesive layer providing a tC1 thermosetting resin composition.

This invention comprises (El) the aforementioned thermosetting resin composition, in particular: (1) 32-13% by volume of thermosetting resin and 68-87% by volume of +11 electrically conductive metal particles; Each dry ink contains an ink for producing a mixture containing per dry ink. Preferably, the ink satisfies the standard test for soldering, the standard test for plating ability, and has a surface resistance of 0.5.
, most preferably 01 ohms/square or less.

The invention further includes (F') a method of manufacturing the aforementioned components and print transfer compositions, including, inter alia, the following steps.

(1) providing a release surface; (2) applying an ink of a thermosetting resin composition containing a desired amount of electrically conductive metal particles to the release surface in an array of at least one electrical circuit element; (i.e., a path); (3) providing a dielectric surface; (5)
Full contact is made between the release surface and the dielectric surface, so that the film of the electrical circuit element faces the dielectric surface and is separated by an adhesive interface, and (6) sufficient heat and pressure are applied to form the component. give,
Thereby, the thermosetting resin is, in principle, fully cured,
The adhesive is transferred from the release surface to the dielectric surface such that in principle the electrical circuit interacts sufficiently so that the electrical circuit is effectively bonded (force separating the release surface from the component and having a resistance of 05 Ohm/square or less, preferably 0
．． An electrical circuit of less than 1 ohm/square, more preferably less than 0.05 ohm/square is obtained.

Other embodiments of the invention are described further below, and will be apparent from the description hereinafter.

A special feature of the present invention is that highly intricate circuit designs can be quickly printed to produce desired printed circuit devices. Such devices include circuit boards, connectors, and various dielectric substrate circuits as well as precision substrate circuits. The ink of the present invention has metal particles highly supported, preferably in the range of 93.94 to 98%. The volume fraction of the ink is 68-87% volume fraction of metal particles and 13-32% volume fraction of gold thermosetting resin, calculated based on the dry weight of the ink. The transfer device transfers the volume percent of metal particles in the path to 5
4-87% volume fraction is a little wide, and the remainder can be carried out in the ink path where the thermosetting resin binder is 93-94% or less by weight, or 68% or less by volume fraction of metal particles.

54 in 1 volume fraction of 90% or less by weight, which is the lower limit for each
% or less, the most advantageous features of the present invention cannot be obtained. In preferred embodiments, optimal soldering performance is achieved that includes a path with good wetting and strong tensile strength. The best plating performance is obtained by transfer methods using an optimal range of metal particles. Thus, electroless nickel and/or copper plating techniques can be used without surface activation to advantage.

The volume fraction of metal particles used in the ink is 6
8-87%, if the resistance is 0.5 ohms/square or less, 0.1-0.01. High conductivity is obtained in the range of t-in/square, preferably less than 0.1 ohm/square, as is obtained when the surface resistance is around 0.005. What is more distinctive about this invention is that
The use of transfer paper and transfer equipment allows for flexibility in circuit patterns, both in single circuit pattern layered devices and in multiple circuit pattern devices. The circuit pattern is formed on the transfer paper, and not only the flat surface of the dielectric board, but also the top surface, for example, is expanded beyond the frame of the boat 9, and the transfer sheet is compressed with respect to the surface angle of the board. However, this flexibility would be greatly improved if it could be transferred to the side or back side.

The ability of metals to conduct electricity is well known in the art. If the metal is capable of converting to an oxide in air, its ability to conduct electricity is determined by the degree of oxidation to the oxide. The oxidized form is nonconductive. If the same metal is subdivided, the area of contact with oxygen increases, making the particles more nonconductive. As a result, when used as an electrical conductance, the desired metal is a noble metal such as silver, gold, palladium, platinum, rhodium, or rutanium, which has relatively low activity toward oxygen. Among the precious metals, Chie has the highest electrical conductivity.
It is most widely used in the manufacture of printed circuits. However, its price is such that it can be replaced with a cheaper metal at any time, and in order to save money, it is always recommended to replace silver with other metals. When an electrically conductive film is made from silver particles in this way, the silver is replaced with another material.

In the future, there are a number of countervailing factors that work against replacing silver with other materials in the fabrication of electrically conductive devices on dielectric substrates. For example, adhesives or bonding resins may be used to properly adhere the silver particles to the insulator surface. However, to meet circuit application requirements, the silver particles must be properly bonded to the dielectric surface, which may require substantial usage of adhesives and/or adhesives. Become. As a result, the silver particles are included (encapsulated) in the adhesive/no2ing.

If the circuit surface is to be soldered or electrolessly metal plated, the proportion of the adhesive/noing that encapsulates the metal can be changed and the solder or electroless metal (i.e. nickel) It can be directly attached to particles. This serves to break the uniformity of the adhesive/binder system and weaken its strength. This problem,
A certain proportion of silver is mixed with other metal particles, such as nickel, copper,
Occurs when replacing with filler materials such as zinc or iron J1.

In these cases, the decomposition of the encapsulating adhesive/glue will expose the wire mesh to oxidation, reducing the conductivity of the circuit.

This invention accomplished many remarkable things. According to the present invention, the electrically conductive metal particles occupy a large portion or a major portion of the volume fraction of the electric circuit element, so that these particles can be bonded together. In a preferred embodiment, the volume fraction of the particles is at least 54% of the volume of the electrical circuit element in the dry state.
%, more preferably at least 68-87%. This changes if the electrically conductive particles are silver particles, with the solids weight percent of the thermosetting resin composition being at least 90%, preferably at least 94%, optimally at least 95%, and up to 9%.
It becomes 8%. Generally, in any system, the higher the electrically conductive metal content, the better the electrical conductivity of the electrical circuit element.

This invention allows metal particles to be fully exposed to the circuit surface without the need to decompose the resin binder. It was determined that a small amount of silver was required to obtain the desired conductivity. For example, by using a high metal loading, the present invention reveals, for example, by using a mixture of 25% silver particles and 75% nickel particles (weight ratio 1:3), using 100% silver particles. 6 of the electrical conductivity obtained
5% is obtained. Generally, as this weight ratio increases, the resulting conductivity also increases.

Ultimately, the electrical circuit elements of the preferred embodiment of the present invention are electroless nickel plated (according to the plating performance standard test described below), which is wetted by solder and has passed the soldering standard test described below. , obtained by separating the functions of the binder used in the ink placed on the printed circuit. Instead of having a binder for electrically conductive metal particles function as an adhesive to a dielectric surface, in this invention it is tailored solely for support with the particles into an electrical circuit element. In the separation step, the particles and the inder are mixed to form a mixture specifically enriched with electrically conductive metal particles. This is a specific, non-purpose composition.

The composition is made more specific by creating a resin binder in which the crosslinks are cured under heat curing conditions. They are therefore referred to as thermoset resins because they are thermoset or capable of being subjected to thermosetting conditions. Its composition consists of a high volume of conductive metal supported on a thermosetting binder. Once cured, the binder most effectively retains the resin particles, resulting in a good electrical circuit element that is wetted by the solder and coated with electroless nickel without the need for an activator.

Next, instead of coating (printing) the metal/binder composition onto a dielectric substrate or circuit board, as is often done in this field, the composition is printed onto a release surface substrate like a film; The composition is loosely held in the desired circuit element configuration. By doing this,
Interesting changes occur in the coated or printed elements. Compatibility of particles.

In particular, due to the high-density adhesion to the resin, precipitation of the particles occurs easily, and when viewed under an electron microscope, the particles appear to form agglomerates to determine the interface of the peeled surface. Since the surface of this film is ultimately the bare surface of the circuit elements, the concentrated area surface is available for soldering and electroless metal plating.

Advantages during mounting are obtained or further enhanced by compressing the wet film or semi-dry 9 film onto the release surface and/or during the transfer step.

Compression provides the release surface/film interface with film strength and particle concentration without using the release surface as a foundation. In this way, heating and compression can be used for vertical printing, and only mounting is no longer required.

The resin/particle composition on the release surface is partially cured. This is also defined in other ways. Resins are often characterized by their partial degree of cross-linking, progressing from one stage to another, such as from A-stage resins to B-stage resins. This aids in adhering the particles to a uniform film that is sufficient for transfer to a dielectric surface.

In the practice of this invention, bonding of the thermoset film carrying metal particles is obtained by creating a separate adhesive interface between the film and the dielectric surface. Therefore, the binder does not require a reagent to act to bind one particle to the dielectric surface. This adhesive interface can result in adhesive material being applied as an overcoat on the film while it is still on the release surface, or applied to the dielectric surface prior to integrating the thermoset film and dielectric surface. This results in a separated and supplied adhesive interface. In other embodiments, the adhesive becomes part of the structure of the dielectric surface.

For example, the dielectric surface may be a thermoset resin, provided with a thermoset film, and then bonded and cured together as a component.

In this invention, the type of bond that is obtained between the thermosetting resin film transferred to the dielectric and the dielectric surface is important. For this invention, this bond must withstand harsh conditions.

The final product must pass standard soldering tests and standard plating tests without any loss in its physical or electrical properties. The final article can be heated to 260°C (500°F) in air without any loss in its physical or electrical properties.
), it must glow for 20 seconds.

A release surface comprising a thermoset film is brought into contact with a dielectric surface, such that the film faces the dielectric surface. In multilayers consisting of a release surface, a thermoset film, an adhesive interface, and a dielectric surface, the film is subjected to sufficient heat and pressure to essentially cure (C stage), imparting adhesive properties to the final article structure. be done. Additionally, the dissociated surface is removed from the cured resin. The more concentrated it is, the more it is carried. That is, if it is dense, the surface of the metal particles in the film will be exposed.

In a preferred embodiment, as the multilayers are formed, they will undergo sufficient compression during curing to provide compression of the thermoset film.

This further strengthens the circuit element and also improves its conductivity. This compaction will remain permanently within the structure of the film as the resin will heat cure under these conditions. It should be noted that such compression does not stain the film, and the fine sharpness of the print is preserved. Preferably, compression of 25-40% of the original channel thickness is desired.

This invention overcomes many of the shortcomings of past printed circuit designs in terms of simplicity, ease of operation, functional utilization and performance. As mentioned above, the present invention ensures interfunctionality of materials which provides advantages not included in prior art products and production methods.

As pointed out above, the basis of this invention is the use of a resin composition consisting of 1. a thermosetting resin and 2. electrically conductive metal particles.

Thermosetting (or thermosetting) resins include organic or inorganic, synthetic or natural resin materials, preferably
It is an organic and synthetic substance that is activated by heat, catalysts, and/or radiation to cause cross-linking reactions. The degree of cross-linking is determined by whether the resin is partially or fully cured.

Curing means that the level of cross-linking is such that the resin is thermoset; that is, the cross-linking is complete and the resin is said to be a cross-linked solid. Thermosetting resins consist of functional groups or moieties that attach to the outer frame of the resin and cause cross-linking. 4 For example, known phenolic resins become cross-linked through condensation reactions with methylol. This condensation is facilitated by equivalent functional groups such as hexamethylenetetraamine. Urea-formaldehyde 9 resin is
It works by a similar methanol condensation, and so do melane-formaldehyde resins. Another thermosetting resin is epoxy resin. These resins react with vicinal epochyl groups and active hydrogen compounds such as amines, phenolic or alcoholic human 90xyls, mercaptans, hydrogen silanates, acids 8, carbamates, ureas and the like or acids and bases. Based on. The silicone resin typically has the following formula: R,5i04-.

] A mean value of about 0.5 to about 1.7, R is an organic group in which the carbon is bonded to a larger organic moiety having a carbon-oxygen-tricon bond to Si or C4 or Si; It is typically formed by hydrolytic condensation of a 7-run 7-mer as follows.

R, 5zX4-rL and R are as described above, and X is a hydrolyzable group, such as halide (chlorine, bromine, fluorine and iodine),
It is alkoxy 7 (preferably having 1 to 4 carbon atoms) or aloki 7 (preferably having a larger than one ring structure). Other resins combine the silicon chemistry described above and the organofunctional interactions noted here. In such resins,
R includes organic functional groups such as aminoalkyl, acryloxyalkyl, methacrinoloquinalkyl, glyc7dyloxyalkyl, 3,4-epoxy7, cyclohexylalkyl, mercaptoalkyl, and the like.

Other thermosetting resins are formed by reacting the incyanate groups forming the resin skeleton with the above and active hydrogen compounds containing water. These resulting polymers are referred to as polyurethanes, polyureas, and combinations thereof.

Other thermosetting resins are formed by free radical addition methods. For example, bis, tris and tetraacrylates and methacrylates can be mixed with free radical inductors in the resin, or
Cross-linking may be achieved by subjecting the resin to suitable radiation that induces the formation of free radicals, such as electron beams, ultraviolet radiation, or any radiation that causes vinylic radicals to interact.

A system that combines these cross-linking methods is most suitable for the practice of this invention. For example, a resin with both condensation and free radical cross-linking capabilities can utilize one of the methods of proceeding with polymerization, and the resin is non-tacky but only partially cured, Nk Final curing is effected by subsequent steps, such as for example, so that the composite product can be applied to the formation and characterization of the print transfer composition.

Specifically, the most suitable thermosetting resin for this invention is as follows.

(1) Unsaturated Polyesters These polyesters are typically the product of the condensation of diols and unsaturated dicarboxylic acids or anhydrides. Diol tlj: Generally ha, ethylene glycol, diethylene glycol, propylene glycol, cyfropylene glycol, neosynthyl glycol, alkoxyl derivative of hisphenol A L 2,2.4-trimethyl-1,3-bentanediol, 2.2 -dimethyl-3-hydroxypropyl,
selected from 2.2-y methyl-3-hydroxypropionate and 1.3-,/tadiol. Unsaturated salts include malic acid and fumaric acid. Acids that have no active double bond and can be used to adjust the amount include Fi, phthalic acid, isophthalic acid, terephthalic acid, and adipic acid.

Anhydrides of the above-mentioned acids, such as malic anhydride and phthalic anhydride, are often used.

Unsaturated polyesters are generally obtained by heating about equimolar amounts of diol and carboxylic acid or anhydride above about 200° C. for about 4 to 24 hours.

Additional groups of polyesters are also contemplated for use herein. These polyesters can be obtained by incorporating dichlorointadiene into the main skeleton of an all-polyester. Such polyesters are used, for example, in U.S. Pat.
,347,806.3.933,757.4,029,
848.4,148,765°4.224,430.

(2) It is shown by the following empirical formula. The average value of the hafestellurium of the hydroxyl-terminated polyester is between about 1.5 and 2, and 1 m is 2-n.

R is the remainder of a hydroxyl-terminated polyester having a molecular weight not exceeding 1,500 and having no hydroxyl group and obtained by the condensation of a diol and a dicarboxylic acid or its anhydride.

These are described in US Pat. No. 4,294,751.

(3) 71- of the organic polyol shown in the following laboratory
Fester OO (ml ()To-C-CH=CHC-0), Rr(O
H).

α is a value with an average value from 1.5 to 4 or less, b is equal to the free valence of R1 smaller than the average value of a, and R1 is the residue without hydroxyl groups of the organic polyol containing 2 to 4 hydroxyl groups. shows.

The organic polyol that reacts with maleic anhydride to form a halfester of formula (III) contains at least 2 carbon atoms and 2 to 4 hydroxyl groups.

The formula (the river Hafestel is shown in U.S. Pat. No. 42, for example)
63413.

Such halfesters are mixed with polyepoxides or unsaturated polyesters.

(4) Poly(acrylate) R3 is the hydroxyl-free remainder of an organic polyhydric alcohol containing alcoholic hydroxyl groups bonded to different carbon atoms, and R2 and R4 are hydrogen or methyl, respectively, as shown in the following empirical formula. C
is 1-3.

The poly(acrylic acid ester) of the organic polyhydric alcohol described above can be obtained by reacting acrylic acid, methacrylic acid, or a simple ester thereof with polyhydric alcohol by a known method.

The above-mentioned Hafestel and polyacrylic acid esters typically have low viscosity and are used in small amounts as filler resins in solvents.

(5) Vinyl ester resin made by adding unsaturated monocarboxylic acid to polyepoxide The vinyl ester used in this invention is obtained by adding unsaturated monocarboxylic acid to polyepoxide. Such vinyl esters are well known in the art and are also commercially available. These include, for example, US Patent No. 3.
377.406; 3,637,618; 4,19
7,340; 3.31? , 365; 3,373,075
;It is described in.

The unsaturated carboxylic acids used here include acrylic acid, methacrylic acid, crotonic acid, or acids obtained by reacting hydroxylated alkyl acrylates or methacrylates with maleic anhydride or phthalic anhydride. Contains.

Epoxides used herein include glycidyl esters of novolac resins, such as phenol-aldehyde concentrates. A preferred example of this type of resin is shown by the following formula.

R5 is hydrogen or an alkyl group, and d takes a value of 0.1 to 5, preferably less than 1.0. The preparation of such polyepoxides is described, for example, in U.S. Pat.
2,658,885.

More preferable polyepoxide is polyhide 9
It is a glyphyl polyester of lime phenol or polyhydric alcohol. Particularly preferably, 2,2-bis(4-hydroxyphenyl) represented by the following formula:
Diglycidyl propane is a polyether.

10-1□-CH-CH2 au, the average molecule I of saturated polyepoxide is 340-2
Take a value that becomes 10OO. Acids modified with vinyl ester resins are also included in this invention. These include 1 e.g. U.S. Pat. No. 3,634,542;
30:3,564,074.

(6) Urethane poly(acrylate) represented by the following empirical formula 6 R6 is hydrogen or methyl; R7 is a linear or branched divalent alkylene or oxyqualkylene group having 2 to 5 carbon atoms; R8 is Divalent groups remaining after reaction of substituted or unsubstituted diisocyanates: R0 is the hydroxyl-free remainder of the organic hydrin alcohol containing hydroxyl groups bonded to different carbon atoms; f has an average value of 2 to 4 value.

These compounds are typical of polyols in which the hydroxyl group is first reacted with a diisocyanate using a monovalent hydroxide per hydroxyl group, and then the free isocyanate group is reacted with a hibiro-qualyl ester of acrylic acid or methacrylic acid. It is a reaction product.

The above-mentioned urethane poly(acrylates) are described in US Pat. No. 3,700,643;
3,837; 3,772,404.

(7) Urethane poly(acrylate) represented by the following empirical formula Rlo is hydrogen or methyl; R1□ is a linear or branched alkylene or oxyalkylene group having 2 to 5 carbon atoms; R1□ is substituted or unsubstituted Multivalent residues remaining after reaction of substituted polyisocyanates: g values with an average value of about 2-4. These compounds are typical products resulting from the reaction of polyisocyanates with acrylic acid or methacrylic acid using monohydric cyclohydroxyalkyl groups per isocyanate group.

Polyisocyanates suitable for urethane poly(acrylate) preparation are known in the art, and certain diisocyanates, including aromatic, aliphatic, and cycloaliphatic polyisocyanates, may be added with small amounts of glycol to raise their melting point. is lowered to provide liquid diiso7anate.

The above-mentioned urethane poly(acrylates) are described, for example, in US Pat. No. 3,297,745; British Patent No. 1,159,552.
It is described in.

(8) Halfester or half amide 9 13 RIll is hydrogen or methyl, and R14 has 2 to 20 carbon atoms, as shown in the following empirical formula.
an aliphatic or aromatic group containing -0- or, independently from -N-, R1, Fi is hydrogen or lower alkyl. Such compounds are typically halfesters or It is half amide.

These include, for example, US Pat. No. 3,150,118 and 3.
367.992.

(9) Unsaturated isocyanurate represented by the following empirical formula R16 is hydrogen or methyl: R17 is a linear group having 2 to 5 carbon atoms or fc is a branched alkylene or oxyalkylene group, R18 is substituted or unsubstituted The divalent radicals remaining after the reaction of diisocyanates, ζ products, are the products of subsequent reaction of hydroquine alkyl esters of acrylic or methacrylic acid with the remaining free isocyanate groups.
It is typically obtained by the trimerization reaction of sitsuquanate.

Such unsaturated isocyanurates are described, for example, in US Pat. No. 4,195,146.

A poly(acid-ester) as shown in the following empirical formula: RlG is separately water or methyl S R2O is separately hydrogen; h is lower alkyl; h is 0 or 1°. It is a typical product of the reaction of acrylic acid or methacrylic acid with a vinyl addition prepolymer enriched in 6-hydro-4H-1,3-ofsazine. Such dfs (amide 9-esters) are described, for example, in British Patent 1,490,308.

01) Poly(acrylamide P) represented by the following experimental formula
or poly(acrylate-acrylamide 9) R23 contains a primary or secondary amine bonded to different carbon atoms, and in the case of an amino alcohol the amine or alcohol group is bonded to different carbon atoms. Polyhydric residue of organic polyhydric amine or polyhydric amino alcohol, R21 and R2□ are hydrogen or methyl separately, K is different, i is 1 to 3.1! , - Examples of the above-mentioned compounds are, for example, Japanese Publication J800305
02, J80030503, J80030504, U.S. Patent 3,470,079, and British Patent 905,18
6.

Any of these resins (1) to 0υ are mixed with an ethylenically unsaturated monomer that can form a liquid homogeneous mixture and copolymerize with these resins. The ethylenically unsaturated monomers contain at least one 0H-(1, group, preferably CH2-), and include styrene and its derivatives, homologues, divinylbenzene, diallylphthalate, acrylic acid or methacrylic acid. non-functional esters (e.g. ethyl acrylate, butyl acrylate, methyl methacrylate, etc.) and unsaturated nitriles (e.g.
Acrylonitrile (methacrylonitrile), etc.
Monomers are vinyl esters, such as evaporation vinyl acetate, vinyl propionate, and the like. Here, lower maleic anhydride is also included. Combinations of the monomers described above are advantageously used in embodiments of the invention.

Inciators are commonly used to initiate the cure of such unsaturated resins and include diacyl peroxides, non-ketals, peresters, and azo compounds.

(Iz Epoxide 9 having at least one epoxy group has the structure of the following formula.

1 Epoxy groups include terminal epoxy groups and internal epoxy groups, and epoxides are mainly cycloaliphatic epoxides. These cycloaliphatic epoxide 9 resins include small amounts of glycidyl-type epoxides, aliphatic epoxides, epoxy fresol novolac resins, polynucleophenol-glycidyl ether derivative resins, aromatic and heterocyclic glycidyl amine resins, and hydantoins. Mixed with epoxy resin 1 etc. and mixtures thereof.

The cycloaliphatic epoxide 9 resin may also be mixed with a trace amount of a cycloaliphatic epoxide having a viscosity of 200 centipoise or less, such as:

Additionally, such cycloaliphatic epoxides are mixed with mixtures of cycloaliphatic epoxides and other epoxides mentioned above. These epoxides are well known in the art and many are commercially available.

Suitable cycloaliphatic epoxide resins for the purpose of the invention have an average of 1 to 2 vicinal epoxy groups per molecule), and a suitable cycloaliphatic epoxide 9 is represented by the following formula: It will be done.

Formula 1 The diepoxide of a cycloaliphatic ester of dicarboxylic acid is represented by the following formula.

R25 to R42, whether the same or different, are hydrogen or an alkyl group generally containing 1 to 9 carbon atoms, preferably containing 1 to 3 carbon atoms, such as methyl, ethyl,
n-fluor, n-1f, ruhexyl, 2-ethylhexyl, ruoctyl, n-nonyl, etc.; R43 generally contains a valence bond or divalent hydrocarbon group of 1 to 20 carbon atoms, preferably, It has 4 to 6 carbon atoms, and is, for example, an alkylene group, trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-ethylhexamethylene, octamethylene, nonamethylene, etc.

Examples of the cycloaliphatic group include 1,4-cyclohexane,
1,3-cyclohexane s 1,2-cyclohexane, etc.

Particularly preferred epoxides are those included in formula 1 in which R4 to R21 are hydrogen and R is 1 to 4 carbon atoms.
This is an alkylene.

Dioxides of specific cycloaliphatic esters of dicarboxylic acids include:

Bis(3,4-epoxycyclohexylmethyl) oxalate Bis(3,4-epoxycyclohexylmethyl)adipate Bis(3,4-epoxy-6-methylcyclohexamethyl)adipate Bis(3,4-epoxycyclohexylmethyl)adipate -epoxycyclohexylmethyl) pimelate, etc.

Other preferred compounds are described, for example, in U.S. Pat.
, 750, 395 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylic acid salts R1 to R1g represented by the following formula may be the same or different.

R25 to R4□ in Formula I are defined. In particularly preferred compounds R1-RIB are hydrogen.

Specific compounds included in formula (1) are represented by the following formula. 3.4-epoxycyclohexylmethyl-3,
4-Epoxycyclohexane carbonate; 3,4-epoxy-1-methylcyclohexylmethyl-3,4-epoxy 7
-1-methylcyclohexane carbonate; 6-methyl-3,
4-epoxy-cyclohexylmethyl-6-methyl-3
,4-epoxycyclohexane carbonate; 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carbonate; 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy -5-Methylcyclohexane carbonate. Other suitable compounds are described, for example, in US Pat. No. 2,890,194.

Dioxides of the formula "are monovalent substituents, which may be the same or different, such as hydrogen, or halogen or monovalent hydrocarbon radicals, i.e. chlorine, bromine, iodine or fluorine, or A particularly preferred compound is one in which all R's are hydrogen.

Other preferred cycloaliphatic epoxides are shown below.

The preferred cycloaliphatic epoxide 9 is as follows. 3
, 4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane carbonate, bis(3,4-epoxycyclohexylmethyl) adipate.

2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, or these compounds.

Epoxides with six-membered ring structures can also be used, such as diglycidyl esters of phthalic acid, a representative diglycidyl ester of phthalic acid, which is partially or fully hydrogenated phthalic acid, can be used according to the following general scheme. It is.

Diglycidyl esters of hexahydrophthalic acid are preferred.

Glycidyl-type epoxide 9 is preferably a diglycidyl ester of bisphenol A derived from bisphenol A and shrimp chlorohibirin, and has the formula shown below.

Fresol-novolak epoxy resins are multifunctional, solid polymers with the characteristics of low ionic, hydrolyzable chlorine impurities, high chemical resistance and temperature performance.

Epoxyphenol novolac resins are generally given by the following formula.

Polynuclear phenol-glycidyl ether derivative resins generally have the following formula. Among the aromatic and heterocyclic glycidyl amine resins included herein, there are the following. Tetraglycidyl triglycidyl-P- with the following structure:
Formula of amine phenol derivative resin, triazine based resin and hydantoin epoxy resin, R44 is methyl group, A suitable curing agent may be added to effectively cure the epoxide compound.

Suitable curing agents are as follows.

1. Phenolic curing agent having at least 2 phenolic hydroxyl groups A, preferably #) having 3 phenolic hydroxyl groups per molecule 2. At least 2 carboxylic acid groups per molecule Examples of suitable phenolic curing agents include the following polyhydric phenols. Catechol, hyde-90quinone, hydroxyhyde-10quinone, chloroglucinol, resorcinol, pyrogallol. Polynuclear phenols such as bisphenols are used in QBel dgr atαl, US Pat. No. 2506
486, such as novolak condensates of phenols and aldehydes, saturated or unsaturated, containing an average of 3 to 20 or more phenylol groups per molecule.

(Reference T, S, CarzwaLL 'Phanopl
asts” 1947 issue 1ntarscianca
Examples of suitable polyphenyrol derivatives consisting of phenol and an unsaturated aldehyde such as acrolein include A, G, May 5, 1959;

U.S. Patent No. 2,885,38 granted to Far Lulu αm
Triphenylol, bantaphenyrol, heftafenylol Kaal described in 5.

Phenol includes alkyl or allyl substitution or halogen, exemplified by alkylresorcinol, tribromoresorcinol, and diphenols substituted with alkyl or halogen on the aromatic ring.

(Bgndgr at aL, U.S. Pat. No. 2,506,4
86) Furthermore, regarding acids, U.S. Pat.
It is taught in 444.

Other suitable polybasic acids are described below as having at least two carboxylic acid groups per molecule. Tricarpallic acid, trimellitic acid, etc. Other suitable polybasic acids include polyesters, B, Ph
1llipt US Pat. No. 2,921,925.

Suitable anhydrides are those of the acids listed above, and preferred curing agents include methyltetrahydride-90 phthalic anhydride, hexahypyrophthalic anhydride, and methylbexahyde-90 phthalic anhydride. .

Epoxides are cured through the use of photoelectric initiators. Photoinitiators herein include one or more metal fluoroborates or bromine trifluoride, which are described in US Pat. No. 3,379,653; bis(nofluoroalkylsulfonyl)methane metal salts are Patent 3
Allyl diazonium compounds are described in US Pat. No. 3,708,296; ■ Aromatic onium salts of α group elements are described in US Pat. No. 4,058,400; aromatic onium salts of Vα group elements are described in US Pat. No. 4,069,055. dicarbonyl chelates of alpha group elements are described in U.S. Pat. No. 4,086,091; thiopyrylium salts are described in U.S. Pat. No. 4,139,655;
vra group elements with MF6- ions selected from h are described in US Pat. No. 4,161,478; triallylsulfonium compound salts are described in US Pat. No. 4,231,951; Sulfonium compound salts are described in US Pat. No. 4,256,828. Suitable photoinitiators include triallylsulfonium compound salts, aromatic sulfonium or iolinium salts of halogen-containing compound ions, mtz, vα
, ■There are aromatic onium salts of α-group elements. Some of these salts are FC-508, FC-509 (M
innazotaMining and Manufa
(available from curing Company) and U
VE-1014 (GgrLaraZELactric
Commercial use is possible, such as available from the Company.

The photoinitiator in the composition of this invention is epoxide 1
It is conventionally used at 1 part by weight, such as 0.1 to 30 parts by weight per 1 part by weight.

(131 Phenol formaldehyde resins with the following formula are greater than 1 and include resols and novolacs.

(14) A polyurethane derivative consisting of a polyol and an isocyanate. For example, polyhydrocarbons with hydride 90-oxy terminals (
(U.S. Pat. No. 2,877,212); Polyphorere (U.S. Pat. No. 2,870,097) that is hybiloxy-terminated; Aliphatic triglyceride 9 (U.S. Pat. No. 2,833,730, 2,878,601); Hyde-90 (oxy-terminated) Polyester (4 U.S. Pat. No. 2,698,838, 2,
No. 921,915, No. 2.591,884, No. 2,866
, No. 762, No. 2.850,476, No. 2,602,78
No. 3, No. 2,729,618, No. 2,779,686,
2,811,493, 2,621,166); hydroxymethyl-terminated perfluoromethylene (U.S. Pat. Nos. 2,911,390, 2,902,473);
British Patent No. 733,624; Polyalkylene Arylene Ether (U.S. Patent 2,8Q.S, 3'l/.); Polyalkylene Ether Triol (U.S. Patent No. 286.674)
>.

The preparation of cyclic ester polymers is described in U.S. Pat.
From No. 021,309 to No. 3,021,317, 3
, No. 169,945, and No. 2,962,524.

Polymers of cyclic esters are disclosed in U.S. Pat.
It is also produced by the method described in No. 2,524.

Other active hydrogen-containing substances useful in inventions include:
British Patent No. 1,063,222 and US Patent No. 3,38
No. 3,351, herein incorporated by reference, is a polymer/polyol obtained by converting an ethylenated unsaturated monomer in a polyol as disclosed.

Incyanates include all suitable polymeric incyanate compositions. It also includes mixtures of one or more of these incyanates. The actual heavy isocyanate was reported by Slggr et al. on July 31, 1954.
No. 2.6;83,730, incorporated by reference in its entirety.

Particularly preferred types of thermosetting resins for combination with the electrically conductive particles include glycidyl ethers of bisphenol A or glycidyl ethers of phenol-formaldehyde resins (such as the epoxidized novolacs described above) or cycloaliphatic epoxides. 9 and mixtures thereof. Each has already been mentioned. These are cross-linked by incorporation of the active hydrogenation moieties defined above, with or without the addition of acid or alkali. Sometimes the cross-linking density is too great to achieve complete coverage with these polymers;
and/or sufficient metal particle wettability may not be effectively achieved when forming the coating (ink) mixture. In order to obtain such resins completely, it is said that thermosetting resins are mixed with epoxy resins and thermoplastic resins capable of reacting in various stages for cross-coupling reactions.

For example, thermoplastic resins include polyvinyl acetate, including hydrolyzed acetate, which provides vinyl alcohol groups; also polyvinyl formal or notyral, which provides vinyl alcohol or vinyloxy groups; , in which a few hydrolyzed groups react with the aromatic monoisocyanate, releasing incyanate and active hydrogen under curing conditions, providing a block of isocyanate structures, and electrically conductive metals in the epoxy resin. Add the solvent on the grains and other items according to the instructions. The thermoplastic resin provides some or all of the active hydrogen required for cross-linking of the epoxy resin;
It becomes part of a cross-linked thermoset structure.

dielectric surface The dielectric surface is made from any known dielectric surface.

In the practice of this invention, an organic resin material is used as the dielectric surface. Suitable organic resins include thermosetting resins, as mentioned above, but they may be used alone or reinforced with fillers and/or fibers. Reinforcing fillers and/or fibers are generally preferred. This will be touched upon in the addition section below. Without such reinforcement, such resins are prone to shrinkage upon curing, and compositions and conditions that minimize such shrinkage are desired. Other dielectric materials include thermoplastic resins and are discussed below.

Thermoplastic resins include polyaryl ether sulfone, poly(allyl ether), polyarylate, polyetherimide 9, polyester, aromatic polycarbonate, styrene resin, poly(allyl acrylate), polyhypyroxylether, poly(allyl) one or more selected from ruphite 9) or polyamide 1.

A, yllJ Allyl Ether Sulfone The polyallyl ether sulfone of this invention is an amorphous thermoplastic polymer containing units of the following formula.

and/or R55 is each hydrogen, an alkyl group of 01 to C6, or a cycloalkyl group of 04 to C8, and “59” are hydrogen, or G1 to C8, respectively.
an alkyl group, α1 is 3 to 8 -S-1-0- or 1 to 3 complete units (the ratio of the ratio to the account of river and/or shout is greater than 1; each unit is Join each other in 10-Naai.

Preferred polymers of this invention containing units of the formula:Other preferred polyallylether sulfones of this invention containing units of the formula:

These units are connected to each other through 10-bonds.

Polyarylether sulfone has a random or regular structure.

In this invention, the polyallyl ether sulfone is
It has a low viscosity of not more than 0.4 to 2.5, measured at 25° in N-methylpyrrolidone or a suitable solvent.

The polyallyl ether sulfone of this invention is prepared by reacting monomers represented by the following formula.

R55J α, X' and R are as defined above, X and Y are each selected from C1, BrlF%NO2,9H, and at least Y is OH, but does not exceed 50%.

The ratio of the OH group concentration to the G1.3r%F and NO2 groups forming the polyallyl ether sulfone is from 0.90 to about 1.10, preferably from about 0.98 to 1. It is .02.

Monomers of formula i, (Vl, (7) and (to)) include: 2.2-bis(4-hybiloxyphenyl)furonone, bis(4-hydro-10xyphenyl)methane, 4. 4'-9 hydroxyphenyl sulfide, 4.4'-dihy 10-oxydiphenyl ether,
4.4'-cyhydroxydiphenylsulfo/2.
4'-Sivite 90xyphenyl sulfone, 4.4'
-dichlorodiphenylsulfone, 4.4'-0 nitrodiphenylsulfone, 4-chloro-4/-hydroxydiphenylsulfone, 4,4-bisphenol, hyde-90quinone, etc.

Suitable monomers include Hyde 90 quinone, 4°4-
Biphenol, 2,2-bis(4-hydro-90xyphenyl)fluorozone, 4,4'-dichlorodiphenylsulfone, and 4,4'-dihydroxydiphenylsulfone or 4-chloro-4'-noite90 It is xydiphenyl sulfone.

The polymers of this invention contain substantially equimolar amounts of hydroxy-containing compounds (as shown in formulas (5) to (9) above) and halo- and/or nitro-containing compounds (formulas 4 and ( Vl) is reacted with 5 to 1.0 mol of alkali metal carbonate per mol of hydroxy compound in solution, and
The solvent is substantially anhydrous between the plates and consists of a mixture of solvents that form an azeotrope with water to keep the reaction mild.

B. Polyallyl ether resin The poly(allyl ether) resin suitable for mixing with polyallyl ether sulfone is different from polyallyl ether sulfone. It is a thermoplastic polyarylene polyether.

-0-E-0-E/- In this formula, E is the residue of a dibasic phenol, and E' is a valence bond that connects an inactive electron at at least one of the ortho and para positions. It is a residue of a penzonoubi compound having a group that attracts ether, both of which are bonded to the oxygen of the ether via an aromatic carbon atom. Such aromatic polyethers are described, for example, in US Pat. Nos. 3,264,536 and 4,175,17.
Polyarylene polyester described in specification No. 5/
'It is included in the class of fats. The dibasic phenol is a weakly acidic dinuclear phenol, such as dihydroxydiphenylalkanes or their nuclear halogenated derivatives, e.g.
2,2-bis(4-bioxyphenyl)furopane, 1,1-his(4-bioxyphenyl)2-phenylethane, his(4-bioxyphenyl)methane, or each aromatic ring Preference is given to chlorinated derivatives having one or two chlorines. Phenols of appropriate length are also preferred as other materials due to their high cost. Such materials may be bonded symmetrically or asymmetrically with respect to, for example, an ether oxygen (-0-), a carbonyl residue C-C-), a sulfone residue (-8-), or a hydrocarbon residue. bisphenols having a group in which the two phenolic nuclei are bonded to the same or different carbon atoms of the residue.

Such dinuclear phenols are characterized as having the following structural formula.

In this formula, Ar is an aromatic group, preferably a phenylene group, and R6□ is the same or a different inert substituent, such as an alkyl group having 1 to 4 carbon atoms, an allyl group, a fluorine atom, etc. , chlorine, bromine or iodine, or an alkoxy group having 1 to 4 carbon atoms, 0' is an integer up to 4, including 0, and R
63 represents a bond between aromatic carbon atoms such as a dihydroxy-diphenyl bond, or represents a divalent group such as 1-C-1-〇-1-S-1-SO-1-S-S -1-S
groups such as O2-, and substituted alkylene, substituted alkydene and substituted alicyclic groups such as alkylene, alkylidene, cycloalkylene, cycloalkyly-7'7, halo)I-substituted alkylene, alkyl-substituted alkylene, allyl-substituted alkylene, It represents an aromatic group and a divalent group such as a fused ring of two of the above Ar groups.

The definition of E' refers not only to the dibasic phenol residue, but also to the dibasic phenol residue after two aromatic hydroxyl groups have been removed. As can be easily understood, the polyarylene polyethers include repeating units of dibasic phenol residues and repeating units of benzonoid compound residues bonded via the oxygen atom of the aromatic ether.

A dihalobenzi having two halogen or nitro groups in the i/zene ring, which has a group that attracts electrons toward the halogen or nitro group at at least one of the ortho position and the noR2 position of benzene IN' Noite 9 compounds or dinitrobenzonoid compounds or mixtures thereof can be used in the present invention. A dihalobenzonoid compound or dinitrobenzinoite9 compound is a mononuclear compound in which a halogen atom or a nitro group is attached to the same benzonoid ring, or a halogen or Any polynuclear compound having different nitro groups attached to indinoites 9 may be used. Fluorine-substituted benzonoid reaction raw materials and chlorine-substituted benzonoid reaction raw materials are preferred; fluorine-substituted benzonoid compounds react quickly, and chlorine-substituted benzonoid compounds are inexpensive. In particular, when trace amounts of water are present in the heavy-duty reaction system, fluorine-substituted benzonoid compounds are most preferred. However, the amount of water present should be maintained at less than about 1 percent, preferably less than 0.5 no cents, for best results.

Electron-withdrawing groups are used as activating groups in these compounds. It must of course be inert under the reaction conditions, but on the other hand there are no restrictions on its structure. Preferred is the benzonoid nucleus substituted with two halogen atoms or nitro groups, and 4.4'-0 chlorodiphenyl sulfone, but other strongly attractive compounds are used herein. The remaining groups described below can be used with similar ease. Stronger electron-withdrawing groups are preferred as they provide more rapid reactions. More preferred are rings that do not include electron-donating groups on the same benzonoid nucleus with a halogen or nitro group, although other groups may be present on the nucleus or on the residue portion of the compound.

Additionally, the polyethers are described in Canadian Patent No. 847.96.
It can be produced by the method described in Specification No. 3,
In that case, the bisphenol compound or dihaloenzenoid compound is heated in the presence of potassium carbonate using a high boiling solvent such as diphenylsulfone.

The poly(allyl ether)s have a reduced viscosity of 0.35 to 1.5 in a suitable solvent at a suitable temperature, for example methylene chloride 9 at 25°C, depending on the particular polyether.

Preferred poly(allyl ether)s have the following repeating unit structure.

Polyarylates suitable for use in the present invention include:
derived from a dibasic phenol and at least one aromatic dicarboxylic acid and having a reduced viscosity of about 0.4 to 1.01, preferably about 0.6 to 0.8 dllin&; When measured at 25°C in another suitable solvent.

Particularly desirable dibasic phenols have the general formula: where Y is independently selected from hydrogen, an alkyl group of 1 to 4 carbon atoms, chlorine or bromine, and each d is 0 to 4.
and R66 independently has a value of 4 and R66 is a divalent saturated or unsaturated aliphatic hydrocarbon group, in particular an alkylene or alkylidine group having 1 to 6 carbon atoms, or up to 9 carbon atoms. a cycloalkylidene or cycloalkylene group, oxygen, C01So2, or S. These dibasic phenols can be used individually or in combination.

The aromatic dicarboxylic acids used in the present invention include terephthalic acid, isophthalic acid, various naphthalene dicarboxylic acids and mixtures thereof, analogs of the dicarboxylic acids substituted with alkyl groups of 1 to 4 carbon atoms, and , halogens, alkyl ethers, or allyl ethers. Acetoxybenzoic acid can be used as well. Preferably a mixture of isophthalic acids and terephthalic acids is used. The ratio of isophthalic acid to terephthalic acid in the mixture is from about 0:100 to about 100:0.2, but most preferably from about 75:25 to about 50:50.

About 0.5 to 20% of aliphatic dicarboxylic acids having 2 to 10 carbon atoms, such as adipic acid, 7/Z cinic acid, etc., can be used concomitantly in the polymerization reaction.

The polyarylate of the present invention can be produced by a reaction between an acid chloride of an aromatic dicarboxylic acid and a dibasic phenol, a reaction between a diallyl ester of an aromatic dicarboxylic acid and a dibasic phenol, or a reaction between an aromatic dicarboxylic acid and a dibasic phenol. It can be produced by any of the conventionally known polyester-forming reactions, such as the reaction of diester derivatives of basic phenols. These methods are described, for example, in U.S. Pat. No. 3,317,464, U.S. Pat. No. 3,948,856, U.S. Pat.
33,898 and especially U.S. Pat. No. 4,321,
No. 355.

D. Polyetherimides Polyetherimides suitable for use in the present invention are well known in the art and are described, for example, in U.S. Pat.
No. 47,867, No. 3,838,097 and No. 4.1
No. 07,147.

The polyetherimide has the following general formula.

In this formula, - is an integer greater than 1, preferably from about 10 to about 10,000 or more, such as -0
-R67-0- is bonded to the 3 or 4 position and the 3' or 4' position, and %R6□ is a substituted or unsubstituted aromatic group such as (al), or Alkyl, allyl or halogen having 1 to 6 carbon atoms, and R7゜ is -〇-1-S-1)l -a-1-SO□-1-so-1 having 1 to 6 carbon atoms R68 is a divalent group selected from the group consisting of alkyline having 1 to 6 carbon atoms, alkylidene having 1 to 6 carbon atoms, or cycloalkylizo having 4 to 8 carbon atoms; Aromatic hydrocarbon groups and their halogenated derivatives, or their alkyl substituents (where the alkyl group contains 1 to 6 carbon atoms), alkylene groups or cycloalkylene groups having 2 to 20 carbon atoms, and carbon It is selected from an alkylene group having 2 to 8 atoms and terminated with a polydiorganosiloxane, or a divalent group having the general formula (wherein R69 and R7o are the same as defined above).

The polyetherimide may also include those of the following general formula.

(wherein R7□ is separately a halogen, lower alkyl or lower alkoxy group) (wherein oxygen is directly attached to the ring and in the ortho or per position with respect to one of the abutments of the carbonyl group) , R67 and R2O selected from
is the same as defined above.

These polyetherimides can be prepared by methods well known in the art, such as U.S. Pat. No. 3,833,544.
No. 87,588, No. 4,017,511 and No. 4.0
No. 24,110.

Preferred polyetherimides 9 include those having repeating units of the following structural formula.

E Polyester Polyesters suitable for use in the present invention include 2
Derived from aliphatic diols or cycloaliphatic diols containing ~10 carbon atoms or mixtures thereof and at least one aromatic dicarboxylic acid. Polyesters derived from aliphatic diols and aromatic dicarboxylic acids have repeating units of the following general formula.

(wherein is an integer from 2 to 10). A preferred polyester is poly(ethylene terephthalate).

In the present invention, repeating units derived from aliphatic acids and/or aliphatic polyols are added in small amounts, for example from about 0.5 to
2 percent can also be used to form a copolyester. Aliphatic polyols include glycols such as polyethylene glycol. These can be made, for example, by the methods disclosed in US Pat. No. 2,465,319 and US Pat. No. 3,047,539.

Polyesters derived from cycloaliphatic diols and aromatic dicarboxylic acids may be either cis- or trans-cycloaliphatic diol isomers (or mixtures thereof), e.g.
It is prepared by condensing cyclohexa/dimetatool and an aromatic dicarboxylic acid to form a polyester having repeating units of the general formula:

(9II In this formula, the cyclohexane ring is selected from their cis and trans isomers; C1R7
□ represents an allyl group containing 6 to 20 carbon atoms as a decarboxylated residue derived from an aromatic dicarboxylic acid.

Preferred polyesters are derived from the reaction of the cis or trans isomer (or mixtures thereof) of 1,4-cyclohexane dimetatool with isophthalic acid and a mixture of terephthalic acid and terephthalic acid. These polyesters have repeating units of the following structural formula.

Preferred copolyesters are the cis or trans isomer of 1,4-cyclohexane dimetatool.

It is derived from the reaction of the columns (or mixtures thereof) and ethylene glycol and terephthalic acid in a 1:2:30 molar ratio. These copolyesters have repeating units of the general formula:

In this formula, the number may be 10-10,000, and may be a block copolymer or a random copolymer.

The polyesters described herein can be purchased commercially or, for example, in U.S. Pat. No. 2,901.4
It can be produced by conventionally known methods such as those described in FI 6.

The polyester used in the present invention is:

It has an intrinsic viscosity of about 0.4 to about 2.0 del I10 on the platform, measured in a 60:40 mixture of phenol/tetrachloroethane or similar solvent at 23-30°C.

F Aromatic Polycarbonate The thermoplastic aromatic polycarbonate used in the present invention is a homopolymer and a copolymer and mixtures thereof, and has a temperature of about 0.4 to 1 O, measured in methylene chloride at 25°C. It has an intrinsic viscosity of This polycarbonate is obtained by reacting a dibasic phenol with a carbonate precursor. Typical examples of dibasic phenols that can be used include bisphenol A1 bis(
4-hydroxyphenyl)methane, 2,2-bis(4-
hydroxy-3-methylphenyl)pronoξ, 4.4
-bis(4-human90xyphenyl)pentane, 2-2
- (3,5,3', 5'-tetrabromo-4,4'
-dihy-10oxydiphenyl)methane, and others. Other dibasic phenols of the bisphenol type are described, for example, in U.S. Pat. No. 2,999,835;
No. 28,365 and No. 3,334,154. Using two or more different types of dibasic phenols, or copolymers of dibasic phenols and glycerol or with hydroxyl-terminated or acid-terminated polyesters. is of course possible.

The carbonate precursor may be a carbonyl halide, carbonate ester or haloformate. Carbonyl halide 1 that can be used in the present invention
are carbonyl bromide, carbonyl chloride and mixtures thereof.

Typical carbonate esters that can be used in the present invention include di(tolyl) carbonate, 9-(halophenyl)carbonate, di(chlorophenyl)carbonate, di(chlorophenyl)carbonate, etc. ) Carbonate, di(naphthyl)carbonate%:
) (chloronaphthyl) carbonate and other di(alkylphenyl)carbo-4-).

or a mixture thereof. Haloformates suitable for use in the present invention include dibasic phenolic bis-
Haloformates such as bischloroformate of bisphenol A, bischloroformate of hyperiquinone, etc.
Also included are glycols such as Everrf Ren glycol, bishaloforme-1-, neointyl glycol, and polyethylene glycol. Although other carbonate precursors will be apparent to those skilled in the art, carbonyl chloride 1, conventionally known as phosgene, is preferred.

Aromatic polycarbonate polymers can be made by methods well known in the art using phosgene or haloformates with molecular weight modifiers, acid acceptors and catalysts.

Aromatic polyester carbonates can also be used. These are described, for example, in US Pat. No. 3,169,121.

Preferred polyester carbonates are obtained from the condensation of phosgene, terephthanoyl chloride 1-4, isophthanoyl chloride 9 with bisphenol A and small amounts of tertiary methylphenol.

G Styrenic Resins Styrenic resins suitable for use in the present invention include A
BS type polymers are included, the molecules of which include two or more moieties of different compositions that are chemically condensed.

The resin is preferably produced by polymerization of a conjugated diene, such as tutadiene, or a conjugated diene and a copolymerizable monomer that provides a polymerizable backbone, such as styrene. After the skeleton is formed, at least one, preferably two, graft monomers are polymerized in the presence of the prepolymerized skeleton to form a graft polymer. Such resins are manufactured by methods well known in the art.

The backbone polymer as described above is preferably a conjugated diene polymer such as polytutadiene, polyimprene, or a copolymer such as butadiene-styrene, butadiene-acrylonitrile, etc.

The specific conjugated diene monomers commonly used to create the backbone of graft polymers are represented by the following general formula.

(In this formula A' is selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, chlorine or bromine.) Examples of dienes that can be used are butadiene, isoprene, 1 .3-heftashiene, methyl-1
, 3-pentadiene, 2.3-dimethyl-1,3-butadiene, 2-ethyl-1°3--4:ytadiene, 1.
Examples include 3- and 2,4-hexadiene, chlorine-substituted or bromine-substituted tutadiene, such as dichlorobutadiene, bromobutadiene, dibromotutadiene, mixtures thereof, and the like.

A preferred conjugated diene is tutadiene.

The monomer or group of monomers that can be polymerized in the presence of the prepolymerized backbone are monovinyl aromatic hydrocarbons. Preferred monovinyl aromatic hydrocarbons are styrene and/or W-
Al with methylstyrene.

The second group of monomers that can be polymerized in the presence of the prepolymerized backbone includes acrylonitrile, substituted acrylonitriles and/or
or acrylic monomers such as acrylic esters, such as acrylonitrile and alkyl acrylates such as ethyl acrylate and methyl methacrylate.

In the preparation of the graft polymer, the conjugated diolefin polymer or copolymer and 1- are exemplified by a 1,3-tutadiene polymer or copolymer comprising about 50% by weight of the total graft polymer composition. Illustrated by styrene and acrylonitrile. The monomers polymerized in the presence of the backbone are about 40 to 95% by weight of the total graft polymer composition.

The second group of graft monomers, exemplified by acrylonitrile, ethyl acrylate or methyl methacrylate, in the grafting platform composition preferably comprises from about 10 to 40% by weight of the total graft copolymer composition. Become. Monovinyl aromatic hydrocarbons, exemplified by styrene, comprise about 30-70% by weight of the total graft polymer composition.

In the production of polymers, grafting 1 to each other on the backbone
The proportion of polymerized monomers that form sand and the proportion of polymerized monomers that form free copolymers generally fall within a certain range of percentages. If styrene is used as one grafting monomer and acrylonitrile is used as the second grafting monomer, some portion of the composition is co-charged with the free styrene-acrylonitrile copolymer. Will. Typically, the elastic skeleton can be an acrylate rubber, such as a skeleton based on loose tyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, etc. Concomitantly, an improved grafting product can be obtained by copolymerizing a minimal amount of diene into the acrylate rubber backbone to form a matrix polymer.

These resins are well known in the art and many are commercially available.

Poly(alkyl acrylate) resins that can be used in the present invention include homopolymers of methyl methacrylate (i.e., polymethacrylate) or methyl methacrylate and vinyl monomers (e.g., acrylonitrile,
N-allylmaleimide V, vinyl chloride or N-vinylmaleimide), or alkyl acrylates of alkyl groups of 1 to 8 carbon atoms or alkyl methacrylates of alkyl groups of 1 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, butyl acrylate, Includes copolymers with ethyl methacrylate and methyl methacrylate. The amount of methyl methacrylate is greater than about 70% by weight of the copolymer resin.

Alkyl acrylate resins are grafted onto unsaturated elastic backbones such as polybutadiene, polyisoprene, and/or butadiene or isoprene copolymers. For graft copolymers, the alkyl acrylate resin comprises greater than about 50% by weight of the graft copolymer.

These resins are well known in the art and are commercially available.

Methyl methacrylate resin is approximately 1.0-2.0 dl/1 at 25°C in a 1 percent chloroform solution.
It has a reduced viscosity of 1.

(2) Poly-10xyether The thermoplastic polyhydroxyether that can be used in the present invention has the following general formula.

(-FOFIO-)j/ In this formula, F is the residue of a digroup phenol,
F' is the residue of an epoxide selected from monoepoxides or diepoxides containing one to two hydroxy groups, and No° is an integer representing the degree of polymerization, at least about 30 and preferably about 82. That's all.

Generally, thermoplastic polyhuman 90-oxyethers are prepared by contacting a dibasic phenol and an epoxide containing one to two epoxy groups in substantially equimolar amounts under polymerization conditions by methods well known in the art. be done.

Any dibasic phenol can be used to form poly-10-oxyethers. Examples of dibasic diphenols include hyde-90 quinone, resorcinol, etc. and polynuclear phenols. Particularly preferred are dibasic polynuclear phenols having the following general formula.

(101) In this formula, G and k represent as previously defined and R75 is an alkylene or alkylidene group, preferably an alkylene or alkylidene group having 1 to 3 carbon atoms, having 6 to 12 carbon atoms. cycloalkylene or cycloalkylidene group.

Dieboxides useful in the preparation of polyhuman 90xyethers can be represented by repeating units having the general formula:

In this formula, R76 represents a bond between two adjacent carbon atoms, or a divalent organic group such as an aliphatic arrangement, an aromatic arrangement, an alicyclic arrangement, a heterocyclic arrangement, or an acrylic arrangement of atoms. Represents a divalent organic group such as an array.

Other usable dieboxides 1 and j~ include dieboxides in which two oxirane groups are linked via an aromatic ether, ie, compounds having the following general formula.

(+02) In this formula, R7□ is a divalent organic group, and J is a divalent aromatic residue of a dibasic phenol, such as the residue listed above for dibasic phenol. and m is an integer from 0 to 1 including zero.

These polyhydroxy ethers are described in US Pat.
, No. 238,087, No. 3,305,528, No. 3,
924,747 and 2,777.051 by methods well known in the art.

Polyamide 9 polymers that can be used in the present invention are well known in the art. Polyamide polymers include homopolymers and copolymers. These polymers can be prepared by condensation of diamines with tribasic acids and concomitant polymerization in a conventional manner as condensation of difunctional monomers.

Aromatic polyamides in which both the diamine and the tribasic acid are aromatic are also used in the present invention.

Tribasic acids include terephthalic acid, isophthalic acid, phthalic acid, etc., and aromatic diamines include orthophenylene diamine, 2,4-diaminotoluene, 4°4'-methylene dianiline, etc.

Polyamide polymers can be produced by direct amidation, which is the reaction of amino groups and carboxyls with water removal, by low-temperature polycondensation of diamines and diacid chlorides, and by opening, which involves the addition of amines to active double bonds. They are prepared by methods well known in the art such as ring polymerization, polymerization of isocyanates, and reaction of formaldehyde with dinitrile.

Polyamide polymers include polyhexamethylene/-adipamide, i.e. nylon 6
．． 6 poly(ε-caprolactam), i.e., nylon-6, polypropiolactam, i.e., nylon-3, polypyro-sin-2-one, i.e., vachinairo 7-4, poly(ω-enansamito 9), i.e., nylon-3. 7. Polycapryllactam, i.e. nylon-8° poly(
ω-pelargonamide), i.e., nylon-9, poly(11-amidodecanoic acid), i.e., nylon-1
0, poly(ω-untecanamyl-″′), ie, nylon-11°, polyhexamethylene terephthalamide 9, ie, nylon-6, T nylon-6,10, and the like.

K, +N (arylene sulfite 9) Poly(arylene sulfite 9) suitable for use in the present invention
) is a solid, has a melting point of at least about 150'F, and is insoluble in common solvents.

Such resins are described in US Pat. No. 3,354,12, for example.
It can be produced in a customary manner by the method described in No. 9. This manufacturing method is (105
) reaction of an alkaline pan-sulfite 9 with a polyhalo ring-substituted aromatic compound in the presence of a suitable polar organic compound;
Examples include the reaction of sodium sulfide and dichlorobenzene to form poly(phenylene sulfide P) in the presence of N-methyl-2-pyrrolidine.

Preferred poly(arylene sulfide) is poly(phenylene sulfide), which is a crystalline polymer having a repeating unit containing a para-substituted inzene ring and a sulfur atom, and has the following general formula: .

(wherein P has a value of at least about 50). Suitable poly(phenylene sulfite 4)s are commercially available from Phillips R Trollium Company under the trade name Rytorb. Preferably, the poly(phenylene sulfide) component has a particle diameter of about 10 to 7000 d measured at 600'F using a 5 kg weight and a standard orifice.
ll, with a melt flow coefficient of 7 minutes.

(106) The term poly(arylene sulfide) refers not only to homopolymers, but also to arylene sulfipico-polymers, terpolymers, and the like.

Liquid Crystal Polyester The liquid crystal polyester used in the present invention is well known in the art. These liquid crystal polyesters are disclosed in, for example, U.S. Pat. No. 3,804,805 and U.S. Pat.
No. 3,845,099, No. 3,318,84
No. 2, No. 4,076,852, No. 4,130,5
No. 45, No. 4,161,470, No. 4,230,
No. 817 and No. 4,265,802. Preferably, the liquid crystalline polyester is derived from one or more of the following: Parahydroxybenzoic acid, meta-hydroxybenzoic acid, terephthalic acid, sophthalic acid, bisphenol A, 2.6-naphthalenediol, 2.6-naphthalenedicarboxylic acid%6
-Hydroxy-2-naphthalic acid and 2,6-dihydroxyanthraquinone. Commercially available liquid crystal copolymers (
Ekkanol, a homopolymer of para-hydroxybenzoic acid, and a copolymer of para-hydroxybenzoic acid, terephthalic acid, isophthalic acid, and 4,4'-biphenol (available from Qarhorundom Corp.) It is Ekkcal. Other useful liquid crystalline polyesters include Nozorahito-90xybenzoic acid and 6-hydroxybenzoic acid.
Copolyesters with a molar ratio of 75/25 of -hydroxy-2-naphthalic acid and copolyesters obtained by polymerizing paraacetoxybenzoic acid in a matrix of polyethylene terephthalate.

In particular, substrates with low moisture absorption are desirable for vapor phase soldering. 2 at 23℃ in case of liquid brazing
Substrates exhibiting an increase of 1 to 0.2 wt.
Must have moisture absorption capacity exceeding approximately 0.05% weight increase when vapor phase soldering is performed at 3°C for 24 hours. Therefore, in some cases it may be desirable to dry the substrate prior to applying either vapor phase soldering or liquid soldering.

Adhesive The adhesive component may be any one or more of the thermosetting resins described above, and may have an apparent thermal resistance sufficient to react with such resin and the bonding agent portion of the single circuit element coating. Plastic resins and/or combinations with other reactive resins that can be mixed to form a cured thermoset interfacial bonding layer between the binder (dielectric surface) and other binders (coating of circuit elements) It may be.

The theory supporting the adhesion phenomenon is well developed. (For example, S
kigit, andhook of Adhagiv
gzJ 2nd edition, 19'17.7) 71111-16°N
ostrand Rginhold Qcompany,
New 'fork, USA New York all 1
Publication) A very wide variety of adhesive materials can be used in practicing the present invention. Without intending to limit the invention, preferred adhesive combinations include:
As described in F3kiast, supra, pages 507-527, it is a mixture of acetal resins, namely polyvinyl acetal and epoxy resin. polyviny (
109) Particularly good results are obtained from mixtures of lupetiral or polyvinyl acetals with epoxy-substituted novolaks as described below. Another desirable adhesive is:
Included are thermoplastic, plastic polyester polyurethanes crosslinked with polyfunctionally encapsulated incyanates, where the crosslinking is accomplished by biuret and/or allophanate linkages.

Linear epoxy systems include cycloaliphatic epoxies mixed with polyols such as polycaprolact/polyols.
Something like is desirable. A catalyst is supplied if the internal reaction is carried out by catalytic reaction. Many resin systems are crosslinked to a cured state by heating alone. If the dielectric surface is pre-impregnated, then the rounded resin that forms the final composition of the dielectric surface can be used as an adhesive layer or interfacial material. Many thermosetting resins can be used not only to bond dielectric surfaces (synthetic formations), but also to establish bonds between circuit element coatings or other adhesive layers. . L7'c There are many options for adhesives, and there are many variations (110). A number of adhesives can be incorporated into the adhesive composition, and these are described in the ``Additives'' section.

Additives Additives that can be used in thermoplastic and/or thermosetting resins for making dielectric substrates, such as printed circuit boards, include reinforcing and/or non-reinforcing fillers such as wollastrite, asvesk, melk, alumina, Includes clay, mica, glass peas, fumed silica, gypsum, etc. Reinforcing fillers include aramit 9, boron, carbon, graphite, and glass. Glass fibers are most commonly used in the form of cut strands, ribbons, yarns, filaments, or woven fabrics. Mixtures of reinforcing and non-reinforcing fillers can be used, such as mixtures of glass fibers and Merck or Wolastrite. These reinforcing fillers can be used in amounts of about 10-80% by weight, while non-reinforcing fillers can be used in amounts up to 50% by weight. Other additives include stabilizers, pigments, flame retardants, plasticizers, mold release agents, processing aids, coupling agents, lubricants, and the like. Each of these additives is used in amounts such that they produce the desired results.

[Brief explanation of the drawing]

In FIGS. 1 and 2, the dielectric substrate is indicated at 10;
The cured adhesive is indicated at 11 and the conductive path (electrical circuitry) is indicated at 122. In this figure, three paths 12 are shown, illustrating the form known as the conductive pattern (circuit, e-turn) of a printed circuit board, into which other elements are fed. 1 and 2, the path is provided with a soldering film surface 13 and still has a solder film surface 13.
A plated metal layer 14 is provided between the path 12 and the path 12 to allow connection and repair of the path. The thickness of the metal plating is typically about 0.25 to 1 mil, and the thickness of the path is typically about 0.1-1.
0 mil, preferably 1-< is between about 0.5 mil and about 3 mil. Most preferably, the metal plating is screen printed,
(by conventional techniques such as transfer rollers or pads) and the print thickness is up to 1 mil. FIG. 3 shows an undesirable specific example. In this figure, the conductive path 12 is placed on top of the conductive material 10 before the binder tightens and hardens. Path 12 is used for printing (offset printing, silk screen printing) or writing ink (
slurry). The channels can be brushed or fed in other conventional ways. An adhesive, most preferably a curable thermosetting adhesive 11, is provided between the substrate 10 and the diameter 1812. Thereafter, the solvent is evaporated and the substrate 10 containing the channels is placed in an oven, for example at 165°C.
(330'F'') for 10 minutes. The board is then pressed between heated press parts 13α and 13h in FIG.
Apply 1s o psi pressure for 20 minutes at 0°F'1-
The pathway is tightened by at least about 25% (113) while the resin binder holding the metal particles and adhesive is completely cured. The contact surface of part 13α contains 5 mil silicone rubber (thermal conductive) and 65
It is most desirable to have a hardness of . Substrate 1
It is understood that 0 can be rigid or flexible. FIG. 5 shows a tightened pathway that has been reduced in thickness by about 25-40% and has partially flowed into the adhesive, preferably by heat. Metal particles such as silver, palladium,
A metal slurry of noble metal particles such as gold and platinum is preferably mixed in combination with particles of other metals such as nickel and tin. They are mixed with a volatile solvent and a small amount of curable plastic binder. The metal content relative to the total solids is very high, e.g. about 93% by weight.
The above content is preferably 94-98% by weight. The lines of slurry 20 in FIG. 6 are applied by silk-screening or other suitable means, such as spraying, in the form of circuit pattern paths which are optimally formed on the peelable layer 19. form. Layer】9 is preferably 1
-< is a peel-off type that can be peeled off (1-(114)). Suitable examples include black paper, which is commercially available and contains a release agent on its surface. Examples of suitable release layers available include:
Warfns TRANSKOTEELT106 DU
It is commercially available as PLEX UNOTO5IDE FR-1. FIG. 7 shows heating for boiling and evaporating the solvent,
Heating for 105) at F is shown. Preferably substrate 1
A release layer 19 is shown disposed over the 0. Then press 150PS for 5 minutes at 330°F.
i can be supplied to tighten the metal particles in line 20 and increase conductivity. Alternatively, adhesive 21, for example a curable adhesive, is first applied over line 20 and release layer 19.
and then tightened by a press consisting of parts 22-1 and 22-2, e.g. 150 ps at 350'F.
i makes it possible to perform a tightening action on the particles in line 20. Preferably, silicone rubber (heat conductive) is used.
5 hardness sheet and a Teflon sheet are placed on either side of the line material in contact with one paper 19 and adhesive 21 as shown in FIGS. After that, the release layer supporting the line 20 and adhesive 21 is attached to the heater 24.
Place in a heated press containing parts 24A and 24B with -1. Sufficient to cure the adhesive and bonding agent and the adhesive and substrate e.g. plastic (dielectric layer) 1
The circuits shown in FIGS. 10 and 11 are formed by pressing for 5 minutes at a temperature such as 330' F. to produce a 0.0 lamination. Further press treatment at 150 pJ? i to tighten the metal particles in the line (conductive path) 20. 11th
The figure shows newly formed circuit lines 20 partially embedded within the thermoplastic matrix when it is softened under heat and pressure is applied. The circuit lines or paths 20 are 1- often placed directly on the surface of the dielectric substrate without being buried. After step 4, layer 19 is removed from the circuit by peeling 1-, as shown in FIGS. 10 and 11. When practicing this method, the contact surfaces of the parts most preferably include a 60 mil silicone rubber layer (thermal conductive) and have a hardness of 65. It is also understood that substrate 10 may be rigid or flexible. Formation of Dielectric Surfaces The thermoplastic and thermoset resins described above can be used to form substrates and dielectric surfaces using conventional techniques. For example, thermoplastic resins can be extruded into injection molded films, sheets or plates. The choice of resin depends in part on the desired mechanical and electrical properties. Mechanical properties of substrate materials that are often important for printed line assembly are water absorption, coefficient of thermal expansion, flexural strength, impact strength, tensile strength, cutting strength and softness. Therefore, comparing the properties of substrate materials can assist designers in selecting the optimal substrate for a given application. The substrate can be subjected to certain treatments, such as swelling treatments and corrosion treatments. In this technique, surface swelling is produced by using a solvent system. The substrate can then be etched with a strongly oxidizing medium such as a mixture of chromic acid and sulfuric acid. This technique is well known in the art (117). Manufacturing a composition containing a conductive material and providing a release surface 1. Next, consider the conductive metal particles. A thermosetting resin composition containing at least 54 vol. 11% of the composition is applied to a solid release surface in an array of at least one electrical circuit element. The vine release surface used in the present invention is suitable for receiving a film of conductive metal particles provided in an array of at least one electrical circuit element. The solid release surface may be a release paper, a film made from the plastics described above that provides a release surface, or a release surface. It may be a rigid plastic or metal release surface. A preferred release surface is release paper, in which the Strip
kotg ER and EHRCIS, Transkotg
ER and EHROIS, Ruhbarlgaf OZC28 (S, D, Wa, T/imztbrook, Maine, USA)
Includes rubber-separated products such as RRAN Qo (available from Co., Ltd.). (118) Metal particles and a bonding agent (heat-cured (resin). Conventional organic printing ink solvents can be used. The viscosity of the ink is suitable for screen printing.For example, the viscosity is about 35 at 25°C.
A Nordsk Field 9 viscosity range of 1,000 to 45,000 centivoices is preferred. The coating is dried by removing the solvent and the coating is transferred from stage A to stage B.
Proceed to step. It is often desirable to fully coat the element with adhesive, and indeed, to better retain the film of conductive metal particles on the release paper, the entire surface of the release paper may be coated with adhesive; is not a limiting matter for the present invention. Thus, in some cases only a coating of conductive metal particles is coated with adhesive. Adhesives are phenol-formaldehyde resins such as resol or novolac resins, the resorcinol-formaldehyde resins mentioned above. Amino-formaldehyde resins such as urea or melamine-formaldehyde 9 resins, epoxy resins such as those derived from the abovementioned epoxy resins, especially bisphenol A and ebichlorohydrin, and epoxy novolak resins, such as those derived from ebichlorohydrin and novolak resins, polyurethane-based adhesives. Polyurethane-based adhesives derived from isocyanates, particularly toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, polymethylene polyphenylisocyanate, and various polyester and polyether glycols. It may be a mixture of an epoxy resin and a polyvinyl acetal derived from an aldehyde and polyvinyl alcohol. The conductive metal is preferably in the form of metal particles, at least a portion of which is noble metal. Precious metals include at least 181 of silver, gold, platinum, .xi.radium, rhodium, and ruthenium. In a broad sense, the metal particles include at least one metal from groups 5h, 6b, 7b, 8, 16, 2h, and 3b of the periodic table of elements. The particle size of the metal is in a range such that all particles pass through a 100 mesh size sieve and remain on a 350 mesh size sieve. The conductive metal particles may be only noble metals such as silver and/or gold. Some of the particles are precious metals such as silver, gold and platinum and the rest of the particles are other metals or solids such as nickel, copper and zinc. Mixtures of particles such as aluminum, gallium, glass, metal oxides and non-metal oxide solids (eg silica, coir, etc.) can be included. In a preferred practice of the invention, the amount of noble metal particles included in the thermosetting resin composition is from at least 15% to up to 100% by weight. In more preferred embodiments, the amount of noble metal is from at least about 20% to up to 100% by weight of the particles in the composition. The combination of precious metals and other materials does not necessarily have to be a simple specific mixture. For example, a hollow glass water sphere coated with nickel, a noble metal coated on copper, or a noble metal (for example silver) can be used. however. (121) In a preferred practice of the present invention, the noble metal used is silver, which allows for maximum contact in the thermosetting resin layer on the adhesive-rich conductive surface, with flakes, Or used in the form of a plate or rod. The shape of the other particle elements can be as narrow as possible to allow suitable silver-to-silver contact of the resin layer and thereby obtain the electrical conductivity described herein for the present invention. It's not critical. In some cases, the conductive particles can be entirely noble metal particles. A preferred conductive metal is silver flake. However, to reduce costs, silver flakes can be used in conjunction with particles (also called powder) of metals such as nickel or tin. A particularly desirable combination consists of 25-50% by weight silver particles and 75-50% by weight nickel particles based on particle content alone. The conductive metal is used in conjunction with a binder and this combination is used to form a conductive path (line). The binder is a curable thermosetting resin (+22). Suitable thermosetting resins are fully described above. Particularly preferred binders include novolac epoxide 9 alone or reacted with novolac epoxide mixed with vinyl acetals such as polyvinyl butyral or polyvinyl formal resins. Contains phenol-blocked isocyanates. Optionally, the capped isocyanate is removed from the thermoset. The conductive metal and binder are mixed in a high boiling point solvent to produce a slurry (ink). Suitable solvents include cellosolve acetate and loose tylcarpitol. Rumethyl-2-pyrrolidine, N,N-dimethylformamide9. Dimethyl sulfoxide, ethylene glycol, anisole, decalin, dimethyl glycol diethyl ether, aniline, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether,
These include glycerol, tetralin, xylene, ethylene glycol monoethyl ether, chlorobenzene, diethyl carbonate, butyl acetate, ethylene glycol monomethyl ether, toluene, and the like. The amount of tri-based resin in the ink is from about 2 to about 10% by weight.
, preferably about 2-6% by weight. The conductive metal is present in the slurry in an amount of at least 90% by weight, preferably from about 94% to 100% by weight. Most preferably about 94% of the 100% solids base
-98% by weight. To achieve the most favorable level of conductivity, e.g.
．． To achieve a surface resistance of 1-0.005 ohms/sq, the content of conductive metal should be between about 94-98% of the total metal composite in the path, or expressed differently. , from about 68 to about 87%, based on the dry film of ink. When dielectric core particles coated with a conductive metal are used, the weight percent of the metal does not determine the conductivity but the capacity classification, so to describe the limit on the content of one particle, approximately 68
The characterization of 87 to about 87 volume i% is a more valuable basis. 17 However, if the highest brazing values, plating ability values, and conductivity values are not required, some of the advantages of the present invention may be achieved by volume fractions of metal particles of 54 volume t% or less. be done. An adhesive layer can be applied to the entire surface of the substrate, which
Additionally or alternatively, the adhesive layer disposed directly in the path supports the conductive metal when removed onto the release surface. The adhesive may be applied completely over the entire surface, supporting only the conductive paths or below the conductive paths. The adhesive contains functional active groups therein that have the ability to react and bond with the thermosetting resin binder composition and the dielectric substrate. The adhesive internally reacts with the thermosetting resin composition and partially or completely cures therein to form a compacted structure. Preferably the adhesive includes epoxides and polyurethanes and epoxides and polyurethanes with isocyanates encapsulated therein. The release surface and the dielectric surface are brought into contact such that the electrical circuit faces the dielectric surface and is separated therefrom by the adhesive resin. Sufficient heat and pressure is applied to form a tightened structure in which the thermoset resin is essentially sufficiently cured and the adhesive is essentially sufficiently internally reacted (125) to which the electrical circuitry is attached to the release surface. and become attached to the dielectric surface. In some cases only the partial curing and/or reaction required is obtained. The release surface is then separated from the %I condensation tank structure and at least 0.1 ohm/
It is preferred to provide an electrical circuit having a surface resistance of zq. The release surface and dielectric surface are heated at a temperature of about 120°C to 180°C, preferably about 130°C to 170°C, and about 100 psi.
About 2000 psi preferably about is. psi -500P'' but under temperatures and pressures not so high as to destroy each element. In the process, the metal in the portion of the thermoset composition is deposited as an electrical circuit in contact with the release surface. The concentration is higher than other parts of the composition for the element.The release surface can be a non-flexible or semi-flexible solid surface, such as part of a drum surface, and The circuit array is deposited on the surface by one of a variety of techniques such as silk-screening, printing, electrostatic transfer, and then the dome is rotated to the next stage where it is bridged (126). The first stage of the bridge reaction. It will be appreciated that sufficient heat is provided to effect the transition from the A one-stage resin to the B-stage resin.
17 includes the use of heated rollers to partially cure and tighten the metal particle composition. The ram is then advanced to another stage in which a coating of adhesive or a solid film of adhesive is applied to the partially cured resin/metal particle composition. This step can include providing the dielectric surfaces together and then passing the assembly through a gap between adjacent pressure calendar rollers to heat or transfer heat to the drum, thereby Complete tightening is performed to finally cure the thermosetting resin, ie, proceed from stage B to stage C. Multilayer electrical circuits are within the scope of this invention. In the manufacture of these multilayer electrical circuits, the release surface on which the thermoset resin and the conductive metal particles have been deposited is treated with a dielectric masking layer leaving exposed contact points of the electrical circuit. The exposed contact points can be electrically interconnected with other circuit elements on the masking layer. The masking layer may be pigmented (i.e. TiO2, a combination of TiO2 and 5tO3, etc.) and the thermosetting resin applied on the release surface or on at least a portion of the electrical circuitry on the masking layer is a dielectric wax. The adhesive may be a brazing agent or a brazing agent, for example of the type described in Example 3. Conductive ink is then printed onto the screen in registration with the mask pattern. Another mask is then screen printed with alignment 1- to the conductive ink pattern. Another layer of conductive ink is then screen printed in register with the other layer of ink and the layer of the mask. Adhesive is applied over the entire surface of this layer. Each of these layers can be created as desired. This assembly is then transferred to or mounted on an adhesive coated dielectric substrate. The assembly is then heated under pressure to initiate adhesion of the conductive ink layer, adhesive layer, and dielectric substrate. Peel the release surface support away from the assembly. However, this operation is omitted for lifting platforms that have already been stripped off in the previous step. FIG. 12 shows a multilayer electrical circuit formed in accordance with one of the inventions as described above. In FIG. 12, a dielectric substrate or circuit board 10 has an adhesive layer 21 on which conductive circuit elements or paths 2o are fitted. Adhesive layer 21 and path 2
The overlay of 0 is a dielectric mask 100 formed from dielectric ink. The layer 100 covers the entire surface except in the area or selected areas of the passages 20, and the passages 2o are electrically coupled to a second set of passages 20A parallel to the plane of the first passages 20. There is. The dielectric layer 100 thus overlies all but selected areas of the path 20. Pathway 2OA is preferably the same as path 20 in terms of composition and is electrically connected via a section B103 formed in a stacked manner by the ink as described above. The overlay of the path 20A can be a conventional low elbow mask 101, which leaves selected areas of the path 20 electrically connected to circuitry or other desired paths. A dielectric substrate was fitted onto a solid support lo. It will be appreciated that the printed circuit arrangement in FIG. 12 may have multiple path layers lying in different planes as desired. In each case. Even though it is sometimes possible to provide multilayer circuitry directly on the substrate, each layer of the path is preferably multilayered by being provided on a transfer sheet as described in the previous section. For example, a transfer sheet having a single planar layer of paths may be
As shown in Figure 2. It can be used to form the first path layer. A dielectric ink mask 100 is then applied directly to the path 1- on the substrate, and a preformed second transfer sheet having a path 2OA with electrical connections 1-1 is applied to the 12th It is used to form a second path as shown in the figure. The method of forming multiple layers on a transfer sheet is preferred for practical use. The pathways, adhesives, and dielectric substrates used in FIG. 12 are the same as described above for like numbered elements. It is shown in FIG. The path 20 in the multilayer printed circuit 104 is of the austere type after being pressurized and heated;
This is indicated by the number 12 in the figure. rlaO) The left end of FIG. 12 shows a path 20B formed according to the invention from an ink containing high metal particles, and also shows two plane parts f+20G in different planes at a constant angle.
It is understood that it spreads at -20D. Effective conductive paths 20B extend from the top surface of the substrate or printed circuit board 10 over its edges and sides. Thus, 3
Dimensional circuits are provided extending from the edge in different directions. This can be done by simply folding the transfer sheet of the invention over the edge of the printing plate when applying pressure and heat to adhere the conductive circuit to the substrate. can. Accordingly, the transfer sheet of the present invention provides a method for forming printing plates with three-dimensional structures in a variety of forms. The various multilayer electrical circuits described above are encompassed by the present invention. The masking layer is partially cured and then fully cured when the assembly is heated under pressure. Additionally, three-dimensional, multilayer electrical circuits are encompassed by the present invention. Since the dielectric surface on which the circuit is printed is flexible. It is possible to provide an extensive intermediate layer to be present in the shadow of the array of cured crimped devices. The printing plate can then be masked leaving contact areas with exposed circuitry on top. The technique of the present invention then allows other circuit devices to be stacked on top of the printing board, thereby creating more complex laminated printed circuits. The test with the Soldering Standard Test establishes three criteria that determine the solderability of printed circuit devices. The tests include determination of the solderability of the A1 circuit element, (B) the tensile strength of the circuit element, ie the amount of adhesion to the dielectric surface, and the electrical conductivity of the circuit element. A printed circuit article shall satisfy the K soldering standard test as described herein if it satisfies the wettability, tensile strength, and conductivity values listed in A, B, and C below, respectively. It is. A. Regarding solder wettability, this is Mgnizcograph % Del A20134
4° or its equivalent (Hollis Engineering
ing, l 5C Jharran Avenue,
Na5hua, New York State, USA). The meniscograph traces the solder-to-circuit wetting process from start to finish by measuring the net force acting between the specimen and the solder.
Cuit wetting procgzz). When recorded as a function of time. It indicates when wetting begins, the rate of wetting, the time to reach equilibrium, and the maximum extent of wetting. When a test piece is immersed in partially molten solder, a downward meniscus forms against the surface of the test piece while the surface of the test piece remains unwetted. At this stage the specimen undergoes hydrostatic uplift or weight loss corresponding to the amount of solder displaced. This is the point of maximum buoyancy. As wetting occurs, the contact angle decreases and the solder gradually moves to the side of the specimen creating a downwardly increasing force. As the weight of the specimen is continuously monitored, the change in force and therefore the progress of wetting can be observed. In a meniscograph, this means suspending the specimen from the funnel 9 cell and adjusting the system to obtain a zero net force (weight) read at the beginning of the test. This is achieved by raising the solder bath until it is immersed in the solder. The push-up and wetting forces are converted into electrical signals by a load cell and sent for recording as a function of time to either a chart recorder or an oscilloscope. The signal read from the meniscograph is a result of the deflection of the cantilever spring system in the load cell mechanism caused by the change in force acting on the test specimen. At the beginning of each test, the weight of the specimen was canceled by zeroing and the only force considered necessary was therefore due to the surface tension of the molten solder acting on the specimen and was replaced by the specimen at the same time as immersion. This is due to the weight of the solder. One surface tension causes a downward meniscus until wetting begins, thus increasing the apparent push-up signal. As wetting progresses, the direction in which surface tension acts changes as the contact angle changes. Ultimately, for an upward meniscus, the force on the specimen acts downward. That is, the sign is opposite to the push-up signal r1a4). When equilibrium wetting conditions are achieved, the normal component of surface tension acting on a unit length of the specimen-solder interface maximum is τ width θ. Here, τ is surface tension and θ is contact angle. Since the depth of immersion is set by the lift mechanism of the bath, the uplift force can be calculated from the specimen geometry and the density of the molten slag. The calibration of the meniscograph is normally set to produce a signal of 50 jllV for an applied load force of 1.9. That is, a signal of E millivolts is E1
5019 weight acting force (i.e. E150g dyne,
However, 1; IIrJ is the constant of gravity. ) is shown. This measured force is equal to the surface tension τ resolved by 1 minus the weight of the solder displaced. That is, E15
0.9-τ匪θ1-Vp (where l is the length of the interface between the test piece and the solder, ■ is the volume of the test piece immersed in the solder,
P is the density of the solder at the test temperature. ) All of these factors, except τ and contact angle, are known or can be measured. Therefore, it is necessary to assume one in order to derive the other. Products with suitable soldering wettability, i.e. wettability that satisfies A, have a positive slope when using a meniscograph, i.e. force increases with increasing time, a plot that continues to be positive or zero. The lowest point of (
starting at the point of maximum buoyancy), i.e. for increasing times of 8 seconds for tests at 215°C and 5 seconds for tests at 260°C, preferably until the completion of the test. It shows a certain amount of power. Determination of the sign of the slope is based on the starting and ending points for each 0.5 second period on the line of the plot. In carrying out the present invention, 1
The absolute value between the lowest point and the peak of the curve (assuming positive force) is at least 0.8. It is F. The specimen used for the wettability test should be a plastic substrate with the following dimensions: Width 0.750" + 0.010" Thickness OJ2' + 0.003'r (excluding circuit elements) Height 1
．． 80' + 〇, IO'' The two sides of the plastic should contain fully coated circuit elements on it. The depth of insertion of the test piece is 3mm, the temperature is 215 °C gas phase. (solderability simulation) or 260°C (wave solderability simulation).Solder E3n60/ph'40.This method uses a suitable flux C, that is,
Prepare a test piece with Kgstgr 1429 etc.
-2 including mounting it on the force transducer holder. 1 to 200rn9/inch on the Y axis. and calibrate the X-Y recorder to a sensitivity of 1 second/inch with respect to the X-axis. Set the timer for 10 seconds and run the test strip. All wetting (and dewetting) results must be recorded; wetting is a positive slope. That is, it is defined as the increase in force as time increases on the curve. Dewetting has a negative slope. That is, it is defined as the decrease in force as time increases on the curve. The following references are cited for further discussion regarding solder wetting. That is, Sγintgd C1rcμ1ts
(1a7) Handhook' 2nd edition, 1979.14-5-14
- pages 8, 19-24 and 19-25, McCrr
Published by aw-Hill Book Go, New York). Regarding the tensile strength of B0 circuit elements, it is 700p for plated circuit elements to meet the tensile strength requirements for testing. . The minimum tensile value should be ζ (pounds per square inch). Regarding this 1
-, and the test is not a beer strength test ((0oorx
bs, supra, pp. 19-23). This is a similar test. This method measures the tensile strength of the bond between electroless Ni-plated circuit elements (described in the ``Plating Capacity'' section) and ultimately determines whether the composite has either insufficient adhesion or insufficient adhesion. It is used to measure. The test piece consists of a plastic substrate layer (cut specimen) having dimensions of 0.06 inches or more in thickness, 0.75 inches or more in length, and 0.75 inches or more in width, and a predetermined thickness on the substrate layer. The adhesive layer is 0.3 inches or more in diameter. Then, the diameter is 0.250±0.0 at the predetermined thickness.
05 ink layer is applied r1a8). The ink is then electrolessly plated with Ni to a predetermined thickness. Length 2 inches, 169α, C straight i 0.05)
Bare copper wire of S60 or S+s solder type S or flux cored (corgd
) soldered vertically to the top layer using type K or RMA. Here, QQL-8-571 is applied in a conical profile around a centrally mounted wire to which it is deposited onto the Ni plate. The specimen was a flat base plate (17f3”rrrin
, steel or aluminum) with a 0.3 to 0.5 inch diameter hole that allows the specimen to be compressed and gripped, and the wire/solder to be centered in the hole. A top cup ζ-plate (%”rail, steel or /4” mLna aluminum) is fixed onto the specimen.A tensile tester is attached and the tip of the tester (
Attach a wire of a test piece that can fit the grip. The test machine (Inztronmodglr 1130.I
n5tron Corpm, Canton. MA, Yoshi Manufacturing) has a constant speed capability of 1 inch/min ± 2% pull force and a force sensitivity of ± 1% of full scale. 1
It has a force capacity of 00 dF 9 mm, and 10 lbs 9 mm. A chart recorder with similar sensitivity is used to take the data. The test specimen is securely mounted between the base and the cover plate, vertically with respect to the wire and aligned with respect to the tensile axis of the tester. Attach the wire to the grip of the testing machine,
This ensures that no force remains on the wire. Scale the recorder to zero. Then begin pulling at 1 inch/minute. Record the force at failure. Concerning the electrical conductivity of C0 circuit elements (unplated or electroless Ni plated). Measured as maximum surface resistivity. To meet this test, unplated circuit elements must have a surface resistivity value of 0.1 ohms/square or less, and plated circuit elements must have a surface resistivity value of 50 milliohms/square or less. Must have a value. However, 0.5
Up to ohms/sq. Preferably 1-< has a maximum surface resistivity of 0.1 to 0.01 ohm/square. Useful unplated circuits can be manufactured in accordance with the present invention. The method that follows is described below, and the surface resistivity is FED-8TD-4.
06 method 4041. The specimen has two 0.25 diameter ends (andpaint)
and 165 square" single line 1 width 0.07" x length 4.55
” ) with a surface area suitable to encompass the circuit contours of any otherwise acceptable dielectric plastic substrate. The circuit terminations were soldered in the manner described under Tensile Testing. The two circuit ends are probed on the wire 0.2 inch from the surface of the board and their size is recorded. Plating Capacity Standard Test This test It establishes criteria to determine the potential for application, adhesion and maintenance of adhesion of electroless nickel plating. (Note: This is not a plating standard test that determines the quality, quantity and process control associated with yield values ) R141) In a plating capacity standard test, a plastic plate substrate with additional wires, each separately physically and electrically isolated from each other, was tested.
HOLU, ILE C0, WEST NORTHERN 1-TOFT 9.
(Manufactured in New York, Connecticut, USA) at 90°C
) is prepared for use during the electroless plating process. The board measures 4 x 4 inches and has two series of 11
Two lines, length 0.5 cIrL. One series is o, oos inches wide and the other series is 0.0
It has a 25 inch wide, e-turn printed circuit line of the present invention. The value that satisfies the plating ability standard test is determined by including the following items. 1. 100% coverage of all different lines accepting plating. (Determined by visual inspection at 10x magnification.) 2. More than 80% of the lines must accept plating. In addition to the test values of 100%, the most preferred products of the present invention have the following percentage characteristics: (142) 1. Substantially all lines accepting plating are determined by visual inspection at 10x magnification for pristors and cracks. ) does not have. 2. Virtually all lines that accept plating are 1, P
,q Test Method Manual Method 2.4.1. The plating adheres and remains as determined by the Adhesive Beer Test according to No. 1, without separation of the plating from the interface of the printed circuit. This test was performed in a salt spray environment (5% neutral salt spray for 72 hours at 95°F) per ASTM B-117.
It is done both before and after following. EXAMPLES The following examples are intended to illustrate specific examples of the invention and are not intended to limit the scope of the invention in any way. Example 1 The following ingredients were blended at room temperature. 3 weight % epoxy novolac resin having an average of 3.6 oxirane groups (per molecule with a viscosity in the range of 0.1100 to 1700 centipoise (52°C)). The epoxy weight ranged from 172 to 179. The average value of repeat units was 0.2 (manufactured by D, E, N. 431, Dow Ohgmica L Co., Michigan, USA). (River molecular weight 10.01) 0 to 15,000 and solution viscosity 100 to 200 centiboise (dibasic ester (note)
:N-methylpyrrolidine-in a 4:1 solution. Poly(vinyl formal) resin zit% (measured as 15 wt. #% at 25° C.). Formυαr5159 is bAonzanto Plastic & RgJli
az Go. It is built in St. Louis, Missouri. (Note) Ester mixture of 23% by weight dimethyl succinate, 56% by weight dimethyl glutarate and 21% by weight dimethyl adipate (trifluoromethane with a pH of 114-6.5).
Sulfonic acid 0.0005% by weight The following ingredients were added to this mixture. +1) Particle size 2-12 microns, apparent density 21.
5-23.511/l113. tap '
a degree 1.5~2.5ti7ir&3 and 10006F
25% by weight silver with a reduction of approximately 1% (...average grain size 12 microns and apparent density 56.
Approximately 100% spherical nickel powder 70.0. Weight % This mixture was stirred at room temperature until completely homogenized 11 then passed twice through a three roll mill with pack rollers at 4-6 mils and front rollers at 1-3 mils. This conductive ink was prepared using conventional techniques.9 VH8Supg
rmat release paper (S, D, Warran Go, V
HZT-HRAOK, manufactured by Yoshi, Maine) to a thickness of approximately 1 mil after drying (U.S. sieve size 25).
0). The printed paper was dried in a convection air oven under 330°C for 5 minutes. The substrate is a linear type: rP-3703, manufactured by Union Calf Zeta. Measured in chloroform of 0.2.9/100 at 25°C.
145) 26.4 wt. Polymer 401jLi1'% containing the following units, having a reduced viscosity of 11%, 0.5 inch chopped glass fiber (197B,
wollastonite (N'/"d 12
50. (manufactured by Nyco) was molded from a composition containing 16.6% by weight. The substrate composition was compression molded at aoooC in a 4X4XO, 20 inch cavity mold using a hydraulic press to form a sheet of that size. (146) The substrate sheet was immersed in a 50% aqueous solution of dimethylformamide solvent at 25 °C for 59+ minutes. The substrate was then rinsed in water at 25°C. The substrate is then soaked in a chromic acid solution containing the following ingredients (C numbers are parts by weight): deionized water 30 chromium trioxide 3.0 85-87% phosphoric acid 10.0 96% sulfuric acid 55.9 ℃ for 5 minutes. The substrate was then rinsed in water at 25°C and further dried at 100°C for 10 minutes. Separately, two external adhesives were prepared containing the following ingredients: Part A (I) Epichlorohydrin and Bisphenol A (Ep
on 1009 F, manufactured by Shell Chemical Co.) 11.41 parts by weight of epoxy resin, tn+ average equivalent weight 260. Hydroxyl group content 6.5%. Maximum acid number 4. Saturated polyester (Dg!rnophtn 110
0° Manufactured by Mobay GhgrnicaL Corp, Pittsburgh% Hansilnoznia 40.88
Weight part. (Nonionic surfactant rFo-4ao, which is a liquid fluorinated alkyl ester, manufactured by 3M GorP-) 0.068 weight 1 part %B Polytoluene diisocyanate containing 6-7% free monomer) (OB- 60, Mohay Chemi
Parts A and B were then mixed. A solvent containing inzolopanol and methyl ethyl ketone (3:2 ratio) was added to obtain a viscosity of 18 seconds ZAα cup number 2 at 25°C. The prepared adhesive was sprayed onto the treated substrate sheet. The adhesive coated substrate is then heated to 149° C. to such an extent that the adhesive coating is dry but not completely cured.
and placed in an open convection mold for 5 minutes. The printed release paper formed as described above brings the adhesive into contact with the substrate to be Ffl-ed, with the printed surface contacting the adhesive surface of the substrate sheet. Then, 1- was laminated at 166° C. for 30 minutes at a pressure of 200,711 JPi. The paper was then peeled away from the assembly. The substrate is then placed in a convection oven for 16
Heating at 6°C for 30 minutes ensured final curing. The printed substrate was then treated with a 6% sulfuric acid solution at 65°C. Preheat to 17°C for 5 minutes. Rinse the substrate with water and add 2 parts of sodium borohydride and sodium hydroxide (1:1 ratio).
% solution at 40°C for 30 seconds. The printed board was placed in an electroless plating tank (Ni-418°Ethong) to coat it with nickel plating.
medium, at 88°C, using pH 4,8-5.2, and 60
The surface of the ink released in ii was plated with nickel in a plating time of 2 min. Example 2 One part system (O part) where the adhesive contains the following components:
The method of Example 1 was repeated except that: (1) Said dibasic ester/ro-methyl-2-pyr14
9) Polyvinyl formal resin (Formvat' 5/95 E, MorLs) in a 4/1 solution of Loride 9
anto plastics & Razinz Qo,
(manufactured by Mobay Chemical Co.) 56.17 parts by weight Cross-linking agent (α) Phenol-blocked toluene diisocyanate (Monctur S., manufactured by Mobay Chemical Co.) 303. 100% solids, manufactured by American Cyanamid 9) 4.21 parts by weight (C) Allyl ether of phenol-formaldehyde resin/l/
(MathyLon 75] 08.100% solids. Manufactured by General Electric Company) 5.6 parts by weight (dl
Dimethyl silicone oil rDc-11, 0.28 parts by weight per Dow Chemical Co., Ltd. All of the above were mixed at room temperature. A solvent containing a 4/1 solution of the dibasic ester/n-methyl-2-pyrrolidone was heated in 2 αn Cups at 42 and 25°C.
It was used to obtain a viscosity of 8 seconds. Then apply the adhesive onto the release paper and open screen R150
) C screen mesh) print and open convection type 2
Dry for 2 minutes at 00'F. The release paper was then laminated onto the substrate as described in Example 1 and heated under 350 for 305+ in a convection open. The substrate was preheated and plated according to the method described in Example IK. Although the adhesive layer is described as being placed on the dielectric surface, if desired it can be applied to the outside of the ink or to the free (not in contact with the ink) surface, rather than when the ink is on the release surface. I can do it. The release surface is then loaded with a conductive pattern and an adhesive layer for transfer to the dielectric surface. Preferably, the adhesive used here is a one-component thermosetting adhesive. Example 3 This example describes the manufacture of a two-layer circuit board. Example 2 A substrate and an adhesive were used. The following solder mask was manufactured. Part A 1, average 3.6 oxirane groups per molecule, t per epoxy
(172-179) and 26.88 parts by weight of an epoxy novolak resin with W -0,2 2, ethyl acrylate and 2-ethylhexyl acrylate copolymer 3 as modifiers, 60% solids in phthanol. Butylated urea-formaldehyde resin (Bgetla resin, manufactured by American Cyanamid 9 Co., Stafford, CT) 5.566 layer 4, high purity titanium dioxide pigment (TitarLoxl 070 L)
W, E, 1. Dwpont daNgmourz,
Manufactured by Wilmington, Praue State) 46.07
Part B by weight 1 Polyamide 9 with amine value 345 (reaction product of dimerized tall oil fat (T, QF, ) acid with ethylenediamine) 1 e.g. Varrvamitt 125
(manufactured by Henkel Ono America, New York, NY) 5.56 parts by weight 2.4:1 of the aforementioned dibasic ester: 12.96 parts by weight of N-2-methylpyrrolidone solvent and B at room temperature. mixed with. The dielectric solder mask was covered on the release carrier and dried in a convection open for 1 minute at 166°C. Cover the ink of Example 1 with a dielectric solder mask pattern. Dry for 2 minutes at 166° C. in an open convection chamber. Cover the dielectric solder mask with ink nozzle turns. It was dried for 1 minute at 166° C. in an open convection chamber. This process was repeated to obtain two layers of dielectric solder mask. The partially completed sub-assembly was compressed at 21'C for 30 seconds at a compression pressure of 1000 P, pL. Cover the ink of Example 1 with another ink layer and a dielectric solder mask layer and heat the assembly at 166°C in a convection open.
I dried it for 3 minutes and completed Sapoor Seven Noli. The sub-assembly is then transferred from the release carrier to the adhesive coated substrate at a temperature of 166° C. and a compression pressure of 500 PSL for 30 seconds (RTSA) to initiate adhesion between the ink, adhesive and substrate. I let it happen. The release carrier was then peeled from the assembly and post-cured for 30 minutes at 166° C. in an open convection mold. A similar result can be achieved by placing the adhesive covering the subassembly on a release carrier rather than placing the adhesive on the substrate. Example 4 A slurry for forming electrically conductive paths is prepared from the following components (parts by weight) as follows. Item Material 1, polyvinyl formal resin (trade name FOI' (MV
AR, 415/95 E) 13.75% in N-methyl-2-pyrrolidone C (manufactured by Monsando Co.) Net type 1114.38; dry weight 1.972, Evoxino, Borac C 100%) DEN431 Dow Chemical Co., Wet and dry f3,0 (154) 3, E3iLtLakg l 35 - Wet and dry l
・254. Nickel powder; wet and dry weight 605,
Tin266; wet and dry weight 106, diacetone alcohol; wet and dry weight 0 Step 1: Mix and stir the three parts of item 1.4.5 and item 6,
Two passes are made through the three roll mill creating a homogeneous mixture. Step ■: Then, mix and stir item 2.3 and 1.5 parts of item 6,
The resulting material is passed twice through a three roll mill to create a homogeneous mixture. Step 2: Combine the mixtures from steps 1 and 2 in three p-lumers until a homogeneous mixture is formed. Step ■: Add 605.5 parts of item to the product of Step ■ to screen or brush onto the substrate on top of the adhesive. Both the adhesive and the over-the-path coating are cured for 45 minutes at 170°C in an Ohnon. Example 5 The method of Example 1 was repeated except that the conductive ink contained the following ingredients. A, polyurethane based on thermoplastic polyester obtained from the reaction of human 10-oxy-terminated polytetramethylene adipate oligomer, 1,4-methanediol and 4,4-diincyanate diphenylmethane (Ex
tant 5715, B, F, Crood-ric
h company) 4.137% by weight (20.55% by volume)゛B,
Phenol-blocked toluene diisocyanate (MorLrlur S. Mabay ChamiaaL Co., Ltd.) 0.085% by weight (4,85% by volume) C0 above FC-4300,05% by volume, 30% by volume) D, These ingredients were mixed and the following ingredients were added to the mixture: E1 particle size 2-15 μIN (average 12 μm), apparent density 21.5-23.511/il3, tap density 1.
Silver (E3iL (Lake, Handy
etndHarmon Chemical Produ
cts Ogntgr), 22% by weight (13,22% by volume) F00 particle method 2-5fl and specific gravity 7.2877/c
Tin powder (Tin 266. At1anti
c Equip-mmnt
,) t-Genfiel t, -T, New Chassis) 73 wt% After covering on paper, the ink was dried at 60°C for 10 minutes
The procedure of Example 1 was repeated, except that the procedure was as follows (see IS below). Additionally, the printed release paper was heated at 121°C at a pressure of 200 psi.
Laminate to the substrate for 3 minutes (see Ip below), then 20 minutes.
Transferred at 149° C. for 4 minutes at 0 psi pressure. Examples 6-10 The method of Example 5 was repeated exactly, except that the amount of silver was varied in the formulations shown in Table 1. The amount of filler was kept at 95% by weight (73.98% by volume) in all R157 formulations. This table shows that if the transfer method of the present invention is not used, a higher amount of silver must be used to obtain a similar surface resistivity. rxs8) (159) 4. Brief description of the drawings Figure 1 is a top view of a circuit board illustrating the present invention, Figure 2 is a sectional view taken along line 2-2 in Figure 1, and Figure 3 is a circuit diagram. a top view of the substrate supporting the thermoset resin paths forming the plate;
4 is a cross-sectional view of the circuit board of FIG. 3 in a heated press to achieve compression of the channels in a preferred embodiment; FIG. 5 shows the height and thickness of the channels after compression, e.g. Figure 6 is an inverted view showing circuit lines (paths) as ink slurry on a transfer (e.g. peel-off) carrier layer; Figure 7 is a view similar to Figure 4 showing the reduction in Figure 8 shows the adhesive being heated to evaporate the solvent in the ink while it is on the support; FIG. Figure 9 shows the electrical path being applied over the entire surface of the path to hold it in place. Figure 10 is a diagram showing the board (boat 9) and circuit path after the transition layer has been removed, Figure 11 is a diagram showing the 10r160
) An enlarged cross-sectional view taken along line 11-11 in the figure (fC and I7). This figure shows a slightly indented path in the plane of the boat, but the path is at the same height as the top surface of the boat. Figure 12 shows that the transfer sheet of the present invention can be used to form laminated layers of conductive circuits. 1 is an enlarged cross-sectional view of the multi-electrical circuit path device used; FIG. Explanation of symbols 10...Dielectric substrate, 11...Adhesive, 12...
Conductive path/13゛°° soldering is coated, 1B'Z,
13h...Pressed part, 14...Plated metal layer, 1
9... Peelable layer, 20... Metal powder line, 20α
, 20h, 20c... electrical path, 21... adhesive,
22-1.22-2...Pressed parts, 24-1.・・・
Heater, 24A, 24B...Pressed parts, 100.
...Conductive ink mask, 101...Top layer, 10
3...Electrical Connection Department Attorney Patent Attorney r8107) Kiyotaka Sasaki (3 others) (161) FIG, 5 ++1++ FIG, 7 FIG, 8 FIG, II IGIO FIG, 12 Continued priority claim from page 1 61984 July 25 [phase] United States (U.S.
) @ 516677 ■ 198 Group June 5 [phase] United States (U.S.
S ) @ 616239 Procedural Amendment August 1980 / Japan Patent Application No. 129032 of 1982 2 Name of the invention Printed circuit 3 Relationship with the case by the person making the amendment: Name of patent applicant Comerix Incorporated Kasumigaseki Building Post Office PO Box No. 49 Eikou Patent Office Telephone: (581)-9601 (Representative) 7
, subject to correction

Claims (1)

Scope of Claims: (I) (α) a solid release surface; (b) at least A layer of an electrical circuit element, wherein the amount of metal particles in the resin composition is from about 54 to about 8 based on the volume of the dry layer.
for use in making an electrically conductive circuit article, consisting of a layer of reactive adhesive applied in a volume fraction of 7% and optionally on a tCl thermosetting resin composition. and a printed transfer article suitable for converting metallic circuits into dielectric solid support surfaces. (2) The preceding paragraph, wherein 1 of the metal particles in the resin composition is about 68 to about 87% by volume based on the dry I- volume (
1) Articles mentioned. (3) The preceding item (1) consisting of a mixed resin composition of a thermosetting resin that can be crosslinked and a thermoplastic resin that has a reactive functional group that can react with a reactive functional group in the crosslinkable resin. 1) Articles mentioned. (4) The article according to item (3) above, wherein the crosslinkable resin is an epoxy resin, and the thermoplastic resin contains a reactive functional group capable of reacting with an adjacent epoxy group or a reaction product of the adjacent epoxy group. (5) The article according to the preceding paragraph (2), in which the layer of the reactive adhesive is supplied, and the electrical circuit element after the transfer, which utilizes the reactive adhesive, satisfies the standard test. . (6) The article according to the preceding paragraph (5), in which the metal particles are present in an amount of about 94 to 98% by weight of (hl), and the electric circuit element after transfer satisfies the plating ability standard test. , the previous item +1, which is mostly applied throughout the year to the part of the layer of the thermosetting resin composition that is in contact with the solid release surface.
1. Items of a bandit. (8) The article according to item (1) above, wherein the adhesive is provided over the entire surface of the thermosetting resin composition and is selected to specifically adhere to polysulfone. (9) The article according to item (8) above, wherein the adhesive contains a reactive functional group therein that has the potential to react with and bond with the thermosetting resin composition. 0α The article according to item (6) above, wherein the adhesive interacts with the thermosetting resin composition to become cured with it, and then forms a composite structure. α1) Article according to the preceding clause θ, in which an additional adhesive layer is provided over the entire surface of the composite structure. 03 The article according to item (8) or (9) above, wherein the adhesive contains blocked isocyanate groups therein. (1) an amount of thermosetting resin in an amount of about 13 to about 32% by volume of (11) and an amount of electrically conductive metal particles corresponding to about 68 to about 87% by volume of (9) dry ink; 04) A printing ink consisting of a mixture of said printing ink, said printing ink being suitable for printing and compression molding and curing into electrical circuit elements which meet standard tests for soldering. The printing ink according to the preceding clause 0, wherein the metal particles consist of noble metal and non-noble metal particles, and the ink satisfies the plating ability standard test after compression molding and curing. (3) applying an ink comprising a thermosetting resin composition containing electrically conductive metal particles to a release surface as a thin film (i.e., a pathway) in the form of at least an electrical circuit element; (3) a dielectric surface; (4) providing a reactive adhesive interface capable of interacting with the thermosetting resin composition of (2) above and a dielectric surface; (5) providing a thin film of the electrical circuit element that is dielectric; ＞, while facing A,
and (6) applying sufficient heat and pressure to form a composite structure so that the thermoset resin cures. , the adhesive will interact with each other, so that the electrical circuit will be transferred from the peeling surface and effectively bonded to the dielectric surface. A method of manufacturing a printed circuit article comprising providing a circuit. The method of claim 09, wherein the release surface is removed from the composite structure and the resin and adhesive are completely cured in step (6). , and the volume portion of the thermosetting resin is about 13 to 32%.
! 9. The method described in 9. 0. The amount of metal particles in the thermosetting resin composition is about 94 to 98% by weight of the composition (method described in 151). The method according to the preceding paragraph 0η, which satisfies the following: Q6) in the preceding paragraph, wherein the metal content is concentrated in the part of the thermosetting composition that is in contact with the release surface more than in the other part of the composition; <1? ) The method described in any one of the following. Ql) The method of item 0 above, wherein the masking layer of thermosetting resin is applied over the entire surface of the electrical circuit portion of the composite structure.翰 Additional electric circuits are used in steps (1), (2), (41
, (5), (6), (7), wherein the masking layer and the unmasked parts of it constitute a dielectric surface for coating purposes. The method described in Q11. (c) Another masking layer according to the method of the previous section Ql is added to the previous section (
B) The method described in the preceding paragraph (2'!J) applied over the entire surface of the treated composite produced as described in 04. The method according to item 05, which comprises coating the electrical circuit with a conductive metal. Non-conductive materials consisting of polyetherimide, polyester, aromatic polycarbonate, styrenic resin, poly(aryl acrylate), polyhydroxyether, poly(arylene sulfite 9), polyamide 9. and plastics reinforced with fillers and/or fibers. 19. The method according to the preceding paragraph 0!19, wherein the solid dielectric support surface has a surface; a first layer or path of conductive metal particles, the metal particles being in a volume fraction amount of about 68 to about 87 percent by weight based on the weight of the layer, and the electrical circuit element being electrolessly plated; A printed circuit article that has good plating ability due to technology. (c) A printed circuit article as described in the preceding paragraph in which the article satisfies the standard test for soldering. (c)
The printed circuit article described. (To) The circuit element according to the preceding paragraph (5), wherein the circuit element has a surface resistivity of 0.1 to 0.01 ohm/square and retains its shape when exposed to a temperature of 260'F for 20 seconds. Printed circuit articles. 01) A layer (A
The printed circuit article according to the preceding item (5), in which the printed circuit article is mostly concentrated in the portion l. 03 The printed circuit article according to the preceding paragraph 61), wherein one metal is silver and the other metal is nickel. (to) the previous section in which the layer (Al is compressed during its thermal curing) (
Printed circuit articles listed in the above article. A second layer overlies the thermosetting resin and said first layer (consisting of electrically conductive metal particles similar to that in BL, and from which areas selected by the electrically conductive material) A printed circuit article according to clause (5), wherein said first and second layers are electrically joined together at another selected area to form a multilayer printed circuit article. The printed circuit article according to the preceding paragraph, wherein the first layer has a portion that lies substantially in a first plane, and a portion of the first layer that is non-planar at an angle thereto. A printed circuit article as described in the preceding paragraph, having a portion extending over the entire surface of the support. Sometimes the solder is formed from a thermosetting resin composition containing conductive metal particles that satisfies standard tests and provides at least an electrical circuit or an element of an electrical circuit with a surface resistivity of less than 0.1 ohm/sq. A printed transfer composition comprising a solid release surface in the form of an electrical circuit element. (To) The printing transfer composition according to the preceding item c37), wherein the thermosetting resin is increased by a certain amount of crosslinking agent. (31) The printed transfer composition according to the above 0η, wherein the electrical circuit satisfies the Menki performance standard test when transferred. (41 (11) dielectric substrate; (3) an adhesive holding said pathway, wherein said pathway is heated at 260° C. for 20 seconds;
An electrical device consisting of something that can last without appreciably changing its shape. (AD The device according to the preceding paragraph f41, in which the board is a plastic substrate and the path is in the form of a circuit pattern. 03 The device according to the preceding paragraph 1, in which the soldering path satisfies the standard test and the Menki performance standard test. (43 Dielectric material , a plurality of electrically conductive paths supported by metal particles 9 of which at least 15% are silver.
It consists of 3-98%. ), and a thin film of solder over the entire surface of the path opposite the dielectric material. 0 (a) The device according to the preceding paragraph (43), wherein a cracked nickel layer is on the path between the solder and the path. (41a) A slurry consisting of a vaporizable solvent, a metal powder, and a small amount of a thermosetting binder is applying the desired circuit pattern to the removable layer; j) vaporizing the medium; c) removing the metal powder and the carrier by covering the metal powder and binder with an adhesive layer; d) causing compaction of the powder by laminated molding of a plastic substrate by pressure and heat and bonding of the compacted powder to the substrate by the adhesive layer; provided that the heating is applied to the adhesive;
A method for forming a circuit pattern on a plastic substrate at low temperature, comprising the steps of: insufficient to destroy the substrate and the removable layer; and separating the Tgl removable layer. (c) The pattern is compressed before or after covering the metal powder and binder with an adhesive (method according to item 49). (47) The plastic substrate is made of polysulfone (method according to item 4!9. (48 circuit) The pattern is about 93% to about 98% by weight of the metal powder
The method described in the preceding paragraph (4), in which the pattern after laminated molding has a substantially uniform thickness that does not vary by more than ±5 microns. A circuit transfer device having a circuit pattern of metal powder substantially free of organic material on its surface, and an adhesive overlying the circuit pattern and at least a portion of the layer. The device described in the preceding paragraph (4!l). 511 The device consists of a dielectric substrate and 90 to 98% by weight of metal powder in the path, with 15 to 50% by weight of precious metal in the path, and the remainder non-noble metals and ( or) a compacted conductive path containing inert particles and an organic, f-inductor, the thickness of said compacted path not varying more than ±5 microns and not more than 0.1 ohm/sq. 153 An electrical device having a conductivity of 153, in which the path is bonded to the substrate by adhesive
The device described in D. It consists of a dielectric substrate supporting a compressed, highly conductive path consisting of an organic Z indica containing 15 to 50% by weight of silver particles, with nickel or tin particles as the balance; A device in which all particles are 90-98% and the paths have substantially the same conductivity that can be achieved when all silver particles are used. 64) Adhesive joins the path to the dielectric substrate (63)
1. The device according to 1. 651 A dielectric substrate, consisting of 90-98% of the particles in the path, and containing 15-50% by weight of noble metal in the path, with the remainder containing non-noble metals and/or inert particles and organic Z indica. consisting of a compressed conductive path,
An electrical device in which the compressed path thickness does not vary by more than ±5 microns and has a surface resistivity of less than 0.1 ohm/square. (from) said support surface carrying said circuit pattern having an inner surface and an outer surface having conductive circuit turns adhered to said insulating support surface by an organic adhesive layer; The organic adhesive layer is a thermosetting organic adhesive, and the conductive circuit pattern has an organic thermosetting adhesive in an amount of about 32% to about 13% by volume of the pattern. the adhesive and binder are stable at temperatures of at least 260° C. for at least 20 seconds, the conductive circuitry further comprises conductive metal particles in an amount of about 68 to about 87% by volume; the circuit pattern has a surface resistivity of 0.1 to 0.01 ohms/square, the circuit pattern has a ) Can be electrolessly plated with nickel without activating the surface. A printed circuit board that: A) can be resoldered repeatedly at a temperature of 260° C. for 20 seconds; C) has high adhesive strength; and d) can be soldered and wetted. 5n layer + AJ and if present layer (C
Coincident with layer (b) and spaced apart from layer (A), at least Printed transfer article according to the preceding clause (1), comprising one additional layer. - Printed transfer article according to clause 571, wherein said further layer and the first-mentioned layer are in electrical contact in selected areas. 591 on the layer + bJ, and if present on the layer (
Below C1 matched the layer fil. and at least one further layer disposed at a distance 'fr from the layer (hl) which acts as another electrical circuit element useful for producing a further multilayer electrically conductive circuit article. Printed transfer article. - Printed transfer article according to the preceding paragraph, wherein the dielectric layer separates said further layer and the first-mentioned layer in a selected area. 6υ A second path in the form of a second circuit element. The printing transfer composition of the preceding clause c3D, wherein the printing transfer composition is overlying and electrically separated from the path in at least selected portions.