JP2002097215A - Conductive paste resin composition and method for producing its sintered body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive paste resin composition (conductive resin paste) for a sinter mold in which the sintered molded product is a conductive sintered molded product and a paste resin composition containing the conductive inorganic powder and an organic binder is excellent in application, formability and sintering property, and to provide a method for producing a conductive sintered body. SOLUTION: In the paste resin composition of the powder for the formation of a conductive sintered body, the conductive paste resin composition excellent in application, formability and sintering property contains (A) a (meth)acryl polymer having the weight average molecular weight, Mw, of 500 to 10,000 and the glass transition temperature (Tg) of -80 to 50 deg.C and (B) a polymerizable polyfunctional monomer having the molecular weight of 100 to 5,000 and 2 to 6 polymerizable unsaturated groups and (C) the powder having the average particle diameter of 0.1 to 20 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paste-like resin composition for a conductive sintered body, and more particularly, to a paste-like conductive composition for a conductive sintered body which is applied and sintered on a ceramic substrate or the like. Resin composition is solventless type, coating properties,
The present invention relates to a paste-like resin composition for a conductive sintered body having excellent shape shapeability and sinterability, and a method for forming a conductive sintered body formed using the same.

[0002]

2. Description of the Related Art In recent years, as electronic devices have become more multifunctional, higher in performance, smaller and thinner, etc., semiconductor devices, which are at the core, are used in various electronic products, mechanical devices used in various manufacturing processes, or Cars, airplanes,
In a ship, an air conditioner, a rice cooker, a VTR, and the like, various kinds of IC chips are incorporated in a memory such as a computer (microcomputer) in a logic and analog manner.

With the rapid progress in the information society in recent years, DSPs (digital signal processors) are used for telephones, audio, DVDs, servers, etc., CCDs (solid-state imaging devices) are used for VTRs, digital cameras, etc. , Gastric cameras, artificial satellites, and electrophotographic image forming devices such as printers, facsimile machines, and copiers. Flash memory is used in mobile phones, electronic notebooks, IC cards, etc. , Information communication, the Internet, and the like.

As described above, in an IC chip and a peripheral device using the IC chip, a conductive member is used as an electrode material or a circuit pattern. Examples of the forming method include a CVD / sintering method, a sputtering method, and a method of applying / sintering a conductive paste. That is, these conductive members are laminated on an insulator layer, a dielectric layer, an insulator layer-dielectric layer, or the like on a ceramic substrate such as alumina or a ceramic green sheet or the like, or are insulated. Formed as an interlayer conductive material such as body layer-conductive layer-insulator layer, insulator layer-dielectric layer-conductor layer-insulator layer, insulator layer-dielectric layer-conductor layer-dielectric layer Have been.

Therefore, the conductive material of the conductive paste for firing has heretofore been exemplified by silver, gold, platinum, silver-palladium, nickel, copper, copper-silver alloy, tungsten, molybdenum, and the like. No. -295614,
A conductive paste for firing is described in which a copper alloy of Ag _x Cu _1-x is used as a conductive material, and a vehicle is made of an acrylic resin such as polybutyl methacrylate and a solvent such as terpenol.

JP-A-5-212833 discloses that a conductive material is a metal such as copper or an alloy thereof, and a vehicle is a polymer such as methyl methacrylate having a molecular weight of 100,000 or more; A photopolymerizable conductive paste comprising a polymerizable polyfunctional monomer and a solvent such as ethylene glycol monoethyl ether is described.

JP-A-5-206600 discloses that a conductive material is a metal or alloy such as copper, and a vehicle is a polymer such as methyl methacrylate having a molecular weight of 1000 or more and a polymer such as methacrylic acid. A laminate for forming a conductor pattern is described in which a photopolymerizable conductive paste composed of a polyfunctional monomer and a solvent such as ethylene glycol monoethyl ether is laminated on a ceramic green sheet that can be fired at 1000 ° C. or lower.

Furthermore, Japanese Patent Application Laid-Open No. 9-282941 describes a multilayer ceramic electronic component in which a conductive paste is screen-printed or filled in a ceramic green sheet to form internal electrodes, through holes or via holes. ing.

[0009]

Under the circumstances described above, various electronic products and their peripheral devices include, for example, ceramic capacitor elements, piezoelectric / pyroelectric elements, and semiconductor devices formed on a substrate. Electronic products incorporate conductive members such as internal electrodes, circuit patterns, and external electrode terminals.

[0010] Such a conductive material is usually formed by patterning a thin film layer on an insulating layer or a dielectric layer on a substrate by a CVD method, a sputtering method, or the like. After applying or embedding the conductive paste on the substrate surface such as ceramic green sheet, drying and curing, the solvent and binder resin etc. are burned off under heat history and removed, and then sintered and conductive. It is formed as a single layer or a laminate of the conductive sintered layer. That is, screen printing, dip coating, spin coating, etc. are used to pattern a circuit or an electrode on a ceramic substrate or a chip component using a conductive paste, but the viscosity stability, applicability, and the like of the paste are used. In addition, shape shapeability and the like are important.

As the conductive metal material, a paste of a noble metal powder such as gold, platinum, palladium, silver or the like is conventionally used because of its oxidation resistance during sintering. In addition, it is difficult to use them for high-frequency circuits, high-density circuits, and high-density mounting due to migration between pattern conductor circuits and solder erosion. Also,
Conventionally, copper metal powder, which is inexpensive in cost, and particularly low in resistance value, basically has inferior oxidation resistance, and thus has many problems that have not been solved yet in handling properties and the like. Therefore, for example, JP-A-6-295614 proposes a conductive paste using a copper alloy powder in which the surface of copper particles is coated with a titanium component in order to improve oxidation resistance during firing. .

Normally, to sinter such a conductive paste, 500 to 110
Sintering is generally performed in a temperature range of 0 ° C. Also,
In the case of sintering in this inert atmosphere, the organic vehicle is sufficiently burned off in an oxygen atmosphere in a temperature range of 200 to 550 ° C., which is a temperature rising process before the sintering. In particular, when the conductive metal powder has low oxidation resistance such as aluminum, silver and copper, the organic vehicle is usually removed while strictly controlling the oxygen concentration in the atmosphere. Therefore, upon such removal, the applied conductive paste layer is exposed to an oxidizing atmosphere, and has a decrease in conductivity, sinterability, and property deterioration such as a decrease in adhesion of a sintered film to a substrate or the like. Tend to come.

Further, as described above, the conventional conductive paste contains a solvent as a dispersion medium of the conductive metal powder and the binder resin. The selection of the solvent type is also an important additive from the viewpoint of exhibiting good coatability to the paste, and the conductive paste for coating prepared by the conventional method contains a large amount of solvent. That is the fact.

Therefore, when sintering a paste layer applied on a substrate or the like, or a paste layer applied on a ceramic green sheet, etc., the sintering before drying, polymerization hardening (curing), or pre-sintering is performed. Under heat history, organic vehicles such as solvents and binder resins must be completely removed. As long as a solvent is used as in the conventional method, in this treatment step, there is a tendency that air bubbles, cracks, bending, peeling, shrinkage, and the like are generated in the coating layer. Therefore, to prevent such troubles,
If necessary, coating and pre-firing are performed in a large number of times to form a coating layer having a predetermined thickness.

[0015] The paste according to the conventional method using a solvent as described above requires work due to organic components such as a solvent which is volatilized and decomposed and scattered during the preparation of the paste and during the pre-sintering before the sintering of the applied paste layer. It is not preferable from the viewpoint of occupational safety and health because it significantly pollutes the environment. In addition, from the standpoint of global environmental protection in recent years, scattering of organic substances such as a solvent contaminates the global environment and causes global warming. Therefore, in the industry, conversion from a solvent type to a non-solvent type has become a very important issue when manufacturing products.

Therefore, most of the solvents conventionally used in such fields have a boiling point in the range of 80 to 260 ° C. and include, for example, n-methylpyrrolidone, ethylene glycol monoethyl ether and ethylene glycol monoethyl ether. High-boiling polyhydric alcohol derivatives such as butyl ether, butyl carbitol acetate, ethylene glycol monoethyl ether acetate, and high-boiling aromatic compounds such as ethyl cellosolve and xylene; methyl lactate, ethyl lactate, ketones, and terpenes. Can be

From the above, an object of the present invention is to replace a conductive resin composition in the form of a paste containing a conductive metal and / or a conductive alloy powder with a conventional solvent-type paste. Although it is a solventless type, it has applicability and shape shapeability before sintering. In addition, compared to the conventional method, a paste-like conductive resin that can perform thick coating and can perform heat treatment through curing, pre-firing, and sintering of the paste layer after application under an inert atmosphere such as nitrogen. It is to provide a composition.

Another object of the present invention is to provide a method for forming a conductive sintered body formed on an alumina ceramic substrate or the like using such a paste-like conductive resin composition.

[0019]

Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above-mentioned problems, and as a result, prepared a paste-like resin composition from a conductive metal powder and an organic vehicle, and prepared a paste after application. The vehicle component in the compact is 20% before sintering.
Focusing on an organic vehicle which is easily thermally decomposed, volatilized and scattered and removed in a nitrogen atmosphere of 0 to 550 ° C., and is burned off in an oxygen atmosphere like a conventional binder resin (organic vehicle). The present invention has been found to find a method capable of completely removing the organic vehicle without using the same.

According to the present invention, the paste-like resin composition is of a solventless type, but does not impair the applicability on a substrate, and furthermore, the organic vehicle including the curing treatment before sintering is heated. Through the pre-firing that is removed under the history, the shape and shape of the applied paste layer can be maintained, and the firing process through the sintering process at a further elevated temperature after the pre-firing is an inert process such as nitrogen. A paste-like conductive resin composition (hereinafter, simply referred to as a conductive resin paste) for a conductive sintered body, which can be formed in an atmosphere.

Further, according to the present invention, in the pre-baking after the application of the conductive resin paste, the formed coating layer or the mold pouring product may have pinholes such as air holes, cracks, or the like. Provided is a non-solvent type conductive resin paste which does not cause bending or contraction. That is, the binder resin composition according to the present invention, which contains a conductive metal powder and / or an alloy powder thereof and makes the whole a paste, has (A) a weight average molecular weight Mw of 50.
0-10000, glass transition temperature (Tg) is -80-
It is characterized by containing a (meth) acrylic polymer at 50 ° C. and (B) a polymerizable polyfunctional monomer having a molecular weight of 100 to 5000 and having 2 to 6 polymerizable unsaturated groups. . In this binder resin composition (organic vehicle),
(C) A conductive resin paste containing at least one kind of conductive inorganic powder having an average particle diameter of 0.1 to 20 μm.

Thus, unlike the conventional paste-like resin composition, the organic vehicle containing (A) and (B) is (M) which is the main component of the vehicle (A).
The organic vehicle according to the present invention is obtained by combining a low polymer in which the acrylic polymer has a specific Mw or a low molecular weight polymerizable polyfunctional monomer (B) with the low polymer. Although it is a solventless type, it is a fluid viscous material having both solvent properties and has wettability with a conductive metal and / or its alloy powder.

The conductive resin paste obtained by adding a conductive metal powder or the like to the organic vehicle has excellent coatability.
Moreover, since the low molecular weight polymerizable polyfunctional monomer (B) is combined, it can be polymerized and cured (cured) by heat or UV after application, so that the applied paste layer after application is excellent. Shape shapeability can be imparted.

Further, unlike the vehicle of the conventional method, the vehicle forming the applied paste layer after curing contains no solvent. Moreover, since the binder resin component is composed of the low polymer described above,
After curing, the binder resin component (vehicle component) does not have to be burned off in an oxygen atmosphere as in the related art. Under low temperature heat history under inert atmosphere such as nitrogen,
Since it is easily thermally decomposed and scattered and removed, the coating paste layer does not leave carbonaceous matter due to coking or the like, which tends to be generated under a heat history like a conventional vehicle.

According to the present invention, (A) the weight average molecular weight Mw is 500 to 10,000 and the glass transition temperature (T
g) a (meth) acrylic polymer in the range of −80 to 50 ° C .; (B) a polymerizable polyfunctional monomer having a molecular weight of 100 to 5000 and having 2 to 6 polymerizable unsaturated groups;
The viscosity (23 ° C.) containing the polymerization initiator is 0.01 to
A resin composition having a pressure of 10 Pa · s is prepared. This resin composition is kneaded with (C) a conductive metal having an average particle diameter in the range of 0.1 to 20 μm and / or an alloy powder thereof to obtain a conductive resin paste. Next, after applying this paste on a substrate or the like, the applied layer is polymerized and cured (cured).
Let it. Then, under an inert atmosphere, in the temperature range of pre-sintering before sintering, after the vehicle resin component in the applied paste layer is thermally decomposed and volatilized to be scattered and removed,
Provided is a method for forming a conductive sintered body, characterized by sintering at a further elevated temperature.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a paste-like conductive resin composition containing a conductive sintered body or a conductive metal powder for forming a layer thereof according to the present invention (hereinafter simply referred to as a conductive resin paste). The embodiment of ()) will be further described.

Therefore, as described above, in the conductive resin paste according to the present invention, the binder resin composition (or organic vehicle) for forming the paste is a solventless type and has a low (meth) acrylic weight. And a polymerizable polyfunctional monomer having 2 to 6 polymerizable unsaturated groups. The organic vehicle in the present invention is preferably based on 100 parts by weight of this particular low polymer.
It is characterized in that the polymerizable polyfunctional monomer is a resin composition in the range of 10 to 900 parts by weight.

In the present invention, if the content of the polymerizable polyfunctional monomer is less than the above-mentioned lower limit of 10 parts by weight, even if the paste layer is polymerized and cured after the application, the shape of the applied paste layer is not changed. The paste cannot be held sufficiently and the shape shapeability of the applied paste is reduced. On the other hand, even if the content exceeds the upper limit of 900 parts by weight, merely increasing the content of the resin component more than necessary and not exhibiting more than necessary shaping properties corresponding to the increased amount is merely economically disadvantageous. It just becomes.

Further, the resin composition of this vehicle has a temperature of 23 ° C.
Is 0.01 to 10 Pa · s, preferably,
It is in the range of 0.05 to 8 Pa · s. When the viscosity is less than the lower limit, depending on the surface wettability of the inorganic powder to be filled, a stable paste is not obtained, and the coatability or the shapeability is reduced. In addition, not only does the filling amount of the inorganic powder significantly decrease, but also the applicability of the paste significantly decreases.

In the present invention, as described above, the vehicle for forming the paste is a solventless type unless otherwise required. Excellent in heat resistance, and through drying, pre-firing and sintering, the temperature is lower than that of the conventional vehicle, that is, 250 to 550 ° C., preferably 350
It is characterized in that the vehicle components are almost completely thermally decomposed, volatilized and scattered and removed in a temperature range of up to 500 ° C. and under an inert atmosphere.

In the present invention, the polymerizable polyfunctional monomer having 2 to 6 polymerizable unsaturated groups, which is a resin component of the vehicle, is used in the present invention even if it is heat polymerizable.
Any photopolymerizable monomer such as V can be suitably used, but preferably, a photopolymerizable polyfunctional monomer such as UV is more conductive than a thermopolymerizable polyfunctional monomer. It is suitable from the viewpoint of the pot life of the resin paste.

That is, by being UV-polymerizable,
Even if the photopolymerization initiator is previously contained in the vehicle, the viscosity of the vehicle does not increase with time,
The pot life of the conductive resin paste according to the present invention is not impaired. However, when the polymerizable polyfunctional monomer is a thermopolymerizable monomer, if the thermopolymerization initiator is brought into contact with the thermopolymerizable monomer with time in advance, the viscosity of the vehicle increases. After forming a paste in which the initiator is dissolved in a (meth) acrylic low polymer containing a conductive inorganic powder, the paste is mixed with a thermopolymerizable monomer immediately before application to form a paste according to the present invention. It can be used as a resin paste.

In the conductive resin paste using the vehicle according to the present invention, various conductive metals and / or alloy powders thereof described below contain the above-mentioned low polymer 100%.
100 to 9000 parts by weight, preferably 50 to 100 parts by weight of conductive inorganic powder having an average particle diameter of 0.1 to 20 μm per part by weight.
It can be contained in the range of 0 to 6000 parts by weight.
Therefore, the organic vehicle according to the present invention having the above viscosity range, the conductive inorganic powder that can be filled in the above range,
It is preferable that the filling amount is as high as possible as long as the obtained conductive resin paste does not impair the applicability and shapeability described above.

[0034] Such a filling amount particularly depends on the wettability of the conductive metal and / or its alloy powder with the vehicle (depending on the oil absorption of the powder itself), and the amount of the powder. From the viewpoint of close packing, particle diameter and particle size distribution, spherical,
It is greatly affected by the shape of particles such as needles and irregular shapes. Therefore, although it cannot be specified unconditionally, from the viewpoint of bringing the powder particles in the paste into a finely packed state, preferably,
The particle shape is almost spherical, satisfying the above average particle size,
A conductive inorganic powder having an appropriate particle size distribution is preferable.

Therefore, as described above, as the (meth) acrylic polymer constituting the binder resin composition according to the present invention, the following low polymerizable polymerizable monomers can be appropriately used.

In the present invention, as the polymerizable monomer for such a low polymer, for example, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert- Butyl methacrylate, n-
Pentyl acrylate, n-pentyl methacrylate,
n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-
Octyl methacrylate, n-decyl acrylate, n
-Decyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and the like. In the present invention, at least one or more of these monomers can be appropriately used.

In order to prepare the low polymer used in the present invention from these monomers, for example, the bulk polymerization method described in JP-A-2000-128911 already applied for a patent by the present inventors has been adopted. Can be suitably suitably prepared. That is, a compound having at least one thiol group and a secondary hydroxyl group represented by the following general formula [I] is used as a catalyst for bulk polymerization of a polymerizable unsaturated compound of the above-mentioned (meth) acrylic monomer. It is.

[0038]

Embedded image However, in the general formula _[I], R 1 ~R ₅ are each independently a hydrogen atom or an alkyl group having a carbon number of _C 1 _{~C 12, R 6} represents a hydroxyl group, the number of carbon atoms _C 1 _{-C 1 2} And at least one group selected from alkyl groups having ₁ to ₁₂ carbon atoms. Also, at least one
It is characterized by having two thiol groups (-SH) and a secondary hydroxyl group.

In this bulk polymerization method using this as a polymerization initiator and a reaction control agent, the reaction can proceed in a substantially solvent-free manner, and even if the above-mentioned highly reactive monomer is used, the reaction can proceed. The polymerization reaction can proceed without runaway. As a result, a low polymer having a narrow molecular weight distribution can be stably subjected to bulk polymerization.

Thus, as the compound represented by the general formula [I], for example, thioglycerol, 1-mercapto-
2,3-propanediol, 2-mercapto-3-butanol, 2-mercapto-3,4-butanediol,
-Mercapto-2,3-butanediol, 1-mercapto-2-butanol, 2-mercapto-3,4,4'-
Butanetriol, 1-mercapto-3,4-butanediol, 1-mercapto-3,4,4′-butanetriol and the like can be mentioned. In the present invention, among these compounds, thioglycerol is particularly preferably used as a catalyst for bulk polymerization.

The bulk polymerization method of polymerizing a polymerizable unsaturated compound using a bulk polymerization catalyst comprising an organometallic compound (metallocene compound) represented by the following formula [II] and a thiol may be appropriately used. It can be suitably prepared.

[0042]

Embedded image However, in the above formula [II], M is the periodic table 4A
A metal selected from the group consisting of metals of the genus, genus 4B, genus 5A, genus 5B, chromium, ruthenium and palladium.
Specifically, M is titanium, zirconium, chromium, ruthenium, vanadium, palladium, tin, or the like. In the formula [II], R1 and R2 may each independently have an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a substituent. It is at least one group selected from the group consisting of a certain aromatic hydrocarbon group, a silicon-containing group which may have a substituent, a hydrogen atom and a single bond. In addition, R1 and R2 may jointly link the two 5-membered rings, and a plurality of adjacent R1 or R2
May form a ring structure together. In the formula [II], a and b each independently represent 1 to
X is an integer of 4, X is a halogen atom such as chlorine, bromine or iodine or a hydrocarbon group in which at least a part of a hydrogen atom may be substituted with a halogen atom, and n is 0
Alternatively, it is an integer of valence-2 of the metal M.

The organometallic compounds represented by the formula [II] include, for example, dicyclopentadiene-Ti-dichloride, dicyclopentadiene-Ti-bisphenyl, dicyclopentadiene-Ti-bis-2,3,3 4,
5,6-pentafluorophenyl-1-yl, dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadiene-Ti-
Titanocene compounds such as bis-2,5,6-trifluorophen-1-yl, dicyclopentadiene-Ti-bis-2,6-difluorophenyl-1-yl; dicyclopentadiene-Zr-dichloride, dicyclopentadiene -Zr-bisphenyl, dicyclopentadiene-Zr-
Bis-2,3,4,5,6-pentafluorophenyl-1
And zirconocene compounds such as -yl; dicyclopentadienyl-V-chloride, bispentamethylcyclopentadienyl-V-chloride and the like. These organometallic compounds can be used alone or in combination of two or more.

The organometallic compound is usually used in a catalytic amount of 1 to 100 parts by weight of the polymerizable unsaturated compound.
0.001 part by weight, preferably 0.01 to 0.005
It is preferably used in parts by weight. Examples of the thiols include alkyl thiols such as ethyl mercaptan, butyl mercaptan, and hexyl mercaptan, phenyl mercaptan, benzyl mercaptan, β-mercaptopropionic acid, 3-mercaptopropyl-trimethoxysilane, and thiophenyl. In this catalyst, the organometallic compound acts as an activating catalyst for the entire reaction, thiols have a polymerization initiating action, and the amount of thiols used affects the molecular weight and the polymerization rate. Therefore,
The organometallic compound and the thiols are usually 100: 1 to 1
It is used in a molar ratio in the range of 1: 50,000. Also, for the purpose of adjusting the polymerization rate and degree of polymerization, disulfide compounds,
Trisulfide compounds and tetrasulfide compounds can be used.

In the present invention, the (meth)
The acrylic polymer preferably has a weight average molecular weight Mw of 500 to 10,000, more preferably 100
A low polymer in the range of 0 to 7000 can be suitably used suitably. If this Mw is less than the lower limit, the shape-forming properties of the polymerized and cured application paste layer will be reduced, and the functional inorganic powder will not exhibit sufficient binding properties. On the other hand, if the Mw exceeds the upper limit, the viscosity of the resin increases, and the viscosity of the paste is increased. Therefore, it is economically disadvantageous because adjustment of the monomer component is increased or the powder concentration is decreased, which is preferable. Absent.

In the present invention, the glass transition temperature (Tg) of the low polymer is preferably from -80 to 50.
Preferably it is in the range of ° C. When the Tg is out of this range, that is, when the Tg exceeds 50 ° C., the flexibility of the coating film after polymerization and curing is low, and the viscosity of the vehicle is high, and the brush breakage property at the time of screen coating and brush coating property are low. It tends to lower workability. On the other hand, if the Tg is lower than -80 ° C, it is not preferable because the shape-forming properties of the coating film after polymerization and curing are poor and the filler retention during firing is lowered.

In the present invention, the acid value of the low polymer is preferably in the range of 60 to 180. That is, in the present invention, it is a binder resin for a paste that is already known, unlike the tendency of a low polymer of an acrylic copolymer having a carboxyl group and an unsaturated group in a side chain, unlike the paste-like composition. The applicability is not impaired by the increase in viscosity over time. In particular, in the present invention, the conductive inorganic powder used in the conductive resin paste of the present invention is affected by the surface wettability of the conductive inorganic powder to be used. On the other hand, it is not preferable because the effect as a dispersant tends to be lost.

In the present invention, examples of the polymerizable polyfunctional monomer having a plurality (2 to 6) of polymerizable unsaturated groups that undergo a radical reaction include ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate. Acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexaglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, 2,2-bis (4- (meth)
Acryloxydiethoxyphenyl) propane, 2,2-
Bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol di Multifunctional acrylates represented by glycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, and corresponding methacrylates It can be acrylate monomer is given.

In particular, in the case of a UV-curable type, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone are used as photopolymerization initiators.
α-aminoacetohenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone,
Dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-2 -Methylpropiophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, benzyldimethylketal, benzylmethoxyethylacetal, benzoinmethylether, benzoinbutylether,
2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,
Toanthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzantrone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (ρ-azidobenzylidene) cyclohexane, 2,6
-Bis (ρ-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2-
(Ο-methoxycarbonyl) oxime, benzothiazole disulfide and the like can be mentioned, and one or more of these photopolymerization initiators can be used in combination. These photopolymerization initiators can be added in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of (B). If the addition amount is less than the lower limit, the photocurability of the conductive resin paste is low, which is not preferable.Also, if added beyond the upper limit, the resin hardens even with visible light, shortens the pot life, and after baking, the residue is removed. It is not preferable because it tends to remain.

If necessary, a photopolymerization initiator may be used in combination with a photopolymerization initiator for inducing a radical reaction, and a photopolymerization initiation aid may be used to promote the photopolymerization initiation reaction to make polymerization curing more efficient. it can. As such a photopolymerization initiation aid,
For example, triethylenetetramine, triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, dimethylthioxanthone,
Aliphatic and aromatic amines such as isopropylthioxanthone, N-methyldiethanolamine and ethyl 4-dimethylaminobenzoate can be mentioned. These photoinitiating assistants are used in an amount of 0.1 to 5 parts by weight based on 1 part by weight of the photopolymerization initiator.
It can be added in the range of parts by weight. Further, by using the photosensitive resin composition as the organic vehicle of the conductive resin paste, a pattern can be formed as a resist coating layer, so that a predetermined pattern can be appropriately formed by a photoresist method.

Further, if necessary, a plasticizer, a dispersant, a thickener, an anti-settling agent,
An antifoaming agent, a leveling agent, a thermal polymerization inhibitor and the like can be appropriately added. For example, examples of the plasticizer added for the purpose of improving the fluidity of the paste include diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dibenzyl phthalate, polyalkylene glycol, triethylene glycol diacetate, and polyethylene okoside. In particular, it can be added in a range that does not impair photocurability sensitivity and thermal decomposition / volatility.

<Method of Forming Conductive Sintered Body> As various electronic products and their peripheral devices, for example, electronic components such as ceramic capacitor elements, piezoelectric elements, pyroelectric elements, and semiconductor devices formed on a substrate. Has built-in conductive members such as internal electrodes, circuit patterns, and external electrode terminals. The formation method can be formed by, for example, a CVD / sintering method, a sputtering method, or a conductive paste application / sintering method.

As already described above, the solvent-free binder resin composition (vehicle) of the present invention is easily kneaded with an inorganic powder of a conductive metal and / or a conductive alloy thereof to easily form a paste. It is possible to prepare the conductive resin paste according to the present invention, which is excellent in the above-described applicability, shapeability, sinterability and the like. The conductive resin paste thus obtained can be applied on a ceramic substrate such as alumina or a substrate of various ceramic green sheets. Examples of the coating method include a screen printing method, a bar coater method, a roll coater method, a slit die coater method, a doctor blade coater method, and a photosensitive resin paste method (photoresist forming method), which can be suitably used as appropriate. .

Examples of applications for applying such a paste include ceramic substrates such as alumina and alumina nitride, and ceramics for low-temperature firing substrates containing cordierite, mullite, steatite and glass components as main components. As an inner layer or outer layer conductor on the green sheet,
Alternatively, a tantalum capacitor, a multilayer ceramic capacitor using a ferroelectric layer of perovskite-type composite oxide particles, a multilayer piezoelectric ceramic element, a multilayer ceramic (L
C) Appropriately applied as an external electrode of a filter or the like and formed by sintering.

The conductive paste applied on the above-mentioned base material such as a ceramic substrate or a ceramic green sheet is formed by lamination on an insulator layer, a dielectric layer, an insulator layer-dielectric layer, and the like. Or an interlayer such as an insulator layer-conductive layer-insulator layer, insulator layer-dielectric layer-conductor layer-insulator layer, insulator layer-dielectric layer-conductor layer-dielectric layer, etc. It will be formed as a conductive material.

When the paste-like resin composition is a photosensitive resin composition as in the present invention, it is preferable that the paste-like resin composition is applied by a resist forming method (photolithography). -Conducting pattern exposure, development-cure-pre-baking-sintering to form a conductive sintered layer as a circuit pattern.

As the conductive material of the conductive resin paste for firing, gold, silver, platinum, palladium, silver-palladium alloy,
Nickel, aluminum, aluminum-Si, aluminum-copper-Si, copper, copper-silver alloy, titanium, titanium-Si, tungsten, tungsten-Si, molybdenum, molybdenum-Si, ITO, and the like.
Further, if necessary, the adhesion of the conductive powder to the substrate is improved or the sinterability, the reduction of the sintering temperature, the improvement of the coefficient of thermal expansion, etc., in the temperature range of 600 to 1100 ° C. are usually performed. Glass frit can be mixed with the conductive resin paste as needed for improvement or the like.

Since the glass frit is preferably a system substantially free of alkali metals and alkaline earth metals, for example, bismuth oxide, silicon oxide, boron oxide, zinc oxide, zirconium oxide, etc. ZnO—B ₂ O ₃ —SiO ₂ based, PbO—
B ₂ O ₃ -SiO _{2 -based, PbO-B 2 O 3 -SiO} 2 -
Al ₂ O ₃ system, mention may be made of _{PbO-ZnO-B 2 O 3} -SiO 2 system, and the like. In the present invention, the glass frit is 0.1 to 10 parts by weight based on 100 parts by weight of the conductive powder.
Parts by weight can be included.

If necessary, the low-melting glass dielectric powder may be used in combination with low-dielectric powders such as alumina, aluminum nitride, mullite, cordierite, crystallized glass, and barium titanate. , Strontium titanate, lead titanate, lead zirconate titanate, neodymium titanate, and other high dielectric constant powders, other silicon nitride, silicon carbide ceramic powders, other high melting point glass, etc. More than one species can be combined and added as a filler.

[0060]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

Reference Example 1 (A) which is a component of a binder resin composition (vehicle) of a conductive resin paste
A low polymer of (meth) acrylic polymer is prepared. A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 100 parts by weight of 2-ethylhexyl methacrylate, and the content in the flask was heated to 80 ° C. while introducing nitrogen gas into the flask. Next, 7 parts by weight of thioglycerol sufficiently purged with nitrogen gas was added to the flask with stirring. Thereafter, cooling and heating were performed for 2 hours so that the temperature of the contents in the flask during stirring could be maintained at 80 ° C. Thereafter, the polymerization reaction is further carried out for 6 hours while cooling and heating so that the temperature of the contents in the stirring flask can be maintained at 95 ° C., and then azobisisobutyronitrile 0.16 The polymerization was carried out at 95 ° C for 2 hours.

After a total of 8 hours of reaction as described above,
The temperature of the reaction product was returned to room temperature, and 0.05 parts by weight of hydroquinone was added to the reaction product to obtain a reaction product (a-1). As a result of measuring the monomer residual ratio of the obtained polymerization reaction product (a-1) by gas chromatography, the polymerization ratio was 9
It was 9.4%. The molecular weight measured by gel permeation chromatography (GPC) is
Mw = 3800, Mn = 1700, and dispersion index =
2.1 and a viscosity at 23 ° C. of 330 (Pa ·
s) was a low polymer of the (meth) acrylic polymer.

(Reference Example 2) The reaction product (a) was polymerized in the same manner as in Reference Example 1 except that MMA (methyl methacrylate) was used as a monomer and the added thioglycerol was 24 parts by weight. -2) was obtained. As a result of measuring the residual monomer ratio of the obtained polymerization reaction product (a-2) by gas chromatography, the polymerization rate was 98.
8%. The molecular weight measured by GPC was Mw = 1100, Mn = 790, and the dispersion index =
1.39 and a viscosity at 23 ° C. of 2.3 (Pa ·
s) was a low polymer of methyl methacrylic polymer.

Reference Example 3 Polymerization was carried out in the same manner as in Reference Example 1 except that the addition amount of thioglycerol was changed to 3.9 parts by weight to obtain a reaction product (a-3). .
As a result of measuring the residual monomer ratio of the obtained polymerization reaction product (a-3) by gas chromatography, the polymerization ratio was 9
9.8%. The molecular weight measured by GPC was Mw = 7400, Mn = 4300, the dispersion index was 1.69, and the viscosity at 23 ° C. was 990.
(Pa · s) was a low polymer of methyl methacrylic polymer.

Example 1 In a 200 ml beaker, 50 parts by weight of the low polymer (a-1) of the (meth) acrylic polymer obtained in Reference Example 1 were added.
Take 50 parts by weight of ethylene glycol dimethacrylate, which is a polymerizable polyfunctional monomer, and stir and mix until sufficiently uniform to obtain (b-1) of the acrylic binder resin composition (vehicle) used in the present invention. Obtained. The viscosity of the obtained vehicle (b-1) was 0.08 at 23 ° C.
(Pa · s).

(Thermopolymerizable paste and its curing) Then, 50 parts by weight of copper powder having an average particle diameter of 3.2 μm, 10 parts by weight of the above-mentioned vehicle (b-1), and 1,1,3,3 as a radical initiator 3-tetramethylbutylperoxy-2
-0.4 parts by weight of ethylhexanol and 0.04 parts by weight of hydroquinone as an inhibitor are sufficiently kneaded by a roll mill to obtain a paste-like conductive resin composition of copper powder (c-
1) was prepared. The viscosity of the obtained paste (c-1) was 6.8 (Pa · s).

Next, the paste (c-1) was applied on an alumina substrate with a bar coater so as to have a thickness of 50 μm, and was heated and cured at 120 ° C. for 5 minutes in a nitrogen atmosphere. The thickness of the obtained coating film was 48 μm, and there was almost no volume reduction, and no cracks or the like were observed on the surface. In addition, during the heat polymerization curing, the coating layer was able to impart good shape-forming properties without collapse.

(UV-Polymerizable Paste and Its Curing) 50 parts by weight of copper powder having an average particle size of 3.2 μm, 10 parts by weight of the above-mentioned vehicle (b-1), (82% by weight of zinc oxide as glass powder, 8 parts by weight of glass frit powder having a composition ratio of 8% by weight of boron and 10% by weight of silicon oxide), 10 parts by weight of the above-mentioned vehicle (b-1) and 0.3% by weight of Irganox I-369 as a UV radical initiator Parts and 0.01 part by weight of hydroquinone as an inhibitor were kneaded to prepare a copper powder paste-like conductive resin composition (d-1). The viscosity of the obtained paste (d-1) is
It was 8.7 (Pa · sec).

Next, the paste (d-1) was applied on an alumina substrate by a bar coater so as to have a thickness of 50 μm, and under a nitrogen atmosphere, a high-pressure mercury lamp was used as a light source and an irradiation intensity of 214 mW / cm ^2. , Integrated light amount 1930m
UV exposure was performed from the coating film surface so as to be J / cm ² . The thickness of the obtained coating film is 49 μm, there is almost no volume decrease, no cracks on the surface, etc. are observed, and at the time of the UV polymerization curing, the coating layer is able to give good shape shapeability without flow collapse. did it.

(Pre-firing and sintering) Then, the test pieces c-1 and d-1 obtained by applying pastes c-1 and d-1 on a substrate and heat- and UV-polymerized were cured under a nitrogen atmosphere. The temperature is raised from room temperature to 350 ° C in 20 minutes,
For 20 minutes. As a result, the organic resin component of the vehicle in the coating layer of each test sample could be completely thermally decomposed and volatilized and removed. That is, in the visual observation through the heat treatment, no residue or soot is seen on the coating layer, and each of the surface and the surface shaved by applying sandpaper is gauze moistened with MEK. After wiping, no stain components adhered on the gauze.

Next, the specimens c-1 and d-1 from which the organic resin component was removed by the pre-baking were held at 900 ° C. for 30 minutes in a nitrogen atmosphere to sinter the copper powder of the coating layer. I let it. As a result, the sintered layer was visually free from abnormalities such as peeling and cracking, and had good copper metallic luster.

Example 2 In a 200 ml beaker, 65 parts by weight of the low-polymer (a-2) of the methyl methacrylic polymer obtained in Reference Example 2 and 35 parts by weight of ethylene glycol dimethacrylate were taken, and sufficiently charged. The mixture was stirred and mixed until it became uniform to obtain (b-2) an acrylic binder resin composition (vehicle) used in the present invention. The viscosity of the obtained vehicle (b-2) was 0.037 (Pa · s) at 23 ° C.

(Thermopolymerizable paste and its curing) Then, 50 parts by weight of copper powder having an average particle diameter of 3.2 μm, 7 parts by weight of the above-mentioned vehicle (b-2), Except for using 0.2 parts by weight, the mixture was sufficiently kneaded with a roll mill in the same manner as in Example 1 to prepare a copper powder paste-like conductive resin composition (c-2). The viscosity of the obtained paste (c-2) is 7.2 (Pa ·
s).

Next, the paste (c-2) was applied on an alumina substrate with a bar coater so as to have a thickness of 50 μm, and was heated and polymerized at 120 ° C. for 5 minutes in a nitrogen atmosphere. The thickness of the obtained coating film is 48 μm, there is almost no volume reduction, no cracks on the surface, etc. are observed, and at the time of the thermal polymerization curing, the coating layer can give good shape shapeability without flow collapse. did it.

(UV-Polymerizable Paste and Curing Thereof) To 50 parts by weight of copper powder having an average particle size of 3.2 μm, to 7 parts by weight of the above-mentioned vehicle (b-2), and to carry out UV-polymerizable copper A powdery paste-like conductive resin composition (d-2) was prepared. The viscosity of the obtained paste (d-2) is
7.2 (Pa · s). Then, the obtained UV-curable paste (d-2) was applied on an alumina substrate by a bar coater so as to have a thickness of 50 μm in the same manner as in Example 1. Under the same conditions as described above, UV exposure was performed to polymerize and cure the coating paste layer.
The thickness of the obtained coating film is 48 μm, there is almost no volume reduction, no cracks on the surface, etc. are observed, and at the time of the UV polymerization curing, the coating layer can give good shape shapeability without flow collapse. did it.

(Pre-firing and sintering) Then, pastes c-2 and d-2 were applied on an alumina substrate, and heat and UV
Heat treatment for pre-baking the polymerized and cured c-2 and d-2 under the same conditions as in Example 1 to remove the organic vehicle in the coating layer of each test body (pre-baking) Was done. As a result, similar to the test piece of Example 1,
The organic resin component of the vehicle in the coating layer of each test piece could be completely thermally decomposed and volatilized and removed.

That is, similar to the test piece of Example 1, in the visual observation through the heat treatment, no residue or soot was found on the coating layer, and the coating layer was shaved off by applying the surface and sandpaper. Each of the washed surfaces was wiped with gauze moistened with MEK, but no stain components adhered to the gauze. Further, the test pieces c-2 and d-2 from which the organic resin component was removed by the above-described pre-baking were sintered in the same manner as the test piece of Example 1. As a result, a sintered layer having good copper metallic luster without visual abnormality in the sintered layer such as peeling or cracking was obtained.

Example 3 In a 200 ml beaker, 70 parts by weight of the low-polymer (a-3) of the methyl methacrylic polymer obtained in Reference Example 3 and 30 parts by weight of ethylene glycol dimethacrylate were taken, and then sufficiently charged. The mixture was stirred and mixed until it became uniform to obtain (b-3) an acrylic binder resin composition (vehicle) used in the present invention. The viscosity of the obtained vehicle (b-3) was 7.8 (Pa · s) at 23 ° C.

(Thermopolymerizable Paste and Its Curing) Example 1 was repeated except that the radical initiator was changed to 0.45 part by weight in Example 1 to 15 parts by weight of the vehicle (b-3).
In the same manner as in the above, a copper powder paste-like conductive resin composition (c
-3) was prepared. The viscosity of the obtained paste (c-3) was 7.2 (Pa · s).

Next, the paste (c-3) was applied on an alumina substrate with a bar coater so as to have a thickness of 50 μm, and was heated and polymerized at 120 ° C. for 5 minutes in a nitrogen atmosphere. The thickness of the obtained coating film is 49 μm, there is almost no volume reduction, no cracks on the surface, etc. are observed, and during the thermal polymerization curing, the coating layer is able to give good shape shapeability without collapse. did it.

(UV Polymerizable Paste and Curing Thereof) In Example 1, 15 parts by weight of this vehicle (b-3)
A paste-form conductive resin composition of copper powder (c-3) was prepared in the same manner as in Example 1 except that the radical initiator was changed to 0.45 parts by weight. The obtained paste (c-
The viscosity of 3) was 7.5 (Pa · s). Then
The obtained UV-curable paste (d-3) was coated on an alumina substrate in the same manner as in Example 1 with a bar coater to a thickness of 5
Example 1 was applied to a thickness of 0 μm under a nitrogen atmosphere.
Under the same conditions as described above, UV exposure was performed to polymerize and cure the coating paste layer. The thickness of the obtained coating film is 49 μm, there is almost no volume decrease, no cracks on the surface, etc. are observed, and at the time of the UV polymerization curing, the coating layer is able to give good shape shapeability without flow collapse. did it.

(Pre-firing and sintering) Next, pastes c-3 and d-3 were applied on a glass substrate, heat- and UV-polymerized and cured to obtain the test specimens c-3 and d-3 in Example 1.
Pre-baking was carried out under the same conditions as described above, and a heat treatment (pre-baking) for removing the organic vehicle in the coating layer of each specimen was performed. As a result, similar to the test piece of Example 1,
The organic resin component of the vehicle in the coating layer of each specimen can be completely thermally decomposed and volatilized and removed. Similarly, visual observation through heat treatment and wiping of MEK in the coating element with gauze moistened No residue and no coking quality were confirmed.
Further, the test pieces c-3 and d-3 from which the organic resin component had been removed by the above-mentioned pre-baking were sintered in the same manner as the test piece of Example 1. As a result, a sintered layer having good copper metallic luster without visual abnormality in the sintered layer such as peeling or cracking was obtained.

Example 4 To 10 parts by weight of the vehicle (b-1) obtained in Example 1,
Example 1 except that 7 parts by weight of glass frit having an average particle size of 2 μm and 45 parts by weight of copper powder having an average particle size of 3.2 μm were used.
Paste (d-1) and in the same manner, _ZnO-B 2 _{O 3}
A paste-like conductive resin composition of a UV-polymerizable copper powder containing a glass frit of an SiO ₂ system is prepared, applied to an alumina substrate with a bar coater so as to have a thickness of 30 μm, and then exposed to a nitrogen atmosphere. Under the same conditions as in Example 1, U
V exposure was performed, and the applied paste layer was polymerized and cured (cured). Next, on the cured coating paste, the paste-form conductive resin composition (d-2) of the UV-polymerizable copper powder prepared in the same manner as in Example 1 was coated with a bar coater to a film thickness of 50 μm. Then, under a nitrogen atmosphere, under the same conditions as in Example 1, UV exposure was performed to polymerize and cure the applied paste layer, thereby forming a conductive paste laminate.

(Play firing and sintering of laminate)
The laminate on this substrate is heated from normal temperature under nitrogen atmosphere to 350 ° C.
And heated at 350 ° C. for 30 minutes. As a result, the organic resin component of the vehicle in the laminated coating layer could be completely thermally decomposed and volatilized and removed without visually causing peeling, cracking, etc. in the laminated coating layer. Next, the sintered layer was held at 870 ° C. for 40 minutes in a nitrogen atmosphere and sintered. The sintered layer had no abnormalities such as peeling and cracking, and had good metallic copper luster.

Comparative Example 1 In Comparative Example 1, Mw 11 used in Example 2 was used.
Low methyl methacrylic polymer (a-2)
A vehicle was prepared using one having a Mw of less than 500 instead of. As a result, the vehicle is shabu-shabu, the applicability is remarkably reduced, and furthermore, in order to optimize solvent properties and cure after application, it is not possible to combine a polymerizable polyfunctional monomer as a vehicle component. The shapeability of the paste was significantly reduced.

Comparative Example 2 In Comparative Example 2, Mw 74 used in Example 3 was used.
Low methyl methacrylic polymer (a-3)
The vehicle was prepared using Mw 11,000 exceeding Mw 10000 instead of As a result, the paste layer after application is cured, and the combination amount of the polyfunctional monomer that exerts shape-forming properties on the application paste layer is increased, so that only the vehicle cost is disadvantageously economically reduced. In addition, the coatability and the amount of powder to be filled are reduced, and therefore, a solvent-type vehicle to which a solvent is added is obtained.

[0087]

As described above, according to the present invention, in the conductive resin paste, the binder resin composition (vehicle) is a low polymer (meth) acrylic polymer having a Mw of about 500 to 10,000, It is formed as a fluid viscous material containing a thermosetting or UV curable low molecular weight polymerizable polyfunctional monomer. Thereby, although this vehicle is solventless, it is excellent in coatability having both solvent properties, and the coating layer after coating is polymerized and cured to impart shapeability to the conductive inorganic powder, and Since the coating layer is easily thermally decomposed and removed at a low temperature, the coating layer is formed of a conductive resin paste that exhibits good sinterability by preventing the occurrence of bubble pores, cracks, bending, and shrinkage. Can be provided.

Further, since the filling amount of the conductive inorganic powder in the paste can be increased as compared with the conventional solvent-type vehicle, the heat shrinkage during the pre-firing and sintering of the coating layer can be reduced. Thus, a conductive sintered body having excellent dimensional stability can be formed.

Further, unlike the conventional paste, the pre-baking for removing the organic vehicle can be performed in an inert atmosphere, and therefore, in particular, a conductive metal such as copper and the like and / or an alloy powder thereof having low oxidation resistance is used. It does not decrease conductivity, sintering property and adhesion to the substrate.

Moreover, since it is a solventless type, it is possible to reduce the organic volatile components which are volatilized and decomposed and scattered during paste preparation, coating and pre-firing, and therefore, from the standpoint of working environment and global environmental protection, A conductive resin paste capable of reducing contamination can be provided.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4J011 PA03 PA05 PA69 PB27 PC02 QA13 QA17 QA23 QA24 QB19 QB20 SA06 SA15 SA22 SA25 SA27 SA28 SA34 SA45 SA54 SA61 SA63 SA64 SA65 SA83 SA84 UA01 VA01 WA01 4J026 AA45 AC29 AC33 AC29 BA30 BB01 DB36 FA05 GA07 GA08

Claims (8)

[Claims] 1. A paste-like resin composition containing a conductive inorganic powder used for forming a conductive sintered body, comprising: (A) a weight average molecular weight Mw of 500 to 10,000 and a glass transition temperature (Tg) of (M) acrylic polymer at −80 to 50 ° C .; (B) a polymerizable polyfunctional monomer having a molecular weight of 100 to 5,000 and having 2 to 6 polymerizable unsaturated groups; and (C) an average particle diameter. A paste-like conductive resin composition containing at least one kind of conductive metal having a diameter of 0.1 to 20 μm and / or an alloy powder thereof and having excellent coatability, shapeability and sinterability. . 2. The paste-like resin composition according to claim 2, wherein
The viscosity of the resin composition containing 10 to 900 parts by weight of (B) and 100 to 9000 parts by weight of (C), and containing (A) and (B), relative to 100 parts by weight. 2
(3 ° C.) is 0.01 to 10 Pa · s. The paste-like conductive resin composition according to claim 1, wherein 3. The method according to claim 1, wherein the conductive inorganic powder is at least one metal powder selected from the group consisting of gold, silver, platinum, palladium, aluminum, copper, nickel, tungsten, molybdenum and titanium, and / or at least one of the metal powders. 3. An alloy powder comprising two elements.
3. The paste-like conductive resin composition according to item 1. 4. The paste according to claim 1, wherein the conductive inorganic powder is a combination of any one of the conductive inorganic powders described in claim 3 and a glass frit. Conductive resin composition. 5. The glass frit is made of Bi ₂ O ₃ —BO.
₂ -SiO _{2 system, BO 2 -SiO 2 -Al 2 O} 3 -Li
₂ O system, _{PbO-BO 2} -SiO 2 system, PbO-ZnO
-BO ₂ -SiO ₂ based paste-like conductive resin composition according to claim 4, characterized in that at least one glass powder selected from the group of. 6. A method for forming a conductive sintered body using a paste-like resin composition containing a conductive inorganic powder, comprising: (A) a weight average molecular weight Mw of 500 to 10,000 and a glass transition temperature (Tg) ) Is in the range of -80 to 50 ° C, and (B) the molecular weight is 100 to
A vehicle resin having a viscosity (23 ° C.) of 0.01 to 10 Pa · s containing a photopolymerizable polyfunctional monomer having 2 to 6 polymerizable unsaturated groups and a UV polymerization initiator; A composition is prepared, and (C) an average particle diameter of 0.1 to 20 μm is added to the resin composition.
m to form a paste-like resin composition containing a conductive metal and / or an alloy powder thereof. Then, the paste-like resin composition after application is cured by UV polymerization under UV irradiation. Then, under an inert atmosphere, the vehicle resin composition in the paste layer applied under a thermal history of a temperature of 250 to 550 ° C. is volatilized and thermally decomposed to be scattered and removed, and then sintered at a further elevated temperature. A method for forming a conductive sintered body, comprising: 7. A method for forming a conductive sintered body using a paste-like resin composition containing a conductive inorganic powder, wherein a (A) weight-average molecular weight Mw to which a thermal polymerization-type polymerization initiator is added is added. 500 to 10,000, glass transition temperature (Tg)
(B) a polymerizable polyfunctional monomer having a molecular weight of 100 to 5000 and having 2 to 6 polymerizable unsaturated groups; A) a conductive resin having an average particle size in the range of 0.1 to 20 μm and / or an alloy powder thereof to obtain a paste-like resin composition; 8
Thermal polymerization and curing under heating at 0 to 180 ° C, and then, under an inert atmosphere, under thermal history at a temperature of 250 to 550 ° C, volatilization and thermal decomposition of the vehicle resin composition in the coating paste layer to thereby remove and scatter. And sintering at a further elevated temperature. 8. The method according to claim 1, wherein the paste-like resin composition comprises (A)
The method for forming a conductive sintered body according to claim 11 or 12, wherein the amount of (B) is 10 to 900 parts by weight and the amount of (C) is 100 to 9000 parts by weight with respect to 100 parts by weight. .