READILY THERMALLY DEGRADABLE ORGANIC RESIN BINDER

Abstract

An object of the present invention is to provide a readily thermally degradable resin binder that is an organic resin binder for use as a binder component in a high-concentration inorganic microparticle dispersion, and that enables firing in a firing process to be carried out at lower temperatures and can inhibit the production of carbon residues, while maintaining the printing characteristics. This object can be achieved by a mixture formed of a specific (meth)acrylic resin and an ethyl cellulose resin in a weight ratio of 5:95 to 50:50. This specific (meth)acrylic resin is a (meth)acrylic polymer having a weight-average molecular weight of 1,000 to 250,000 and having a monomer unit given by the following general formula (1)

##STR00001##

[in the formula, R.sup.1 represents hydrogen or a methyl group and R.sup.2 represents hydrogen or a C.sub.1-12 straight-chain hydrocarbon group, branched-chain hydrocarbon group or hydroxyl group-bearing hydrocarbon group, or a polyalkylene oxide-containing group].

Claims

1-6. (canceled)

7. A process for forming a printed pattern on a ceramic substrate which comprises: printing a desired pattern on a ceramic substrate by screen printing with use of a high-concentration inorganic microparticle dispersion which comprises (a) inorganic microparticles, (b) an organic resin binder which comprises a (meth)acrylic resin and an ethyl cellulose resin, the weight ratio of (meth)acrylic resin to ethyl cellulose resin ranging from 5:95 to 50:50, and (c) a solvent, and heating the printed pattern at a temperature lower than the thermal degradation temperature of ethyl cellulose resin and thereby thermally degrading the organic resin binder, wherein the (meth)acrylic resin is a (meth)acrylic resin having a weight-average molecular weight of 1,000 to 250,000 and composed of a monomer unit of the following formula (1): ##STR00003## wherein R.sup.1 is hydrogen or a methyl group, and R.sup.2 is hydrogen, a C.sub.1-12 straight-chain, branched-chain or hydroxyl group-containing hydrocarbon group, or a polyalkylene oxide-containing group.

8. The process according to claim 7, wherein, in the formula (1), R.sup.1 is hydrogen or a methyl group, and R.sup.2 is a C.sub.1-4 alkyl group, a 2-ethylhexyl group, a lauryl group, a hydroxyethyl group or a methoxy polyethylene glycol group.

9. The process according to claim 7, wherein the (meth)acrylic resin has a weight-average molecular weight of 2,000 to 200,000.

10. The process according to claim 7, wherein the inorganic microparticles are silver microparticles.

Description

MODE FOR CARRYING OUT THE INVENTION

[0018] The readily thermally degradable organic resin binder and high-concentration inorganic microparticle dispersion of the present invention are described in detail in the following.

[0019] 1. The Readily Thermally Degradable Organic Resin

[0020] The readily thermally degradable organic resin binder of the present invention is obtained by mixing a prescribed (meth)acrylic resin and an ethyl cellulose resin so as to provide a weight ratio between (meth)acrylic resin and ethyl cellulose resin of 5:95 to 50:50, and has the ability to lower the amount of carbon residue production during the firing step from that for an ethyl cellulose resin binder.

[0021] The (meth)acrylic resin used by the present invention is an acrylic polymer having a monomer unit given by the following general formula (1)

[C1]

[0022] ##STR00002##

[in the formula, R.sup.1 represents hydrogen or a methyl group and R.sup.2 represents hydrogen or a C.sub.1-12 and particularly a C.sub.1-4 straight-chain hydrocarbon group, branched-chain hydrocarbon group or hydroxyl group-bearing hydrocarbon group, or a polyalkylene oxide-containing group].

[0023] The monomer constituting the (meth)acrylic resin can be exemplified by (meth)acrylic acid; the alkyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, tert-pentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, n-octyl (meth)acrylate, tert-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; the hydroxyalkyl esters of (meth)acrylic acid, such as hydroxyethyl (meth)acrylate; the polyalkylene glycol esters of (meth)acrylic acid, such as the polyethylene glycol esters of (meth)acrylic acid and the polypropylene glycol esters of (meth)acrylic acid; polyalkylene glycol (meth)acrylates such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, etc.; and alkoxy polyalkylene glycol (meth)acrylates such as methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, etc. These may be used individually or in combination.

[0024] The weight-average molecular weight of this (meth)acrylic resin is 1,000 to 250,000 and preferably 2,000 to 200,000. When the weight-average molecular weight of the (meth)acrylic resin is less than 1,000, a viscosity adequate for screen printing and adherence to the printed substrate are not obtained, and the accuracy of the circuit pattern may then decline. When the weight-average molecular weight of the (meth)acrylic resin exceeds 250,000, the compatibility with the ethyl cellulose resin then worsens and the thermal degradation-promoting action that is a goal of the present invention is not obtained to an adequate degree.

[0025] The (meth)acrylic resin is preferably obtained by a solution polymerization method. A (meth)acrylic resin obtained by an emulsion polymerization method is disfavored because the electrical characteristics can be impaired by the alkali metal component originating with the emulsifying agent used and because a decline in the adherence to substrate can occur due to the interfacial orientation of the emulsifying agent component.

[0026] The ethyl cellulose resin used by the present invention is an ethylated derivative of cellulose and is commercially available in a variety of grades. Examples here are STD-4, STD-7, STD-10, STD-20, STD-45, and STD-100 from The Dow Chemical Company. The ethyl cellulose resin for the present invention, however, is not limited to these product numbers.

[0027] With the goal of facilitating blending to give the high-concentration inorganic microparticle dispersion, the readily thermally degradable organic resin binder of the present invention may as necessary contain an organic solvent. The organic solvent used can be exemplified by aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ketones, esters, alcohols, ethers, polyglycols, terpenes, and so forth. A solvent adapted to the system used is desirably selected.

[0028] The organic solvent can be specifically exemplified by methyl alcohol, ethyl alcohol, normal-propyl alcohol, isopropyl alcohol, normal-butyl alcohol, isobutyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ethyl acetate, normal-propyl acetate, isopropyl acetate, normal-butyl acetate, isobutyl acetate, hexyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, ethylene glycol monoisopropyl ether acetate, diethylene glycol monoisopropyl ether acetate, triethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, nonane, normal-decane, isodecane, normal-dodecane, isododecane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, toluene, xylene, terpineol, dihydroterpineol, and dihydroterpineol acetate. A single one of these may be used by itself or a combination may be used.

[0029] 2. The High-Concentration Inorganic Microparticle Dispersion

[0030] The high-concentration inorganic microparticle dispersion of the present invention has inorganic microparticles and the readily thermally degradable organic resin binder as essential components and has organic solvent and other additives as optional components, and each of the components is desirably specifically selected in conformity to the use application.

[0031] The inorganic microparticles can be exemplified by microparticles of gold, silver, copper, aluminum, nickel, cobalt, tin, zinc, lead, tungsten, carbon, rare-earth metals, alloys of these metals, alumina, silica, zirconia, yttria, ferrite, zinc oxide, titanium oxide, barium titanate, lead titanate zirconate, boron oxide, boron nitride, silicon nitride, silicon carbide, tungsten carbide, and so forth, that have the particle diameters customary for application in electroconductive pastes, printing inks, and paints. A single one of these may be used by itself or a combination may be used, but the inorganic microparticle must be selected in conformity to the use application.

[0032] The content of the inorganic microparticles in the high-concentration inorganic microparticle dispersion of the present invention is not particularly limited, but a preferred lower limit is 30 weight % and a preferred upper limit is 95 weight %. When the inorganic microparticle content is less than 30 weight %, the obtained dispersion does not have an adequate viscosity and the printability and coatability may be diminished. When the inorganic microparticle content exceeds 95 weight %, the viscosity of the obtained dispersion is then too high and the printability and coatability may worsen.

[0033] The content of the readily thermally degradable organic resin binder in the high-concentration inorganic microparticle dispersion of the present invention is not particularly limited, but a preferred lower limit is 0.5 weight % and a preferred upper limit is 30 weight %. When the resin binder content is less than 0.5 weight %, the obtained dispersion does not have an adequate viscosity and as a consequence the storage stability may worsen and sedimentation of the inorganic microparticles may occur. When the resin binder content exceeds 30 weight %, the amount of production of organic residue increases and the electrical properties and mechanical properties after the firing step may then be reduced.

[0034] In addition to the inorganic microparticles and readily thermally degradable organic resin binder, the high-concentration dispersion of the present invention may contain an organic solvent with the goal of adjusting the viscosity of the inorganic microparticle dispersion. This organic solvent can be exemplified by methyl alcohol, ethyl alcohol, normal-propyl alcohol, isopropyl alcohol, normal-butyl alcohol, isobutyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol butyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ethyl acetate, normal-propyl acetate, isopropyl acetate, normal-butyl acetate, isobutyl acetate, hexyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, ethylene glycol monoisopropyl ether acetate, diethylene glycol monoisopropyl ether acetate, triethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, nonane, normal-decane, isodecane, normal-dodecane, isododecane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, toluene, xylene, terpineol, dihydroterpineol, and dihydroterpineol acetate. A single one of these may be used by itself or a combination may be used, but the type of organic solvent and its amount of incorporation are desirably established in conformity with the use application.

[0035] There are no particular limitations on the content of the organic solvent used, but a preferred range is 0 to 70 weight % with reference to the weight of the high-concentration inorganic microparticle dispersion. When the content of the organic solvent exceeds 70 weight %, an adequate viscosity is not obtained for the resulting dispersion and the printability and coatability may then deteriorate.

[0036] In addition to the inorganic microparticles and the readily thermally degradable organic resin binder that are its essential components, the high-concentration inorganic microparticle dispersion of the present invention may also contain a dispersing agent with the goal of facilitating the dispersion of the inorganic microparticles. There are no particular limitations on the dispersing agent as long as it has the ability to disperse the inorganic microparticles in the medium, and commercially available dispersing agents can be used, such as an amine compound such as octylamine, hexylamine, or oleylamine; a sulfur compound such as dodecanethiol; a carboxylic acid compound such as oleic acid; a branched polymer compound bearing the ammonium group; a dithiocarbamate group-bearing low molecular weight compound or high molecular weight compound; a dendrimer or hyperbranched polymer; a hyperbranched polymer having the ammonium group at the molecular terminals; a phosphate ester-type dispersing agent; or a polyethyleneimine graft polymer-type dispersing agent. A single dispersing agent may be used by itself or two or more may be used in combination.

[0037] In addition to the inorganic microparticles and the readily thermally degradable organic resin binder, the high-concentration inorganic microparticle dispersion of the present invention may also contain a viscosity modifier with the goal of adjusting the rheological characteristics during printing. There are no particular limitations on the viscosity modifier, and commercially available viscosity modifiers can be used that contain an inorganic compound such as silica, bentonite, or calcium carbonate, or that contain an organic compound such as hydrogenated castor oil types, amide types, polyolefin types, polymerized vegetable oil types, and surfactant types. A single one of these viscosity modifiers may be used by itself or two or more may be used in combination.

[0038] It is known that an improvement in the stringiness that is a cause of printing defects can be obtained through the judicious use of a viscosity modifier as above. The use of an appropriate viscosity modifier is preferred in order to appropriately realize the effects of the present invention.

[0039] The high-concentration inorganic microparticle dispersion of the present invention may also contain, within a range in which its properties and the objects of the present invention are not impaired, other substances, for example, surfactants, leveling agents, flame retardants, plasticizers, adhesion promoters, colorants, static inhibitors, oxidation inhibitors, photostabilizers, release agents, and coupling agents.

[0040] 3. Production of the High-Concentration Inorganic Microparticle Dispersion

[0041] The high-concentration inorganic microparticle dispersion of the present invention can be produced by mixing and kneading the inorganic microparticles, resin binder, organic solvent, dispersing agent, viscosity modifier, and other necessary components. The kneading step can be carried out by the usual methods. The kneading apparatus can be exemplified by Henschel mixers, ribbon mixers, Nauta mixers, paddle mixers, high-speed flow mixers, paint shakers, roll mills, ball mills, attritors, sand mills, and bead mills.

[0042] There are no particular limitations on the applications of the high-concentration inorganic microparticle dispersion of the present invention, and it can be advantageously used for printing patterns, e.g., prescribed interconnects, electrodes, resistive elements, capacitors, coils, and so forth, or for the application of a coating with the goal of imparting specific functionalities to an electronic component, in the production of electronic components such as electronic circuits, electrodes, photovoltaic cell panels, microstrip antennas, capacitors, inductors, layered ceramic capacitors, and plasma display panels.

EXAMPLE

[0043] The present invention is specifically described below using examples. The present invention is in no way limited to or by these examples. Unless specifically indicated otherwise, % and parts in the examples indicate weight % and weight parts.

Example 1

[0044] 100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 95 C. while introducing nitrogen gas; and 100 parts of a mixture of methyl methacrylate (ACRYESTER M from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator LUPEROX 219 (3,5,5-trimethylhexanoyl peroxide from ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 75 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 40% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-1]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 15,000.

Example 2

[0045] 100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 155 C. while introducing nitrogen gas; and 200 parts of a mixture of n-butyl methacrylate (ACRYESTER B from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator LUPEROX DTA (di-tert-amyl peroxide from ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-2]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 8,000.

Example 3

[0046] 100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 155 C. while introducing nitrogen gas; and 200 parts of a mixture of i-butyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator LUPEROX DTA (ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-3]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 7,500.

Example 4

[0047] 100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 155 C. while introducing nitrogen gas; and 200 parts of a mixture of 2-ethylhexyl methacrylate (ACRYESTER EH from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator LUPEROX DTA (ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-4]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 6,000.

Example 5

[0048] 30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 135 C. while introducing nitrogen gas; and 70 parts of a mixture of lauryl methacrylate (ACRYESTER L from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator LUPEROX 570 (tert-amyl-3,5,5-trimethylhexane peroxoate from ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-5]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 9,500.

Example 6

[0049] 30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 155 C. while introducing nitrogen gas; and 70 parts of a mixture of isobutyl acrylate (IBA from Mitsubishi Chemical Corporation) and the polymerization initiator LUPEROX 570 (ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-6]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 14,000.

Example 7

[0050] 30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 155 C. while introducing nitrogen gas; and 70 parts of a mixture of 2-ethylhexyl acrylate (HA from Mitsubishi Chemical Corporation) and the polymerization initiator LUPEROX 570 (ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-7]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 10,000.

Example 8

[0051] 100 parts of butyl carbitol (BDG from Nippon Nyukazai Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 155 C. while introducing nitrogen gas; and 200 parts of a mixture of hydroxyethyl methacrylate (ACRYESTER HO from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator LUPEROX DTA (ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-8]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 2,000.

Example 9

[0052] 30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 155 C. while introducing nitrogen gas; and 70 parts of a mixture of i-butyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.), a methoxy polyethylene glycol acrylate having a molecular weight of 400 for the polyethylene glycol segment (AM-90G from Shin-Nakamura Chemical Co., Ltd.), and the polymerization initiator LUPEROX 570 (ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-9]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 20,000.

Example 10

[0053] 30 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 155 C. while introducing nitrogen gas; and 70 parts of a mixture of i-butyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator LUPEROX DTA (ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-10]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 2,000.

Example 11

[0054] 100 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 135 C. while introducing nitrogen gas; and 200 parts of a mixture of i-butyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator LUPEROX 570 (ARKEMA Yoshitomi, Ltd.) was then dripped in at a constant rate over 90 minutes from a dripping apparatus. After heating and stirring for an additional 4 hours, cooling was carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 50% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate to obtain a (meth)acrylic resin [A-11]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 21,000.

Example 12

[0055] 150 parts of a mixture of i-butyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator V59 (2,2-azobis(2-methylbutyronitrile) from Wako Pure Chemical Industries, Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 80 C. while introducing nitrogen gas; heating and stirring were carried out for an additional 4 hours; and cooling was then carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 40% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) to obtain a (meth)acrylic resin [A-12]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 50,000.

Example 13

[0056] 150 parts of a mixture of i-butyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator V65 (2,2-azobis(2,4-dimethylvaleronitrile) from Wako Pure Chemical Industries, Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 70 C. while introducing nitrogen gas; heating and stirring were carried out for an additional 4 hours; and cooling was then carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 40% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) to obtain a (meth)acrylic resin [A-13]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 170,000.

Example 14

[0057] 150 parts of a mixture of i-butyl methacrylate (ACRYESTER IB from Mitsubishi Rayon Co., Ltd.) and the polymerization initiator V65 (Wako Pure Chemical Industries, Ltd.) was introduced into a 1-L reaction vessel equipped with a stirring apparatus, thermometer, reflux condenser, and nitrogen gas introduction port; the temperature was raised to 70 C. while introducing nitrogen gas; heating and stirring were carried out for an additional 4 hours; and cooling was then carried out to room temperature and the polymerization was ended. After the end of the polymerization, the solids fraction was adjusted to 30% with 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (KYOWANOL M from KH Neochem Co., Ltd.) to obtain a (meth)acrylic resin [A-14]. The weight-average molecular weight of the synthesized acrylic copolymer, as polystyrene measured by gel permeation chromatography, was 240,000.

COMPARATIVE EXAMPLES

[0058] The ethyl cellulose resins STD-4 (The Dow Chemical Company) (R-1) and STD-100 (The Dow Chemical Company) (R-2), which are in general use as resin binders, were used as comparative examples.

Test Example 1

[0059] A solution of the readily thermally degradable resin was prepared by mixing a (meth)acrylic resin from Examples 1 to 9 with a 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate solution of an ethyl cellulose resin (STD-4 or STD-100 from The Dow Chemical Company) so as to provide a weight ratio between (meth)acrylic resin and ethyl cellulose resin solids fraction of 20:80. This readily thermally degradable resin solution was coated on a glass plate with a 4-mil applicator followed by drying to obtain a dry film of the readily thermally degradable resin. The results of inspection of the appearance of the dry film are given in Table 1.

[0060] [Table 1]

TABLE-US-00001 TABLE 1 Appearance of the dry films from the readily thermally degradable resins: composition verification ethyl cellulose resin dry film appearance (meth)acrylic resin STD-4 STD-100 A-1 MW 15,000 methyl methacrylate ** *** A-2 MW 8,000 n-butyl methacrylate *** *** A-3 MW 7,500 i-butyl methacrylate *** *** A-4 MW 6,000 2-ethylhexyl methacrylate *** *** A-5 MW 9,500 lauryl methacrylate ** ** A-6 MW 14,000 i-butyl acrylate *** *** A-7 MW 10,000 2-ethylhexyl acrylate *** *** A-8 MW 2,000 hydroxyethyl methacrylate ** *** A-9 MW 20,000 i-butyl acrylate, *** *** methoxy polyethylene glycol acrylate having a molecular weight of 400 for the polyethylene glycol segment R-1 *** R-2 *** (legend for coating film appearance) ***: transparent **: slight turbidity *: separation

[0061] Based on the test results in Table 1, the conclusion can be drawn that the range for R.sup.2 in (meth)acrylic resin with general formula (1) that is compatible with ethyl cellulose is a C.sub.1-12 straight-chain hydrocarbon group, branched-chain hydrocarbon group or hydroxyl group-bearing hydrocarbon, or a polyalkylene oxide-containing group.

Test Example 2

[0062] Using a TG/DTA instrument (DTG-60A (from Shimadzu Corporation)), thermal degradability tests were carried out on the dry films produced in Test Example 1, using an aluminum cell under a nitrogen atmosphere at a temperature ramp rate of 10 C./minute, and the temperature at which the weight was reduced by at least 95% was taken to be the degradation temperature. The carbon residue remaining after the measurement was also rated. The results of the tests are given in Table 2.

[0063] [Table 2]

TABLE-US-00002 TABLE 2 Thermal degradability of the dry films from the readily thermally degradable resins: composition verification ethyl cellulose resin STD-4 STD-100 degradation degradation degradation degradation acrylic resin temperature residue temperature residue A-1 538 C. ** 483 C. ** A-2 422 C. *** 433 C. *** A-3 429 C. *** 403 C. *** A-4 409 C. *** 415 C. *** A-5 416 C. *** 461 C. *** A-6 467 C. *** 471 C. ** A-7 466 C. *** 453 C. ** A-8 502 C. ** 550 C. ** A-9 466 C. *** 507 C. ** R-1 565 C. * R-2 509 C. * (legend for degradation residue) ***: residue not present or present at a trace level **: some ash *: the entire surface of the cell is black

[0064] The test results in Table 2 show that the readily thermally degradable resin according to the present invention has a better thermal degradability than ethyl cellulose resin and is superior for firing applications.

Test Example 3

[0065] A solution of the readily thermally degradable resin was prepared by mixing a 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate solution of an ethyl cellulose resin (STD-4 or STD-100 from The Dow Chemical Company) with a methacrylic resin from Examples 10 to 14 so as to provide a weight ratio between (meth)acrylic resin and ethyl cellulose resin solids fraction of 20:80. This readily thermally degradable resin solution was coated on a glass plate with a 4-mil applicator followed by drying to obtain a dry film of the readily thermally degradable resin. The results of inspection of the appearance of the dry films are given in Table 3.

[0066] [Table 3]

TABLE-US-00003 TABLE 3 Appearance of the dry films from the readily thermally degradable resins: molecular weight verification ethyl cellulose resin dry film appearance (meth)acrylic resin STD-4 STD-100 A-10 MW 2,000 *** *** A-3 MW 7,500 *** *** A-11 MW 21,000 ** *** A-12 MW 50,000 ** *** A-13 MW 170,000 ** *** A-14 MW 240,000 * ** R-1 *** R-2 *** (legend for coating film appearance) ***: transparent **: slight turbidity *: separation

[0067] Based on the test results in Table 3, it can be understood that the weight-average molecular weight of (meth)acrylic resin that can form the readily thermally degradable resin according to the present invention desirably does not exceed 200,000 considered in terms of the appearance of the dry film.

Test Example 4

[0068] Using a TG/DTA instrument (DTG-60A (from Shimadzu Corporation)), thermal degradability tests were carried out on the dry films produced in Test Example 3, using an aluminum cell under a nitrogen atmosphere at a temperature ramp rate of 10 C./minute, and the temperature at which the weight was reduced by at least 95% was taken to be the degradation temperature. The carbon residue remaining after the measurement was also rated. The results of the tests are given in Table 4.

[0069] [Table 4]

TABLE-US-00004 TABLE 4 Thermal degradability of the dry films from the readily thermally degradable resins: molecular weight verification ethyl cellulose resin STD-4 STD-100 (meth)acrylic degradation degradation degradation degradation resin temperature residue temperature residue A-10 437 C. *** 414 C. *** A-3 429 C. *** 403 C. *** A-11 395 C. *** 419 C. *** A-12 388 C. *** 390 C. *** A-13 410 C. *** 401 C. *** A-14 382 C. *** 376 C. ** R-1 565 C. * R-2 509 C. * (legend for degradation residue) ***: residue not present or present at a trace level **: some ash *: the entire surface of the cell is black

[0070] The test results in Table 4 show that the readily thermally degradable resins prepared in Test Example 3 have a better thermal degradability than ethyl cellulose resin and are superior for firing applications.

Test Example 5

[0071] Solutions of the readily thermally degradable resins were prepared by mixing a 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate solution of an ethyl cellulose resin (STD-4 or STD-100 from The Dow Chemical Company) with the methacrylic resin from Example 3 so as to provide a weight ratio between methacrylic resin and ethyl cellulose resin solids fraction of 5:95, 20:80, and 50:50. The readily thermally degradable resin solutions were coated on glass plates with a 4-mil applicator followed by drying to obtain dry films of the readily thermally degradable resins. The results of inspection of the appearance of the dry films are given in Table 5.

TABLE-US-00005 TABLE 5 Appearance of the dry films from the readily thermally degradable resins: blending ratio verification ethyl cellulose resin dry film appearance (meth)acrylic resin STD-4 STD-100 A-3 (meth)acrylic resin:ethyl cellulose *** *** resin mixing ratio 5:95 A-3 (meth)acrylic resin:ethyl cellulose *** *** resin mixing ratio 20:80 A-3 (meth)acrylic resin:ethyl cellulose *** *** resin mixing ratio 50:50 R-1 *** R-2 *** (legend for coating film appearance) ***: transparent **: slight turbidity *: separation

[0072] Based on the test results in Table 5, it can be understood that suitable mixing ratios for the (meth)acrylic resin and ethyl cellulose resin used in the readily thermally degradable resin according to the present invention are ratios (weight ratio) of 5:95 to 50:50.

Test Example 6

[0073] Using a TG/DTA instrument (DTG-60A (from Shimadzu Corporation)), thermal degradability tests were carried out on the dry films produced in Test Example 5, using an aluminum cell under a nitrogen atmosphere at a temperature ramp rate of 10 C./minute, and the temperature at which the weight was reduced by at least 95% was taken to be the degradation temperature. The carbon residue remaining after the measurement was also rated. The results of the tests are given in Table 6.

TABLE-US-00006 TABLE 6 Thermal degradability of the dry films from the readily thermally degradable resins: blending ratio verification ethyl cellulose resin STD-4 STD-100 degradation degradation degradation degradation acrylic resin temperature residue temperature residue (meth)acrylic 519 C. *** 480 C. *** resin:ethyl cellulose mixing ratio 5:95 (meth)acrylic 429 C. *** 403 C. *** resin:ethyl cellulose mixing ratio 20:80 (meth)acrylic 396 C. *** 400 C. *** resin:ethyl cellulose mixing ratio 50:50 R-1 565 C. * R-2 509 C. * (legend for degradation residue) ***: residue not present or present at a trace level **: some ash *: the entire surface of the cell is black

[0074] The test results in Table 6 show that the readily thermally degradable resins prepared in Test Example 5 have a better thermal degradability than ethyl cellulose resin and are superior for applications that require a firing step.

Test Example 7

[0075] A silver micropowder (particle diameter=3 m), glass powder (particle diameter=2 m), a solution of the readily thermally degradable resin as prepared in Test Example 1 or Test Example 2, solvent (KYOWANOL M from KH Neochem Co., Ltd.), and a dispersing agent (HIPLAAD ED 119 from Kusumoto Chemicals, Ltd.) were mixed and a high-concentration silver microparticle dispersion with the composition shown in Table 7 was obtained by dispersion using a roll mill.

TABLE-US-00007 TABLE 7 Composition of the high-concentration silver micropowder dispersion starting materials amount blended (parts) silver micropowder 90.0 glass powder 1.5 readily thermally degradable resin 4.5 solvent 3.1 dispersing agent 0.9

[0076] The viscosity of the high-concentration silver micropowder dispersion was measured at 25 C. using an E-type viscometer and a 3R9.7 mm cone rotor. The T. I. (thixotropic index) value represents the ratio, for measurement at 25 C., of the viscosity at a shear rate of 0.4 [1/sec.] with the viscosity at a shear rate of 4 [1/sec.], i.e., viscosity at a shear rate of 0.4 [1/sec.]/viscosity at a shear rate of 4 [1/sec.]. The viscosity and the T. I. value of the high-concentration silver micropowder dispersions are given in Table 8.

[0077] Fine lines were printed on a ceramic substrate from the obtained high-concentration silver micropowder dispersion by a screen printing method using a #640 mesh screen having a line width of 50 m, and the characteristics of the high-concentration silver micropowder dispersions were evaluated by measuring the printed line width and printed line height and observing the state of the printing. The results of the evaluations are given in Table 8.

TABLE-US-00008 TABLE 8 Test results for the high-concentration silver micropowder dispersions readily thermally printed printed degradable resin line line or comparative Viscosity T. I. width height state of the example Pa .Math. s value m m printing A-2 85 4.3 65 9.9 excellent A-3 81 4.5 57 10.0 excellent A-4 89 4.7 65 10.3 excellent A-7 74 4.4 65 10.2 excellent A-11 88 4.7 62 10.0 excellent A-12 88 4.7 58 9.8 excellent R-1 108 4.2 70 9.8 missing portions are present in the lines

[0078] As is clear from the test results in Table 8, the high-concentration silver micropowder dispersions that use the readily thermally degradable resin binder of the present invention exhibit a viscosity-modification effect better adapted to screen printing than for the use of ethyl cellulose resin as the binder and provide an excellent printed state.

INDUSTRIAL APPLICABILITY

[0079] The firing behavior and printing characteristics are improved when the high-concentration inorganic microparticle dispersion of the invention is used in the printing of patterns, e.g., prescribed interconnects, electrodes, resistive elements, capacitors, coils, and so forth, in the production of electronic components (for example, electronic circuits, electrodes, photovoltaic cell panels, microstrip antennas, capacitors, inductors, layered ceramic capacitors, plasma display panels, and so forth). As a consequence, the present invention can be expected to contribute to enhancing the electronic component properties still further, to facilitating the mass production of electronic components, and to saving energy in the production process.