Resin composition, inorganic fine particle-dispersed slurry composition, inorganic fine particle-dispersed sheet, method for manufacturing all-solid-state battery, and method for manufacturing laminated ceramic capacitor

Abstract

A resin composition which has excellent decomposability at low temperature, can provide a molded article having high strength, and enables an increase in the number of layers and thinning so as to enable production of an all-solid-state battery and a ceramic laminate having excellent properties. An inorganic fine particle-dispersed slurry composition containing the resin composition, an inorganic fine particle-dispersed sheet, a method for producing an all-solid-state battery, and a method for producing a multilayer ceramic capacitor. A resin composition containing a (meth)acrylic resin, the (meth)acrylic resin containing 20 to 70% by weight in total of a segment derived from methyl methacrylate and a segment derived from isobutyl methacrylate, 1 to 10% by weight of a segment derived from a glycidyl group-containing (meth)acrylate, and 5 to 40% by weight of a segment derived from a (meth)acrylate containing an ester substituent having a carbon number of 8 or more.

Claims

1. A resin composition comprising a (meth)acrylic resin having a glass transition temperature of 40° C. or higher and 60° C. or lower, wherein the (meth)acrylic resin comprises a segment derived from methyl methacrylate, a segment derived from isobutyl methacrylate, a segment derived from a glycidyl group-containing (meth)acrylate, and a segment derived from a (meth)acrylate containing an ester substituent having a carbon number of 8 or more, a total amount of the segment derived from methyl methacrylate and the segment derived from isobutyl methacrylate is 55 to 70% by weight, an amount of the segment derived from a glycidyl group-containing (meth)acrylate is 1 to 10% by weight, an amount of the segment derived from a (meth)acrylate containing an ester substituent having a carbon number of 8 or more is 15 to 40% by weight, the (meth)acrylic resin has a weight average molecular weight (Mw) of 100,000 to 3,000,000, a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of the (meth)acrylic resin is 2 or higher and 8 or lower, and the (meth)acrylic resin is obtained by copolymerizing a monomer mixture containing 55 to 70% by weight in total of methyl methacrylate and isobutyl methacrylate, 1 to 10 by weight of a glycidyl group-containing (meth)acrylate and 15 to 40% by weight of a (meth)acrylate containing an ester substituent having a carbon number of 8 or more.

2. The resin composition according to claim 1, wherein in the (meth)acrylate containing an ester substituent having a carbon number of 8 or more, the ester substituent has a carbon number of 8 to 20 and has a branched chain structure.

3. The resin composition according to claim 1, wherein the (meth)acrylate containing an ester substituent having a carbon number of 8 or more is a (meth)acrylate containing a branched alkyl group having a carbon number of 8 to 20 or a polyalkylene glycol methacrylate having a branched alkylene glycol structure wherein the total number of carbon atoms in the ester substituent is 8 or more.

4. The resin composition according to claim 1, wherein a weight ratio of the amount of the segment derived from methyl methacrylate to the amount of the segment derived from isobutyl methacrylate in the (meth)acrylic resin is 15:85 to 95:5.

5. The resin composition according to claim 1, wherein the (meth)acrylic resin molded into a sheet form having a thickness of 20 μm has a maximum stress of 20 N/mm.sup.2 or more in a tensile test.

6. The resin composition according to claim 1, wherein the amount of the segment derived from a glycidyl group-containing (meth)acrylate is 2 to 10% by weight.

7. An inorganic fine particle-dispersed slurry composition comprising: the resin composition according to claim 1; inorganic fine particles; an organic solvent; and a plasticizer.

8. The inorganic fine particle-dispersed slurry composition according to claim 7, wherein the inorganic fine particles comprise lithium or titanium.

9. The inorganic fine particle-dispersed slurry composition according to claim 7, wherein the plasticizer comprises: a component derived from adipic acid, triethylene glycol, or citric acid; and an alkyl group having a carbon number of 4 or more, and the plasticizer has a carbon:oxygen ratio of 5:1 to 3:1.

Description

DESCRIPTION OF EMBODIMENTS

(1) The present invention is more specifically described in the following with reference to, but not limited to, examples.

Example 1

(2) (1) Preparation of Resin Composition

(3) A 2-L separable flask equipped with a stirrer, a condenser, a thermometer, a water bath, and a nitrogen gas inlet was provided. The 2-L separable flask was charged with monomers in amounts shown in Table 1. Then, the monomers were mixed with 100 parts by weight of butyl acetate as an organic solvent to give a monomer mixture.

(4) The following monomers were used.

(5) MMA: methyl methacrylate

(6) iBMA: isobutyl methacrylate

(7) iDMA: isodecyl methacrylate (carbon number of ester

(8) substituent: 10)

(9) GMA: glycidyl methacrylate

(10) BMA: n-butyl methacrylate

(11) HEMA: 2-hydroxyethyl methacrylate

(12) The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen. Thereafter, the separable flask system was purged with nitrogen gas, and the temperature was raised with stirring until the water bath came to a boil. A solution obtained by diluting a polymerization initiator in butyl acetate was added. During polymerization, the solution containing the polymerization initiator in butyl acetate was added several times.

(13) Seven hours after the start of the polymerization, the contents of the flask was cooled to room temperature to complete the polymerization. Thus, a resin composition containing a (meth)acrylic resin was obtained.

(14) (2) Preparation of Inorganic Fine Particle-Dispersed Slurry Composition

(15) To 40 parts by weight of the obtained resin composition were added Li.sub.2S—P.sub.2S.sub.5 glass (average particle size: 2.0 μm) as inorganic fine particles, di(butoxyethyl) adipate as a plasticizer, and butyl acetate as a solvent in amounts shown in Table 1. The mixture was kneaded with a high-speed stirrer to give an inorganic fine particle-dispersed slurry composition.

(16) (3) Preparation of Inorganic Fine Particle-Dispersed Sheet

(17) The obtained inorganic fine particle-dispersed slurry composition was applied using a blade coater to a release-treated polyethylene terephthalate (PET) support film (width: 400 mm, length: 30 m, thickness 38 μm). The formed coating film was dried at 40° C. for 10 hours to remove the solvent, whereby an inorganic fine particle-dispersed sheet having a thickness of 50 μm was formed on the support film.

(18) (4) Preparation of all-Solid-State Battery

(19) The obtained inorganic fine particle-dispersed sheet was separated from the support film. Indium metallic foil as a negative electrode was bonded to the inorganic fine particle-dispersed sheet to give a negative electrode/solid electrolyte laminated sheet.

(20) To 40 parts by weight of a solution of the (meth)acrylic resin obtained in “(1) Preparation of resin composition” in butyl acetate were added 50 parts by weight in total of the following materials: 20 parts by weight of LiCoO.sub.2 (average particle size: 1 μm) as inorganic fine particles, 27 parts by weight of Li.sub.2S—P.sub.2S.sub.5 glass (average particle size: 2.0 μm), and 3 parts by weight of acetylene black (primary particle size: 35 nm) as a conductive aid. Thereafter, 10 parts by weight of di(butoxyethyl) adipate as a plasticizer was added, and the mixture was kneaded with a high-speed stirrer to give an inorganic fine particle-dispersed slurry composition for a positive electrode.

(21) A positive electrode sheet was prepared using the obtained inorganic fine particle-dispersed slurry composition for a positive electrode in the same manner as in “(3) Preparation of inorganic fine particle-dispersed sheet”.

(22) The obtained positive electrode sheet was bonded to the negative electrode/solid electrolyte laminated sheet using a laminator to give a negative electrode/solid electrolyte/positive electrode laminated sheet.

(23) A piece having a size of 2 cm×1 cm was punched out of the obtained laminated sheet. The piece was fired on an alumina substrate for six hours in an electric furnace set at 300° C. to remove the binder and the plasticizer. Thus, a glass laminate was obtained.

(24) Then, 20 parts by weight of the resin composition obtained in “(1) Preparation of resin composition” was kneaded with 10 parts by weight of low-melting-point glass frit (average particle size: 2 μm), 70 parts by weight of silver palladium particles (average particle size: 1 μm), and 50 parts by weight of terpineol as a plasticizer using a high-speed stirrer, whereby an electrode slurry composition was obtained.

(25) Next, the ends of the obtained glass laminate were brought into contact with the electrode slurry composition to form collector electrodes. The glass laminate was then fired at a 300° C. oven for one hour to degrease the electrodes, whereby an all-solid-state battery was obtained.

Examples 2 to 27 and Comparative Examples 1 to 18

(26) A resin composition, an inorganic fine particle-dispersed slurry composition, an inorganic fine particle-dispersed sheet, and an all-solid-state battery were prepared as in Example 1 except that in “(1) Preparation of resin composition”, monomers were mixed in amounts shown in Tables 1 and 2 and the formulations of the (meth)acrylic resin and the plasticizer were as shown in Tables 1 and 2.

(27) The following monomers were used.

(28) 2EHMA: 2-ethylhexyl methacrylate (carbon number of ester substituent: 8)

(29) iNMA: isononyl methacrylate (carbon number of ester substituent: 9)

(30) LMA: lauryl methacrylate (carbon number of ester substituent: 12)

(31) iSMA: isostearyl methacrylate (carbon number of ester substituent: 18)

(32) PEOMA: polyethylene glycol methacrylate (carbon number of ester substituent: 8)

(33) EPOMA: ethoxypolypropylene glycol methacrylate (carbon number of ester substituent: 11)

(34) MPOMA: methoxytriisopropylene glycol methacrylate (carbon number of ester substituent: 10)

(35) MPPMA: methoxypolypropylene glycol methacrylate (carbon number of ester substituent: 10)

(36) BEOMA: isobutoxydiethylene glycol methacrylate (carbon number of ester substituent: 8)

(37) PPBMA: polypropylene glycol-polybutylene glycol methacrylate (carbon number of ester substituent: 27)

(38) ECHMA: 3,4-epoxycyclohexylmethyl methacrylate HBAG: 4-hydroxybutyl acrylate glycidyl ether

(39) MAA: methyl acrylate

(40) EMA: ethyl methacrylate

(41) In Comparative Examples 7, 9, 15, and 16, the obtained resin compositions were brittle, and the coating films were shattered before drying in “(3) Preparation of inorganic fine particle-dispersed sheet”. The inorganic fine particle-dispersed sheet thus could not be prepared, so that the all-solid-state battery could not be prepared.

(42) In Comparative Examples 8, 10, and 18, the inorganic fine particle-dispersed sheets lacked resilience and broke when they were separated from the support film in “(4) Preparation of all-solid-state battery”. The all-solid-state battery thus could not be prepared.

Examples 28 to 31 and Comparative Examples 19 to 22

(43) (5) Preparation of Conductive Paste

(44) The resin composition obtained in Example 1 was dried, and dissolved in a terpineol solvent to a resin solid content of 11% by weight to give a resin composition solution. To 44 parts by weight of the obtained resin composition solution were added 1 part by weight of oleic acid as a dispersant and 55 parts by weight of nickel powder (“NFP201”, JFE Mineral Co., Ltd.) as conductive fine particles. The components were mixed with a triple roll mill to give a conductive paste.

(45) (6) Preparation of Ceramic Green Sheet

(46) The resin compositions obtained in Examples 1, 6, 9, and 19 and Comparative Examples 1, 3, 5, and 14, barium titanate (“BT-02”, available from Sakai Chemical Industry Co., Ltd., average particle size: 0.2 μm) as inorganic fine particles, and butyl acetate as a solvent were used. The (meth)acrylic acid resin, a plasticizer, the solvent, and the inorganic fine particles were added according to the formulation in Table 3 and mixed with a ball mill to give an inorganic fine particle-dispersed slurry composition.

(47) The obtained inorganic fine particle-dispersed slurry was applied to a release-treated polyester film to a dry thickness of 1 μm. The applied slurry was dried at room temperature for one hour, followed by drying at 80° C. for 3 hours with a hot air drier and then by drying at 120° C. for two hours. Thus, a ceramic green sheet was prepared.

(48) (7) Preparation of Ceramic Fired Body

(49) The obtained conductive paste was applied to one surface of the obtained ceramic green sheet to a dry thickness of 1.5 μm by a screen printing method. The paste was dried to form a conductive layer, whereby a ceramic green sheet with a conductive layer was obtained. The obtained ceramic green sheet with a conductive layer was cut to a 5-cm square. One hundred 5-cm square ceramic green sheets were stacked together and pressure-bonded with heat for 10 minutes under the conditions of a temperature of 70° C. and a pressure of 150 kg/cm.sup.2, whereby a laminate was obtained. The obtained laminate was heated in a nitrogen atmosphere to 400° C. at a temperature increase rate of 3° C./min, held at the temperature for five hours, then heated to 1,350° C. at a temperature increase rate of 5° C./min, and held at the temperature for 10 hours. Thus, a ceramic fired body was prepared.

(50) In Comparative Examples 19 and 20, the ceramic green sheets could not be stacked together, so that the ceramic fired body could not be prepared.

(51) TABLE-US-00001 TABLE 1 (Meth)acrylic resin formulation (% by weight) Total Component derived from (meth)acrylate containing Component Component amount ester substituent having carbon number of 8 or more derived derived of MMA (carbon number of ester substituent) from from and 2EHMA iNMA iDMA iSMA EPOMA MPOMA MPPMA BEOMA PPBMA MMA iBMA iBMA (8) (9) (10) (18) (11) (10) (10) (8) (27) Total Example 1 45 15 60 — — 10 — — — — — — 10 Example 2 50 — 50 — — 39 — — — — — — 39 Example 3 20 30 50 10 — — — — — — — — 10 Example 4 42 — 42 — 20 — — — — — — — 20 Example 5 50 — 50 — — — 10 — — — — — 10 Example 6 40 — 40 — — — — 10 — — — — 10 Example 7 20 34 54 — 10 — — — — — — — 10 Example 8 7.5 42.5 50 — 25 — — — — — — — 25 Example 9 21.7 48.3 70 24 — — — — — — — — 24 Example 10 47.5 2.5 50 23 — — — — — — — — 23 Example 11 63 7 70 — — 28 — — — — — — 28 Example 12 8 59 67 — — — 19 — — — — — 19 Example 13 53 3 56 — — — — — 38 — — — 38 Example 14 63 7 70 — — — — — — — 23 — 23 Example 15 20 48 68 — — — — — 15 — — — 15 Example 16 — 63 63 26 — — — — — — — — 26 Example 17 — 40 40 28 — — — — — — — — 28 Example 18 — 30 30 22 — — — — — — — — 22 Example 19 — 20 20 24 — — — — — — — — 24 Example 20 16 16 32 30 — — — — — — — — 30 Example 21 — 50 50 25 — — — — — — — — 25 Example 22 10 30 40 15 — — — — — — — — 15 Example 23 15 20 35 20 — — — — — — — — 20 Example 24 — 60 60 — — — — — — — — 5 5 Example 25 — 65 65 — — — — — — 10 — — 10 Example 28 10 60 70 — — — — — — — — 5 5 Example 27 7 60 67 — — — — — — — — 5 5 (Meth)acrylic resin formulation (% by weight) Component derived from glycidyl group-containing Component derived from Inorganic fine particle-dispersed slurry composition (% by weight) (meth)acrylate other monomers Resin Plasticizer Organic Inorganic fine GMA ECHMA HBAG EMA BMA HEMA component Type Amount solvent particle Example 1 5 — — — 20 5 10 Di(butoxyethyl) adipate 0.2 54.8 35 Example 2 6 — — — — 5 10 Triethylene glycol bis(2- 0.2 54.8 35 ethylhexanoate) Example 3 5 — — — 30 5 10 Tributyl acetylcitrate 0.2 54.8 35 Example 4 4 — — — 30 4 10 Di(butoxyethyl) adipate 1.2 53.8 35 Example 5 1 — — — 36 3 10 Triethylene glycol bis(2- 1.2 53.8 35 ethylhexanoate) Example 6 10  — — — 40 — 10 Triethylene glycol dihexanoate 1.2 53.8 35 Example 7 3 — — — 30 3 10 Tributyl acetylcitrate 1.2 53.8 35 Example 8 5 — — — 19 1 10 Di(butoxyethyl) adipate 1.2 53.8 35 Example 9 3 — — — — 3 10 Di(butoxyethyl) adipate 1.2 53.8 35 Example 10 3 — — — 20 4 10 Di(butoxyethyl) adipate 1.2 53.8 35 Example 11 1 — — — — 1 10 Di(butoxyethyl) adipate 1.2 53.8 35 Example 12 8 — — — 6 10 Di(butoxyethyl) adipate 1.2 53.8 35 Example 13 4 — — — — 2 10 Triethylene glycol bis(2- 1.2 53.8 35 ethylhexanoate) Example 14 — — 6 — — 1 10 Triethylene glycol dihexanoate 1.2 53.8 35 Example 15 — 6 — —  8 3 10 Tributyl acetylcitrate 1.2 53.8 35 Example 16 4 — —  4 — 3 10 Di(butoxyethyl) adipate 1.2 53.8 35 Example 17 1 — — 30 — 1 10 Triethylene glycol bis(2- 1.2 53.8 35 ethylhexanoate) Example 18 4 — — 40 — 4 10 Triethylene glycol dihexanoate 1.2 53.8 35 Example 19 7 — — 27 15 7 10 Triethylene glycol bis(2- 1.2 53.8 35 ethylhexanoate) Example 20 7 — — 24 — 7 10 Triethylene glycol dihexanoate 1.2 53.8 35 Example 21 4 — — 17 — 4 10 Triethylene glycol bis(2- 1.2 53.8 35 ethylhexanoate) Example 22 5 — — — 35 5 10 Triethylene glycol dihexanoate 1.2 53.8 35 Example 23 4 — — 20 17 4 10 Tributyl acetylcitrate 1.2 53.8 35 Example 24 3 — — 32 — — 10 Di(butoxyethyl) adipate 1.2 53.8 35 Example 25 1 — — 24 — — 10 Triethylene glycol dihexanoate 1.2 53.8 35 Example 28 3 — — — 22 — 10 Triethylene glycol bis(2- 1.2 53.8 35 ethythexanoate) Example 27 3 — — 10 15 — 10 Di(butoxyethyl) adipate 1.2 53.8 35

(52) TABLE-US-00002 TABLE 2 (Meth)acrylic resin formulation (% by weight) Component Component derived from (meth)acrylate derived Total containing ester substituent having carbon from glycidyl Component Component amount number of 8 or more group- derived derived of MMA (carbon number of ester substituent) containing Component derived from from from and 2EHMA iDMA LMA PEOMA (meth)acrylate other monomers MMA iBMA iBMA (8) (10) (12) (8) Total GMA MAA Comparative Example 1 60 31 91 —  9 — — 9 — — Comparative Example 2 10 — 10 — 40 — — 40 — — Comparative Example 3 10 — 10 —  9 — — 9 — — Comparative Example 4 — 60 60 30 — — — 30 — — Comparative Example 5 — 60 60 29 — — — 29 11 — Comparative Example 6 60 — 60 — 40 — — 40 — — Comparative Example 7 — 100  100 — — — — 0 — — Comparative Example 8 — 63 63 27 — — — 27 — — Comparative Example 9 — 90 90 7.5 — — — 7.5 — 2.5 Comparative Example 10 12.5 75 87.5 — — 12 — 12 0.5 — Comparative Example 11 45  2 47 — — 41 — 41 12 — Comparative Example 12 25 40 65 — — 35 — 35 — — Comparative Example 13 — — 0 — — 20 — 20 — — Comparative Example 14 9 — 9 — — 10 — 10 11 — Comparative Example 15 60 15 75 — —  5 — 5 5 — Comparative Example 16 — 66 66 — —  4 — 4 3 — Comparative Example 17 35.6 20 55.6 — — 24 — 24 0.4 — Comparative Example 18 — 54 54 — — — 31 31 — (Meth)acrylic resin formulation (% by weight) Component derived from Inorganic fine particle-dispersed slurry composition (% by weight) other monomers Resin Plasticizer Organic Inorganic EMA BMA HEMA component Type Amount solvent fine particle Comparative Example 1 — — — 10 Dibutyl phthalate 0.2 54.8 35 Comparative Example 2 — 50 — 10 Di-n-octyl phthalate 0.2 54.8 35 Comparative Example 3 — 81 — 10 Benzylbutyl phthalate 0.2 54.8 35 Comparative Example 4 — — 10 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 5 — — — 10 Di-n-octyl phthalate 1.2 53.8 35 Comparative Example 6 — — — 10 Benzylbutyl phthalate 1.2 53.8 35 Comparative Example 7 — — — 10 Di(butoxyethyl) 1.2 53.8 35 adipate Comparative Example 8 — — 10 10 Di(butoxyethyl) 1.2 53.8 35 adipate Comparative Example 9 — — — 10 Di(butoxyethyl) 1.2 53.8 35 adipate Comparative Example 10 — — — 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 11 — — — 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 12 — — — 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 13 40 40 — 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 14 — 70 — 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 15 — 15 — 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 16 27 — — 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 17 —  9 11 10 Dibutyl phthalate 1.2 53.8 35 Comparative Example 18 — 15 — 10 Dibutyl phthalate 1.2 53.8 35

(53) TABLE-US-00003 TABLE 3 (Meth)acrylic resin formulation (% by weight) Component Component derived from (meth)acrylate derived Total containing ester substituent having carbon from glycidyl Component Component amount number of 8 or more group- Component derived derived of MMA (carbon number of ester substituent) containing derived from from from and 2EHMA iDMA LMA EPOMA (meth)acrylate other monomers MMA iBMA iBMA (8) (10) (12) (11) Total GMA EMA Example 28 45 15 60 — 10  — — 10 5 — Example 29 40 — 40 — — — 10 10 10 — Example 30   21.7   48.3 70 24 — — — 24 3 — Example 31 — 20 20 24 — — — 24 7 27 Comparative 60 31 91 — 9 — — 9 — — Example 19 Comparative 10 — 10 — 9 — — 9 — — Example 20 Comparative — 60 60 29 — — — 29 11 — Example 21 Comparative  9 — 9 — — 10 — 10 11 — Example 22 (Meth)acrylic resin formulation (% by weight) Inorganic fine particle-dispersed slurry composition (% by weight) Component derived from Plasticizer other monomers Resin Resin Organic Inorganic fine BMA HEMA component Type Amount solvent particle Example 28 20 5 6 Di(butoxyethyl) adipate 1.2 62.8 30 Example 29 40 — 6 Triethylene glycol bis(2- 1.2 62.8 30 ethylhexanoate) Example 30 — 3 6 Triethylene glycol 1.2 62.8 30 dihexanoate Example 31 15 7 6 Tributyl acetylcitrate 1.2 62.8 30 Comparative — — 6 Dibutyl phthalate 1.2 62.8 30 Example 19 Comparative 81 — 6 Di-n-octyl phthalate 1.2 62.8 30 Example 20 Comparative — — 6 Benzylbutyl phthalate 1.2 62.8 30 Example 21 Comparative 70 — 6 Dibutyl phthalate 1.2 62.8 30 Example 22
<Evaluation>

(54) The following evaluations were performed on the (meth)acrylic resins, inorganic fine particle-dispersed slurry compositions, inorganic fine particle-dispersed sheets, all-solid-state batteries, ceramic green sheets, and ceramic fired bodies obtained in the examples and comparative examples. Tables 4 to 6 show the results.

(55) (1) Measurement of Average Molecular Weight

(56) The weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the obtained (meth)acrylic resin were measured by gel permeation chromatography using a column LF-804 (Shoko Science Co., Ltd.). The obtained Mw and Mw/Mn were analyzed.

(57) o (Good): The Mw was within the range of 100,000 to 3,000,000 and the Mw/Mn was 2 or higher and 8 or less.

(58) x (Poor): The requirement of “o (Good)” was not satisfied.

(59) (2) Measurement of Glass Transition Temperature

(60) The glass transition temperature (Tg) of the obtained (meth)acrylic resin was measured using a differential scanning calorimeter (DSC). The obtained Tg was analyzed and evaluated according to the following criteria.

(61) o (Good): The Tg was 30° C. or higher and 60° C. or lower.

(62) x (Poor): The Tg was lower than 30° C. or higher than 60° C.

(63) (3) Resin Sheet Tensile Test

(64) The obtained resin composition was applied to a release-treated PET film with an applicator, and dried at 100° C. for 10 minutes with a fan oven to prepare a resin sheet having a thickness of 20 μm. Graph paper was used as a cover film. A strip-shaped specimen having a width of 1 cm was prepared with scissors.

(65) The obtained specimen was subjected to a tensile test under the conditions of 23° C. and 50 RH using an autograph AG-IS (available from Shimadzu Corp.) at an inter-chuck distance of 3 cm and a pulling speed of 10 mm/min. The stress-strain characteristics (presence or absence of yield stress and maximum stress measurement) were determined. The results were evaluated according to the following criteria.

(66) o (Good): Yield stress was exhibited and the maximum stress was 20 N/mm.sup.2 or higher.

(67) x (Poor): The requirement of the “o (Good)” was not satisfied.

(68) (4) Sinterability

(69) The obtained inorganic fine particle-dispersed slurry composition was put in an alumina pan of a TG-DTA device, and heated at 10° C./min to evaporate the solvent and thermally decompose the resin and the plasticizer. Thereafter, the temperature at which the weight was 36% by weight (90% by weight degreasing was finished) was measured, and taken as the decomposition ending temperature. The obtained decomposition ending temperature was evaluated according to the following criteria.

(70) oo (Excellent): The decomposition ending temperature was 270° C. or lower.

(71) o (Good): The decomposition ending temperature was higher than 270° C. and 300° C. or lower.

(72) x (Poor): The decomposition ending temperature was higher than 300° C.

(73) (5) Battery Performance Evaluation

(74) The obtained all-solid-state battery was charged to 4.0 V at 0.1 mA and discharged to 3.5 V using a charge-discharge test system TOSCAT-3000 (available from Toyo System Co., Ltd). This cycle was repeated 30 times. The discharge capacity at the 30th cycle was evaluated according to the following criteria. In Comparative Examples 1, 2, and 5 to 10, the all-solid-state battery could not be prepared, so that the charge-discharge evaluation could not be performed. The negative electrode/solid electrolyte/positive electrode laminated sheets obtained in Comparative Examples 3 and 11 turned brown, and the resulting all-solid-state batteries did not function as a battery. In Comparative Examples 12 to 16 and 18, the inorganic fine particle-dispersed sheets had too high tackiness, and thus wrinkled or broke when separated from the support film. The all-solid-state batteries obtained therefrom could not be electrified after several charge-discharge cycles.

(75) oo (Excellent): The discharge capacity was 60 mAh or higher.

(76) o (Good): The discharge capacity was 10 mAh or higher and lower than 60 mAh.

(77) x (Poor): The discharge capacity was lower than 10 mAh or the charge-discharge evaluation could not be performed.

(78) TABLE-US-00004 TABLE 4 Sinterability Tensile test Decomposition Battery performance Maximum ending Discharge Average molecular weight Resin Tg Yield stress temperature capacity Mw Mw/Mn Rating (° C.) Rating stress (N/mm.sup.2) Rating (° C.) Rating (mAh) Rating Example 1 100,000 2 ∘ 60 ∘ Present 27 ∘ 300 ∘ 18.3 ∘ Example 2 3,000,000 8 ∘ 42 ∘ Present 28 ∘ 300 ∘ 14.7 ∘ Example 3 1,000,000 6 ∘ 47 ∘ Present 28 ∘ 300 ∘ 17.2 ∘ Example 4 500,000 2 ∘ 49 ∘ Present 27 ∘ 295 ∘ 12.0 ∘ Example 5 1,000,000 8 ∘ 56 ∘ Present 24 ∘ 292 ∘ 18.3 ∘ Example 6 3,000,000 5 ∘ 48 ∘ Present 33 ∘ 300 ∘ 10.2 ∘ Example 7 100,000 4 ∘ 46 ∘ Present 25 ∘ 295 ∘ 18.3 ∘ Example 8 100,000 2 ∘ 31 ∘ Present 20 ∘ 280 ∘ 50 ∘ Example 9 1,000,000 6 ∘ 48 ∘ Present 32 ∘ 280 ∘ 54.3 ∘ Example 10 1,000,000 6 ∘ 56 ∘ Present 32 ∘ 280 ∘ 54.3 ∘ Example 11 3,000,000 8 ∘ 59 ∘ Present 25 ∘ 280 ∘ 62.5 ∘ Example 12 450,000 4 ∘ 40 ∘ Present 37 ∘ 280 ∘ 33.3 ∘ Example 13 300,000 4 ∘ 49 ∘ Present 35 ∘ 280 ∘ 52.6 ∘ Example 14 400,000 4 ∘ 59 ∘ Present 38 ∘ 280 ∘ 29.4 ∘ Example 15 500,000 5 ∘ 50 ∘ Present 38 ∘ 280 ∘ 31.2 ∘ Example 16 500,000 4 ∘ 37 ∘ Present 39 ∘ 280 ∘ 48.2 ∘ Example 17 100,000 3 ∘ 39 ∘ Present 21 ∘ 280 ∘ 56.0 ∘ Example 18 2,800,000 8 ∘ 44 ∘ Present 46 ∘ 280 ∘ 47.3 ∘ Example 19 1,000,000 8 ∘ 35 ∘ Present 44 ∘ 280 ∘ 42.2 ∘ Example 20 300,000 4 ∘ 45 ∘ Present 37 ∘ 280 ∘ 48.6 ∘ Example 21 400,000 4 ∘ 39 ∘ Present 36 ∘ 280 ∘ 41.9 ∘ Example 22 500,000 5 ∘ 37 ∘ Present 36 ∘ 280 ∘ 42.1 ∘ Example 23 100,000 2 ∘ 45 ∘ Present 21 ∘ 280 ∘ 39.7 ∘ Example 24 700,000 4 ∘ 48 ∘ Present 40 ∘ 270 ∘∘ 61 ∘∘ Example 25 1,000,000 6 ∘ 38 ∘ Present 26 ∘ 270 ∘∘ 66 ∘∘ Example 26 700,000 4 ∘ 44 ∘ Present 42 ∘ 270 ∘∘ 63 ∘∘ Example 27 700,000 4 ∘ 46 ∘ Present 43 ∘ 270 ∘∘ 63 ∘∘

(79) TABLE-US-00005 TABLE 5 Sinterability Tensile test Decomposition Battery performance Maximum ending Discharge Average molecular weight Resin Tg Yield stress temperature capacity Mw Mw/Mn Rating (° C.) Rating stress (N/mm.sup.2) Rating (° C.) Rating (mAh) Rating Comparative 80,000 2 x 76 x Absent 20 x 380 x — x Example 1 Comparative 500,000 3 ∘ 4 x Absent 7 x 380 x — x Example 2 Comparative 500,000 3 ∘ 10 x Absent 8 x 380 x — x Example 3 Comparative 3,000,000 10 x 34 ∘ Absent 10 x 300 x 9 x Example 4 Comparative 80,000 2 x 33 ∘ Absent 18 x 420 x — x Example 5 Comparative 1,000,000 3 ∘ 47 ∘ Absent 10 x 350 x — x Example 6 Comparative 1,000,000 2 ∘ 53 ∘ Absent 15 x 320 x — x Example 7 Comparative 180,000 2 ∘ 36 ∘ Absent 12 x 330 x — x Example 8 Comparative 150,000 2 ∘ 50 ∘ Absent 9 x 350 x — x Example 9 Comparative 3,100,000 9 x 45 ∘ Absent 50 x 280 x — x Example 10 Comparative 80,000 2 x 26 x Absent 3 x 450 x — x Example 11 Comparative 500,000 4 ∘ 25 x Absent 16 x 320 x — x Example 12 Comparative 4,000,000 9 x 21 x Absent 13 x 390 x — x Example 13 Comparative 200,000 4 ∘ 21 x Absent 10 x 440 x — x Example 14 Comparative 80,000 2 x 72 x Absent 25 x 470 x — x Example 15 Comparative 1,000,000 6 ∘ 51 ∘ Absent 19 x 270 ∘∘ — x Example 16 Comparative 1,000,000 6 ∘ 40 ∘ Present 33 ∘ 380 x 1 x Example 17 Comparative 1,000,000 6 ∘ 11 x Absent 5 x 300 x — x Example 18

(80) In Examples 1 to 23, excellent characteristics were shown in all of the evaluations. In Examples 24 to 27, better decomposability at low temperature was exhibited and particularly excellent battery characteristics were achieved.

(81) On the other hand, the formulations of Comparative Examples 1 to 16 and 18 did not exhibit yield stress in the tensile test, and the samples broke at a strain of less than 10%. As no yield stress was exhibited and a strong plasticizer effect was exerted in processing the resin composition into the inorganic sheets, the green sheets lacked resilience and thus had poor handleability. The inorganic fine particle-dispersed sheets obtained in Comparative Examples 17 and 18 turned brown, and a large amount of firing residue was produced.

(82) (6) Sheet Windability

(83) A release-treated PET film as a protective film was bonded to one side of the ceramic green sheet obtained in each of Examples 28 to 31 and Comparative Examples 19 to 22 to prepare an inorganic fine particle-dispersed sheet for evaluation.

(84) The obtained inorganic fine particle-dispersed sheet was wound around a polypropylene pipe having a diameter of 15 cm and a length of 50 cm to give a roll. The roll was allowed to stand at a room temperature of 23° C. for 24 hours.

(85) The ceramic green sheet was unwound from the roll. A 20 cm×45 cm sheet was cut out from each of a portion 5 m away from the end and a portion 10 m away from the end to prepare evaluation sheets. The state of the evaluation sheets was visually observed. In Comparative Example 20, the ceramic green sheet could not be separated from the roll, so that the evaluation sheets could not be prepared and the sheet windability could not be evaluated.

(86) o (Good): No crack was observed.

(87) x (Poor): Evaluation sheets could not be prepared or crack(s) was observed.

(88) (7) Sheet Adhesiveness

(89) Each of the ceramic fired bodies obtained in Examples 28 to 31 and Comparative Examples 19 to 22 was cooled to room temperature. Each ceramic fired body was cut in a direction perpendicular to the lamination surface in the center portion. The state of the sheet cross section near the 50th layer was observed with an electron microscope to determine the presence or absence of separation between the ceramic layer and the conductive layer. The evaluation was performed according to the following criteria. In Comparative Examples 19 and 20, the laminate could not be prepared, so that the ceramic fired body could not be prepared. The sheet adhesiveness thus could not be evaluated.

(90) o (Good): No separation between the layers was observed.

(91) x (Poor): The ceramic fired body could not be prepared or separation between the layers was observed.

(92) TABLE-US-00006 TABLE 6 Sheet adhesivemess Average molecular weight Resin Tg Sheet windability Observation of Mw Mw/Mn Rating (° C.) Rating Results Rating sheet cross-section Rating Example 28 100,000 2 ∘ 60 ∘ No cracks ∘ No separation between layers ∘ Example 29 3,000,000 5 ∘ 48 ∘ No cracks ∘ No separation between layers ∘ Example 30 1,000,000 6 ∘ 48 ∘ No cracks ∘ No separation between layers ∘ Example 31 1,000,000 8 ∘ 35 ∘ No cracks ∘ No separation between layers ∘ Comparative 80,000 2 x 76 x Cracks observed x Evaluation impossible x Example 19 Comparative 500,000 3 ∘ 10 x Evaluation impossible x Evaluation impossible x Example 20 Comparative 80,000 2 x 33 ∘ No cracks ∘ Separation between layers observed x Example 21 Comparative 200,000 4 ∘ 21 X No cracks ∘ Separation between layers observed x Example 22

(93) In Examples 28 to 31, excellent characteristics were shown in all of the evaluations. On the other hand, in Comparative Example 19, cracks were observed in the sheet windability evaluation. In Comparative Example 20, the ceramic green sheet could not be separated from the roll, and the sheet windability could not be evaluated. In Comparative Examples 19 and 20, the laminate could not be prepared, so that the ceramic fired body could not be prepared. In Comparative Examples 21 and 22, although no cracks were observed in the sheet windability evaluation, the inorganic fine particle-dispersed sheets turned brown and a large amount of firing residue was produced. In addition, the cross-sectional observation of the ceramic fired body showed separation between the layers due to the firing residue.

INDUSTRIAL APPLICABILITY

(94) The present invention can provide a resin composition which has excellent decomposability at low temperature, can provide a molded article having high strength, and enables an increase in the number of layers and thinning so as to enable production of an all-solid-state battery and a ceramic laminate (e.g., a multilayer ceramic capacitor) having excellent properties. The present invention can also provide an inorganic fine particle-dispersed slurry composition containing the resin composition, an inorganic fine particle-dispersed sheet, a method for producing an all-solid-state battery, and a method for producing a multilayer ceramic capacitor.