JP2021042370A - Slurry composition for dispersing inorganic fine particle, inorganic fine particle dispersion sheet, and manufacturing method of inorganic fine particle dispersion sheet - Google Patents

Abstract

To provide a slurry composition for dispersing inorganic fine particles, which has excellent decomposability at low temperature, can obtain a compact having high strength, and realizes further multi-layer and thinning and can manufacture a ceramic laminate such as an all solid-state battery or a laminate ceramic capacitor having excellent properties, an inorganic fine particle dispersion sheet and a manufacturing method of the inorganic fine particle dispersion sheet using the slurry composition for dispersing inorganic fine particles.SOLUTION: A slurry composition for dispersing inorganic fine particles is a slurry composition containing a (meth)acrylic resin, inorganic fine particles, and an organic solvent, in which the (meth)acrylic resin has a weight average molecular weight (Mw) of 200, 000 or larger and 2,000,000 or smaller and the glass transition temperature (Tg) of 40°C or higher and 60°C or lower, the (meth)acrylic resin contains a segment derived from isobutyl methacrylate of 40 wt.% or larger and 60 wt.% or smaller, a segment derived from n-butyl methacrylate of 20 wt.% or larger and 50 wt.% or smaller, and a segment derived from ethyl methacrylate of 1 wt.% or larger and 40 wt.% or smaller.SELECTED DRAWING: None

Description

INDUSTRIAL APPLICABILITY According to the present invention, a molded product having excellent decomposability at a low temperature and having high strength can be obtained, and further multi-layering and thin-filming can be realized, and ceramics such as an all-solid-state battery and a multilayer ceramics capacitor having excellent characteristics can be obtained. The present invention relates to an inorganic fine particle dispersion slurry composition capable of producing a laminate. The present invention also relates to an inorganic fine particle dispersion sheet and a method for producing an inorganic fine particle dispersion sheet using the inorganic fine particle dispersion slurry composition.

In recent years, compositions in which inorganic fine particles such as ceramic powder and glass particles are dispersed in a binder resin have been used in the production of laminated electronic components such as laminated ceramic capacitors.
Such multilayer ceramic capacitors are generally manufactured by the following methods. First, additives such as a plasticizer and a dispersant are added to a solution in which a binder resin is dissolved in an organic solvent, then a ceramic raw material powder is added and mixed uniformly using a ball mill or the like to obtain an inorganic fine particle dispersion slurry composition. obtain.
The obtained inorganic fine particle-dispersed slurry composition was cast-molded on the surface of a support such as a polyethylene terephthalate film or a SUS plate that had undergone mold release treatment using a doctor blade, a reverse roll coater, or the like to remove volatile components such as an organic solvent. After being distilled off, it is peeled off from the support to obtain a ceramic green sheet.
Next, a conductive paste serving as an internal electrode is applied onto the obtained ceramic green sheet by screen printing or the like, and a plurality of the conductive pastes are stacked, heated and pressure-bonded to obtain a laminated body. The obtained laminate is heated to thermally decompose and remove components such as a binder resin, that is, a so-called degreasing treatment, and then fired to obtain a ceramic fired body having an internal electrode. Further, an external electrode is applied to the end face of the obtained ceramic fired body and fired to complete a laminated ceramics capacitor.

In such an inorganic fine particle dispersion slurry composition, polyvinyl acetal resin (PVB) is generally used as a binder, but since PVB has a high decomposition temperature, it can be used in applications where low temperature firing is desirable. There was a problem that there was no.
Therefore, it has been studied to use a (meth) acrylic resin that can be fired at a low temperature and has a small residual carbon component after firing.

For example, Patent Document 1 copolymerizes 60 to 99% by weight of isobutyl methacrylate, 1 to 39% by weight of 2-ethylhexyl methacrylate, and 1 to 15% by weight of a methacrylic acid ester having a hydroxyl group at the β-position or the ω-position. Described is a binder resin for ceramic molding made of a methacrylic acid ester copolymer having a molecular weight of 160,000 to 180,000.

Further, in Patent Document 2, it is considered to use a mixture of a component A having a low resin Tg and a component B having a high resin Tg.
Further, in Patent Document 3, a resin A having a molecular weight of 10,000 or less and a resin Tg of −20 ° C. or less is mixed with a resin component B having a molecular weight of 100,000 or more and a Tg of 40 ° C. or more in order to improve brittleness. Is being considered.

Japanese Unexamined Patent Publication No. 10-167836 Japanese Patent No. 6371616 Japanese Unexamined Patent Publication No. 2018-79616

However, the resin described in Patent Document 1 has a problem that the glass transition temperature (Tg) is about 28 ° C. to about 52 ° C. and is brittle as a whole. When an inorganic fine particle dispersion slurry is prepared using such a resin composition and dried on a release PET to form an inorganic fine particle dispersion sheet, the obtained inorganic fine particle dispersion sheet is very brittle and can be peeled off from the release PET. There is a problem that it breaks at the time.

Further, when a large amount of plasticizer is added to the inorganic fine particle-dispersed slurry composition to produce a sheet, there is a problem that the obtained sheet loses its elasticity and a sheet having a uniform thickness cannot be produced.
Further, in order to produce an inorganic fine particle dispersion sheet having excellent handleability, a resin having a high yield stress and a large breaking elongation is preferable in a tensile test of the resin sheet, and a (meth) acrylic resin having excellent thermal decomposability. The yield stress increases by increasing the resin Tg, but the resin becomes brittle in proportion to it. Further, when the breaking elongation is increased, it is necessary to lower the resin Tg, and the sheet loses its waist, so that it is very difficult to achieve both a high yield stress and a breaking elongation.

In Reference 2, since the high molecular weight (meth) acrylic resins do not mix with each other having different monomer compositions, the molecular weight of the component B having a high resin Tg is set to 10,000 or less, but the yield stress of the resin mixed sheet is the molecular weight. Therefore, there is a problem that a high yield stress cannot be obtained. Further, in Cited Document 3, since the properties of the two polymer compositions are different, there is a problem that the resins are difficult to mix with each other, and the inorganic powder dispersion sheet using these resin compositions is very brittle.

INDUSTRIAL APPLICABILITY According to the present invention, a molded product having excellent decomposability at a low temperature and having high strength can be obtained, and further multi-layering and thin-filming can be realized, and ceramics such as an all-solid-state battery and a multilayer ceramics capacitor having excellent characteristics can be obtained. An object of the present invention is to provide an inorganic fine particle-dispersed slurry composition capable of producing a laminate. Another object of the present invention is to provide an inorganic fine particle dispersion sheet and a method for producing an inorganic fine particle dispersion sheet using the inorganic fine particle dispersion slurry composition.

The present invention is an inorganic fine particle dispersion slurry composition containing a (meth) acrylic resin, inorganic fine particles, and an organic solvent, and the (meth) acrylic resin has a weight average molecular weight (Mw) of 200,000 or more and 2 million. The glass transition temperature (Tg) is 40 ° C. or higher and 60 ° C. or lower, and the (meth) acrylic resin contains 40% by weight or more and 60% by weight or less of a segment derived from isobutyl methacrylate and n-butyl methacrylate. It is an inorganic fine particle dispersion slurry composition containing 20% by weight or more and 50% by weight or less of a segment derived from, and 1% by weight or more and 40% by weight or less of a segment derived from ethyl methacrylate.
The present invention will be described in detail below.

The present inventors contain a segment derived from isobutyl methacrylate, a segment derived from n-butyl methacrylate, and a segment derived from ethyl methacrylate in a predetermined ratio, and the weight average molecular weight and the glass transition temperature are predetermined. It was found that the (meth) acrylic resin in the above range has excellent low-temperature decomposability and a small amount of firing residue. Further, the slurry composition containing such a (meth) acrylic resin exhibits extremely excellent low-temperature decomposability, a high-strength molded product can be obtained, and the obtained ceramic green sheet can be further laminated and further laminated. We have found that it is possible to manufacture an all-solid-state battery having excellent characteristics by realizing a thin film, and have completed the present invention.

<(Meta) acrylic resin>
The inorganic fine particle dispersion slurry composition of the present invention contains a (meth) acrylic resin.
The (meth) acrylic resin contains a segment derived from isobutyl methacrylate, a segment derived from n-butyl methacrylate, and a segment derived from ethyl methacrylate.
By containing the above segment, a resin having excellent low temperature decomposability can be obtained.

The content of the segment derived from isobutyl methacrylate in the (meth) acrylic resin is 40% by weight or more and 60% by weight or less.
Within the above range, excellent low temperature decomposability can be exhibited. In addition, the strength of the obtained laminate can be sufficiently improved.
The content of the segment derived from isobutyl methacrylate is preferably 45% by weight or more, more preferably 47% by weight or more, preferably 57% by weight or less, and 55% by weight or less. Is more preferable.

The content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin is 20% by weight or more and 50% by weight or less.
Within the above range, excellent low temperature decomposability can be exhibited. In addition, the strength of the obtained laminate can be sufficiently improved.
The content of the segment derived from n-butyl methacrylate is preferably 25% by weight or more, more preferably 30% by weight or more, preferably 45% by weight or less, and 40% by weight or less. More preferably.

The content of the segment derived from ethyl methacrylate in the (meth) acrylic resin is 1% by weight or more and 40% by weight or less.
Within the above range, excellent low temperature decomposability can be exhibited. In addition, the strength of the obtained laminate can be sufficiently improved.
The content of the segment derived from ethyl methacrylate is preferably 10% by weight or more, more preferably 15% by weight or more, preferably 30% by weight or less, and 25% by weight or less. Is more preferable.

Further, in the (meth) acrylic resin, the total content of the segment derived from isobutyl methacrylate, the segment derived from n-butyl methacrylate and the segment derived from ethyl methacrylate is 70% by weight or more. Is preferable, 90% by weight or more is preferable, 100% by weight or less is preferable, and 98% by weight or less is preferable.

The (meth) acrylic resin may contain a segment derived from a (meth) acrylic acid ester having 8 or more carbon atoms in the ester substituent for the purpose of lowering the glass transition temperature (Tg). The fact that the ester substituent has 8 or more carbon atoms means that the total number of carbon atoms other than the carbons constituting the (meth) acryloyl group in the (meth) acrylic acid ester is 8 or more.
By having the segment derived from the (meth) acrylic acid ester having 8 or more carbon atoms in the ester substituent, the decomposition completion temperature of the (meth) acrylic resin can be sufficiently lowered, and the obtained inorganic fine particles can be sufficiently lowered. The dispersion sheet can be made tough.
In the (meth) acrylic acid ester having 8 or more carbon atoms of the ester substituent, it is preferable that the ester substituent has a branched chain structure.
The preferable upper limit of the number of carbon atoms of the ester substituent is 10, and the more preferable upper limit is 9.

Examples of the (meth) acrylic acid ester having 8 or more carbon atoms in the ester substituent include a (meth) acrylic acid ester having an alkyl group having 8 or more carbon atoms in a linear or branched chain, and a polyalkylene glycol. Examples include (meth) acrylate.

Examples of the (meth) acrylic acid ester having a linear or branched alkyl group include 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, and isononyl (meth) acrylate. N-decyl acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, isolauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, etc. Be done.
Among them, a (meth) acrylic acid ester having a branched chain-like alkyl group having 8 or more carbon atoms is preferable, and 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, (meth). ) Isostearyl acrylate is more preferred.
2-Ethylhexyl methacrylate and isodecyl methacrylate are particularly excellent in decomposability as compared with other long-chain alkyl methacrylates.

Examples of the polyalkylene glycol (meth) acrylate include those having an ethylene glycol unit (oxyethylene unit), a propylene glycol unit (oxypropylene unit), a butylene glycol unit (oxybutylene unit), and the like.
Further, the polyalkylene glycol (meth) acrylate may have an alkoxy group at the end or an ethylhexyl group at the end.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group and the like. The alkoxy group may be linear, may be branched, and is preferably branched.
Further, the polyalkylene glycol (meth) acrylate preferably has a branched alkylene glycol structure.
Of these, a polyalkylene glycol (meth) acrylate having at least one of an ethylene glycol unit, a propylene glycol unit, and a butylene glycol unit is preferable. Further, polyethylene glycol methacrylate, ethoxypolypropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, polybutylene glycol methacrylate, and polypropylene glycol-polybutylene glycol methacrylate are more preferable.
Compared with other alkylene glycol (meth) acrylates, methoxypolypropylene glycol methacrylate, polypropylene glycol methacrylate, polybutylene glycol methacrylate, and propylene glycol-polybutylene glycol methacrylate have less calcination residue and are particularly excellent in low temperature decomposability.

The content of the segment derived from the (meth) acrylic acid ester in which the number of carbon atoms of the ester substituent in the (meth) acrylic resin is 8 or more is preferably 1% by weight, more preferably 4% by weight, and more preferable. The upper limit is 10% by weight, and the more preferable upper limit is 7% by weight.
Within the above range, the toughness of the obtained inorganic fine particle dispersion sheet can be enhanced.

The (meth) acrylic acid has a segment derived from isobutyl methacrylate, a segment derived from n-butyl methacrylate, a segment derived from ethyl methacrylate, and a (meth) acrylic acid having an ester substituent having 8 or more carbon atoms. It may have a segment derived from a (meth) acrylic acid ester other than the segment derived from the ester.
Examples of the other (meth) acrylic acid ester include a (meth) acrylic acid ester having a glycidyl group, an alkyl (meth) acrylic acid ester having an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or a carboxyl group. Examples thereof include (meth) acrylic acid ester having. Of these, (meth) acrylic acid having a glycidyl group, an alkyl (meth) acrylic acid ester having an alkyl group having 1 to 6 carbon atoms, and a (meth) acrylic acid ester having a hydroxyl group or a carboxyl group are preferable.

Examples of the (meth) acrylic acid ester having a glycidyl group include glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate.

The (meth) acrylic acid ester having an alkyl group having 1 to 6 carbon atoms is an alkyl (meth) acrylic acid ester other than ethyl methacrylate, n-butyl methacrylate and isobutyl methacrylate, and is a linear alkyl. Examples thereof include alkyl (meth) acrylates having a group, alkyl (meth) acrylates having a branched alkyl group, and alkyl (meth) acrylates having a cyclic alkyl group.
Examples of the alkyl (meth) acrylate having a linear alkyl group include methyl (meth) acrylate, ethyl acrylate, n-propyl (meth) acrylate, n-butyl acrylate, and n (meth) acrylate. -Pentyl, n-hexyl (meth) acrylate and the like can be mentioned.
Examples of the alkyl (meth) acrylate having a branched alkyl group include isopropyl (meth) acrylate, isobutyl acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and (meth). Examples thereof include isopentyl acrylate, neopentyl (meth) acrylate, sec-pentyl (meth) acrylate, and tert-pentyl (meth) acrylate.
Examples of the alkyl (meth) acrylate having a cyclic alkyl group include cyclohexyl (meth) acrylate and the like.
Of these, alkyl (meth) acrylates having a linear alkyl group are preferable, and methyl (meth) acrylate is preferable.

The (meth) acrylic acid ester having a hydroxyl group or a carboxyl group is not particularly limited as long as it has a functional group capable of reacting with the (meth) acrylic acid ester having a glycidyl group. Specific examples thereof include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and (meth) acrylic acid.
Of these, (meth) acrylate having a hydroxyl group is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.

Regarding the content of the segment derived from the other (meth) acrylic acid ester in the (meth) acrylic resin, the preferable lower limit is 1% by weight, the more preferable lower limit is 2% by weight, the further preferable lower limit is 4% by weight, and the preferable upper limit is 4% by weight. Is 10% by weight, a more preferable upper limit is 7% by weight, and a more preferable upper limit is 6% by weight.
Within the above range, the low temperature decomposability of the obtained (meth) acrylic resin can be sufficiently improved, and the toughness of the obtained inorganic fine particle dispersion sheet can be improved.

In a preferred embodiment of the present invention, the (meth) acrylic resin does not have a segment derived from an acid-containing monomer. When the (meth) acrylic resin does not contain a segment derived from an acid-containing monomer, the degradability at low temperature can be further enhanced.
Examples of the acid-containing monomer include carboxylic acid-containing monomers such as (meth) acrylic acid. The segment derived from the acid-containing monomer has an acid such as a carboxyl group.

The weight average molecular weight (Mw) of the (meth) acrylic resin is 200,000 or more and 2 million or less.
Within the above range, the inorganic fine particle-dispersed slurry composition has a sufficient viscosity, and the printability can be sufficiently improved.
The Mw is preferably 300,000 or more, more preferably 400,000 or more, preferably 1.5 million or less, and more preferably 1 million or less.
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (meth) acrylic resin is preferably 2 or more, and preferably 8 or less.
When the content is within the above range, a component having a low degree of polymerization is appropriately contained, so that the viscosity of the inorganic fine particle-dispersed slurry composition is in a suitable range, and productivity can be enhanced. In addition, the sheet strength of the obtained inorganic fine particle dispersion sheet can be made appropriate. Further, the surface smoothness of the obtained ceramic green sheet can be sufficiently improved.
The Mw / Mn is more preferably 3 or more, and more preferably 6 or less.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, a column LF-804 (manufactured by Showa Denko) as a column. it can.

The glass transition temperature (Tg) of the (meth) acrylic resin is 40 ° C. or higher and 60 ° C. or lower.
Within the above range, the amount of the plasticizer added can be reduced, and the low temperature decomposability can be improved.
The Tg is preferably 42 ° C. or higher, more preferably 45 ° C. or higher, preferably 58 ° C. or lower, and more preferably 55 ° C. or lower.
The glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC) or the like.

The (meth) acrylic resin contains the above-mentioned segment derived from isobutyl methacrylate, segment derived from n-butyl methacrylate, segment derived from ethyl methacrylate, weight average molecular weight (Mw) and glass as a whole mixture. As long as the transition temperature (Tg) is satisfied, it may be a mixture of two or more kinds of (meth) acrylic resins having different compositions.
In general, (meth) acrylic resins having different compositions do not mix with each other with high molecular weights, the resin solution becomes turbid, and the fluidity of the solution becomes very poor. Therefore, the (meth) acrylic resins having different compositions have different compositions. The surface smoothness of the sheet using the mixture of the above is poor, and a sheet having high strength cannot be obtained.
Therefore, when two or more kinds of (meth) acrylic resins are mixed, the segments constituting each (meth) acrylic resin preferably have 4 or less transesterifying groups, and the segments derived from isobutyl methacrylate are present. It is desirable to be included.

When the above (meth) acrylic resin is a mixture of two or more kinds of (meth) acrylic resins, the (meth) acrylic resin (A) having a low glass transition temperature (Tg) and the (meth) acrylic resin having a high glass transition temperature (Tg) It is preferably a mixture with the acrylic resin (B).
Since it is such a mixture of (meth) acrylic resin, it is possible to obtain a (meth) acrylic resin which has high low-temperature degradability, does not make the resin solution turbid, and can produce a tough inorganic fine particle dispersion sheet.
In a preferred embodiment of the present invention, the difference in glass transition temperature (Tg) between the (meth) acrylic resin (A) and the (meth) acrylic resin (B) is determined from the viewpoint of low temperature degradability and toughness. It is preferably 8 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 12 ° C. or higher, preferably 50 ° C. or lower, more preferably 45 ° C. or lower, still more preferably 40 ° C. or lower.

The (meth) acrylic resin (A) having a low Tg preferably contains a segment derived from isobutyl methacrylate and a segment derived from n-butyl methacrylate.
The content of the segment derived from isobutyl methacrylate in the (meth) acrylic resin (A) is preferably 30% by weight or more, more preferably 40% by weight or more, and preferably 60% by weight or less. It is preferably 55% by weight or less, more preferably 55% by weight or less.
The content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin (A) is preferably 40% by weight or more, more preferably 45% by weight or more, and 70% by weight or less. It is preferably 60% by weight or less, and more preferably 60% by weight or less.

Further, the (meth) acrylic resin (A) may contain a (meth) acrylic resin having 8 or more carbon atoms in the above-mentioned ester substituent in order to lower the glass transition temperature (Tg).
The content of the (meth) acrylic resin in the (meth) acrylic resin (A) having 8 or more carbon atoms of the ester substituent has a preferable lower limit of 5% by weight and a preferable upper limit of 40% by weight. Within the above range, the toughness of the obtained inorganic fine particle dispersion sheet can be enhanced.

Further, the (meth) acrylic resin (A) preferably contains a segment derived from ethyl methacrylate in addition to a segment derived from isobutyl methacrylate and a segment derived from n-butyl methacrylate. It may also contain a segment derived from the other (meth) acrylic acid ester described above.

The content of the segment derived from ethyl methacrylate in the (meth) acrylic resin (A) is preferably 2% by weight or more, more preferably 5% by weight or more, and preferably 15% by weight or less. It is preferably 10% by weight or less, and more preferably 10% by weight or less.
When the content of the segment derived from ethyl methacrylate in the (meth) acrylic resin (A) is at least the above lower limit, the compatibility with the (meth) acrylic resin (B) described later is improved, and the mixed resin solution becomes It is transparent and can improve fluidity. When the content of the segment derived from ethyl methacrylate in the (meth) acrylic resin (A) is not more than the above upper limit, the resin Tg does not become too high, and the embrittlement of the obtained inorganic fine particle dispersion sheet can be suppressed. it can.

The weight average molecular weight (Mw) of the (meth) acrylic resin (A) is preferably 200,000 or more, more preferably 400,000 or more, preferably 2 million or less, and preferably 1 million or less. Is more preferable.
Within the above range, the obtained inorganic fine particle dispersion sheet does not become brittle, and a ceramic laminate having suitable strength can be produced.

The glass transition temperature (Tg) of the (meth) acrylic resin (A) is preferably 30 ° C. or higher, more preferably 32 ° C. or higher, preferably 40 ° C. or lower, and 35 ° C. or lower. Is more preferable.
Within the above range, the obtained inorganic fine particle dispersion sheet does not become brittle, and a ceramic laminate having suitable hardness can be produced.

The (meth) acrylic resin (B) having a high Tg preferably contains a segment derived from isobutyl methacrylate and a segment derived from ethyl methacrylate.
The content of the segment derived from isobutyl methacrylate in the (meth) acrylic resin (B) is preferably 50% by weight or more, more preferably 55% by weight or more, and more preferably 70% by weight or less. It is preferably 65% by weight or less, and more preferably 65% by weight or less.
By including the segment of isobutyl methacrylate contained in the (meth) acrylic resin (A) in the (meth) acrylic resin (B), the compatibility is enhanced when the respective resin solutions are mixed.
The content of the segment derived from ethyl methacrylate in the (meth) acrylic resin (B) is preferably 30% by weight or more, more preferably 35% by weight or more, and 50% by weight or less. It is preferably 45% by weight or less, and more preferably 45% by weight or less.

The (meth) acrylic resin (B) preferably contains a segment derived from n-butyl methacrylate in addition to a segment derived from isobutyl methacrylate and a segment derived from ethyl methacrylate. It may also contain a segment derived from the other (meth) acrylic acid ester described above.

The content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin (B) is preferably 5% by weight or more, more preferably 10% by weight or more, and 20% by weight or less. It is preferably 15% by weight or less, and more preferably 15% by weight or less.
When the content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin (B) is at least the above lower limit, the compatibility is improved when mixed with the (meth) acrylic resin (A) resin solution. be able to. When the content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin (B) is not more than the above upper limit, the resin Tg does not become too high and the embrittlement of the obtained inorganic fine particle dispersion sheet is suppressed. be able to.

Further, since the (meth) acrylic resin (B) can sufficiently improve the strength of the obtained ceramic laminate, even if it contains a segment derived from the (meth) acrylic acid ester having a glycidyl group. Good.

The content of the segment derived from the (meth) acrylic acid ester having a glycidyl group in the (meth) acrylic resin (B) is preferably 10% by weight or less, preferably 7% by weight or less, from the viewpoint of low temperature decomposition. It is more preferably 5% by weight or less, further preferably 4% by weight or less, and particularly preferably 3% by weight or less. The lower limit is not particularly limited, and is preferably 0% by weight or more, and more preferably 1% by weight or more.
Within the above range, the solvent resistance of the obtained inorganic fine particle dispersion sheet can be improved, and an all-solid-state battery having excellent electrical characteristics can be produced when used in the production of an all-solid-state battery. In addition, the low temperature decomposability of the (meth) acrylic resin can be sufficiently improved.

The weight average molecular weight (Mw) of the (meth) acrylic resin (B) is preferably 50,000 or more, more preferably 100,000 or more, preferably 1 million or less, and 500,000 or less. Is more preferable.
Within the above range, the obtained inorganic fine particle dispersion sheet does not become brittle, and a ceramic laminate having suitable strength can be produced.

The glass transition temperature (Tg) of the (meth) acrylic resin (B) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, preferably 60 ° C. or lower, and 59 ° C. or lower. Is more preferable.
Within the above range, the obtained inorganic fine particle dispersion sheet does not become brittle, and a ceramic laminate having suitable strength can be produced.

When the (meth) acrylic resin is a mixture of the (meth) acrylic resin (A) and the (meth) acrylic resin (B), the above (from the viewpoint of compatibility of the two resins in the resin solution, the above ( It is desirable that the (meth) acrylic resin (A) and the (meth) acrylic resin (B) are composed of the same monomer components.
The (meth) acrylic resin (A) and the (meth) acrylic resin (B) contain a segment derived from isobutyl methacrylate, a segment derived from n-butyl methacrylate, and a segment derived from ethyl methacrylate. It is preferable to do so.
Further, the content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin (B) is higher than the content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin (A). It is desirable that it is less than 30% by weight.
Further, the content of the segment derived from ethyl methacrylate in the (meth) acrylic resin (B) is 20% by weight or more than the content of the segment derived from ethyl methacrylate in the (meth) acrylic resin (A). It is desirable that there are many. The mixing ratio of the (meth) acrylic resin (A) and the (meth) acrylic resin (B) in the (meth) acrylic resin is not particularly limited, but is preferably 10:90 to 90:10.
When two kinds of resins showing compatibility are mixed, the resin Tg of the mixed resin follows the formula of FOX.
With such a composition, the compatibility between the (meth) acrylic resin (A) and the (meth) acrylic resin (B) can be particularly improved in the resin solution. Therefore, when the ceramic green sheet is produced, the ceramic green sheet can be made hard to crack due to the influence of the (meth) acrylic resin (A), and the waist is affected by the influence of the (meth) acrylic resin (B). Handleability is good as a certain sheet.

Further, for the (meth) acrylic resin, the (meth) acrylic resin (A) and the (meth) acrylic resin (B) were polymerized in separate containers, mixed, and heated and mixed at a temperature of 70 ° C. or higher. It is preferable that the material is one.
With the above configuration, the compatibility of the mixed resin solution is enhanced, and the fluidity of the resin solution is improved.

The preferred upper limit of the 90% by weight decomposition temperature of the (meth) acrylic resin when heated at 10 ° C./min is 300 ° C.
As a result, it is possible to realize extremely high low temperature decomposability and shorten the time required for degreasing.
The preferable lower limit of the 90% by weight decomposition temperature is 230 ° C., the more preferable lower limit is 250 ° C., the more preferable upper limit is 290 ° C., the further preferable upper limit is 280 ° C., and the further preferable upper limit is 270 ° C.
The 90% by weight decomposition temperature can be measured using, for example, TG-DTA or the like.

The (meth) acrylic resin preferably has a maximum stress of 20 N / mm ² or more in a tensile test when formed into a sheet having a thickness of 20 μm.
The maximum stress can be measured by a tensile test using an autograph.
Normally, (meth) acrylic resin is hard and brittle, so when it is formed into a sheet and pulled, it breaks with a strain of less than 5%. Therefore, if the composition has a low glass transition temperature, it does not show a yield value.
On the other hand, in the resin composition of the present invention, by adjusting the composition of the (meth) acrylic resin, the yield stress is exhibited even when the resin composition is formed into a sheet and pulled. At this time, the sheet thickness is preferably about 500 μm.

The method for producing the (meth) acrylic resin is not particularly limited. For example, an organic solvent or the like is added to a raw material monomer mixture containing isobutyl methacrylate, n-butyl methacrylate, ethyl methacrylate, and other monomers added as needed to prepare a monomer mixture, which is further obtained. A method of copolymerizing the raw material monomer by adding a polymerization initiator to the prepared monomer mixture can be mentioned.
The method of polymerization is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Of these, solution polymerization is preferable.

Examples of the polymerization initiator include P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, t-butylhydroxyperoxide, and excess. Examples thereof include cyclohexanone oxide and peroxide disuccinate.
Examples of these commercially available products include Permenta H, Park Mill P, Per Octa H, Park Mill H-80, Perbutyl H-69, Perhexa H, and Parloyl SA (all manufactured by NOF CORPORATION).

When the (meth) acrylic resin is a mixture of the (meth) acrylic resin (A) and the (meth) acrylic resin (B), the method for producing the (meth) acrylic resin is as described above (meth). ) A method of separately polymerizing the acrylic resin (A) and the above-mentioned (meth) acrylic resin (B) and then heating and mixing them can be mentioned.
Examples of the method for producing the (meth) acrylic resin (A) and the (meth) acrylic resin (B) include isobutyl methacrylate, n-butyl methacrylate, ethyl methacrylate, and other additions as necessary. A monomer mixture is prepared by adding an organic solvent or the like to the raw material monomer mixture containing the monomer. Then, further, a method of adding a polymerization initiator to the obtained monomer mixed solution to copolymerize the raw material monomer can be mentioned.
The method of polymerization is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Of these, solution polymerization is preferable.
The temperature at the time of heating and mixing is preferably 70 ° C. or higher, and more preferably 80 ° C. or higher, from the viewpoint that a temperature higher than both resins Tg is desirable.

<Organic solvent>
The inorganic fine particle dispersion slurry composition of the present invention contains an organic solvent.
The organic solvent is not particularly limited, but it is preferable that the organic solvent is excellent in coatability, drying property, dispersibility of the inorganic powder, etc. when producing the inorganic fine particle dispersion sheet.
For example, toluene, ethyl acetate, butyl acetate, isopropanol, methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono. Isobutyl ether, trimethylpentanediol monoisobutyrate, butyl carbitol, butyl carbitol acetate, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol acetate, texanol, isophorone, butyl lactate, dioctylphthalate, dioctyl adipate, benzyl alcohol, phenylpropylene Glycol, cresol and the like can be mentioned. Of these, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, butyl carbitol acetate, and texanol are preferable. Further, terpineol, terpineol acetate, dihydroterpineol, and dihydroterpineol acetate are more preferable. These organic solvents may be used alone or in combination of two or more.

The boiling point of the organic solvent is preferably 90 to 160 ° C. When the boiling point is 90 ° C. or higher, evaporation does not become too fast and the handling property is excellent. By setting the boiling point to 160 ° C. or lower, it is possible to improve the strength of the inorganic fine particle dispersion sheet.

The content of the organic solvent in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but a preferable lower limit is 10% by weight and a preferable upper limit is 60% by weight. Within the above range, the coatability and the dispersibility of the inorganic fine particles can be improved.

<Inorganic fine particles>
The inorganic fine particle dispersion slurry composition of the present invention contains inorganic fine particles.
The inorganic fine particles are not particularly limited, and examples thereof include glass powder, ceramic powder, phosphor fine particles, silicon oxide, and other metal fine particles.

The above glass powder is not particularly limited, and for example, glass powder such as bismuth oxide glass, silicate glass, lead glass, zinc glass, and boron glass, CaO-Al ₂ O _3- SiO ₂ system, MgO-Al ₂ O, etc. ₃ -SiO ₂ based _glass powder or the like of the LiO ₂ -Al ₂ O 3 -SiO ₂ system such as various silicon oxide and the like.
Further, as the glass powder, SnO-B ₂ O _3- P ₂ O _5- Al ₂ O ₃ mixture, PbO-B ₂ O _3- SiO ₂ mixture, BaO-ZnO-B ₂ O _3- SiO ₂ mixture, ZnO _{-Bi 2 O 3 -B 2 O 3} -SiO 2 _{mixture, Bi 2 O 3 -B 2 O} 3 -BaO-CuO _{mixture, Bi 2 O 3 -ZnO-B} 2 O 3 -Al 2 O 3 -SrO mixture _{ZnO-Bi 2 O 3 -B 2} O 3 _mixture, Bi ₂ O 3 -SiO _{2 mixture, P 2 O 5 -Na 2 O} -CaO-BaO-Al 2 O 3 -B 2 O 3 _mixture, P 2 _{O 5} -SnO _{mixture, P 2 O 5 -SnO-B} 2 O 3 _{mixture, P 2 O 5 -SnO-SiO} 2 mixture, _{CuO-P 2} O 5 -RO _{mixture, SiO 2 -B 2 O 3 -ZnO} -Na 2 O-Li ₂ O-NaF-V ₂ O ₅ mixture, P ₂ O _5- ZnO-SnO-R ₂ O-RO mixture, B ₂ O _{3 -SiO 2-} ZnO mixture, B ₂ O _3- SiO _2- Al ₂ O _3- ZrO ₂ mixture, SiO _2- B ₂ O _3- ZnO-R ₂ O-RO mixture, SiO _2- B ₂ O _3- Al ₂ O _3- RO-R ₂ O mixture, SrO-ZnO-P _{Glass powders such as 2} O ₅ mixture, SrO-ZnO-P ₂ O ₅ mixture, and BaO-ZnO-B ₂ O _3- SiO ₂ mixture can also be used. R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe and Mn.
In particular, _{glass powder of PbO-B 2} O _3- SiO ₂ mixture, lead-free BaO-ZnO-B ₂ O _{3 -SiO 2} mixture, ZnO-Bi ₂ O _3- B ₂ O _3- SiO ₂ mixture, etc. Lead-free glass powder is preferred.

The ceramic powder is not particularly limited, and for example, alumina, ferrite, zirconia, zircon, barium titanate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, Lantern titanate, neodium titanate, lead zirconite titanate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium titanate, calcium titanate, magnesium silicate, mulite, steatite, cordierite, forsterite, etc. Be done.
Further, ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttria-stabilized zirconia, gadolinium-doped ceria, nickel oxide, lanthanum chromite and the like can also be used.
The above-mentioned fluorescent substance fine particles are not particularly limited, and for example, as the fluorescent substance, a blue fluorescent substance, a red fluorescent substance, a green fluorescent substance and the like conventionally known as a fluorescent substance for display are used. Examples of the blue phosphor material include MgAl ₁₀ O ₁₇ : Eu, Y ₂ SiO ₅ : Ce system, CaWO ₄ : Pb system, BaMgAl ₁₄ O ₂₃ : Eu system, BaMgAl ₁₆ O ₂₇ : Eu system, BaMg ₂ Al ₁₄ O ₂₃ : Eu system, BaMg ₂ Al ₁₄ O ₂₇ : Eu system, ZnS: (Ag, Cd) system are used. Examples of the red phosphor material include Y ₂ O ₃ : Eu system, Y ₂ SiO ₅ : Eu system, Y ₃ Al ₅ O ₁₂ : Eu system, Zn ₃ (PO ₄ ) ₂ : Mn system, YBO ₃ : Eu. System, (Y, Gd) BO ₃ : Eu system, GdBO ₃ : Eu system, ScBO ₃ : Eu system, LuBO ₃ : Eu system are used. Examples of the green phosphor material include Zn ₂ SiO ₄ : Mn-based, BaAl ₁₂ O ₁₉ : Mn-based, SrAl ₁₃ O ₁₉ : Mn-based, CaAl ₁₂ O ₁₉ : Mn- _{based, YBO 3} : Tb-based, BaMgAl ₁₄ O. ₂₃ : Mn system, LuBO ₃ : Tb system, GdBO ₃ : Tb system, ScBO ₃ : Tb system, Sr6Si ₃ O ₃ Cl ₄ : Eu system are used. In addition, ZnO: Zn system, ZnS: (Cu, Al) system, ZnS: Ag system, Y ₂ O ₂ S: Eu system, ZnS: Zn system, (Y, Cd) BO ₃ : Eu system, BaMgAl ₁₂ O ₂₃ : Eu type can also be used.

The metal fine particles are not particularly limited, and examples thereof include powders made of iron, copper, nickel, palladium, platinum, gold, silver, aluminum, tungsten, alloys thereof, and the like.
Further, metals such as copper and iron, which have good adsorption characteristics with a carboxyl group, an amino group, an amide group and the like and are easily oxidized, can also be preferably used. These metal powders may be used alone or in combination of two or more.
Further, in addition to the metal complex, various carbon blacks, carbon nanotubes and the like may be used.

The inorganic fine particles preferably contain lithium or titanium. Specifically, for example, low melting point glass such as _{LiO 2} , Al ₂ O ₃ , SiO _{2 inorganic glass, lithium sulfur glass such as Li 2} S-M _x S _y (M = B, Si, Ge, P). , LiCeO _{2 and} other lithium cobalt composite oxides, LiMnO _{4 and} other lithium manganese composite oxides, lithium nickel composite oxides, lithium vanadium composite oxides, lithium zirconium composite oxides, lithium hafnium composite oxides, lithium silicate (Li) _3.5 Si _0.5 P _0.5 O ₄ ), Lithium Titanium Phosphate (LiTi ₂ (PO ₄ ) ₃ ), Lithium Titanium (Li ₄ Ti ₅ O ₁₂ ), Li _4/3 Ti _5/3 O ₄ , LiCoO ₂ , Lithium germanium phosphate (LiGe ₂ (PO ₄ ) ₃ ), Li _2- SiS-based glass, Li ₄ GeS _{4- Li 3} PS _4- based glass, LiSiO ₃ , LiMn ₂ O ₄ , Li ₂ S- P ₂ S ₅ series glass ceramics, Li ₂ O-SiO ₂ , Li ₂ O-V ₂ O ₅ -SiO ₂ , LiS-SiS _{2 -Li 4} SiO ₄ series glass, ionic conductive oxides such as LiPON, Li _{2 O-P 2 O 5 -B} 2 O 3, Li 2 O-GeO 2 lithium oxide compounds such as _{Ba, Li x Al y Ti z} (PO 4) 3 type _glass, La _x Li y TiO _z glass, Li _x Ge _y P _z O ₄ -based _{glass, Li 7 La 3 Zr 2 O} 12 _{glass, Li v Si w P x S} y Cl z -based glass, lithium niobate oxides such LiNbO _3, Li-beta-such as alumina Examples thereof include a lithium alumina compound and a lithium zinc oxide such as _{Li 14} Zn (GeO ₄ ) _4.

The content of the inorganic fine particles in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but a preferable lower limit is 10% by weight and a preferable upper limit is 90% by weight. When it is 10% by weight or more, it can have sufficient viscosity and excellent coatability, and when it is 90% by weight or less, it can be excellent in dispersibility of inorganic fine particles. Can be done.

<Others>
The inorganic fine particle dispersion slurry composition of the present invention may further contain a plasticizer.
Examples of the plasticizer include di (butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis (2-ethylhexanoate), triethylene glycol dihexanoate, and acetyl. Examples thereof include triethyl citrate, tributyl acetylcitrate, diethyl acetylcitrate, dibutyl acetylcitrate, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, diethyl ethoxymalonate and the like.
By using these plasticizers, it is possible to reduce the amount of the plasticizer added as compared with the case of using a normal plasticizer (when about 30% by weight is added to the binder, 25% by weight). Hereinafter, it can be further reduced to 20% by weight or less).
Among them, it is preferable to use a non-aromatic plasticizer that does not contain an aromatic ring such as a benzene ring in the structure, and it is more preferable to contain a component derived from adipic acid, triethylene glycol, citric acid or succinic acid. preferable. A plasticizer having an aromatic ring is not preferable because it easily burns to form soot.

Further, as the plasticizer, those having an alkyl group having 2 or more carbon atoms such as an ethyl group and a butyl group are preferable, and those having an alkyl group having 4 or more carbon atoms are more preferable.
Since the plasticizer contains an alkyl group having 2 or more carbon atoms, it suppresses the absorption of water into the plasticizer and prevents the obtained inorganic fine particle dispersion sheet from causing problems such as voids and blisters. can do. In particular, the alkyl group of the plasticizer is preferably located at the end of the molecule.
Further, the plasticizer preferably has a functional group having 2 carbon atoms such as an ethyl group, a functional group having 4 carbon atoms such as a butyl group, and a functional group such as butoxyethyl group. The functional group is preferably present in the terminal molecular chain.
A plasticizer having a functional group having 2 carbon atoms such as an ethyl group in the terminal molecular chain is compatible with a segment derived from ethyl methacrylate, and a plastic having a functional group having 4 carbon atoms such as a butyl group in the terminal molecule. The agent is compatible with the segment derived from butyl methacrylate. A plasticizer having a functional group having 2 or 4 carbon atoms has good compatibility with the (meth) acrylic resin according to the present invention, and can preferably improve the brittleness of the resin. Furthermore, the butoxyethyl group is compatible with the composition of both the segment derived from ethyl methacrylate and the segment derived from butyl methacrylate and can be preferably used.

The plasticizer preferably has a carbon: oxygen ratio of 5: 1-3: 1.
By setting the carbon: oxygen ratio in the above range, the combustibility of the plasticizer can be improved and the generation of residual carbon can be prevented. In addition, the compatibility with the (meth) acrylic resin can be improved, and the plasticizing effect can be exhibited even with a small amount of plasticizer.
Further, a high boiling point organic solvent having a propylene glycol skeleton or a trimethylene glycol skeleton can also be preferably used as long as it contains an alkyl group having 4 or more carbon atoms and the carbon: oxygen ratio is 5: 1-3: 1.

The boiling point of the plasticizer is preferably 240 ° C. or higher and lower than 390 ° C. By setting the boiling point to 240 ° C. or higher, it becomes easy to evaporate in the drying step, and it is possible to prevent the residue on the molded product. Further, when the temperature is lower than 390 ° C., residual carbon can be prevented from being generated. The boiling point is the boiling point at normal pressure.

The content of the plasticizer in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but a preferable lower limit is 0.1% by weight and a preferable upper limit is 3.0% by weight. Within the above range, the baking residue of the plasticizer can be reduced.

The content of the (meth) acrylic resin in the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but a preferable lower limit is 5% by weight and a preferable upper limit is 30% by weight.
By setting the content of the (meth) acrylic resin within the above range, an inorganic fine particle-dispersed slurry composition that can be degreased even when fired at a low temperature can be obtained.
The content of the (meth) acrylic resin has a more preferable lower limit of 6% by weight and a more preferable upper limit of 12% by weight.

The inorganic fine particle dispersion slurry composition of the present invention may further contain an additive such as a surfactant.
The above-mentioned surfactant is not particularly limited, and examples thereof include a cationic surfactant, an anionic surfactant, and a nonionic surfactant.
The nonionic surfactant is not particularly limited, but is preferably a nonionic surfactant having an HLB value of 10 or more and 20 or less. Here, the HLB value is used as an index showing the hydrophilicity and lipophilicity of the surfactant, and several calculation methods have been proposed. For example, the saponification value of the ester-based surfactant is used. Is S, the acid value of the fatty acid constituting the surfactant is A, and the HLB value is 20 (1-S / A). Specifically, a nonionic surfactant having a polyethylene oxide having an alkylene ether added to a fat chain is preferable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether and the like are preferably used. Be done. The nonionic surfactant has good thermal decomposability, but if it is added in a large amount, the thermal decomposability of the inorganic fine particle-dispersed slurry composition may decrease. Therefore, the preferable upper limit of the content is 5% by weight. ..

The viscosity of the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, but the preferable lower limit of the viscosity when measured at 20 ° C. using a B-type viscometer at a probe rotation speed of 5 rpm is 0.1 Pa · s. The preferred upper limit is 100 Pa · s.
By setting the viscosity to 0.1 Pa · s or more, the obtained inorganic fine particle dispersion sheet can maintain a predetermined shape after coating by a die coat printing method or the like. Further, by setting the viscosity to 100 Pa · s or less, it is possible to prevent problems such as the bleeding marks of the die not disappearing and to improve the printability.

The method for producing the inorganic fine particle-dispersed slurry composition of the present invention is not particularly limited, and conventionally known stirring methods can be mentioned. Specific examples thereof include the (meth) acrylic resin, the inorganic fine particles, the organic solvent, and the like. Examples thereof include a method of stirring other components such as a plasticizer added as needed with a three-roll or the like.

An inorganic fine particle dispersion sheet can be produced by applying the inorganic fine particle dispersion slurry composition of the present invention onto a support film subjected to a single-sided release treatment, drying the organic solvent, and forming the sheet into a sheet shape. .. Such an inorganic fine particle dispersion sheet is also one of the present inventions.
The inorganic fine particle dispersion sheet of the present invention preferably has a thickness of 1 to 20 μm.

As a method for producing the inorganic fine particle dispersion sheet of the present invention, for example, the inorganic fine particle dispersion slurry composition of the present invention is uniformly coated on a support film by a coating method such as a roll coater, a die coater, a squeeze coater, or a curtain coater. And the like.
When producing an inorganic fine particle dispersion sheet, it is preferable to use the polymerization solution as it is as an inorganic fine particle dispersion slurry composition and process it into an inorganic fine particle dispersion sheet without drying the (meth) acrylic resin.
When the (meth) acrylic resin is dried, undried particles called particles are generated when the acrylic resin is re-solved, and it is difficult to remove such particles even by filtration using a cartridge filter or the like, and an inorganic fine particle dispersion sheet. This is because it adversely affects the strength of the particles.

The support film used in producing the inorganic fine particle dispersion sheet of the present invention is preferably a resin film having heat resistance, solvent resistance, and flexibility. Since the support film has flexibility, the inorganic fine particle dispersion slurry composition can be applied to the surface of the support film by a roll coater, a blade coater, or the like, and the obtained inorganic fine particle dispersion sheet forming film is wound into a roll. Can be stored and supplied in the same state.

Examples of the resin forming the support film include fluororesins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
The thickness of the support film is preferably, for example, 20 to 100 μm.
Further, it is preferable that the surface of the support film is subjected to a mold release treatment, which makes it possible to easily perform the peeling operation of the support film in the transfer step.

An inorganic fine particle dispersion sheet can be produced by applying and drying the inorganic fine particle dispersion slurry composition of the present invention. A method for producing an inorganic fine particle dispersion sheet using the inorganic fine particle dispersion slurry composition of the present invention is also one of the present inventions.
Further, a laminated ceramics capacitor can be manufactured by using the inorganic fine particle dispersion slurry composition and the inorganic fine particle dispersion sheet of the present invention for a dielectric green sheet and an electrode paste.

As a method for manufacturing the all-solid-state battery, a step of forming a slurry for an electrode active material layer containing an electrode active material and a binder for the electrode active material layer to prepare an electrode active material sheet, the electrode active material sheet and the present Examples thereof include a manufacturing method including a step of laminating the inorganic fine particle dispersion sheet of the present invention to prepare a laminated body and a step of firing the laminated body.

The electrode active material is not particularly limited, and for example, the same material as the inorganic fine particles can be used.

As the binder for the electrode active material layer, the (meth) acrylic resin can be used.

Examples of the method of laminating the electrode active material sheet and the inorganic fine particle dispersion sheet of the present invention include a method of thermocompression bonding by a hot press, heat laminating, and the like after forming each sheet.

In the firing step, the preferred lower limit of the heating temperature is 250 ° C., and the preferred upper limit is 350 ° C.

An all-solid-state battery can be obtained by the above manufacturing method.
The all-solid-state battery may have a structure in which a positive electrode layer containing a positive electrode active material, a negative electrode layer containing a negative electrode active material, and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer are laminated. preferable.

The method for manufacturing the laminated ceramics capacitor includes a step of printing and drying a conductive paste on the inorganic fine particle dispersion sheet of the present invention to prepare a dielectric sheet, and a step of laminating the dielectric sheets. Can be mentioned.

The conductive paste contains a conductive powder.
The material of the conductive powder is not particularly limited as long as it is a conductive material, and examples thereof include nickel, palladium, platinum, gold, silver, copper, and alloys thereof. These conductive powders may be used alone or in combination of two or more.

The method for printing the conductive paste is not particularly limited, and examples thereof include a screen printing method, a die coat printing method, an offset printing method, a gravure printing method, and an inkjet printing method.

In the method for manufacturing a laminated ceramic capacitor, a laminated ceramic capacitor can be obtained by laminating a dielectric sheet on which the conductive paste is printed.

According to the present invention, a molded product having excellent decomposability at low temperature, high fluidity and transparency, and high strength can be obtained, and further multi-layering and thinning can be realized, and excellent characteristics can be obtained. It is possible to provide an inorganic fine particle dispersion slurry composition capable of producing a ceramic laminate such as an all-solid-state battery or a laminated ceramic capacitor. Further, it is possible to provide a method for producing an inorganic fine particle dispersion sheet and an inorganic fine particle dispersion sheet using the inorganic fine particle dispersion slurry composition.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
(1) Preparation of (Meta) Acrylic Resin A 2L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen gas inlet was prepared. A total of 100 parts by weight of the monomers were placed in a 2 L separable flask so as to have the formulation shown in Table 1. Further, 50 parts by weight of butyl acetate was mixed as an organic solvent to obtain a monomer mixed solution.
The following monomers were used as the monomers.
iBMA: Isobutyl methacrylate nBMA: n-Butyl methacrylate EMA: Ethyl methacrylate MMA: Methyl methacrylate GMA: Glycidyl methacrylate 2EHMA: 2-ethylhexyl methacrylate

Dissolved oxygen was removed by bubbling the obtained monomer mixed solution with nitrogen gas for 20 minutes, and then the temperature was raised until the hot water bath boiled while replacing the inside of the separable flask system with nitrogen gas and stirring. A solution of the polymerization initiator diluted with butyl acetate was added. In addition, a butyl acetate solution containing a polymerization initiator was added several times during the polymerization.
After 7 hours from the start of the polymerization, the mixture was cooled to room temperature to complete the polymerization. As a result, a resin composition containing a (meth) acrylic resin was obtained.

(2) Preparation of Inorganic Fine Particle Dispersion Slurry Composition In 40 parts by weight of the obtained resin composition, Li ₂ SP ₂ S ₅ system glass (average particle diameter 2.0 μm) as inorganic fine particles and diadipate as a plasticizer (Butoxyethyl) and butyl acetate as an organic solvent were added at the blending ratios shown in Table 1 and kneaded with a high-speed stirrer to obtain an inorganic fine particle-dispersed slurry composition.

(Examples 2 and 3 and Comparative Examples 1 to 10)
In "(1) Preparation of (meth) acrylic resin", the monomer composition was changed as shown in Table 1 and the amount of the organic solvent added was as shown in Table 1 in the same manner as in Example 1 ((1) Preparation of (meth) acrylic resin). Meta) Acrylic resin was prepared.
An inorganic fine particle-dispersed slurry composition was prepared in the same manner as in Example 1 except that the obtained (meth) acrylic resin was used.

(Examples 4 to 24, Comparative Examples 11 and 12)
In "(1) Preparation of (meth) acrylic resin", the (meth) acrylic resin (A) was prepared in the same manner as in Example 1 except that the compounding of the monomer and the amount of the organic solvent added were changed as shown in Table 2. A resin composition (A) containing the resin composition (A) was prepared.
Further, in "(1) Preparation of (meth) acrylic resin", the (meth) acrylic resin (B) was the same as in Example 1 except that the compounding of the monomer and the amount of the organic solvent added were changed as shown in Table 2. ) Is contained in the resin composition (B). After cooling the resin compositions (A) and (B) to room temperature, they are mixed in a closed container so that the weight ratio of the resin solid content of the (meth) acrylic resin (A) and the (meth) acrylic resin (B) is 1: 1. Then, the mixture was kneaded under the condition of 80 ° C. for 4 hours to obtain a resin solution containing a mixture of the (meth) acrylic resin (A) and the (meth) acrylic resin (B).
Using the obtained resin solution, an organic solvent, a plasticizer, and inorganic fine particles were mixed so as to have the composition shown in Table 2, and the mixture was stirred with a high-speed stirrer to obtain an inorganic fine particle dispersion slurry composition.

<Evaluation>
The (meth) acrylic resin and the inorganic fine particle-dispersed slurry composition obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 3 and 4.

(1) Measurement of average molecular weight With respect to the obtained (meth) acrylic resin, LF-804 (manufactured by SHOKO) was used as a column, and the weight average molecular weight (Mw) and the number average molecular weight (Mw) in terms of polystyrene were measured by gel permeation chromatography. Mn) was measured. In Examples 4 to 24 and Comparative Examples 11 and 12, the obtained (meth) acrylic resin (A), (meth) acrylic resin (B), and (meth) acrylic resin (A) and (meth) were obtained. ) The mixture with the acrylic resin (B) was measured.

(2) Measurement of glass transition temperature The glass transition temperature (Tg) of the obtained (meth) acrylic resin was measured using a differential scanning calorimeter (DSC). Specifically, the temperature from room temperature to 150 ° C. was evaluated at a heating rate of 5 ° C./min under a nitrogen atmosphere at a flow rate of 50 mL / min. In Examples 4 to 24 and Comparative Examples 11 and 12, the obtained (meth) acrylic resin (A), (meth) acrylic resin (B), and (meth) acrylic resin (A) and (meth) were obtained. ) The mixture with the acrylic resin (B) was measured.

(3) Tensile Test The resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 10 are applied to a PET film that has been mold-released using an applicator, and dried in a 100 ° C. blowing oven for 10 minutes. , A resin sheet having a thickness of 20 μm was prepared on a PET film that had been mold-released. Using graph paper as a cover film, it was cut into strips with a width of 1 cm with scissors, and the resin sheet was peeled off from the film to prepare test pieces.
Further, test pieces were prepared in the same manner except that the resin solutions obtained in Examples 4 to 24 and Comparative Examples 11 and 12 were used.
The obtained test piece was subjected to a tensile test under the conditions of 23 ° C. and 50 RH using Autograph AG-IS (manufactured by Shimadzu Corporation) at a chuck distance of 3 cm and a tensile speed of 10 mm / min, and stress-strain characteristics (stress-strain characteristics). The presence or absence of yield stress, maximum stress measurement, and breaking elongation measurement) were confirmed. The results were evaluated according to the following criteria.
◯: Yield stress is indicated, the maximum stress is 20 N / mm ² or more, and the elongation at break is 50% or more.

(4) Sinterability The obtained inorganic fine particle-dispersed slurry composition was packed in an alumina pan of TG-DTA and heated at 10 ° C./min to evaporate the solvent and thermally decompose the resin and plasticizer. Then, the temperature at which the weight showed 36% by weight (90% by weight degreasing was completed) was measured and used as the decomposition end temperature. The obtained decomposition end temperature was evaluated according to the following criteria.
◯: When the decomposition end temperature exceeds 270 ° C and is 300 ° C or less ×: When the decomposition end temperature exceeds 300 ° C

(5) Transparency and fluidity The resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 10 and the resin solutions obtained in Examples 4 to 24 and Comparative Examples 11 and 12 were transferred to a glass bottle and in a state. Was visually confirmed. Transparency and fluidity were evaluated according to the following criteria.
<Transparency>
◯: It was transparent.
Δ: No turbidity was seen, but it was cloudy.
X: It was cloudy.
<Liquidity>
◯: Flowed smoothly when the container was tilted.
Δ: It flowed when the container was tilted, but it took a considerable amount of time for the swell on the liquid surface to flatten.
X: It was in the form of a sol or gel and did not flow smoothly when the container was tilted.

(6) Sheet Strength The inorganic fine particle-dispersed slurry composition obtained in Examples and Comparative Examples was applied to a PET film that had been mold-released by adjusting the gap so that the sheet thickness was 30 μm using an applicator. It was dried in an oven set at 100 ° C. for 30 minutes to obtain an inorganic fine particle dispersion sheet on a PET film that had been released from the mold.

The obtained inorganic fine particle dispersion sheet is cut into strips having a width of 1 cm, the inorganic fine particle dispersion sheet is peeled off from the film, and the sheet strength of the inorganic fine particle dispersion sheet is determined according to the following criteria in the same manner as in "(3) Tensile test". evaluated.
〇: When the maximum stress is 6 N / mm ² or more and the elongation at break is 10% or more ×: When other than the above 〇

(7) Sheet winding property The inorganic fine particle dispersion sheet obtained in "(6) Sheet strength" is cut into strips having a width of 1 cm, and a vinyl chloride pipe having a diameter of 10 cm is left in a state where the PET film that has been released from the mold is left. It was wrapped around and cured at room temperature for 1 week. After curing for 1 week, the PET film was peeled off, the state of the inorganic fine particle dispersion sheet was observed with a microscope, and the evaluation was made according to the following criteria.
〇: The sheet is not cracked or cracked and maintains a precise state.
X: Cracks and cracks were found on the surface and edges.

In the examples, excellent characteristics were confirmed in all the evaluations. In particular, in Examples 6 and 9 using a mixture of two kinds of (meth) acrylic resins (A) and (B), very high strength characteristics were obtained even though the molecular weight was not so high.
On the other hand, in the composition of the comparative example, the maximum stress and the elongation at break were low in the tensile test, the obtained resin sheet was brittle, and there was a problem in handleability when the ceramic green sheet was used.
In addition, the inorganic fine particle dispersion sheet obtained in the comparative example was brittle and crumbled when attached to the chuck of the tensile tester, causing a problem. Further, in the evaluation of the winding property of the inorganic fine particle dispersion sheet, the inorganic fine particle dispersion sheet obtained in the comparative example had cracks and cracks during curing, but the inorganic fine particle dispersion sheet obtained in the example was made of resins and plasticized. Since the compatibility with the agent was good, no cracks or cracks occurred even during long-term curing.

According to the present invention, an all-solid-state battery, a multilayer ceramic capacitor, etc., which have excellent decomposability at low temperatures, can obtain a molded product having high strength, realize further multi-layering and thin-filming, and have excellent characteristics. It is possible to provide an inorganic fine particle dispersion slurry composition capable of producing a ceramic laminate of. Further, it is possible to provide a method for producing an inorganic fine particle dispersion sheet and an inorganic fine particle dispersion sheet using the inorganic fine particle dispersion slurry composition.

Claims (10)

An inorganic fine particle dispersion slurry composition containing a (meth) acrylic resin, inorganic fine particles, and an organic solvent.
The (meth) acrylic resin has a weight average molecular weight (Mw) of 200,000 or more and 2 million or less, and a glass transition temperature (Tg) of 40 ° C. or more and 60 ° C. or less.
The (meth) acrylic resin contains 40% by weight or more and 60% by weight or less of a segment derived from isobutyl methacrylate, 20% by weight or more and 50% by weight or less of a segment derived from n-butyl methacrylate, and ethyl methacrylate. Contains 1% by weight or more and 40% by weight or less of the derived segment.
Inorganic fine particle dispersion slurry composition. The (meth) acrylic resin contains at least (meth) acrylic resin (A) and (meth) acrylic resin (B).
The (meth) acrylic resin (A) has a weight average molecular weight (Mw) of 200,000 or more and 2 million or less, a glass transition temperature (Tg) of 30 ° C. or more and 40 ° C. or less, and is derived from n-butyl methacrylate. 40% by weight or more and 70% by weight or less, and 30% by weight or more and 60% by weight or less of the segment derived from isobutyl methacrylate.
The (meth) acrylic resin (B) has a weight average molecular weight (Mw) of 50,000 or more and 1 million or less, a glass transition temperature (Tg) of 50 ° C. or more and 60 ° C. or less, and a segment derived from ethyl methacrylate. The inorganic fine particle dispersion slurry composition according to claim 1, which contains 30% by weight or more and 50% by weight or less, and 50% by weight or more and 70% by weight or less of a segment derived from isobutyl methacrylate. The inorganic fine particle dispersion slurry composition according to claim 2, wherein the (meth) acrylic resin (A) further contains a segment derived from ethyl methacrylate. The content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin (B) is 30% by weight based on the content of the segment derived from n-butyl methacrylate in the (meth) acrylic resin (A). The inorganic fine particle-dispersed slurry composition according to any one of claims 2 to 3, which is less than the above. The content of the segment derived from ethyl methacrylate in the (meth) acrylic resin (B) is 20% by weight or more higher than the content of the segment derived from ethyl methacrylate in the (meth) acrylic resin (A). The inorganic fine particle dispersion slurry composition according to any one of 2 to 4. Further, any one of claims 1 to 5, which contains a plasticizer, wherein the plasticizer is a non-aromatic plasticizer and has at least one selected from the group consisting of an ethyl group, a butyl group and a butoxyethyl group. The inorganic fine particle dispersion slurry composition according to. The inorganic fine particle dispersion slurry composition according to any one of claims 2 to 6, wherein the (meth) acrylic resin (B) further contains 1 to 10% by weight of a segment derived from the (meth) acrylic acid ester having a glycidyl group. Stuff. Claims 2 to 5 and 7 are characterized in that the (meth) acrylic resin (A) and the (meth) acrylic resin (B) are polymerized in separate containers, mixed, and heated and mixed at a temperature of 70 ° C. or higher. The inorganic fine particle dispersion slurry composition according to any one of. An inorganic fine particle dispersion sheet obtained by using the inorganic fine particle dispersion slurry composition according to any one of claims 1 to 8. A method for producing an inorganic fine particle dispersion sheet, which uses the inorganic fine particle dispersion slurry composition according to any one of claims 1 to 8.