CN115772330A - Inorganic microparticle dispersion slurry composition and method for producing inorganic microparticle dispersible tablet using same - Google Patents

Abstract

The present invention relates to a method for producing an inorganic particle-dispersed slurry composition and an inorganic particle-dispersed tablet using the same. The present invention provides an inorganic particle dispersion that is excellent in low-temperature decomposability, capable of degreasing perovskite-type inorganic materials below the Curie point, capable of suppressing deterioration of the magnetic force and piezoelectric properties of perovskite-type inorganic materials, and excellent in printability slurry composition. An inorganic microparticle dispersion slurry composition comprising (meth)acrylic resin (A), inorganic microparticles (B) and a solvent (C), wherein the inorganic microparticles (B) are a three-element system having a perovskite structure An inorganic material or a four-element inorganic material, wherein the (meth)acrylic resin (A) has at least one of a polypropylene glycol block segment and a polytetramethylene ether glycol block segment.

Description

Production of inorganic fine particle dispersion slurry composition and inorganic fine particle dispersion tablet using same method

technical field

The present invention relates to a method for producing an inorganic fine particle dispersion slurry composition and an inorganic fine particle dispersion tablet using the same.

Background technique

A composition obtained by dispersing inorganic fine particles such as ceramic powder and glass particles in a binder resin is used in the production of various electronic components. Among them, inorganic fine particles having a perovskite structure possessing excellent characteristics are used as functional inorganic materials in various fields.

Examples of functional inorganic materials having a perovskite structure include neodymium magnets (Nd ₂ Fe ₁₄ B), PZT piezoelectric elements (Pb(Zr,Ti)O ₃ ), LLTO electrolytes for all-solid batteries (Li _0.33 La _0.56 TiO ₃ ), etc. These functional inorganic materials are known to be composed of three or more elemental units, and the three elements exert various properties by forming a crystal structure called perovskite.

For example, regarding neodymium magnets, which are called the strongest magnets, an alloy containing neodymium, iron, and boron is pulverized to a size of a few microns with a jet mill, and then kneaded with a binder and a solvent to process it into inorganic fine particles Disperse slurry. Thereafter, it is formed by coating, pouring into a mold, pressing in a magnetic field, etc., and then degreasing and sintering in a firing furnace. Generally, cellulose resin etc. are used as a binder.

For example, in Patent Document 1, it is studied to form a thin film by sputtering a magnet component while heating a support to 250 to 400° C. near the Curie temperature. In addition, in Patent Document 2, the following content is studied: using a block polymer of polystyrene-b-poly(4-vinylpyridine) as an adhesive, and using a phase-separated structure formed by these polymers, The inorganic group is fired with an ideal structure.

prior art literature

patent documents

Patent Document 1: International Publication No. 2021/065254

Patent Document 2: Japanese Patent No. 6770704

Contents of the invention

The problem to be solved by the invention

According to the method described in Patent Document 1, since a binder is not used for film formation, there is no concern of thermal degradation associated with degreasing, but it is difficult to obtain an ideal perovskite crystal structure. In addition, in the method described in Patent Document 2, the decomposition temperature of polystyrene-b-poly(4-vinylpyridine) used as a binder is as high as that of cellulose, and it is necessary to degrease at 700° C. The high-temperature treatment for 6 hours required treatment at a temperature higher than the Curie temperature, and thus there was a problem of performance degradation.

The object of the present invention is to provide a product that is excellent in low-temperature decomposability, degreases the perovskite-type inorganic material below the Curie point, can suppress the deterioration of the magnetic force and piezoelectric characteristics of the perovskite-type inorganic material, and is also excellent in printability. Inorganic fine particle dispersion slurry composition. Another object of the present invention is to provide a method for producing an inorganic fine particle-dispersed tablet using the inorganic fine particle-dispersed slurry composition.

means to solve the problem

The present invention relates to an inorganic microparticle dispersion slurry composition, which contains (meth)acrylic resin (A), inorganic microparticles (B) and solvent (C), and the above-mentioned inorganic microparticles (B) have a perovskite structure In the 3-element inorganic material or the 4-element inorganic material, the (meth)acrylic resin (A) has at least one of a polypropylene glycol block segment and a polytetramethylene ether glycol block segment.

Hereinafter, the present invention will be described in detail.

The present inventors have found that by using (meth)acrylic resin (A) having polypropylene glycol block segments or polytetramethylene ether glycol block segments as the perovskite-type inorganic particles (B) The binder can be sintered at 300°C near the Curie temperature of inorganic particles. In addition, the inventors have found that it is possible to produce a molded article while maintaining the excellent characteristics of the perovskite-type inorganic fine particles (B), and have completed the present invention.

＜(Meth)acrylic resin (A)＞

The inorganic fine particle dispersion slurry composition of this invention contains (meth)acrylic resin (A).

The (meth)acrylic resin (A) has at least one of a polypropylene glycol block segment and a polytetramethylene ether glycol block segment.

By having the above-mentioned structure, the inorganic fine particles maintain a desired crystal structure even after firing, and the excellent characteristics of the inorganic fine particles having a perovskite structure can be maintained.

The inorganic fine particle dispersion slurry composition of the present invention preferably has the above-mentioned polypropylene glycol block segment or the above-mentioned polytetramethylene ether glycol block segment in the graft chain.

By making the (meth)acrylic resin (A) have a comb-shaped polymer structure having graft chains, it is easy to form an intramolecular phase separation structure, and the inorganic fine particles can more easily maintain the perovskite structure by firing.

When the average length of the main chain of the (meth)acrylic resin (A) is set to 100, the polypropylene glycol block segment and polytetramethylene ether bismuth in the above (meth)acrylic resin (A) The average length of the alcohol block segment is preferably 0.1 or more, preferably 5.0 or less.

When the above-mentioned average length is 0.1 or more, the effect of maintaining the properties of the inorganic fine particles having a perovskite structure can be sufficiently exhibited by introducing a block segment. When the above-mentioned average length is 5.0 or less, polymer chains are less likely to be entangled, and the printability of the inorganic fine particle-dispersed slurry composition can be sufficiently improved.

The above average length is preferably 1.0 or more, more preferably 2.0 or more, preferably 4.5 or less, more preferably 4.0 or less.

Regarding the average length of the above-mentioned polypropylene glycol block segment and polytetramethylene ether glycol block segment, it is obtained by setting the number average molecular weight (Mn) of the (meth)acrylic resin (A) to 100 The value converted from the ratio of the molecular weight of the polypropylene glycol block segment and the polytetramethylene ether glycol block segment. In addition, in the measurement of the number average molecular weight (Mn) of a (meth)acrylic resin based on polystyrene conversion mentioned later, there is no influence by the molecular weight of a graft chain. Therefore, from the ratio between the Mn of the (meth)acrylic resin (A) and the molecular weight of the polypropylene glycol block segment and the polytetramethylene ether glycol block segment, the ratio of Mn to the main chain can be obtained. average length, the average length of the grafted chains.

The above average length can be measured, for example, by GPC analysis comparison before and after saponification.

The composition ratio of the polypropylene glycol block segment and the polytetramethylene ether glycol block segment in the (meth)acrylic resin (A) is preferably 5% by weight or more, more preferably 7% by weight or more, Preferably it is 20 weight% or less, More preferably, it is 15 weight% or less.

When the above-mentioned composition ratio is 5% by weight or more, the effect of maintaining the characteristics of the inorganic fine particles having a perovskite structure can be sufficiently exhibited by introducing block segments. If the composition ratio is 20% by weight or less, the intramolecular phase separation structure will not contain too many island components, and the inorganic fine particles will more easily maintain the perovskite structure by firing.

In addition, the said composition ratio shows the weight ratio of only the graft chain part except a main chain part in a (meth)acrylic resin (A).

The said composition ratio can be measured, for example by evaluating the dry weight before and after saponification, or performing GPC analysis and comparison of (meth)acrylic resin.

When the above-mentioned (meth)acrylic resin (A) has the above-mentioned polypropylene glycol block segment or the above-mentioned polytetramethylene ether glycol block segment in the graft chain, the above-mentioned (meth)acrylic resin (A) ), the content of the block segment as the graft chain is preferably 5% by weight or more, more preferably 7% by weight or more, preferably 20% by weight or less, more preferably 15% by weight or less.

When the content of the block segment as the graft chain is 5% by weight or more, the effect of maintaining the properties of the inorganic fine particles having a perovskite structure can be sufficiently exhibited by introducing the block segment. If the content of the block segment as the above-mentioned graft chain is 20% by weight or less, the island component will not become too much in the intramolecular phase separation structure, and the inorganic fine particles will more easily maintain the perovskite by firing. structure.

In addition, the said content shows the weight ratio of the structural unit which has the said graft chain in (meth)acrylic resin (A).

The content of the block segment as the above-mentioned graft chain can be obtained, for example, by saponifying (meth)acrylic resin with aqueous sodium hydroxide solution to hydrolyze the ester chain, and obtaining The oil droplet component was separated, the weight of the dried oil droplet component and the saponified (meth)acrylic resin (A) as a whole was measured, and the composition ratio of the block segment as a graft chain was calculated from the following formula.

Content of block segments as grafted chains = (weight of dried oil droplet component/weight of saponified (meth)acrylic resin (A)) x 100

The above-mentioned (meth)acrylic resin (A) preferably has a segment derived from isobutyl methacrylate.

By having a segment derived from isobutyl methacrylate, the low-temperature decomposability of the (meth)acrylic resin (A) can be further improved.

The content of the isobutyl methacrylate-derived segment in the (meth)acrylic resin (A) is preferably 50% by weight or more, and preferably 80% by weight or less.

When the said content is 50 weight% or more, the low temperature decomposability of a (meth)acrylic-type resin (A) can be improved more. When the above-mentioned content is 80% by weight or less, the block segment can be sufficiently introduced into the (meth)acrylic resin (A), and the effect of introducing the block segment can be sufficiently exhibited.

The content of the segment derived from isobutyl methacrylate in the (meth)acrylic resin (A) is more preferably 55% by weight or more, still more preferably 60% by weight or more, and still more preferably 75% by weight or less, More preferably, it is 70 weight% or less.

By setting it as the said range, low-temperature decomposability and printability will fully improve, and inorganic microparticles|fine-particles will maintain a perovskite structure more easily.

The content of the isobutyl methacrylate-derived segment in the (meth)acrylic resin (A) is preferably 50 mol % or more, preferably 80 mol % or less.

The low-temperature decomposability of a (meth)acrylic resin (A) can be further improved that the said content is 50 mol% or more. When the said content is 80 mol% or less, a block segment can be fully introduced into a (meth)acrylic resin (A), and the effect of introducing a block segment can fully be exhibited.

The content of the segment derived from isobutyl methacrylate in the (meth)acrylic resin (A) is more preferably 55 mol % or more, still more preferably 60 mol % or more, more preferably 75 mol % or less, More preferably, it is 70 mol% or less.

By setting it as the said range, low-temperature decomposability and printability will fully improve, and inorganic microparticles|fine-particles will maintain a perovskite structure more easily.

The said content can be measured by thermal decomposition GC-MS, for example.

The above-mentioned (meth)acrylic resin (A) may have a segment other than a polypropylene glycol block segment, a polytetramethylene ether glycol block segment, and a segment derived from isobutyl methacrylate. .

As said other segment, the segment etc. which originate in the C1 to 10 (meth)acrylate of the carbon number of an ester substituent are mentioned.

The glass transition temperature of (meth)acrylic-type resin (A) can be raised by containing the segment of (meth)acrylic acid ester with carbon number 1-10 derived from the said ester substituent. In addition, brittleness can be improved.

Examples of (meth)acrylates having a carbon number of 1 to 10 in the ester substituent include alkyl (meth)acrylates having straight-chain alkyl groups having 1 to 10 carbons, branched Shaped (meth)acrylates, cyclic (meth)acrylates, etc.

More specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate ester, n-hexyl (meth)acrylate, etc. Also, isopropyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, etc. In addition, cyclohexyl (meth)acrylate etc. are mentioned.

Among them, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate are preferred, methyl methacrylate, methyl Ethyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate.

The content of the (meth)acrylic acid ester segment derived from the ester substituent having 1 to 10 carbon atoms in the (meth)acrylic resin (A) is preferably 1% by weight or more, more preferably 10% by weight or more, preferably 40% by weight or less, more preferably 30% by weight or less.

Moreover, as said other segment, the (meth)acrylate which has a glycidyl group, the (meth)acrylate which has a hydroxyl group or a carboxyl group, etc. are mentioned other than these.

Examples of (meth)acrylates having a glycidyl group include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate. wait.

Examples of (meth)acrylates having a hydroxyl or carboxyl group include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, (meth) Acrylic etc.

The content of the other segments in the (meth)acrylic resin is preferably 1% by weight or more, more preferably 4% by weight or more, preferably 10% by weight or less, more preferably 7% by weight or less.

By setting it as the said range, the low-temperature decomposability of a (meth)acrylic-type resin (A) can fully be improved, and the toughness of the inorganic fine particle dispersion sheet obtained can be improved.

The weight average molecular weight (Mw) of the (meth)acrylic resin (A) is preferably 20,000 or more, and preferably 100,000 or less.

When the said Mw is 20,000 or more, the viscosity of the inorganic fine particle dispersion slurry composition will not become low too much, and the dispersibility of an inorganic fine particle can be made favorable. When the said Mw is 100,000 or less, the printability of the inorganic fine particle dispersion slurry composition can be made favorable.

The aforementioned Mw is preferably 30,000 or more, more preferably 40,000 or more, preferably 80,000 or less, more preferably 70,000 or less.

In addition, the number average molecular weight (Mn) of the (meth)acrylic resin (A) is preferably 10,000 or more, more preferably 15,000 or more, preferably 40,000 or less, more preferably 35,000 or less.

Furthermore, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (meth)acrylic resin (A) is preferably 1.5 or more and preferably 5 or less.

By setting it as the said range, since the component with a low degree of polymerization is contained moderately, the viscosity of the inorganic fine particle dispersion slurry composition becomes a desirable range, and productivity can be improved. In addition, it is possible to moderate the tablet strength of the obtained inorganic fine particle disperse tablet. In addition, the surface smoothness of the obtained ceramic green sheet can be sufficiently improved.

The above-mentioned Mw/Mn is more preferably 2 or more, and more preferably 3 or less.

It should be noted that 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 GPC measurement using, for example, a column LF-804 (manufactured by Showa Denko Co., Ltd.) .

The glass transition temperature (Tg) of the (meth)acrylic resin (A) is preferably 30°C or higher, more preferably 40°C or higher, preferably 80°C or lower, more preferably 70°C or lower.

In addition, the said glass transition temperature (Tg) can be measured using a differential scanning calorimeter (DSC), etc., for example.

The content of the (meth)acrylic resin (A) in the inorganic fine particle dispersion slurry composition of the present invention is not particularly limited, but is preferably 5% by weight or more and preferably 30% by weight or less.

By making content of the said (meth)acrylic resin into the said range, even if it bakes at low temperature, it can be set as the inorganic fine particle dispersion slurry composition which can degrease.

The content of the (meth)acrylic resin is more preferably 6% by weight or more, and more preferably 12% by weight or less.

The method for producing the above-mentioned (meth)acrylic resin (A) is not particularly limited, for example, the following method is mentioned: first, add (meth)acrylic acid containing (meth)acrylic acid, glycidyl (meth)acrylate, etc. An organic solvent or the like is added to the raw material monomer mixture of the ester to prepare a monomer mixed liquid. Furthermore, a polymerization initiator is added to the obtained monomer mixed liquid to perform polymerization to prepare a raw material (meth)acrylic resin. Next, react a compound having a propylene glycol chain, a compound having a polytetramethylene ether glycol chain, and a raw material (meth)acrylic resin to introduce propylene glycol block segments, polytetramethylene ether glycol block chains, etc. The (meth)acrylic resin (A) is prepared by segmenting the segments.

In addition, the method of reacting polypropylene glycol, polytetramethylene ether glycol, maleic anhydride, 2-methacryloyloxyethyl isocyanate, etc. Monomer of tetramethylene ether glycol block segment. Next, the obtained monomer is mixed with (meth)acrylate, etc. to prepare a raw material monomer mixture, further, an organic solvent, etc. are added to prepare a monomer mixed liquid, and further, the obtained monomer is mixed with A polymerization initiator was added in a liquid to perform polymerization to prepare a (meth)acrylic resin (A).

In addition, methods such as mixing and reacting (meth)acrylic acid esters such as (meth)acrylic acid and glycidyl (meth)acrylate, polypropylene glycol and polytetramethylene ether glycol, A (meth)acrylic resin (A) is produced.

The method for performing polymerization is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among them, solution polymerization is preferable.

Examples of the polymerization initiator include dilauroyl peroxide, p-menthane hydroperoxide, dicumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, peroxide Hydrogen cumene, tert-butyl hydroperoxide, cyclohexanone peroxide, disuccinic acid peroxide, etc.

Examples of these commercially available products include PERMENTA H, PERCUMYL P, PEROCTA H, PERCUMYL H-80, PEROYL 355, PERBUTYL H-69, PERHEXA H, PEROYL SA, PEROYL L (all manufactured by NOF Corporation), Trigonox 27. Trigonox 421 (both manufactured by Nouryon Company) and the like.

＜Inorganic particles (B)＞

The inorganic fine particle dispersion slurry composition of this invention contains an inorganic fine particle (B).

The above-mentioned inorganic fine particles (B) are tri-element or quadruple-element inorganic materials having a perovskite structure.

The so-called perovskite structure is an inorganic particle having the same crystal structure as perovskite CaTiO ₃ , and basically contains the three constituent elements of ABX ₃ , A atoms are arranged at the body center of the cubic crystal, and B atoms are arranged at each vertex , X atoms are arranged at the face centers of the cubic crystal. In addition, it may be a quaternary element system such as PZT (Pb(ZrTi)O ₃ ) which is a mixed crystal of lead zirconate (PbZrO ₃ ) and lead titanate (PbTiO ₃ ).

Like Nd ₂ Fe ₁₄ B (Curie point temperature 312°C) and PbZrTiO ₃ (Curie point temperature 350°C), many perovskite-type inorganic particles have a Curie point at around 300°C. By firing at 300°C, which is the point temperature, it is possible to manufacture inorganic material products that maintain their original characteristics.

Combining the above-mentioned inorganic fine particles (B) having a perovskite structure and the above-mentioned (meth)acrylic resin (A) to prepare an inorganic fine particle dispersion slurry composition, and further firing to obtain an inorganic fine particle dispersion molded body , whereby a molded body can be obtained without impairing the excellent characteristics of the inorganic fine particles having a perovskite structure.

Inorganic fine particles (B) having a perovskite structure are not particularly limited, and include: Sm ₂ Fe ₁₇ N ₃ , Nd ₂ Fe ₁₄ B, MnAlC, L ₁₀ FeNi, La _2/3-x Li _3x TiO ₃ , La _(1-x)/3 Li _x NbO ₃ , LaGaO ₃ , LaScO ₃ , CaZrO ₃ , (La _0.875 Sr _0.125 )MnO ₃ , Pb(Zr,Ti)O ₃ , SrBi ₂ Ta ₂ O ₉ , BiFeO ₃ , KNbO _3. PbVO ₃ , BiCo ₃ , Bi(Zn _1/2 Ti _1/2 ) ₃ , etc. Among them, Nd ₂ Fe ₁₄ B and Pb(Zr,Ti)O ₃ are preferable.

The content of the above-mentioned inorganic fine particles (B) in the inorganic fine particle dispersion slurry composition of the present invention is preferably 40% by weight or more, preferably 90% by weight or less.

When the said content is 40 weight% or more, the density of the inorganic fine particle (B) in a molded object can fully be raised. When the said content is 90 weight% or less, the dispersibility of an inorganic fine particle (B) can be fully made, and moldability can be improved.

The content of the above-mentioned inorganic fine particles (B) is preferably 50% by weight or more, preferably 80% by weight or less.

If it is the said range, the coatability and printability of the inorganic fine particle dispersion slurry composition can fully be improved, and the compact molded object after firing can be obtained.

The average particle diameter of the inorganic fine particles (B) is preferably 0.1 μm or more, more preferably 0.5 μm or more, preferably 100 μm or less, more preferably 50 μm or less.

By setting it as the said range, the specific surface area of an inorganic fine particle (B) does not become large too much, binder residue can be reduced, and a dense molded object can be obtained by firing.

The said average particle diameter can be measured, for example by observing with SEM.

＜Solvent (C)＞

The inorganic fine particle dispersion slurry composition of the present invention contains an organic solvent.

The above-mentioned organic solvent is not particularly limited, and is preferably an organic solvent excellent in applicability, drying property, dispersibility of inorganic powder, etc. when producing an inorganic fine particle dispersible tablet.

For example, toluene, ethyl acetate, butyl acetate, hexyl acetate, isopropanol, methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol ethyl ether, ethyl Glycol Monobutyl Ether, Ethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoisobutyl Ether, Trimethylpentanediol Monoisobutyrate , Butyl Carbitol, Butyl Carbitol Acetate, Terpineol, Terpineol Acetate, Dihydroterpineol, Dihydroterpineol Acetate, TEXANOL, Isophorone, Lactic Acid Butyl esters, dioctyl phthalate, dioctyl adipate, benzyl alcohol, propylene glycol, cresol, ethyl carbitol acetate, etc. Among them, butyl acetate, hexyl acetate, ethyl carbitol acetate, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol acetate, diethylene glycol Monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, butyl carbitol acetate, TEXANOL. Moreover, butyl acetate, hexyl acetate, terpineol, and ethyl carbitol acetate are more preferable. It should be noted that such organic solvents may be used alone or in combination of two or more.

The boiling point of the above-mentioned organic solvent is preferably 90 to 230°C. When the said boiling point is 90 degreeC or more, evaporation will not become too fast, and the inorganic fine particle dispersion slurry composition excellent in handling property can be obtained. When the above-mentioned boiling point is 230° C. or lower, the inorganic fine particle dispersion slurry composition is less likely to be dried, and excellent printability can be obtained.

The content of the organic solvent in the inorganic fine particle dispersion slurry composition of the present invention is not particularly limited, but the lower limit is preferably 10% by weight, and the upper limit is preferably 60% by weight. By setting it as the said range, coatability and the dispersibility of an inorganic fine particle can be improved.

＜Other＞

The inorganic fine particle dispersion slurry composition of the present invention may further contain a plasticizer.

Examples of the plasticizer include: bis(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl ether, triethylene glycol bis (2-Ethylhexanoate), Triethylene Glycol Dihexanoate, Triethyl Acetyl Citrate, Tributyl Acetyl Citrate, Diethyl Acetyl Citrate, Dibutyl Acetyl Citrate, Sebacic Acid Dibutyl ester, triacetin, diethyl acetoxymalonate, diethyl ethoxymalonate, etc.

By using these plasticizers, compared with the case of using common plasticizers, the amount of plasticizer added can be reduced (when adding about 30% by weight relative to the binder, it can be reduced to 25% by weight or less, It can further be 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 its structure, and it is more preferable to use a component derived from adipic acid, triethylene glycol, citric acid, or succinic acid. In addition, since the plasticizer which has an aromatic ring burns easily and becomes soot, it is unpreferable.

In addition, as the above-mentioned plasticizer, a plasticizer having an alkyl group having 2 or more carbon atoms such as an ethyl group or a butyl group is preferable, and a plasticizer having an alkyl group having 4 or more carbon atoms is more preferable.

The above-mentioned plasticizer contains an alkyl group having 2 or more carbon atoms, thereby suppressing the absorption of water into the plasticizer, and preventing defects such as voids and swelling in the obtained inorganic fine particle dispersed sheet. In particular, it is preferable that the alkyl group of the plasticizer is located at a molecular terminal.

In addition, 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, or a functional group such as a butoxyethyl group. It is preferable that the above-mentioned functional group exists at a molecular terminal.

A plasticizer having a functional group having 2 carbons such as an ethyl group at the end of the molecule has good compatibility with a segment derived from ethyl methacrylate, and a plasticizer having a functional group having 4 carbons such as a butyl group at the end of the molecule The compatibility of the agent with the segment derived from butyl methacrylate is good. 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. In addition, the butoxyethyl group has good compatibility with the composition of both the ethyl methacrylate-derived segment and the butyl methacrylate-derived segment, and can be preferably used.

Among the above plasticizers, the carbon:oxygen ratio is preferably 5:1 to 3:1.

By making the carbon:oxygen ratio into the above-mentioned range, the combustibility of the plasticizer can be improved and generation of residual carbon can be prevented. Moreover, compatibility with (meth)acrylic resin can be improved, and even a small amount of plasticizer can exhibit a plasticizing effect.

In addition, high-boiling-point organic solvents having a propylene glycol skeleton or a trimethylene glycol skeleton can be preferably used if they also contain an alkyl group having 4 or more carbon atoms and have a carbon:oxygen ratio of 5:1 to 3:1.

The boiling point of the above-mentioned plasticizer is preferably 240°C or more and less than 390°C. By making the said boiling point into 240 degreeC or more, it becomes easy to evaporate in a drying process, and it can prevent remaining in a molded object. Moreover, generation|occurrence|production of residual carbon can be prevented by setting it as less than 390 degreeC. In addition, the said boiling point means the boiling point under normal pressure.

The content of the plasticizer in the inorganic fine particle dispersion slurry composition of the present invention is not particularly limited, but the lower limit is preferably 0.1% by weight, and the upper limit is preferably 3.0% by weight. By setting it as the said range, the baking residue of a plasticizer can be reduced.

The inorganic fine particle dispersion slurry composition of the present invention may further contain additives such as surfactants.

The said surfactant is not specifically limited, For example, cationic surfactant, anionic surfactant, and nonionic surfactant are mentioned.

The above-mentioned 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 so-called HLB value is a value used as an index showing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed, for example, the following definitions: For ester-based surfactants, Let the saponification value be S, let the acid value of the fatty acid which comprises a surfactant be A, and let the HLB value be 20 (1-S/A). Specifically, a nonionic surfactant having polyoxyethylene added to an aliphatic chain with an alkylene ether is preferred. Specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene cetyl ether are preferably used. base ether etc. In addition, the thermal decomposability of the said nonionic surfactant is good, but when added in large quantities, the thermal decomposability of the inorganic fine particle dispersion slurry composition may fall, Therefore The preferable upper limit of content is 5 weight%.

The viscosity of the inorganic particle dispersion slurry composition of the present invention is not particularly limited, and the preferred lower limit of the viscosity when measured at 20° C. using a B-type viscometer and setting the probe rotation speed at 5 rpm is 0.1 Pa·s, and the preferred upper limit is is 100Pa·s.

By setting the above-mentioned 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 coating printing method or the like. Moreover, by making the said viscosity into 100 Pa*s or less, troubles, such as die|dye smear marks (Japanese: smear marks) not disappearing, can be prevented, and printability is excellent.

The method for preparing the inorganic fine particle dispersion slurry composition of the present invention is not particularly limited, and conventionally known stirring methods may be mentioned. Specifically, for example, the following: mixing the above-mentioned (meth)acrylic resin (A), the above-mentioned inorganic A method in which fine particles (B), the solvent (C) and, if necessary, other components such as a plasticizer are stirred with a three-roll machine or the like.

An inorganic fine particle dispersed sheet can be produced by applying and drying the inorganic fine particle dispersion slurry composition of the present invention to produce a sheet, and further firing the obtained sheet at a temperature of 350° C. or lower.

A method for producing an inorganic fine particle dispersed sheet comprising a step of applying and drying the inorganic fine particle dispersed slurry composition of the present invention to obtain a sheet, and a step of firing the sheet at 350°C or lower is also one of the present invention.

An inorganic fine particle dispersion sheet can be produced by applying the inorganic fine particle dispersion slurry composition of the present invention on a support film subjected to one-sided mold release treatment, drying the organic solvent, and forming it into a sheet.

The thickness of the dispersed inorganic fine particle sheet of the present invention is preferably 1 to 20 μm.

The printing and molding methods of the inorganic particle dispersion slurry composition of the present invention are not particularly limited, and a screen plate with a U-shaped opening is applied alternately up and down to form a coil shape, or directly printed on a substrate to form a laminate, or The substrate may be dip-coated with the inorganic fine particle dispersion slurry composition. By using an organic solvent with a high boiling point, it is possible to perform molding by screen printing or the like.

In addition, as the above-mentioned coating method, for example, the inorganic particle dispersion slurry composition of the present invention is uniformly coated on a support by a coating method such as a roll coater, a die coater, an extrusion coater, or a curtain coater. A method of forming a coating film on a film, etc.

As a method of the said drying, heat drying etc. are mentioned, for example. The drying temperature is preferably 80 to 130°C.

The support film used in the production of the inorganic fine particle disperse tablet of the present invention is preferably a resin film having heat resistance and solvent resistance and flexibility. By making the support film flexible, the inorganic fine particle dispersion slurry composition can be coated on the surface of the support film by a roll coater, a doctor blade coater, etc., and the obtained inorganic fine particle dispersion sheet can be formed into a film in a roll It is stored and supplied in a rolled state.

Examples of resins that form the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluorinated Fluorine-containing resins such as vinyl, nylon, cellulose, etc.

The thickness of the support film is preferably, for example, 20 to 100 μm.

In addition, it is preferable to perform a release treatment on the surface of the support film, thereby facilitating the peeling operation of the support film in the transfer step.

In the above-mentioned firing step, the heating temperature is preferably not more than 350°C and not less than 250°C.

For example, in the inorganic particle dispersion slurry composition of the present invention, when using Nd ₂ Fe ₁₄ B as the inorganic particle (B), the above-mentioned slurry is printed on a ferrite magnet substrate and dried, and magnetic pressing (Japanese: magnetic force press), firing at about 300°C while orienting magnetically. Accordingly, it is possible to manufacture a neodymium magnet in which a decrease in magnetic force is suppressed.

In addition, for example, in the inorganic fine particle dispersion slurry composition of the present invention, Li _0.33 La _0.56 TiO ₃ (LLTO) is used as the inorganic fine particle (B) to prepare a slurry composition, and then perform solid printing on the negative electrode Li foil. Drying, and lamination with a positive electrode sheet containing the same Li _0.33 La _0.56 TiO ₃ (LLTO) as inorganic fine particles (B), acetylene black as a conductive additive, and niobium lithium oxide as a positive electrode active material, at 300°C By firing, an all-solid-state battery with a large capacity can be manufactured.

When the sintering properties of the inorganic fine particles (B) are not sufficient when firing at about 300° C., borosilicate, phosphate, or the like may be added as a sintering aid.

In addition, a multilayer ceramic 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 or an electrode paste.

As a method of manufacturing the above-mentioned all-solid-state battery, a manufacturing method having the following steps: forming an electrode active material layer slurry containing an electrode active material and a binder for an electrode active material layer to produce an electrode active material sheet Steps; a step of laminating the above-mentioned electrode active material sheet and the dispersed inorganic fine particle sheet of the present invention to form a laminate; and a step of firing the above-mentioned laminate.

The above-mentioned electrode active material is not particularly limited, and for example, the same material as that of the above-mentioned inorganic fine particles is used.

The above-mentioned (meth)acrylic resin can be used for the said binder for electrode active material layers.

As a method of laminating the above-mentioned electrode active material sheet and the inorganic fine particle dispersed sheet of the present invention, there may be mentioned a method of performing thermocompression bonding by thermocompression, thermal lamination, etc. after forming the sheets respectively.

In the above-mentioned firing step, the lower limit of the heating temperature is preferably 250°C, and the upper limit of the heating temperature is 350°C.

When the heating temperature is within the above range, the excellent properties of the inorganic fine particles (B) can be maintained.

Through the above-mentioned manufacturing method, an all-solid-state battery can be obtained.

The above-mentioned all-solid-state battery preferably has 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.

As a method of manufacturing the above-mentioned laminated ceramic capacitor, a manufacturing method including the steps of printing a conductive paste on the inorganic fine particle dispersion sheet of the present invention and drying to prepare a dielectric sheet; and stacking the dielectric sheet is mentioned.

The above-mentioned conductive paste contains conductive powder.

The material of the conductive powder is not particularly limited as long as it has conductivity, 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 of printing the said conductive paste is not specifically limited, For example, the screen printing method, the die-coating printing method, the offset printing method, the gravure printing method, the inkjet printing method etc. are mentioned.

In the above-mentioned method for producing a multilayer ceramic capacitor, the dielectric sheets on which the above-mentioned conductive paste is printed are stacked to obtain a multilayer ceramic capacitor.

Invention effect

According to the present invention, it is possible to provide excellent low-temperature decomposability, degreasing of perovskite-type inorganic materials below the Curie point, suppression of deterioration of magnetic force and piezoelectric properties of perovskite-type inorganic materials, and excellent printability. Inorganic particle dispersion slurry composition. In addition, a method for producing an inorganic fine particle-dispersed sheet using the inorganic fine particle-dispersed slurry composition can be provided.

Detailed ways

Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

(Manufacturing example 1)

A 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet was prepared. 60 parts by weight of isobutyl methacrylate (iBMA), 5 parts by weight of glycidyl methacrylate (GMA), and 30 parts by weight of n-butyl methacrylate (nBMA) were added to a 2 L separable flask. Further, it was mixed with 500 parts by weight of butyl acetate as an organic solvent to obtain a monomer mixed liquid.

After bubbling the obtained monomer mixture liquid with nitrogen gas for 20 minutes to remove dissolved oxygen, the inside of the separable flask system was replaced with nitrogen gas, and the internal temperature was set to 80°C while stirring, and addition was performed with butyl acetate. dilute polymerization initiator solution. In addition, the polymerization initiator solution was added several times during the polymerization. In addition, dilauroyl peroxide was used as a polymerization initiator.

After 7 hours from the start of the polymerization, the polymerization was completed by cooling to room temperature, and a composition containing a (meth)acrylic resin was obtained.

5 parts by weight of polypropylene glycol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., propylene glycol segment length: 1500) and 2 parts by weight of 0.01N hydrochloric acid were added to the resin composition as a block segment, and reacted at 80° C. for 2 hours. As a result of evaluating the remaining polypropylene glycol by GPC and FTIR, it was found that almost all of it was provided to the (meth)acrylic resin as a graft chain. Thus, a (meth)acrylic resin (A) having a polypropylene glycol block segment as a graft chain was obtained.

The obtained (meth)acrylic resin (A) was dried in an oven, dissolved in THF so that the resin concentration was 0.1% by weight, and the polystyrene-equivalent molecular weight was measured by GPC using SHODEX LF-804 as a column. Yes, the number average molecular weight is 30,000, and the weight average molecular weight is 60,000.

In addition, the dried (meth)acrylic resin (A) is hydrolyzed with an ester chain by saponification with an aqueous sodium hydroxide solution. Acrylic resin dissolves in water, and the oil droplet-like component separates.

The separated oil drop-shaped component was dried and measured, and the content of the block segment as a graft chain with respect to the whole (meth)acrylic resin (A) was calculated by the following formula, and it was 10% by weight.

In addition, the molecular weight of the oil droplet-shaped component was confirmed by GPC, and the number average molecular weight was confirmed to be 1500. In addition, the number average molecular weight of the (meth)acrylic resin (A) after saponification was measured and calculated. When the average length is set to 100, the average length of the polypropylene glycol block segment as the graft chain is 5.

In addition, the ratio of the iBMA segment was confirmed by thermal decomposition GC-MS, and it was 60% by weight.

It should be noted that in Table 1, the content of the graft chain represents the weight ratio of the structural units having the graft chain in the (meth)acrylic resin (A), and the composition ratio of the graft chain represents the weight ratio of the (meth)acrylic resin (meth)acrylic resin (A). The ratio by weight of only the graft chain portion other than the main chain portion in the resin (A).

(Manufacturing example 2)

A 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet was prepared. Add 5 parts by weight of maleic anhydride, 10 parts by weight of polypropylene glycol (propylene glycol segment length: 230), and 40 parts by weight of ethyl carbitol acetate (boiling point: 217° C.) as a solvent in a 2 L separable flask, and place in a nitrogen atmosphere. Under stirring at 150° C. for 2 hours, the maleic anhydride and polypropylene glycol were reacted. Furthermore, 60 parts by weight of iBMA and 25 parts by weight of methyl methacrylate (MMA) were added. Furthermore, 700 parts by weight of ethyl carbitol acetate as an organic solvent was added and mixed to obtain a monomer mixed liquid. The polymerization initiator was added in divided portions while adjusting the liquid temperature to be 80° C., and the polymerization was completed.

When measured by GPC in the same manner, the number average molecular weight was 10,000 and the weight average molecular weight was 20,000.

In addition, as a result of evaluating the remaining polypropylene glycol by GC-MS, it was found that almost all of it was provided to the (meth)acrylic resin as a graft chain. Thus, a (meth)acrylic resin (A) having a polypropylene glycol block segment as a graft chain was obtained.

(Manufacturing example 3)

A 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet was prepared. In another flask, 4.6 parts by weight of 2-methacryloxyethyl isocyanate (manufactured by Showa Denko, Karenz MOI) and 5.4 parts by weight of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, PTMG250) were added, The reaction was carried out at 60° C. for 2 hours under a nitrogen atmosphere to obtain a methacrylic monomer having a polytetramethylene ether glycol chain.

10 parts by weight of the obtained methacrylic monomer was transferred to a 2L separable flask, and 70 parts by weight of iBMA, 20 parts by weight of 2-ethylhexyl methacrylate (2EHMA), and hexyl acetate as an organic solvent were added. 20 parts by weight of ester (boiling point 170°C), and polymerized by adding a polymerization initiator several times at 80°C under a nitrogen atmosphere to obtain a (meth)acrylic acid having a polytetramethylene ether glycol block segment Resin (A).

When measured by GPC in the same manner, the number average molecular weight was 200,000, and the weight average molecular weight was 400,000.

(Manufacturing example 4)

A 100mL separable flask was provided with a fractionation tube Wittmer (Japanese: ウィットマー), an L-shaped connecting tube, and a Dimroth cooling tube, and 20 parts by weight of methacrylic acid (MAc), polytetramethylene ether glycol ( Molecular weight 1000) 200 parts by weight were mixed and reacted at 120° C. for 1 hour while decompressing to −0.1 MPa with a vacuum pump. The reaction solution was diluted with chloroform, and unreacted MAc was removed using an LC column. Chloroform was evaporated with an air blower to obtain a (meth)acrylic resin having a polytetramethylene ether glycol block segment.

20 parts by weight of the obtained (meth)acrylic resin, 50 parts by weight of iBMA, ethyl methacrylate (EMA ) 20 parts by weight, 10 parts by weight of 2EHMA, 400 parts by weight of terpineol as an organic solvent, add a polymerization initiator several times at 80°C under a nitrogen atmosphere and polymerize to obtain polytetramethylene ether glycol with polytetramethylene ether glycol Block segment (meth)acrylic resin (A).

When measured in the same manner by GPC, the number average molecular weight was 20,000, and the weight average molecular weight was 40,000.

(Manufacturing example 5)

A 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet was prepared. 40 parts by weight of propylene glycol monomethacrylate (PMA), 40 parts by weight of iBMA, and 20 parts by weight of nBMA were added to a 2 L separable flask. Furthermore, 100 parts by weight of butyl acetate was added and mixed as an organic solvent to obtain a monomer mixed liquid.

After bubbling the obtained monomer mixture liquid with nitrogen gas for 20 minutes to remove dissolved oxygen, the inside of the separable flask system was replaced with nitrogen gas, and the internal temperature was set to 80°C while stirring, and addition was performed with butyl acetate. dilute polymerization initiator solution. The polymerization initiator solution was added several times during the polymerization.

After 7 hours from the start of the polymerization, it was cooled to room temperature to complete the polymerization. Thereby, the (meth)acrylic resin (A) which has a propylene oxide group is obtained.

When measured in the same manner by GPC, the number average molecular weight was 100,000, and the weight average molecular weight was 200,000.

(Manufacturing example 6)

A 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet was prepared. 10 parts by weight of stearyl methacrylate (SMA), 80 parts by weight of iBMA, and 10 parts by weight of MMA were added to a 2 L separable flask as a monomer having a long-chain ester substituent. Furthermore, 90 parts by weight of ethyl carbitol acetate (217 degreeC of boiling point) was added and mixed as an organic solvent, and the monomer mixed liquid was obtained.

While adjusting the obtained monomer mixture liquid so that it might become 80 degreeC, the polymerization initiator was added in multiple times, and polymerization was completed, and the (meth)acrylic-type resin (A) which has a stearyl group was obtained.

When measured in the same manner by GPC, the number average molecular weight was 100,000, and the weight average molecular weight was 200,000.

(Manufacturing example 7)

A 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet was prepared. 4 parts by weight of polyethylene glycol monomethacrylate, 70 parts by weight of iBMA, and 26 parts by weight of 2EHMA were added to a 2 L separable flask as a monomer having a polyethylene glycol block. Furthermore, 600 parts by weight of hexyl acetate (170 degreeC of boiling point) was added and mixed as an organic solvent, and the monomer mixed liquid was obtained.

While adjusting the obtained monomer mixture to 80° C., a polymerization initiator was added in several batches to complete the polymerization, and a (meth)acrylic resin (A) having a polyethylene glycol block segment was obtained. ).

When measured in the same manner by GPC, the number average molecular weight was 20,000, and the weight average molecular weight was 40,000.

(Manufacturing example 8)

A 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet was prepared. 20 parts by weight of butanediol monomethacrylate, 40 parts by weight of iBMA, and 40 parts by weight of EMA were added to a 2 L separable flask as a monomer having a tetramethylene structure in an ester substituent. Furthermore, 200 parts by weight of hexyl acetate (170 degreeC of boiling point) was added and mixed as an organic solvent, and the monomer mixed liquid was obtained.

While adjusting the obtained monomer mixture liquid so that it might become 80 degreeC, the polymerization initiator was added several times, and superposition|polymerization was completed, and the (meth)acrylic resin (A) which has an oxybutylene group was obtained.

When measured by GPC in the same manner, the number average molecular weight was 40,000, and the weight average molecular weight was 80,000.

(Examples 1-8, Comparative Examples 1-4)

(1) Preparation of inorganic particle dispersion slurry composition

Using the (meth)acrylic resin (A) shown in Table 1, the inorganic fine particles (B) having a perovskite structure (B), and the organic solvent (C), mix them so that they become the formulations in Table 1, and perform the mixing with a high-speed mixer. Kneading was carried out to obtain an inorganic fine particle dispersion slurry composition.

(2) Preparation of inorganic particle dispersible tablets

Using a knife coater, the resulting inorganic particle dispersion slurry composition is coated on a support film (width 400mm, length 30m, thickness 38 μm), the formed coating film was dried at 100° C. for 10 minutes to remove the solvent, and a 50 μm thick inorganic fine particle dispersed sheet was formed on the support film.

The support film was peeled off, and the inorganic fine particle dispersed sheet was laminated to prepare a sheet with a thickness of 500 μm.

(3) Production of inorganic sintered body

The obtained sheet was mounted on a ceramic dish, and heated at 300° C. for 10 hours in an electric furnace to degrease the binder. After the curing was carried out until it became normal temperature, it was taken out from the oven and pressed with a magnetic field pressing device under a magnetic field of 10KOe and 10MPas to obtain a magnetically oriented inorganic sintered body.

[Table 1]

＜Evaluation＞

The following evaluations were performed on the inorganic fine particle dispersion slurry compositions and inorganic sintered bodies obtained in Examples and Comparative Examples. The results are shown in Table 2.

(1) sheet printability

In "(2) Preparation of inorganic fine particle dispersion sheet", the coating film before drying was visually confirmed, and the sheet printability was evaluated according to the following criteria.

〇: The surface is smooth and glossy, and it is in a good state.

Δ: Although coatable, the surface is not smooth.

×: Wrinkles and scratches exist, and neat application is not possible.

(2) Degreasing

With respect to the obtained inorganic sintered body, residual carbon was confirmed using a carbon-sulfur analyzer manufactured by Horiba Corporation, and the degreasing property (low-temperature decomposing property) was evaluated on the basis of the following criteria.

It can be said that the lower the amount of residual carbon, the better the low-temperature decomposability.

〇: Residual carbon is 50 ppm or less.

Δ: Residual carbon is more than 50 ppm and less than 100 ppm.

×: Residual carbon is 100 ppm or more.

(3) Crystal analysis

For the obtained inorganic sintered body, the crystal formation state was confirmed using a wide-angle X-ray diffractometer manufactured by Rigaku Co., Ltd. using CuKα rays, and the crystal formability was evaluated according to the following criteria.

If the crystal formability is excellent, performance as a theoretical value can be expected.

⊚: A strong diffraction peak around 2θ=30° can be confirmed, and there is no small scattering up to 40°.

〇: A strong diffraction peak can be confirmed around 2θ=30°, and there is little scattering between 30° and 40°.

Δ: Diffraction peak splits into double around 2θ=30°.

×: The diffraction peak around 2θ=30° is split into two, and there is strong scattering between 30° and 40°.

(4) Characteristics of sintered body

The magnetic force of the obtained inorganic sintered body was measured using an AC magnetic susceptibility measuring device (XacQuan, Heki Research Institute). In addition, piezoelectric characteristics were confirmed using a ferroelectric evaluation system (FCE10, TOYO Corporation). In addition, samples were produced by compacting the inorganic fine particles having a perovskite structure used in Examples and Comparative Examples without using a binder, and similarly confirmed magnetic and piezoelectric properties.

Regarding the magnetic force or piezoelectric properties of the compacted samples, the degree of deterioration of the magnetic force or piezoelectric properties of the inorganic sintered body was confirmed, and the properties of the sintered body were evaluated according to the following criteria.

⊚: The degree of deterioration of the magnetic or piezoelectric characteristics is less than 10%.

◯: The degree of deterioration of magnetic force or piezoelectric properties is 10% or more and less than 20%.

Δ: The degree of deterioration of the magnetic or piezoelectric properties is 20% or more and less than 30%.

×: The degree of deterioration of the magnetic force or piezoelectric characteristics is 30% or more.

[Table 2]

In Examples 1 to 8, excellent properties were confirmed in all evaluations. Especially for Examples 1, 2, 5, and 6 in which the average length of the block segment is 2 to 5 relative to the average length of the main chain, a very good crystal structure is obtained, and there are almost no magnetic or piezoelectric properties deterioration.

On the other hand, the inorganic sintered bodies obtained in Comparative Examples 1 to 4 had a large amount of residual carbon and a complicated crystal structure, and their magnetic and piezoelectric properties were remarkably deteriorated.

Industrial availability

According to the present invention, it is possible to provide a product that is excellent in low-temperature decomposability, degreases the perovskite-type inorganic material below the Curie point, can suppress the deterioration of the magnetic force and piezoelectric characteristics of the perovskite-type inorganic material, and is also excellent in printability. Inorganic fine particle dispersion slurry composition. In addition, a method for producing an inorganic fine particle-dispersed sheet using the inorganic fine particle-dispersed slurry composition can be provided.

Claims (6)

1. An inorganic microparticle dispersion slurry composition, which contains (meth)acrylic resin A, inorganic microparticles B and solvent C, The inorganic particles B are 3-element inorganic materials or 4-element inorganic materials having a perovskite structure, The (meth)acrylic resin A has at least one of a polypropylene glycol block segment and a polytetramethylene ether glycol block segment. 2. The inorganic particle dispersion slurry composition according to claim 1, wherein, (meth)acrylic resin A has polypropylene glycol block segment or polytetramethylene ether glycol block chain in graft chain part. 3. The inorganic particle dispersion slurry composition according to claim 1 or 2, wherein, when the average length of the main chain of the (meth)acrylic resin A is set to 100, the (meth)acrylic resin A The average length of the polypropylene glycol block segment and the polytetramethylene ether glycol block segment in is not less than 0.1 and not more than 5.0. 4. The inorganic particle dispersion slurry composition according to any one of claims 1 to 3, wherein the polypropylene glycol block segment and polytetramethylene ether glycol in (meth)acrylic resin A The composition ratio of the block segment is not less than 5% by weight and not more than 20% by weight. 5. The inorganic fine particle dispersion slurry composition according to any one of claims 1 to 4, wherein the (meth)acrylic resin A contains 50% by weight to 70% by weight of Segments of butyl esters. 6. A method for producing an inorganic fine particle dispersion tablet, comprising: applying the inorganic fine particle dispersion slurry composition according to any one of claims 1 to 5 and drying it to obtain a sheet; The step of firing the sheet at a temperature of 350° C. or lower.