JP5885622B2 - Slurry composition containing basic ceramics - Google Patents

Description

  The present invention relates to a basic ceramic-containing slurry composition.

  The slurry composition containing the ceramic fine powder is used for ceramic electronic components in the electronic equipment field by sheet molding. In particular, in the production of electroceramic parts in the field of advanced electronic equipment, a ceramic molded product (ceramic sheet) before firing produced from a basic ceramic-containing slurry composition is preferably used. Therefore, the antistatic property of the ceramic sheet is required.

  Patent Document 1 discloses a slurry composition for producing ceramics containing organic hydrochloric acid of an amidinium cation as a dispersant having antistatic properties.

JP 2002-321981 A

  In multilayer ceramic electronic components, electronic devices have been reduced in size and performance, and accordingly, the ceramic material has been reduced in particle size and the ceramic sheet has been reduced in thickness. However, with the reduction in the particle size of the ceramic material and the thinning of the ceramic sheet, the handling problems such as the insufficient strength of the ceramic sheet and the deterioration of the peelability have become larger than before. Patent Document 1 discloses improvement in antistatic properties of ceramic sheets, but performance is insufficient with respect to handling properties such as strength and releasability, and problems associated with the production of ceramic sheets having a thickness of 15 μm or less. The recognition of is also not shown.

  The present invention provides a basic ceramic-containing slurry composition capable of producing a ceramic sheet having excellent handling properties. Preferably, the present invention provides a basic ceramic-containing slurry composition capable of producing a ceramic sheet having a small peel charge amount and peel force and excellent sheet strength, that is, toughness.

  The present invention relates to a slurry composition containing a cationic compound containing a nitrogen-containing heteroaromatic quaternary ammonium cation group, a polymer dispersant, a non-aqueous solvent, a basic ceramic material, and a polyvinyl acetal resin.

  ADVANTAGE OF THE INVENTION According to this invention, provision of the basic ceramic containing slurry composition which is excellent in antistatic property, peelability, and toughness in a ceramic sheet | seat is attained. Therefore, according to the basic ceramic-containing slurry composition of the present invention, it is preferable that a multilayer ceramic electronic component with improved quality can be efficiently manufactured by improving the handling characteristics of the ceramic sheet. Further, if the ceramic sheet is made thinner, higher strength and releasability than before are required. However, according to the present invention, for example, even in a thin ceramic sheet having a thickness of 15 μm or less, handling characteristics are improved. It is possible to manufacture a high-quality multilayer ceramic electronic component.

  In the present invention, a slurry composition containing a non-aqueous solvent, a basic ceramic material, and a polyvinyl acetal resin contains a cation compound containing a nitrogen-containing heteroaromatic quaternary ammonium cation group as an antistatic agent, and a polymer. It is based on the knowledge that a thin-layered ceramic sheet excellent in antistatic properties, peelability and toughness can be produced by containing a dispersant.

  The details of the mechanism of the effect of the present invention are not clear, but are estimated as follows. First, since a cation compound containing a nitrogen-containing heteroaromatic quaternary ammonium cation group to be contained as an antistatic agent delocalizes π electrons and cations due to its aromaticity, the basicity in the slurry composition The interaction between the ceramic material and the polymer dispersant is reduced, and therefore bleed-out to the surface of the ceramic sheet easily occurs, and excellent antistatic ability and good peelability are exhibited. Further, the polymer dispersant is adsorbed on the surface of the ceramic material, so that the cationic compound is prevented from adsorbing on the surface of the ceramic material, and the toughness of the ceramic sheet is obtained by uniformly dispersing on the ceramic sheet and imparting plasticity. Will improve. However, these are estimations, and the present invention is not limited to these mechanisms.

  That is, the present invention is, in one embodiment, a slurry composition comprising a cation compound containing a nitrogen-containing heteroaromatic quaternary ammonium cation group, a polymer dispersant, a non-aqueous solvent, a basic ceramic material, and a polyvinyl acetal resin. (Hereinafter also referred to as “slurry composition of the present invention”). According to the slurry composition of this invention, the effect that the antistatic property of a ceramic sheet obtained, peelability, and toughness is excellent can be show | played. That is, firstly, the slurry composition of the present invention can satisfactorily prevent charging of the ceramic sheet obtained from the basic ceramic-containing slurry composition and reduce the peeling force. Secondly, the slurry composition of the present invention can improve the toughness of the ceramic sheet obtained from the basic ceramic-containing slurry composition. Specifically, it is possible to produce a ceramic sheet that is easy to stretch and has a high breaking stress.

  In the present specification, “antistatic property” means that the degree of peeling charge amount of a ceramic sheet before firing obtained by forming a ceramic material into a sheet shape using a slurry composition is low, and peeling of the ceramic sheet. The smaller the absolute value of the charge amount, the better the “antistatic property” of the ceramic material. In this specification, “peelability” means that a small force (peeling force) required to peel a ceramic sheet coated and dried on a base film from the base film is small. The smaller the value, the better the “peelability” of the ceramic sheet. In this specification, the “toughness” of a ceramic sheet is one of the strength indicators of the ceramic sheet, and means that the breaking stress is large and the breaking strain (elongation) is large in the tensile test, and the breaking stress is large. The greater the elongation, the better the “toughness” of the ceramic sheet.

［式（１）中、Ｒ₁は、炭素数１〜４のアルキル基を示し、Ｒ₂、Ｒ₃及びＲ₄は、同一又は異なり、水素原子、又は水酸基を有していてもよい炭素数１〜４のアルキル基を示す。式（２）中、Ｒ₅及びＲ₆は、同一又は異なり、炭素数１〜４のアルキル基を示し、Ｒ₇及びＲ₈は、同一又は異なり、水素原子、又は水酸基を有していてもよい炭素数１〜４のアルキル基を示す。式（３）中、Ｒ₉及びＲ₁₀は、同一又は異なり、炭素数１〜４のアルキル基を示し、Ｒ₁₁は水素原子、又は水酸基を有していてもよい炭素数１〜４のアルキル基を示す。］ [Cationic compound]
The slurry composition of the present invention contains a cationic compound containing a nitrogen-containing heteroaromatic quaternary ammonium cationic group as an antistatic agent. The nitrogen-containing heteroaromatic quaternary ammonium cation group is a cation group having a quaternary ammonium in an aromatic ring from the viewpoint of producing a ceramic sheet excellent in antistatic property, peelability and toughness. A quaternary ammonium cation group of a nitrogen five-membered or six-membered heteroaromatic compound is preferred. The quaternary ammonium cation group of the nitrogen-containing five-membered ring or six-membered heteroaromatic compound includes a quaternary ammonium cation group having a structure such as pyridinium, pyrazolium, imidazolium, pyrimidinium, pyrazinium, pyridazinium and pyrrolium. Among them, preferred is a quaternary ammonium cationic group having a pyridinium, pyrazolium or imidazolium structure, and more preferred is a cationic group represented by the following general formulas (1), (2) and (3). A cationic group selected from the group consisting of The slurry composition of the present invention may contain two or more kinds of cationic compounds.

[In formula (1), R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₃ and R ₄ are the same or different and may have a hydrogen atom or a hydroxyl group. 1-4 alkyl groups are shown. In formula (2), R ₅ and R ₆ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and R ₇ and R ₈ are the same or different and may have a hydrogen atom or a hydroxyl group. A good alkyl group having 1 to 4 carbon atoms is shown. In formula (3), R ₉ and R ₁₀ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and R ₁₁ is a hydrogen atom or an alkyl having 1 to 4 carbon atoms which may have a hydroxyl group. Indicates a group. ]

As the cationic group represented by the general formula (1), R ₁ is an alkyl group having 1 to 4 carbon atoms from the viewpoint of improving antistatic properties, peelability and toughness of the ceramic sheet, and may be a methyl group or an ethyl group. Group is preferred, and an ethyl group is more preferred. From the same viewpoint, R ₂ , R ₃ , and R ₄ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms that may be substituted with a hydroxyl group. The C1-C2 alkyl group which may be substituted by is preferable, and a hydrogen atom, a methyl group, or a hydroxymethyl group is more preferable. Examples of the cationic group represented by the general formula (1) include 1-methylpyridinium, 1-ethylpyridinium, 1-ethyl-3-hydroxymethylpyridinium, 1-ethyl-3-methylpyridinium, 1-propylpyridinium, Cationic groups such as 1-butylpyridinium, 1-butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium and the like can be mentioned. Among these, 1-ethyl-3-methylpyridinium and 1-ethyl-3-hydroxymethylpyridinium are preferable from the viewpoint of improving the antistatic property, peelability, and toughness of the ceramic sheet.

As the cationic group represented by the general formula (2), R ₅ and R ₆ are the same or different and are alkyl groups having 1 to 4 carbon atoms from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet. And at least one of R ₅ and R ₆ is preferably a methyl group or an ethyl group, and more preferably a methyl group. From the same viewpoint, the total number of carbon atoms of R ₅ and R ₆ is preferably 2 to 5, more preferably 2 to 3, and still more preferably 2. Further, from the same viewpoint, R ₇ and R ₈ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, and are substituted with a hydrogen atom or a hydroxyl group. An alkyl group having 1 to 2 carbon atoms which may be preferable is preferable, a hydrogen atom, a methyl group or a hydroxymethyl group is more preferable, a hydrogen atom or a methyl group is more preferable, and the total number of carbon atoms of R ₇ and R ₈ is 1. Even more preferred. Examples of the cationic group represented by the general formula (2) include 1,2-dimethylpyrazolium, 1-methyl-2-ethylpyrazolium, 1-methyl-2-propylpyrazolium, 1-methyl. 2-butylpyrazolium, 1,2-diethylpyrazolium, 1,2-dipropylpyrazolium, 1,2-dibutylpyrazolium, 1,2,4-trimethylpyrazolium, 1,2 , 3,5-tetramethylpyrazolium, 1-ethyl-2,3,5-trimethylpyrazolium, 1-ethyl-3-methoxy-2,5-dimethylpyrazolium, 1-propyl-2,3 , 5-trimethylpyrazolium, 1-butyl-2,3,5-trimethylpyrazolium, and other cationic groups. Among these, 1,2,4-trimethylpyrazolium is preferable from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet.

As the cationic group represented by the general formula (3), R ₉ and R ₁₀ are the same or different and are alkyl groups having 1 to 4 carbon atoms from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet. And at least one of R ₉ and R ₁₀ is preferably a methyl group or an ethyl group, more preferably a methyl group. Also, the total number of carbon atoms of R ₉ and R ₁₀ from the same viewpoint, preferably 2-5, 3-5 is more preferable. From the same viewpoint, R ₁₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, and 1 to 1 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group. 2 alkyl groups are preferred, hydrogen atoms, methyl groups or hydroxymethyl groups are more preferred, and hydrogen atoms are more preferred. Examples of the cationic group represented by the general formula (3) include 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-3-methylimidazolium, and 1,3-diethylimidazolium. 1-ethyl-2,3-dimethylimidazolium, 1,2,3-triethylimidazolium, 1-propyl-3-methylimidazolium, 1-propyl-2,3-dimethylimidazolium, 1-butyl- Cationic groups such as 3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazolium and the like can be mentioned. Among these, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, and 1-butyl-3-methylimidazole from the viewpoint of improving the antistatic property, peelability, and toughness of the ceramic sheet. Rium is preferred, and 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium are more preferred.

  The cationic group in the present invention is preferably a cationic group represented by the general formulas (1) and (3), more preferably a cationic group represented by the general formula (3), from the viewpoint of improving the antistatic property of the ceramic sheet. preferable. Moreover, the cationic group represented by General formula (3) is preferable from a viewpoint of the peelability improvement of a ceramic sheet. Moreover, from a viewpoint of the toughness improvement of a ceramic sheet, the cationic group represented by General formula (2) and (3) is preferable, and the cationic group represented by General formula (3) is more preferable. Taking these viewpoints together, the cationic group in the present invention is more preferably a cationic group represented by the general formula (3).

  The molecular weight of the cationic group is preferably 300 or less, more preferably 200 or less, still more preferably 150 or less, and even more preferably 120 or less, from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet. From the same viewpoint, the molecular weight of the cationic group is preferably 90 or more, more preferably 95 or more, and further preferably 100 or more. When these viewpoints are put together, the molecular weight of the cationic group is preferably 90 to 300, more preferably 95 to 300, still more preferably 95 to 200, still more preferably 100 to 150, and even more preferably 100 to 120.

  The cationic compound may be a salt of the aforementioned cationic group and anionic group, or a solution of a non-aqueous solvent. The anionic group is preferably an organic anionic group because it does not contain a halogen compound that can cause the antistatic property, releasability and toughness of the ceramic sheet to be improved, and the electrical characteristics can be lowered or rusted.

  Examples of the organic anionic group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, undecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, isobutyric acid , Isovaleric acid, isocaproic acid, ethyl butyric acid, methyl valeric acid, isocaprilic acid, propyl valeric acid, ethyl caproic acid, acrylic acid, crotonic acid, methacrylic acid, isocrotonic acid, 3-butenoic acid, pentenoic acid, hexenoic acid, heptin Saturated and unsaturated aliphatic carboxylic acids such as acids, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, oleic acid, 3-methylcrotonic acid; toluic acid, ethylbenzoic acid, propylbenzoic acid, isopropylbenzoic acid Acid, butylbenzoic acid, isobutylbenzoic acid, sec-butyl Aromatic carboxylic acids such as benzoic acid, tert-butylbenzoic acid, resorcin benzoic acid, hydroxybenzoic acid and phenylacetic acid; alkyl oxalic acids such as methyl oxalic acid and ethyl oxalic acid; methyl sulfonic acid, ethyl sulfonic acid, methane sulfone Acid, ethanesulfonic acid, 1,2-ethanedisulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, alkyl (carbon number 8-24) benzenesulfonic acid , Sulfonic acids such as anthraquinone sulfonic acid, naphthalene sulfonic acid, naphthol sulfonic acid and styrene sulfonic acid, and anionic groups such as alkyl sulfuric acid and methyl alkyl sulfuric acid such as methyl sulfuric acid, ethyl sulfuric acid and hydroxyethyl sulfuric acid. Among these, anionic groups of alkyl oxalic acid, alkyl sulfuric acid and aliphatic carboxylic acid are preferred, and anionic groups of alkyl sulfuric acid and aliphatic carboxylic acid are more preferred, from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet, Anionic groups of methylsulfuric acid, ethylsulfuric acid and acetic acid are more preferred, and anionic groups of ethylsulfuric acid are even more preferred from the viewpoint of improving antistatic properties and toughness.

  The content of the cationic compound in the slurry composition of the present invention is preferably 0.05 parts by weight or more with respect to 100 parts by weight of the basic ceramic material from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet. 0.1 parts by weight or more is more preferable, 0.2 parts by weight or more is more preferable, and 0.3 parts by weight or more is even more preferable. In addition, from the viewpoint of suppressing the increase in plasticity of the polyvinyl acetal resin and maintaining the strength of the ceramic molded product, the content of the cationic compound in the slurry composition is 2.0% with respect to 100 parts by weight of the basic ceramic material. Parts by weight or less are preferred, 1.8 parts by weight or less are more preferred, 1.5 parts by weight or less are more preferred, and 1.2 parts by weight or less are even more preferred. Summing up these viewpoints, the content of the cationic compound in the slurry composition is preferably 0.05 to 2.0 parts by weight, more preferably 0.1 to 1 part per 100 parts by weight of the basic ceramic material. 0.8 parts by weight, more preferably 0.2 to 1.5 parts by weight, still more preferably 0.3 to 1.2 parts by weight.

  Furthermore, the content of the cationic compound in the slurry composition of the present invention is 0.01 parts by weight or more with respect to 1.0 part by weight of the polyvinyl acetal resin from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet. More preferably, it is 0.015 weight part or more, More preferably, it is 0.02 weight part or more, More preferably, it is 0.03 weight part or more. Moreover, from the viewpoint of suppressing the increase in plasticity of the polyvinyl acetal resin and maintaining the strength of the ceramic molded article, the content of the cationic compound in the slurry composition is 0.2 with respect to 1.0 part by weight of the polyvinyl acetal resin. It is preferably no greater than 0.1 parts by weight, more preferably no greater than 0.18 parts by weight, even more preferably no greater than 0.15 parts by weight, and even more preferably no greater than 0.12 parts by weight. Summing up these viewpoints, the content of the cationic compound in the slurry composition is preferably 0.01 to 0.2 parts by weight, more preferably 0.015 to 0 parts by weight based on 1.0 part by weight of the polyvinyl acetal resin. .18 parts by weight, more preferably 0.02 to 0.15 parts by weight, even more preferably 0.03 to 0.12 parts by weight.

  The slurry composition of the present invention may contain an antistatic agent other than the cationic compound as an antistatic agent. The content of the cationic compound in the antistatic agent is preferably 80% by weight or more, more preferably 90% by weight or more, and more preferably 95% or more with respect to the antistatic agent, from the viewpoint of improving antistatic properties, peelability and toughness. Even more preferably, it is substantially 100% by weight.

[Polymer dispersant]
The slurry composition of the present invention contains a polymer dispersant. Examples of the polymer dispersant include a cationic polymer, a nonionic polymer, and an anionic polymer.

  One aspect of the polymer dispersant is a vinyl copolymer that is soluble in a non-aqueous solvent. Examples of the vinyl copolymer include one or more (meth) acrylic acid esters and allyl ethers. And vinyl copolymers of radically unsaturated monomers mainly composed of olefins. Specific examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, t- Butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylic acid ester having an alkyl group having 1 to 22 carbon atoms such as acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate; and methoxypolyethylene glycol (meth) acrylate, methoxy Polypropylene glycol (meth) acrylate, polyoxyalkylene (meth) acrylate having a polyoxyalkylene group such as methoxy polybutylene glycol (meth) acrylate. Examples of the allyl ether include (alkoxy-) polyoxyalkylene-allyl ethers such as (methoxy-) polyethylene glycol-allyl ether and (butoxy-) polyethylene glycol-polypropylene glycol-allyl ether. Examples of the olefin include α-olefins such as hexadecene and eicosene.

  By copolymerizing the one or more (meth) acrylic acid ester, allyl ether or olefin and an acidic monomer such as (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, itaconic acid, An anionic polymer dispersant is obtained. Commercially available products include “Marialim AKM-053”, “Marialim AWS-0551”, “Marialim AAB-0551”, and “Marialim AFB-1521” manufactured by NOF Corporation.

  Further, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5- A cationic polymer dispersant is obtained by copolymerizing a basic monomer such as vinylpyridine, N-vinylimidazole, 2-methyl-N-vinylimidazole or the like. Commercially available products include “Efca 4310” and “Efca 4320” manufactured by BASF. In addition, a monomer having a neutral functional group such as (meth) acrylamide, vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate is copolymerized. Thus, a nonionic polymer dispersant can be obtained. Examples of commercially available products include “Antalon V-216 (vinyl pyrrolidone / hexadecene copolymer)” and “Antalon V-220 (vinyl pyrrolidone / eicosene copolymer)” manufactured by ISP Japan.

  The polymer dispersant is not limited to the vinyl copolymer, and polymer dispersants such as modified polyamide, modified polyurethane, modified polyester, and polyvinylpyrrolidone can also be used. For example, an amide or salt formed by reacting a polyalkyleneimine or polyallylamine such as polyethyleneimine with a polyester having a free carboxylic acid group such as a polymer of hydroxystearic acid or a polymer of cyclic esters. And a dispersant in which two or more polyester chains are bonded to each polyalkyleneimine main chain or polyallylamine main chain. As a commercial product, “Solsperse 26000”, “Solsparse 28000”, “Solspers 32000”, “Solspers 33000”, “Solspers 36000”, “Solspers 39000” manufactured by Lubrizol, “Ajispur PB-711” manufactured by Ajinomoto Fine Techno Co., Ltd. , “Ajisper PB-821”, “Azisper PB-822”, “Azisper PB-814”, “Azisper PB-824”, and the like. In addition, a polyester having a free carboxylic acid, or a hydroxyl group, an amino group, a triazole group, a pyrimidine group, an imidazole group, a pyridine group, a morpholine group, a pyrrolidine group, a piperazine group, a benzoimidazoline group, with respect to the isocyanate group of the polyisocyanate compound. Examples thereof include a dispersant obtained by subjecting a compound having a functional group selected from a benzothiazole group and a triazyl group to an addition reaction. Commercially available products include “DISPERBYK-161”, “DISPERBYK-162”, “DISPERBYK-167” manufactured by Big Chemie Japan, and “Solsperse 76500” manufactured by Lubrizol. Furthermore, a product obtained by addition reaction of polyisocyanate to a copolymer of styrene or a derivative thereof, (meth) acrylic acid or an ester thereof, or a (meth) acrylic acid ester having a hydroxyl group, and an amino group or imidazole. Examples thereof include a dispersant obtained by addition reaction of a group-containing compound. Commercially available products include “Efca 4046” and “Efca 4047” manufactured by BASF. Furthermore, a polyvinyl pyrrolidone type dispersing agent is mentioned, As a commercial item, "PVP K-15", "PVP K-30", "PVP K-60", "PVP K-" made by IS Japan Co., Ltd. 90 ".

  The polymer dispersant used in the slurry composition of the present invention is preferably a copolymer from the viewpoint of improving antistatic properties, peelability and toughness, and improving the dispersibility of a basic ceramic material. A copolymer having a structural unit (adsorption unit) having a high affinity for the porous ceramic material and a structural unit (dispersion unit) having a high affinity for the non-aqueous solvent is more preferable. It is considered that the copolymer having the adsorption unit is efficiently adsorbed on the surface of the ceramic material and easily covers the ceramic material in the slurry composition. In addition, the dispersion unit spreads three-dimensionally in a non-aqueous solvent, and the interaction between the basic ceramic material in the slurry composition and the cation compound of the present invention becomes smaller, resulting in better antistatic ability and better It is considered that excellent peelability is exhibited and the toughness of the ceramic sheet is further improved.

  Examples of the copolymer adsorption unit include cationic, nonionic and anionic constituent units. The cationic structural unit is preferably a structural unit derived from alkyleneimine or allylamine from the viewpoint of improving antistatic properties, peelability and toughness. Moreover, as the nonionic structural unit, structural units derived from (meth) acrylamide and vinylpyrrolidone are preferable from the same viewpoint. The anionic structural unit is preferably a structural unit derived from (meth) acrylic acid and (anhydrous) maleic acid from the same viewpoint, and from the viewpoint of improving antistatic properties, a structure derived from (meth) acrylic acid. Units are more preferred.

  Examples of the copolymer dispersion unit include structural units having a polyoxyalkylene group, a polyester group, a poly (hydroxy) alkyl (meth) acrylate group, an alkyl group, and an alkylene group. Among these, a structural unit having a group selected from a polyoxyalkylene group, a polyester group, a polyhydroxyethyl methacrylate group, a polymethyl methacrylate group, an alkyl group, and an alkylene group is preferable from the viewpoint of improving antistatic properties, peelability, and toughness. , A structural unit having a group selected from a polyoxyalkylene group, a polycaprolactone group and an alkyl group is more preferred, a structural unit having a polyoxyalkylene group is more preferred, and a structural unit having a polyoxyethylene group is even more preferred. From the same viewpoint, (alkoxy-) polyoxyalkylene (meth) acrylate, (alkoxy-) polyoxyalkylene-allyl ether, polyester having a carboxy group and α-olefin-derived structural units are preferred, and (alkoxy-) poly A structural unit derived from oxyalkylene (meth) acrylate is more preferred.

  The polymer dispersant used in the slurry composition of the present invention is preferably cationic and anionic from the viewpoint of improving antistatic properties, and nonionic and anionic from the viewpoint of improving peelability. Preferably there is. Taking these viewpoints together, an anionic polymer dispersant is more preferable as the polymer dispersant. The cationic polymer dispersant is composed of an amide or a salt formed by a reaction between polyethyleneimine and a polyester of hydroxystearic acid from the viewpoint of improving antistatic properties, peelability, and toughness. A copolymer in which two or more polyester chains are bonded to the imine main chain is preferred. The nonionic polymer dispersant is selected from the group consisting of (meth) acrylic acid esters, (alkoxy) polyoxyalkylene (meth) acrylates and (meth) acrylamides from the viewpoint of antistatic properties, peelability and toughness. Preferred are copolymers of monomers and copolymers of vinyl pyrrolidone and α-olefin. From the viewpoint of antistatic properties and toughness, (meth) acrylates, (alkoxy) polyoxyalkylenes (meth) More preferred is a copolymer of monomers selected from the group consisting of acrylates and (meth) acrylamides. Furthermore, as the anionic polymer dispersant, (meth) acrylic acid or (anhydrous) maleic acid and (alkoxy) polyoxyalkylene (meta) are used as monomers from the viewpoint of antistatic properties, peelability and toughness. ) Acrylate or a copolymer comprising (alkoxy) polyoxyalkylene allyl ether is preferred. From the viewpoint of antistatic properties, (meth) acrylic acid and (alkoxy) polyoxyalkylene (meth) are used as monomers. A copolymer comprising acrylate is more preferable.

  The weight average molecular weight of the polymer dispersant is preferably 2000 or more, more preferably 4000 or more, further preferably 6000 or more, and further preferably 8000 or more from the viewpoint of antistatic property of the ceramic sheet and dispersibility of the basic ceramic material. More preferred. Moreover, from a viewpoint of the peelability of a ceramic sheet | seat and the dispersibility of a basic ceramic material, 200000 or less are preferable, 120,000 or less are more preferable, 60000 or less are more preferable, and 36000 or less are still more preferable. When these viewpoints are put together, the weight average molecular weight of the polymer dispersant is preferably 2000 to 200000, more preferably 4000 to 120,000, still more preferably 6000 to 60000, and even more preferably 8000 to 36000.

The content of the polymer dispersant in the slurry composition of the present invention is generally adjusted by the specific surface area of the basic ceramic material, and the standard content is parts by weight with respect to 100 parts by weight of the basic ceramic material. As a guide, a value obtained by dividing the BET specific surface area [unit m ² / g] by 5 can be used. For example, when barium titanate is used as the basic ceramic material, the content of the polymer dispersant with respect to 100 parts by weight of barium titanate is 1 part by weight if the particle size is 200 nm (specific surface area 5 m ² / g), If the particle size is 100 nm (specific surface area 10 m ² / g), 2 parts by weight, and if the particle size is 50 nm (specific surface area 20 m ² / g), 4 parts by weight can be used as a guide.

The content of the polymer dispersant is 5 parts by weight with respect to 100 parts by weight of the basic ceramic material. From the viewpoint of dispersibility of the basic ceramic material, the BET specific surface area [unit m ² / g] of the basic ceramic material is 5 The divided value is preferably 0.3 times or more, and more preferably 0.4 times or more. Further, from the viewpoint of peelability of the ceramic sheet, the BET specific surface area [unit m ² / g] of the basic ceramic material is preferably 1.5 times or less, more preferably 1.2 times or less the value obtained by dividing by 5. . Summing up these viewpoints, the content of the polymer dispersant is a value obtained by dividing the BET specific surface area [unit m ² / g] of the basic ceramic material by 5 as parts by weight with respect to 100 parts by weight of the basic ceramic material. 0.3 to 1.5 times is preferable, and 0.4 to 1.2 times is more preferable.

If the BET specific surface area of the basic ceramic material is 5 m ² / g, the content of the polymer dispersant is 0.3 from 100 parts by weight of the basic ceramic material from the viewpoint of dispersibility of the basic ceramic material. Part by weight or more is preferable, and more preferably 0.4 part by weight or more. Moreover, from a peelable viewpoint of a ceramic sheet, 1.5 weight part or less is preferable with respect to 100 weight part of basic ceramic materials, More preferably, it is 1.2 weight part or less.

If the BET specific surface area of the basic ceramic material is 10 m ² / g, the content of the polymer dispersant is 0.6 from 100 parts by weight of the basic ceramic material from the viewpoint of dispersibility of the basic ceramic material. Part by weight or more is preferable, and more preferably 0.8 part by weight or more. Further, from the viewpoint of peelability of the ceramic sheet, 3.0 parts by weight or less is preferable with respect to 100 parts by weight of the basic ceramic material, and more preferably 2.4 parts by weight or less.

If the BET specific surface area of the basic ceramic material is 20 m ² / g, the content of the polymer dispersant is 1.2 from 100 parts by weight of the basic ceramic material from the viewpoint of dispersibility of the basic ceramic material. Part by weight or more is preferable, and more preferably 1.6 parts by weight or more. Further, from the viewpoint of the peelability of the ceramic sheet, the amount is preferably 6.0 parts by weight or less, more preferably 4.8 parts by weight or less with respect to 100 parts by weight of the basic ceramic material. When the BET specific surface area of the basic ceramic material has other values, the preferable content of the polymer dispersant can be determined by calculating in the same manner.

[Non-aqueous solvent]
The slurry composition of the present invention contains a non-aqueous solvent. The non-aqueous solvent is not particularly limited as long as it is non-aqueous (organic solvent). Examples of the non-aqueous solvent include methanol, ethanol, n-propanol, iso-propanol (IPA), n-butanol, sec-butanol, n-octanol, diacetone alcohol, terpineol, butyl carbitol and other alcohols; methyl cellosolve Cellosolves such as ethyl cellosolve and butyl cellosolve; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK); N, N-dimethylacetamide, N, N-dimethylformamide, N- Amides such as methyl-2-pyrrolidone; Esters such as methyl acetate, ethyl acetate, isopropyl acetate, and n-butyl acetate; Ethers such as ethyl ether, dioxane, and tetrahydrofuran; Naphtha, n-he Sun, hydrocarbons such as cyclohexane; toluene, xylene, aromatic compounds such as pyridine.

  From the viewpoint of solubility of the polyvinyl acetal resin contained in the slurry composition of the present invention, the non-aqueous solvent is preferably alcohols and cellosolves, more preferably alcohols, and more preferably methanol, ethanol, and iso-propanol. Even more preferred is ethanol. Furthermore, from the viewpoint of gently removing the non-aqueous solvent from the slurry composition to form a uniform ceramic sheet, a mixture of two or more organic solvents having different boiling points is preferable, and it is difficult to azeotrope with alcohols and cellosolves. A mixture of the above organic solvent with alcohols and cellosolves is more preferred. Other organic solvents that are difficult to azeotrope with the alcohols and cellosolves are preferably hydrocarbons and aromatics, more preferably aromatics, and even more preferably toluene. Taking these viewpoints together, the non-aqueous solvent is preferably a mixture of aromatics and alcohols, more preferably a mixture of toluene and ethanol. From the same viewpoint, the volume ratio of toluene and ethanol (toluene / ethanol) in the non-aqueous solvent is preferably 10/90 to 75/25, more preferably 25/75 to 65/35, and 40/60 to 55/45. Is more preferable.

[Basic ceramic materials]
The slurry composition of the present invention contains a basic ceramic material. In the present specification, the “basic ceramic material” is an inorganic compound having a base amount larger than the acid amount, and includes, for example, metal oxides, metal carbonates, composite oxides, and the like. Specifically, metal oxides such as titanium oxide, magnesium oxide, barium oxide and aluminum oxide, metal carbonates such as magnesium carbonate and barium carbonate, and barium zirconate, calcium zirconate, calcium titanate and barium titanate And composite oxides such as strontium titanate. Among these, from the viewpoint of improving the performance of the multilayer ceramic electronic component, a complex oxide of zirconic acid and a complex oxide of titanic acid are preferable, a complex oxide of titanic acid is more preferable, and barium titanate is more preferable.

  In general, the surface of a ceramic material has both an acid point and a base point. The amount of acid points (acid amount) and the amount of base points (base amount) can each be determined by back titration, thereby identifying whether the ceramic material is acidic or basic. it can. The reverse titration method is a method in which a basic reagent (or acidic reagent) whose concentration is known in advance is mixed with a ceramic material at a certain ratio, sufficiently neutralized, and then solid-liquid separated with a centrifuge, The supernatant is titrated, and the acid amount (or base amount) is determined from the reduced amount of basic reagent (or acid reagent). In the present specification, the amount of base and the amount of acid are determined as follows.

1) How to determine the amount of base 2 g of ceramic material is precisely weighed (sample amount), put into 30 mL of a 1 / 100N acetic acid-toluene / ethanol (volume ratio 48/52) solution, and an ultrasonic cleaner (Branson, model 1510J). -MT) for 1 hour. After leaving still for 24 hours, a part of the ceramic material dispersion is subjected to solid-liquid separation using a centrifuge (model CP-56G manufactured by Hitachi, Ltd.) at 25,000 rpm for 60 minutes. 10 mL of the separated liquid part is added to 20 mL of a toluene / ethanol (volume ratio 2/1) solution to which a phenolphthalein indicator is added, and then neutralized with a 1 / 100N potassium hydroxide-ethanol solution. Assuming that the titer at this time is XmL, the titer required to neutralize 10 mL of 1 / 100N acetic acid-toluene / ethanol (volume ratio 48/52) solution is BmL, and the sample amount is Sg, The amount of base is determined.
Base amount (μmol / g) = 30 × (BX) / S

2) Determination of acid amount Weighing 2 g of ceramic material (sample amount), put it in 30 mL of 1 / 100N n-butylamine-toluene / ethanol (volume ratio 48/52) solution, ultrasonic cleaner (Branson, For 1 hour with a model 1510J-MT). After leaving still for 24 hours, a part of the ceramic material dispersion is subjected to solid-liquid separation using a centrifuge (model CP-56G manufactured by Hitachi, Ltd.) at 25,000 rpm for 60 minutes. 10 mL of the separated liquid part is added to 20 mL of a toluene / ethanol (volume ratio 2/1) solution to which bromocresol green indicator is added, and then neutralized with a 1/100 N hydrochloric acid-ethanol solution. Assuming that the titer at this time is XmL, the titer required to neutralize 10 mL of 1 / 100N n-butylamine-toluene / ethanol (volume ratio 48/52) solution is BmL, and the sample amount is Sg, the following formula Thus, the acid amount is determined.
Acid amount (μmol / g) = 30 × (BX) / S

  The content (solid content) of the basic ceramic material in the slurry composition of the present invention is preferably 10 to 50% by weight, more preferably 15%, based on the slurry composition, from the viewpoint of being suitable for sheet molding. It is -45 weight%, More preferably, it is 20-40 weight%.

  The average particle diameter based on the BET specific surface area of the basic ceramic material in the present invention is preferably 500 nm or less, more preferably 200 nm or less, and further preferably 120 nm or less from the viewpoint of thinning the ceramic sheet. Moreover, 5 nm or more is preferable from a viewpoint of handling of a slurry composition, and the coexistence of the fine dispersibility of a basic ceramic material, and the antistatic property of a ceramic sheet, More preferably, it is 10 nm or more, More preferably, it is 20 nm or more. Taking these viewpoints together, the average particle size of the basic ceramic material is preferably 5 to 500 nm, more preferably 10 to 200 nm, and still more preferably 20 to 120 nm.

In the present specification, the average particle diameter of the basic ceramic material (average particle diameter based on the BET specific surface area) is preferably the average particle diameter of the powdered basic ceramic material, and the particle diameter R (m) Assuming a sphere, it can be obtained using the BET specific surface area S (m ² / g) measured by the nitrogen adsorption method and the specific gravity ρ (g / cm ³ ) of the basic ceramic material. That is, since the BET specific surface area is a surface area per unit weight, assuming that the surface area is A (m ² ) and the weight of the particles is W (g),
S (m ² / g) = A (m ² ) / W (g)
= [4 × π × (R / 2) ² ] / [4/3 × π × (R / 2) ³ × ρ × 10 ⁶ ]
= 6 / (R × ρ × 10 ⁶ )
Is obtained. When the unit of particle size is converted,
R (nm) = 6000 / (S × ρ)
The average particle diameter (average particle diameter based on BET specific surface area) can be obtained. For example, if the BET specific surface area of barium titanate (specific gravity 6.0) is 5.0 (m ² / g), the average particle diameter (average particle diameter based on the BET specific surface area) is 200 nm.

[Polyvinyl acetal resin]
The slurry composition of the present invention contains a polyvinyl acetal resin. The polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol. The method of acetalization is not particularly limited. For example, polyvinyl alcohol is dissolved in warm water, this aqueous polyvinyl alcohol solution is maintained at a predetermined temperature, an aldehyde and an acid catalyst are added, and the acetalization reaction is allowed to proceed while stirring. Then, after aging by raising the reaction temperature to complete the reaction, there may be mentioned a method of neutralizing, washing and drying.

  The aldehyde used in the acetalization reaction is not particularly limited. For example, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde Aliphatic aldehydes such as 2-ethylhexylaldehyde, n-heptylaldehyde, n-octaldehyde, n-nonylaldehyde, n-decylaldehyde, amylaldehyde, benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde, etc. Aromatic aldehydes, and the like. These aldehydes may be used alone or in combination of two or more. As the aldehyde, butyraldehyde and acetaldehyde, which are excellent in acetalization reaction and can impart various properties such as pressure-bonding properties when laminating ceramic sheets, are preferable. More preferred.

  The polyvinyl acetal resin preferably has an acetalization degree of 55 to 80 mol%, more preferably 65 to 75 mol%. When the degree of acetalization is 55 mol% or more, the solubility in a nonpolar solvent is improved, and the flexibility of the ceramic sheet is improved. On the other hand, when the degree of acetalization is 80 mol% or less, the coating film strength of the resulting ceramic sheet is improved. Here, the degree of acetalization refers to the proportion of hydroxyl groups acetalized among the hydroxyl groups of polyvinyl alcohol. For example, in the case of polyvinyl butyral resin, it can be measured in accordance with JIS K 6728.

  The polyvinyl acetal resin preferably has a residual hydroxyl group content of 10 to 45 mol%, more preferably 15 to 40 mol%. When the residual hydroxyl group amount is 10 mol% or more, the toughness of the polyvinyl acetal resin is improved and the dispersibility of the basic ceramic material is improved. On the other hand, when the residual hydroxyl group amount is 45 mol% or less, it becomes easily soluble in an organic solvent. For example, in the case of a polyvinyl butyral resin, the amount of residual hydroxyl groups of the polyvinyl acetal resin can be measured according to JIS K 6728.

  The polyvinyl acetal resin may be appropriately manufactured or may be a commercially available product. The polyvinyl acetal resin is preferably a polyvinyl butyral resin from the viewpoint of the flexibility of the ceramic sheet and the pressure-bonding property when the ceramic sheet is laminated. As commercially available products of polyvinyl butyral resin, “BL-1”, “BL-2”, “BL-5”, “BM-1”, “BM-2”, “BM” of S-LEC B series manufactured by Sekisui Chemical Co., Ltd. -5 "," BH-3 "," BX-1 "," BX-3 "and" BX-5 ", Denkabuthirar series" # 3000-1 "," # 3000-2 "manufactured by Denki Kagaku Kogyo Co., Ltd. , “# 3000-4” and “# 3000-K” and “B30T”, “B30H”, “B45M”, “B45H”, “B60T”, “B60H” and the like of the Kuraray Mobital series.

  The content of the polyvinyl acetal resin in the slurry composition of the present invention is 2% with respect to 100 parts by weight of the basic ceramic material from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet and exhibiting the binder function. Part or more, preferably 4 parts by weight or more, and more preferably 6 parts by weight or more. Further, from the viewpoint of improving the antistatic property, peelability and toughness of the ceramic sheet and reducing the viscosity of the slurry composition to facilitate the formation of the sheet, the amount is 20 parts by weight or less with respect to 100 parts by weight of the basic ceramic material. Preferably, it is 18 parts by weight or less, more preferably 16 parts by weight or less. Taking these viewpoints together, the content of the polyvinyl acetal resin in the slurry composition of the present invention is preferably 2 to 20 parts by weight, more preferably 4 to 18 parts by weight, based on 100 parts by weight of the basic ceramic material. More preferably, it is 6 to 16 parts by weight.

[Other ingredients]
The slurry composition of the present invention is a conventionally known addition of a low molecular weight compound such as a binder resin such as an acrylic resin or a cellulose resin, a plasticizer, a lubricant, or a dispersion aid, as long as the effects of the present invention are not impaired. An agent may be contained. The plasticizer is not particularly limited, and examples thereof include phthalic acid diesters such as dioctyl phthalate (DOP) and dibutyl phthalate (DBP), adipic acid diesters such as dioctyl adipate, and alkylene glycol diesters such as triethylene glycol 2-ethylhexyl. Can be mentioned. Among these, DOP is preferable because it is low in volatility and easily maintains the flexibility of the sheet. The content of the plasticizer in the slurry composition of the present invention is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and more preferably 15 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin from the viewpoint of the flexibility of the ceramic sheet. Part or more is more preferable. Moreover, from a peelable viewpoint of a ceramic sheet, 40 weight part or less is preferable with respect to 100 weight part of polyvinyl acetal resin, 30 weight part or less is more preferable, and 25 weight part or less is further more preferable. When these viewpoints are put together, the content of the plasticizer in the slurry composition is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, with respect to 100 parts by weight of the polyvinyl acetal resin. Is more preferable.

[Slurry composition]
The slurry composition of the present invention can be produced, for example, by a production method including a step of mixing the polymer dispersant, the basic ceramic material, and the non-aqueous solvent. The mixing step includes, for example, mixing the polymer dispersant, the basic ceramic material, and the non-aqueous solvent together with zirconia beads and the like. Then, the remaining component containing the said cation compound and the said polyvinyl acetal resin can be contained, and the slurry composition of this invention can be obtained. The content of each component can be determined with reference to the above description.

  The slurry composition of this invention can be used for the ceramic molded product used for the electronic device field | area. For example, when a thin ceramic sheet is formed using a basic ceramic-containing slurry composition by a molding method such as sheet, casting, pressing, extrusion, or injection, the slurry composition of the present invention can be charged. The prevention and peelability can be improved, and the toughness (breaking stress and elongation) of the sheet can be improved. In the present specification, the “thinned ceramic sheet” or “thin ceramic sheet” refers to a ceramic sheet having a thickness of preferably less than 15 μm, more preferably 10 μm or less, and even more preferably 8 μm or less. The lower limit of the thickness is not particularly limited, but exceeds 0 μm, for example, 0.02 μm or more.

  The present disclosure further relates to one or more of the following embodiments.

  <1> A slurry composition containing a cationic compound containing a nitrogen-containing heteroaromatic quaternary ammonium cation group, a polymer dispersant, a non-aqueous solvent, a basic ceramic material, and a polyvinyl acetal resin.

［式（１）中、Ｒ₁は、炭素数１〜４のアルキル基を示し、Ｒ₂、Ｒ₃及びＲ₄は、同一又は異なり、水素原子、又は水酸基を有していてもよい炭素数１〜４のアルキル基を示す。式（２）中、Ｒ₅及びＲ₆は、同一又は異なり、炭素数１〜４のアルキル基を示し、Ｒ₇及びＲ₈は、同一又は異なり、水素原子、又は水酸基を有していてもよい炭素数１〜４のアルキル基を示す。式（３）中、Ｒ₉及びＲ₁₀は、同一又は異なり、炭素数１〜４のアルキル基を示し、Ｒ₁₁は水素原子、又は水酸基を有していてもよい炭素数１〜４のアルキル基を示す。］
＜５＞ 前記カチオン基が、前記一般式（３）で表されるカチオン基である、＜１＞から＜４＞のいずれかに記載のスラリー組成物。
＜６＞ 前記カチオン基が、前記一般式（３）で表されるカチオン基であり、前記一般式（３）におけるＲ₉及びＲ₁₀の炭素数の合計が、２〜５である、＜１＞から＜５＞のいずれかに記載のスラリー組成物。
＜７＞ 前記カチオン基の分子量が、３００以下、好ましくは２００以下、より好ましくは１５０以下、さらに好ましくは１２０以下であり、又は、９０以上、好ましくは９５以上、より好ましくは１００以上であり、又は、９０〜３００、好ましくは９５〜３００、より好ましくは９５〜２００、さらに好ましくは１００〜１５０、さらにより好ましくは１００〜１２０である、＜１＞から＜６＞のいずれかに記載のスラリー組成物。
＜８＞ 前記カチオン化合物が、前記カチオン基と、アニオン基との塩であり、前記アニオン基が、有機アニオン基である、＜１＞から＜７＞のいずれかに記載のスラリー組成物。
＜９＞ 前記アニオン基が、アルキル硫酸及び脂肪族カルボン酸からなる群から選ばれる１種以上の酸のアニオン基である、＜１＞から＜８＞のいずれかに記載のスラリー組成物。
＜１０＞ 前記カチオン化合物の含有量が、前記塩基性セラミックス材料１００重量部に対して０．０５重量部以上、好ましくは０．１重量部以上、より好ましくは０．２重量部以上、さらに好ましくは０．３重量部以上であり、又は、塩基性セラミックス材料１００重量部に対して２．０重量部以下、好ましくは１．８重量部以下、より好ましくは１．５重量部以下、さらに好ましくは１．２重量部以下であり、又は、塩基性セラミックス材料１００重量部に対して０．０５〜２．０重量部好ましくは０．１〜１．８重量部、さらに好ましくは０．２〜１．５重量部、よりさらに好ましくは０．３〜１．２重量部である、＜１＞から＜９＞のいずれかに記載のスラリー組成物。
＜１１＞ スラリー組成物中の前記カチオン化合物の含有量が、ポリビニルアセタール樹脂１．０重量部に対し０．０１重量部以上、好ましくは０．０１５重量部以上、より好ましくは０．０２重量部以上、さらに好ましくは０．０３重量部以上であり、又は、ポリビニルアセタール樹脂１．０重量部に対し０．２重量部以下、好ましくは０．１８重量部以下、より好ましくは０．１５重量部以下、さらに好ましくは０．１２重量部以下であり、又は、ポリビニルアセタール樹脂１．０重量部に対し０．０１〜０．２重量部、好ましくは０．０１５〜０．１８重量部、より好ましくは０．０２〜０．１５重量部、さらに好ましくは０．０３〜０．１２重量部である、＜１＞から＜１０＞のいずれかに記載のスラリー組成物。
＜１２＞ 前記高分子分散剤の重量平均分子量が、２０００以上、好ましくは４０００以上、より好ましくは６０００以上、さらに好ましくは８０００以上であり、又は、２０００００以下、好ましくは１２００００以下、より好ましくは６００００以下、さらに好ましくは３６０００以下であり、又は、２０００〜２０００００、好ましくは４０００〜１２００００、より好ましくは６０００〜６００００であり、さらに好ましくは８０００〜３６０００である、＜１＞から＜１１＞のいずれかに記載のスラリー組成物。
＜１３＞ スラリー組成物中の前記高分子分散剤の含有量が、塩基性セラミックス材料１００重量部に対する重量部として、塩基性セラミックス材料のＢＥＴ比表面積［単位ｍ²／ｇ］を５で割った値の０．３倍以上、好ましくは０．４倍以上であり、又は、塩基性セラミックス材料のＢＥＴ比表面積［単位ｍ²／ｇ］を５で割った値の１．５倍以下、好ましくは１．２倍以下であり、又は塩基性セラミックス材料のＢＥＴ比表面積［単位ｍ²／ｇ］を５で割った値の０．３〜１．５倍、好ましくは０．４〜１．２倍である、＜１＞から＜１２＞のいずれかに記載のスラリー組成物。
＜１４＞ 前記高分子分散剤が、アニオン性高分子分散剤である、＜１＞から＜１３＞のいずれかに記載のスラリー組成物。
＜１５＞ 前記スラリー組成物がさらに、フタル酸ジエステル、アジピン酸ジエステル、及びアルキレングリコールジエステルからなる群から選択される可塑剤を含み、好ましくはフタル酸ジエステルを含み、より好ましくはジオクチルフタレートを含む、＜１＞から＜１４＞のいずれかに記載のスラリー組成物。
＜１６＞ 前記可塑剤の含有量が、ポリビニルアセタール樹脂１００重量部に対して５重量部以上、好ましくは１０重量部以上、より好ましく１５重量部以上であり、又は、ポリビニルアセタール樹脂１００重量部に対して４０重量部以下、好ましくは３０重量部以下、より好ましくは２５重量部以下であり、又は、ポリビニルアセタール樹脂１００重量部に対して５〜４０重量部、好ましくは１０〜３０重量部、より好ましくは１５〜２５重量部である、＜１５＞記載のスラリー組成物。
＜１７＞ 前記塩基性セラミックス材料が、ジルコン酸の複合酸化物及びチタン酸の複合酸化物からなる群から選択される１種以上であり、好ましくはチタン酸の複合酸化物であり、より好ましくはチタン酸バリウムである、＜１＞から＜１６＞のいずれかに記載のスラリー組成物。
＜１８＞ 前記塩基性セラミックス材料のＢＥＴ比表面積に基づく平均粒径が、５００ｎｍ以下、好ましくは２００ｎｍ以下、より好ましくは１２０ｎｍ以下であり、又は、５ｎｍ以上、好ましくは１０ｎｍ以上、より好ましくは２０ｎｍ以上であり、又は、５〜５００ｎｍ、好ましくは１０〜２００ｎｍ、より好ましくは２０〜１２０ｎｍである、＜１＞から＜１７＞のいずれかに記載のスラリー組成物。
＜１９＞ 前記ポリビニルアセタール樹脂が、ポリビニルブチラール樹脂である、＜１＞から＜１８＞のいずれかに記載のスラリー組成物。
＜２０＞ 前記高分子分散剤が、共重合体、好ましくは塩基性セラミックス材料に対する親和性の高い構成単位と非水系溶媒に対する親和性の高い構成単位とを有する共重合体、より好ましくは（メタ）アクリル酸由来の構成単位とポリオキシエチレン基を有する構成単位とを有する項重合体である、＜１＞から＜１９＞のいずれかに記載のスラリー組成物。
＜２１＞ 前記非水系溶媒が、アルコール類及びセロソルブ類から選ばれる非水系溶媒を有し、好ましくはアルコール類を有し、より好ましくはエタノールを有する、＜１＞から＜２０＞のいずれかに記載のスラリー組成物。
＜２２＞ 前記非水系溶媒が、炭化水素類及び芳香族類から選ばれる非水系溶媒を有し、好ましくは芳香族類を有し、より好ましくはトルエンを有する、＜１＞から＜２１＞のいずれかに記載のスラリー組成物。
＜２３＞ ＜１＞から＜２２＞のいずれかに記載のスラリー組成物を用いてセラミックシートを形成することを含む、セラミックシートの製造方法。 <2> The slurry composition according to <1>, wherein the cationic group is a cationic group having a quaternary ammonium in an aromatic ring.
<3> The <1> or <2> description, wherein the cationic group is a cationic group having at least one structure selected from the group consisting of pyridinium, pyrazolium, imidazolium, pyrimidinium, pyrazinium, pyridazinium and pyrrolium structures. Slurry composition.
<4> The above cationic group is any one of <1> to <3>, which is a cationic group selected from the group consisting of cationic groups represented by the following general formulas (1), (2) and (3) The slurry composition described.

[In formula (1), R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₃ and R ₄ are the same or different and may have a hydrogen atom or a hydroxyl group. 1-4 alkyl groups are shown. In formula (2), R ₅ and R ₆ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and R ₇ and R ₈ are the same or different and may have a hydrogen atom or a hydroxyl group. A good alkyl group having 1 to 4 carbon atoms is shown. In formula (3), R ₉ and R ₁₀ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and R ₁₁ is a hydrogen atom or an alkyl having 1 to 4 carbon atoms which may have a hydroxyl group. Indicates a group. ]
<5> The slurry composition according to any one of <1> to <4>, wherein the cationic group is a cationic group represented by the general formula (3).
<6> The cationic group is a cationic group represented by the general formula (3), and the total number of carbon atoms of R ₉ and R ₁₀ in the general formula (3) is 2 to 5, <1 The slurry composition according to any one of <5> to <5>.
<7> The molecular weight of the cationic group is 300 or less, preferably 200 or less, more preferably 150 or less, still more preferably 120 or less, or 90 or more, preferably 95 or more, more preferably 100 or more, Alternatively, the slurry according to any one of <1> to <6>, which is 90 to 300, preferably 95 to 300, more preferably 95 to 200, still more preferably 100 to 150, and even more preferably 100 to 120. Composition.
<8> The slurry composition according to any one of <1> to <7>, wherein the cationic compound is a salt of the cationic group and an anionic group, and the anionic group is an organic anionic group.
<9> The slurry composition according to any one of <1> to <8>, wherein the anionic group is an anionic group of one or more acids selected from the group consisting of alkylsulfuric acid and aliphatic carboxylic acid.
<10> The content of the cationic compound is 0.05 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, further preferably 100 parts by weight of the basic ceramic material. Is 0.3 parts by weight or more, or 2.0 parts by weight or less, preferably 1.8 parts by weight or less, more preferably 1.5 parts by weight or less, even more preferably 100 parts by weight of the basic ceramic material. Is 1.2 parts by weight or less, or 0.05 to 2.0 parts by weight, preferably 0.1 to 1.8 parts by weight, more preferably 0.2 to 0.2 parts by weight with respect to 100 parts by weight of the basic ceramic material. The slurry composition according to any one of <1> to <9>, which is 1.5 parts by weight, more preferably 0.3 to 1.2 parts by weight.
<11> The content of the cationic compound in the slurry composition is 0.01 parts by weight or more, preferably 0.015 parts by weight or more, more preferably 0.02 parts by weight with respect to 1.0 part by weight of the polyvinyl acetal resin. Or more, more preferably 0.03 parts by weight or more, or 0.2 parts by weight or less, preferably 0.18 parts by weight or less, more preferably 0.15 parts by weight with respect to 1.0 part by weight of the polyvinyl acetal resin. In the following, it is more preferably 0.12 parts by weight or less, or 0.01 to 0.2 parts by weight, preferably 0.015 to 0.18 parts by weight, more preferably 1.0 parts by weight of polyvinyl acetal resin. Is a slurry composition according to any one of <1> to <10>, wherein 0.02 to 0.15 parts by weight, more preferably 0.03 to 0.12 parts by weight.
<12> The polymer dispersant has a weight average molecular weight of 2000 or more, preferably 4000 or more, more preferably 6000 or more, further preferably 8000 or more, or 200000 or less, preferably 120,000 or less, more preferably 60000. Or less, more preferably 36000 or less, or 2000 to 200000, preferably 4000 to 120,000, more preferably 6000 to 60000, and further preferably 8000 to 36000, any one of <1> to <11> The slurry composition according to 1.
<13> The BET specific surface area [unit m ² / g] of the basic ceramic material is divided by 5 as the content of the polymer dispersant in the slurry composition is based on 100 parts by weight of the basic ceramic material. 0.3 times or more, preferably 0.4 times or more of the value, or 1.5 times or less of the value obtained by dividing the BET specific surface area [unit m ² / g] of the basic ceramic material by 5, preferably 1.2 times or less, or 0.3 to 1.5 times, preferably 0.4 to 1.2 times the value obtained by dividing the BET specific surface area [unit m ² / g] of the basic ceramic material by 5 The slurry composition according to any one of <1> to <12>, wherein
<14> The slurry composition according to any one of <1> to <13>, wherein the polymer dispersant is an anionic polymer dispersant.
<15> The slurry composition further includes a plasticizer selected from the group consisting of a phthalic acid diester, an adipic acid diester, and an alkylene glycol diester, preferably includes a phthalic acid diester, and more preferably includes dioctyl phthalate. <1> to the slurry composition according to any one of <14>.
<16> The plasticizer content is 5 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin, preferably 10 parts by weight or more, more preferably 15 parts by weight or more, or 100 parts by weight of the polyvinyl acetal resin. 40 parts by weight or less, preferably 30 parts by weight or less, more preferably 25 parts by weight or less, or 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the polyvinyl acetal resin. The slurry composition according to <15>, preferably 15 to 25 parts by weight.
<17> The basic ceramic material is at least one selected from the group consisting of a complex oxide of zirconic acid and a complex oxide of titanic acid, preferably a complex oxide of titanic acid, more preferably The slurry composition according to any one of <1> to <16>, which is barium titanate.
<18> The average particle diameter based on the BET specific surface area of the basic ceramic material is 500 nm or less, preferably 200 nm or less, more preferably 120 nm or less, or 5 nm or more, preferably 10 nm or more, more preferably 20 nm or more. Or a slurry composition according to any one of <1> to <17>, which is 5 to 500 nm, preferably 10 to 200 nm, more preferably 20 to 120 nm.
<19> The slurry composition according to any one of <1> to <18>, wherein the polyvinyl acetal resin is a polyvinyl butyral resin.
<20> The polymer dispersant is a copolymer, preferably a copolymer having a structural unit having high affinity for a basic ceramic material and a structural unit having high affinity for a non-aqueous solvent, more preferably (meta The slurry composition according to any one of <1> to <19>, which is a term polymer having a structural unit derived from acrylic acid and a structural unit having a polyoxyethylene group.
<21> The nonaqueous solvent has a nonaqueous solvent selected from alcohols and cellosolves, preferably has alcohols, and more preferably has ethanol, <1> to <20> The slurry composition described.
<22> The nonaqueous solvent has a nonaqueous solvent selected from hydrocarbons and aromatics, preferably has aromatics, more preferably has toluene, <1> to <21> The slurry composition in any one.
<23> A method for producing a ceramic sheet, comprising forming a ceramic sheet using the slurry composition according to any one of <1> to <22>.

  Hereinafter, the present invention will be described by way of examples.

1. Preparation of slurry compositions (Examples 1 to 11 , 13 to 17, Reference Example 12 and Comparative Examples 1 to 9) Cationic compounds A1 to A13 shown in Table 1 below, polymer dispersants B1 to B7 shown in Table 2 below, Slurry compositions of Examples 1 to 11 , 13 to 17 , Reference Example 12 and Comparative Examples 1 to 9 were prepared using a basic ceramic material and a polyvinyl acetal resin.

[Cationic compound]
In the slurry compositions of Examples 1 to 11 , 13 to 17 , Reference Example 12 and Comparative Example 7, the following cation compounds A1 to A8 were used. On the other hand, in Comparative Examples 2 to 6 and Comparative Example 9, the following cation compounds A9 to A13 were used instead of the cation compounds A1 to A8. The used cation compounds A1 to A13 are summarized in Table 1 below together with the molecular weight of the cation moiety.

A1: 1-ethyl-3-methylimidazolium ethyl sulfate (manufactured by Sigma-Aldrich)
A2: 1-ethyl-3-methylimidazolium acetate (manufactured by Sigma-Aldrich)
A3: 1-ethyl-2,3-dimethylimidazolium ethyl sulfate (manufactured by Sigma-Aldrich)
A4: 1-butyl-3-methylimidazolium ethyl sulfate (manufactured by Sigma-Aldrich)
A5: 1-butyl-3-methylimidazolium acetate (manufactured by Sigma-Aldrich)
A6: 1,2,4-trimethylpyrazolium methyl sulfate (manufactured by Sigma-Aldrich)
A7: 1-ethyl-3-methylpyridinium ethyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.)
A8: 1-ethyl-3-hydroxymethylpyridinium ethyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.)
A9: 1-methylimidazolium hydrogen sulfate (manufactured by Sigma-Aldrich)
A10: Tris (2-hydroxyethyl) methylammonium methyl sulfate (manufactured by Sigma-Aldrich)
A11: Tributylmethylammonium methyl sulfate (manufactured by Sigma-Aldrich)
A12: Octyl-2-hydroxyethylimidazolinium ethyl sulfate (manufactured by Sigma-Aldrich)
A13: Laurylethylbis (2-hydroxyethyl) ammonium ethyl sulfate (a quaternary ammonium salt synthesized by reacting a laurylamine ethylene oxide 2-mole adduct with diethyl sulfate)

[Polymer dispersant]
In the slurry compositions of Examples 1 to 11 , 13 to 17, Reference Example 12, Comparative Examples 1 to 6 , 8, and 9, polymer dispersants B1 to B7 shown in Table 2 below were used. The polymer dispersants B3, B5, and B6 were synthesized under the following conditions. Moreover, the measurement of the non volatile matter of each polymer dispersing agent and the weight average molecular weight were performed on the following conditions.

[Production Example 1 of Polymer Dispersant]
In a separable flask equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 1.5 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries), methoxypolyethylene glycol (23) methacrylate (PEGMA23: manufactured by Shin-Nakamura Chemical Co., Ltd.) NK -Ester M-230G, average added mole number of ethylene oxide 23) 5.5 g, methacrylamide (manufactured by Wako Pure Chemical Industries) 3.0 g, ethanol (manufactured by Wako Pure Chemical Industries) 12.25 g were charged, and the atmosphere was replaced with nitrogen. , Heated to 65 ° C. After the tank temperature reached 65 ° C., a mixture of 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) and 2.5 g of ethanol was added. Thereafter, a mixture of 13.5 g of methyl methacrylate, 49.5 g of PEGMA23, 27.0 g of methacrylamide, 110.25 g of ethanol, and 2.7 g of V-65 was added dropwise over 3 hours. After aging at 65 ° C. for 3 hours, the mixture was cooled to room temperature. Ethanol was added to adjust the concentration to obtain an ethanol solution of the polymer dispersant B3. The nonvolatile content of the polymer dispersant B3 solution was 33.6% by weight, and the weight average molecular weight of the polymer dispersant B3 was 32900.

[Production Example 2 of Polymer Dispersant]
To a separable flask equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, methoxypolyethylene glycol (23) methacrylate (PEGMA23: NK-ester M-230G, Shin-Nakamura Chemical Co., Ltd., average addition mole number of ethylene oxide 23) 8.5 g, 1.5 g of methacrylic acid (manufactured by Wako Pure Chemical Industries), 10 g of ethanol (manufactured by Wako Pure Chemical Industries), 0.1 g of 3-mercapto-1,2-propanediol (manufactured by Wako Pure Chemical Industries) Charge, purge with nitrogen, and heat to 65 ° C. After the tank temperature reached 65 ° C., a mixture of 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) and 2.5 g of ethanol was added. Thereafter, a mixture of 76.5 g of PEGMA23, 13.5 g of methacrylic acid, 90 g of ethanol, 2.7 g of V-65, and 0.9 g of 3-mercapto-1,2-propanediol was added dropwise over 3 hours. After aging at 65 ° C. for 3 hours, the mixture was cooled to room temperature. Ethanol was added to adjust the concentration to obtain an ethanol solution of the polymer dispersant B5. The nonvolatile content of the polymer dispersant B5 solution was 53.2% by weight, and the weight average molecular weight of the polymer dispersant B5 was 17,400.

[Production Example 3 of Polymer Dispersant]
In a separable flask equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 1.5 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries), methoxypolyethylene glycol (23) methacrylate (PEGMA23: manufactured by Shin-Nakamura Chemical Co., Ltd.) NK -Ester M-230G, average added mole number of ethylene oxide 23) 7.0 g, methacrylic acid (manufactured by Wako Pure Chemical Industries) 1.5 g, ethanol (manufactured by Wako Pure Chemical Industries) 15 g, 3-mercapto-1,2 -Propanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.3 g was charged, purged with nitrogen, and heated to 65 ° C. After the temperature in the tank reached 65 ° C., a mixture of 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65: manufactured by Wako Pure Chemical Industries, Ltd.) and 2.5 g of ethanol was added. . Then, a mixture of methyl methacrylate 13.5 g, PEGMA23 63.0 g, methacrylic acid 13.5 g, ethanol 135 g, V-65 2.7 g, 3-mercapto-1,2-propanediol 2.7 g was taken over 3 hours. And dripped. After aging at 65 ° C. for 3 hours, the mixture was cooled to room temperature. Ethanol was added to adjust the concentration to obtain an ethanol solution of the polymer dispersant B6. The nonvolatile content of the polymer dispersant B6 solution was 52.0% by weight, and the weight average molecular weight of the polymer dispersant B6 was 8300.

[Measurement of non-volatile content]
The nonvolatile content of the polymer dispersant solution was measured as follows. That is, a glass rod and 10 g of dry anhydrous sodium sulfate are weighed into a petri dish, and 2 g of the polymer solution is added thereto, mixed with the glass rod, and dried for 2 hours with a 105 ° C. vacuum dryer (pressure 8 kPa). The weight after drying was measured, and the value obtained from the following formula was defined as the nonvolatile content.
Nonvolatile content = {[sample amount− (weight after drying− (weight of petri dish + weight of glass rod + weight of anhydrous sodium sulfate)]] / sample amount} × 100

(Measurement of weight average molecular weight)
The weight average molecular weight of the polymer dispersant was measured as follows. That is, the eluent was flowed at a flow rate of 1 mL per minute, and the column was stabilized in a constant temperature bath at 40 ° C. Measurement was performed by injecting 100 μL of the sample solution. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. For the preparation of the calibration curve, the following monodisperse polystyrene was used as a standard sample.
Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation)
Measurement conditions Sample solution: 0.5 wt% N, N-dimethylformamide solution Eluent: N, N-dimethylformamide solution column with H ₃ PO ₄ : 60 mmol / L and LiBr: 50 mmol / L: α-M + α -M (Tosoh Corporation)
Detector: Differential refractive index calibration curve: Polystyrene 5.26 × 10 ² , 1.02 × 10 ⁵ , 8.42 × 10 ⁶ manufactured by Tosoh Corporation; Polystyrene 4.0 × 10 ³ , 3.0 × manufactured by Nishio Kogyo Co., Ltd. 10 ⁴ , 9.0 × 10 ⁵ (numbers are molecular weights)

[Preparation of slurry composition]
[Preparation of slurry composition of Example 1]
The slurry composition of Example 1 was prepared as follows. Barium titanate (BET specific surface area 20 m ² / g, average particle size 50 nm calculated from BET specific surface area, base amount 90 μmol / g, acid amount 10 μmol / g) 20 g, and polymer dispersant B6 0.8 g (effective amount ( Nonvolatile content)) is placed in a 100 mL container together with 50 g of zirconia beads having a diameter of 1 mm, and a mixed solvent of toluene / ethanol = 48/52 (volume ratio) is added, so that the solid content concentration of barium titanate is 50% by weight. The dispersion treatment was performed for 96 hours using a desktop ball mill. Next, polyvinyl butyral resin (acetalization degree 68 mol%, residual hydroxyl group amount 31 mol%) 2.8 g, dioctyl phthalate 0.56 g, cationic compound A1 0.2 g, and toluene / ethanol = 48/52 (volume ratio) A mixed solvent was added to adjust the solid content concentration of barium titanate to 35% by weight with respect to the slurry composition. After mixing for 2 hours in a desktop ball mill, the zirconia beads were removed by filtration. 1 was obtained (Table 3 below).

[Preparation of slurry compositions of Examples 2 to 8 and Comparative Examples 1 to 6]
Slurry compositions of Examples 2 to 8 and Comparative Examples 2 to 6 were prepared in the same manner as in Example 1 except that the cationic compounds shown in Table 3 below were used instead of the cationic compound A1. As Comparative Example 1, a slurry composition was prepared in the same manner as in Example 1 except that the cation compound A1 was not used.

[Preparation of slurry composition of Example 9]
The slurry composition of Example 9 was prepared as follows. Barium titanate (BET specific surface area 20 m ² / g, average particle size 50 nm calculated from BET specific surface area, base amount 90 μmol / g, acid amount 10 μmol / g) 20 g, and polymer dispersant B1 0.8 g (effective portion ( Nonvolatile content)) is placed in a 100 mL container together with 50 g of zirconia beads having a diameter of 1 mm, and a mixed solvent of toluene / ethanol = 48/52 (volume ratio) is added, so that the solid content concentration of barium titanate is 50% by weight. The dispersion treatment was performed for 96 hours using a desktop ball mill. Subsequently, polyvinyl butyral resin (degree of acetalization 68 mol%, residual hydroxyl group amount 31 mol%) 1.6 g, dioctyl phthalate 0.32 g, cationic compound A1 0.16 g, and toluene / ethanol = 48/52 (volume ratio) A mixed solvent was added to adjust the solid content concentration of barium titanate to 35% by weight with respect to the slurry composition. After mixing for 2 hours in a desktop ball mill, the zirconia beads were removed by filtration. 9 slurry compositions were obtained (Table 3 below).

[Preparation of slurry compositions of Examples 10 to 11 , 13 to 15, Reference Example 12 and Comparative Example 7]
Slurry compositions of Examples 10 to 11, 13 to 15 and Reference Example 12 were prepared in the same manner as in Example 9, except that the polymer dispersant in Table 3 below was used instead of the polymer dispersant B1. As Comparative Example 7, a slurry composition was prepared in the same manner as in Example 9 except that the polymer dispersant B1 was not used.

[Preparation of slurry composition of Example 16]
The slurry composition of Example 16 was prepared as follows. Barium titanate (BET specific surface area 10 m ² / g, average particle size 100 nm calculated from BET specific surface area, base amount 90 μmol / g, acid amount 10 μmol / g) 20 g, and polymer dispersant B5 0.32 g (effective portion ( Nonvolatile content)) is placed in a 100 mL container together with 50 g of zirconia beads having a diameter of 1 mm, and a mixed solvent of toluene / ethanol = 48/52 (volume ratio) is added, so that the solid content concentration of barium titanate is 50% by weight. The dispersion treatment was performed for 96 hours using a desktop ball mill. Next, polyvinyl butyral resin (acetalization degree 68 mol%, residual hydroxyl group amount 31 mol%) 2.8 g, dioctyl phthalate 0.56 g, cation compound A1 0.1 g, and toluene / ethanol = 48/52 (volume ratio) A mixed solvent was added to adjust the solid content concentration of barium titanate to 35% by weight with respect to the slurry composition. After mixing for 2 hours in a desktop ball mill, the zirconia beads were removed by filtration. Sixteen slurry compositions were obtained (Table 3 below).

[Preparation of slurry compositions of Example 17 and Comparative Examples 8 to 9]
A slurry composition of Example 17 and Comparative Example 9 was prepared in the same manner as in Example 16 except that the cationic compound shown in Table 3 below was used instead of the cationic compound A1. As Comparative Example 8, a slurry composition was prepared in the same manner as in Example 16 except that the cation compound A1 was not used.

2. Molding and Evaluation of Ceramic Sheet A ceramic sheet was molded using the slurry compositions of Examples 1 to 11 , 13 to 17 , Reference Example 12 and Comparative Examples 1 to 9, and the amount of peel charge, peel force, and breakage of the ceramic sheet Measurements of strength and elongation were made.

[Ceramic sheet forming]
Using the slurry applicators of Examples 1-11 , 13-17 , Reference Example 12 and Comparative Examples 1-9 using a film applicator (gap 50 μm), a silicone-treated release film (Purex manufactured by Teijin DuPont) was used. It was coated and dried at 60 ° C. for 16 hours to form a ceramic sheet. In addition, the thickness of the ceramic sheet after drying was 5 to 8 μm.

[Measurement of peeling charge amount]
Using the molded ceramic sheet, the peel charge amount was measured by the following method. That is, together with the release film, the ceramic sheet was cut into test pieces having a short side of 4 cm and a long side of 10 cm, and the 90 ° peel test jig was mounted with the side opposite to the coating surface (film side) facing down. It fixed using the double-sided tape to the base of the desktop type | mold precision testing machine (Shimadzu Corporation autograph AGS-X). Next, one end of the short side of the ceramic sheet test piece was peeled from the release film by 1 cm, and then sandwiched with clips to fix the clips to the load cell. Thereafter, the load cell is raised at a rate of 1 cm / sec to perform 90-degree peeling, and the electrostatic charge sensor (peeling charge amount) on the peeling surface side of the ceramic sheet is set at a distance of 3 cm from the peeling surface ( Measured with SK-200 manufactured by Keyence Corporation. The results are shown in Table 3 below. The smaller the absolute value of the peel charge amount, the better the antistatic property.

[Measurement of peel force]
In the measurement of the peel charge amount, the load applied to the load cell when the ceramic sheet was peeled 90 degrees at a speed of 1 cm / second was measured. Specifically, the average value of the load applied to the load cell from the time when the load cell was raised by 3 cm to the time when it was raised by 6 cm was defined as the peeling force. The results are shown in Table 3 below. The smaller the peel force, the better the peelability.

[Measurement of breaking stress and elongation]
The ceramic sheet is cut into dumbbell-shaped No. 1 defined in JIS K6251. Before peeling the ceramic sheet from the release film, the thickness is measured, and the thickness of the ceramic sheet is determined from the difference from the thickness of the release film itself. Next, the peeled ceramic sheet is attached to a load cell attached to a desktop precision tester (Autograph EZ-TEST manufactured by Shimadzu Corporation), pulled at a test speed of 6 cm / min, The breaking strain (elongation) is measured. The results are shown in Table 3 below. The greater the breaking stress and the greater the elongation, the better the toughness.

  As shown in Table 3, in the ceramic sheet formed from the slurry composition of Examples 1-8, compared with the ceramic sheets of Comparative Examples 1-6, the peel charge amount is reduced and the antistatic property is improved, The peel strength was small, the peelability was excellent, the measured values of breaking stress and elongation were large, and the toughness was improved. Similarly, the ceramic sheets formed from the slurry compositions of Examples 16 to 17 were improved in antistatic properties, peel strength and toughness as compared with the ceramic sheets of Comparative Examples 8 to 9. From the viewpoint of improving antistatic properties, a slurry composition containing a cationic compound having a cationic group represented by the general formulas (1) and (3) is preferable. From the viewpoint of improving peelability, the general formula ( A slurry composition containing a cationic compound having a cationic group represented by 3) is preferred, and from the viewpoint of toughness, a slurry containing a cationic compound having a cationic group represented by the general formulas (2) and (3). Compositions have been shown to be preferred. When these viewpoints are put together, it was shown that the cationic group represented by the general formula (3) is even more preferable as the cationic group in the present invention.

Moreover, as shown in the said Table 3, in Examples 9-11, 13-15, and the reference example 12 , all the polymer dispersing agents of cationic, nonionic, and anionic do not use a polymer dispersing agent ( Compared with Comparative Example 7), the peel charge amount and peel force were reduced and the breaking stress and elongation were improved, indicating that the antistatic property, peelability and toughness were excellent. Further, as the polymer dispersant used in the slurry composition of the present invention, it is shown that it is preferable to be cationic and anionic from the viewpoint of improving antistatic properties, and from the viewpoint of improving peelability, It has been shown that it is preferably nonionic and anionic. And it was shown that an anionic polymer dispersing agent is more preferable from the viewpoint of achieving both improvement of antistatic property and improvement of peelability.

  The present invention is useful in the field of forming ceramics, for example, in the field of manufacturing ceramic electronic parts.

Claims (14)

Cationic compounds containing a nitrogen-containing five-membered ring or six-membered heterocyclic aromatic quaternary ammonium cation group, a polymer dispersant weight average molecular weight of 6000 to 200,000, a non-aqueous solvent, a basic ceramic material and polyvinyl acetal resin A slurry composition comprising:   The slurry composition according to claim 1, wherein the cationic group is a cationic group having quaternary ammonium in an aromatic ring.   The slurry composition according to claim 1 or 2, wherein the cationic group is a cationic group having at least one structure selected from the group consisting of pyridinium, pyrazolium, imidazolium, pyrimidinium, pyrazinium, pyridazinium and pyrrolium structures. The slurry composition according to any one of claims 1 to 3, wherein the cationic group is a cationic group selected from the group consisting of cationic groups represented by the following general formulas (1), (2), and (3). .

[In formula (1), R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₃ and R ₄ are the same or different and may have a hydrogen atom or a hydroxyl group. 1-4 alkyl groups are shown. In formula (2), R ₅ and R ₆ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and R ₇ and R ₈ are the same or different and may have a hydrogen atom or a hydroxyl group. A good alkyl group having 1 to 4 carbon atoms is shown. In formula (3), R ₉ and R ₁₀ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and R ₁₁ is a hydrogen atom or an alkyl having 1 to 4 carbon atoms which may have a hydroxyl group. Indicates a group. ]   The slurry composition according to any one of claims 1 to 4, wherein the cationic group is a cationic group represented by the general formula (3). The cationic group is a cationic group represented by the general formula (3), and the total number of carbon atoms of R ₉ and R ₁₀ in the general formula (3) is 2 to 5. The slurry composition according to any one of the above.   The slurry composition according to any one of claims 1 to 6, wherein the molecular weight of the cationic group is 90 to 300.   The slurry composition according to any one of claims 1 to 7, wherein the cationic compound is a salt of the cationic group and an anionic group, and the anionic group is an organic anionic group.   The slurry composition according to any one of claims 1 to 8, wherein the anionic group is an anionic group of one or more acids selected from the group consisting of an alkyl sulfuric acid and an aliphatic carboxylic acid.   The slurry composition according to any one of claims 1 to 9, wherein a content of the cationic compound is 0.05 parts by weight or more and 2.0 parts by weight or less with respect to 100 parts by weight of the basic ceramic material.   The slurry composition according to any one of claims 1 to 10, wherein the polymer dispersant is an anionic polymer dispersant.   The slurry composition according to any one of claims 1 to 11, wherein the basic ceramic material is barium titanate.   The slurry composition according to any one of claims 1 to 12, wherein the polyvinyl acetal resin is a polyvinyl butyral resin. The content of the polymer dispersant in the slurry composition is 0, which is a value obtained by dividing the BET specific surface area [unit m ² / g] of the basic ceramic material by 5 as part by weight with respect to 100 parts by weight of the basic ceramic material. The slurry composition according to any one of claims 1 to 13, which is 3 times or more and 1.5 times or less.