WO2007114152A1 - Barium titanate dispersion composition - Google Patents

Barium titanate dispersion composition Download PDF

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Publication number
WO2007114152A1
WO2007114152A1 PCT/JP2007/056611 JP2007056611W WO2007114152A1 WO 2007114152 A1 WO2007114152 A1 WO 2007114152A1 JP 2007056611 W JP2007056611 W JP 2007056611W WO 2007114152 A1 WO2007114152 A1 WO 2007114152A1
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WO
WIPO (PCT)
Prior art keywords
barium titanate
compound
dispersion composition
terminated
acid
Prior art date
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PCT/JP2007/056611
Other languages
French (fr)
Japanese (ja)
Inventor
Yoshiaki Ueno
Yoshiyuki Morikawa
Original Assignee
Sakata Inx Corp.
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Publication date
Application filed by Sakata Inx Corp. filed Critical Sakata Inx Corp.
Priority to JP2008508556A priority Critical patent/JP5257935B2/en
Publication of WO2007114152A1 publication Critical patent/WO2007114152A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/002—Inorganic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics

Definitions

  • the present invention relates to a barium titanate dispersion composition, and more particularly to a barium titanate dispersion composition used for dielectric use of a multilayer ceramic capacitor.
  • the mobile phone on the receiving side is expected to have two-way video communication and game play. To realize this, a large amount of information data is instantly received. The ability to process is required. However, if advanced information processing capabilities are added, the number of parts that make up a mobile phone will inevitably increase, and a large-capacity battery that matches the power consumption will have to be installed. Even today, it has a lot of functions such as cameras, TVs, GPS, etc., and it is not only limited in space, but also for high-functionality mobile phones that require a lightweight, space-saving and sophisticated design. How to place the increasing number of parts inside is a very big problem.
  • a multilayer ceramic capacitor is provided with a plurality of composite layers in which a ceramic dielectric layer is sandwiched between electrodes.
  • a dielectric layer based on barium titanate having a high dielectric constant is useful. Used.
  • a method for facilitating the formation of the dielectric layer a method of coating a dispersion composition containing barium titanate and then firing it to obtain a dielectric layer has been performed.
  • the dielectric layer is formed with a thickness of 1 m or less. Depending on the capacity, tens to thousands of layers are laminated.
  • this dielectric layer it is necessary to finely disperse barium titanate and to disperse it stably in a dispersion medium.
  • it has sufficient fluidity to give the coating film surface smoothness, and is used as a polar organic solvent-based coating agent as a final composition. I must be able to do it.
  • a technique using a condensed hydroxycarboxylic acid of LOO or a salt thereof obtained by condensing hydroxycarboxylic acid as a dispersant for dispersing an inorganic pigment: LOO for example, see Patent Document 1
  • degree of condensation 2 A technique using the above-described ester of a polyhydroxycarboxylic acid and a polyhydric alcohol (for example, see Patent Document 2) has been proposed.
  • dispersibility since these dispersants have low solubility in polar solvents, when disperse barium titanate in polar solvents using these dispersants, initial dispersibility and dispersion stability (these Are sometimes referred to as dispersibility).
  • Patent Document 1 Japanese Patent Publication No. 54-34009
  • Patent Document 2 Japanese Patent Laid-Open No. 06-15157
  • Patent Document 3 Japanese Patent Application Laid-Open No. 09-169821
  • the problem to be solved by the present invention is that the dispersibility of the barium titanate powder in the polar solvent is good and the barium titanate dispersion composition applied to the polar solvent is coated and baked.
  • the object is to provide a barium titanate dispersion composition free of residues.
  • the present invention provides (1) a barium titanate dispersion composition obtained by dispersing barium titanate powder having an average primary particle diameter of 10 to LOOOnm in a dispersion medium using a carboxy group-terminated polylatatone compound as a dispersant. A thing,
  • the carboxy group-terminated polylatatin compound compound is obtained by ring-opening polymerization of a ratatoni compound using at least one selected as an initiator and a group force that also has a condensate force of hydroxycarboxylic acid and hydroxycarboxylic acid, and
  • the present invention relates to a barium titanate dispersion composition having a weight average molecular weight of 500 to 5,000 for the carboxy group-terminated polylatatone compound.
  • At least one of the above dispersants is selected from the group power consisting of 12-hydroxystearic acid, condensate of 12-hydroxystearic acid and bishydroxymethylpropionic acid.
  • a carboxy group terminal poly force prolatatone compound obtained by ring-opening polymerization of force prolatatone as an agent, and
  • the initiator is selected from the group consisting of 12-hydroxystearic acid, a condensate of 12-hydroxystearic acid having a condensation degree of 2, and bishydroxymethylpropionic acid. At least one, and
  • the barium titanate dispersion composition described in (2) above, wherein the weight average molecular weight of the carboxy group-terminated poly force prolatatone compound is 1000 to 3000.
  • the present invention also relates to (4) the barium titanate dispersion composition described in (1), (2) or (3) above, wherein the dispersion medium is a polar solvent.
  • the present invention is (5) a method for producing a barium titanate dispersion composition according to the above (1), (2), (3) or (4),
  • Average primary particle size 10 to: having a step of kneading a raw material composition containing LOOOnm barium titanate powder, a carboxy-terminated polylacton compound and a dispersion medium,
  • the carboxy group-terminated polylatatin compound compound is obtained by ring-opening polymerization of a ratatoni compound using at least one selected as an initiator and a group force that also has a condensate force of hydroxycarboxylic acid and hydroxycarboxylic acid, and
  • the present invention relates to a method for producing a barium titanate dispersion composition in which the weight average molecular weight of the carboxy group-terminated polylatatin compound is 500 to 5,000.
  • the content of the barium titanate powder is not particularly limited, but 1 to 70 parts by mass is preferable in 100 parts by mass of the barium titanate dispersion composition 10 to 50 parts by mass Is more preferable.
  • the content of barium titanate powder is less than 1 part by mass, the amount of barium titanate in the film obtained by a single coating may be insufficient.
  • the content is more than 70 parts by mass, the barium titanate powder is dispersed. May decrease.
  • the dispersant for dispersing the barium titanate powder is a carboxy group-terminated polylatatonic compound obtained by ring-opening polymerization of a latatin compound, and has a weight average molecular weight of 500 to 5,000. is there.
  • the ring-opening polymerization at least one selected from the group power as a condensate of hydroxycarboxylic acid and hydroxycarboxylic acid is used as an initiator.
  • hydroxycarboxylic acid examples include ricinoleic acid, ricinoleic acid, and 12-hydride.
  • linear hydroxycarboxylic acids having 8 or more carbon atoms and hydroxycarboxylic acids having 2 or more hydroxyl groups are preferred. More preferred are stearic acid and bishydroxymethylpropionic acid.
  • Examples of the condensate of the hydroxycarboxylic acid include those obtained by dehydrating and condensing one or more of the hydroxycarboxylic acids by a conventionally known method.
  • a linear hydroxycarboxylic acid condensate having 8 or more carbon atoms is preferred from the viewpoint of dispersibility of the barium titanate powder, and a 12-hydroxystearic acid condensate is more preferred. Yes.
  • the degree of condensation is 3 or less, more preferably 2 in view of the solubility of the polar solvent.
  • valerolatatone 13 propiolatataton, ⁇ butyrolatataton, 4-methylcaprolataton, 2-methylcaprolataton, and other latatones can be exemplified, and from the dispersibility of barium titanate powder, It is preferable to use force prolatatones such as 2-methylcaprolataton.
  • force prolatatones such as 2-methylcaprolataton.
  • the weight average molecular weight of the carboxy group-terminated polylatathony compound obtained by ring-opening polymerization of the ratatoni compound is in the range of 500 to 5000, preferably in the range of 1000 to 3000. Even if the weight average molecular weight of the force l-oxyl-terminated polylatatonic compound is less than 500 or more than 5000, the dispersibility tends to decrease.
  • the weight average molecular weight can be measured by a column chromatography method.
  • Water 2690 Water 2690 (Wotars). 1 ⁇ 61 5 ⁇ ⁇ MIXED-D (Polymer Laboratori can be obtained as polystyrene-equivalent weight average molecular weight.
  • the carboxy group-terminated polylatatonic compound can be produced by a conventionally known method, for example, at least one selected from the group force consisting of hydroxycarboxylic acid and a condensate of hydroxycarboxylic acid in a nitrogen atmosphere.
  • a rataton compound can be obtained by heating at 90 to 210 ° C. in the presence of a catalyst to perform ring-opening polymerization of the ratatones.
  • the above-mentioned catalysts include alkali metals, alkaline earth metals, alkali metal and alkaline earth metal hydrides, alkoxides, complexes, and other ion-on polymerization catalysts, AlEt and ZnEt.
  • catalysts such as organometallic compounds such as 3 can be used.
  • the amount of the carboxy group-terminated polylatatonic compound used is preferably 1 to: 3 to 20 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of barium titanate. It is determined as appropriate depending on the surface area and type of rum.
  • the amount used is less than 1 part by mass, the dispersibility of the barium titanate powder tends to decrease, and if the amount used is greater than 100 parts by mass, the shrinkage of the coating film after firing increases. There are problems such as an increase in the amount of energy required during firing.
  • an organic solvent capable of dissolving the above-described force-oxy group-terminated polylatatonic compound can be used as a dispersion medium constituting the barium titanate dispersion composition.
  • organic solvents such as toluene, ester solvents such as propyl acetate, butyl acetate and ethyl acetate, ketone solvents such as methyl ethyl ketone, and ether solvents such as polyethylene glycol monomethyl ether.
  • the polar solvent can be illustrated.
  • additives such as a binder resin, a leveling agent, an antifoaming agent, and a surfactant are appropriately added in addition to the above-described constituent materials as necessary. be able to.
  • the method for producing the barium titanate dispersion composition include a method including a step of kneading the raw material composition containing the barium titanate powder, the carboxy group-terminated polylatatone compound, and the dispersion medium. Specifically, the barium titanate powder, the carboxy group-terminated polylatatone compound, the dispersion medium, and an additive as necessary are stirred and mixed, and beads such as zirconia beads ceramic beads and glass beads are added. It can be obtained by kneading with a media mill, sand mill, ball mill or the like used as the grinding media. As the above beads, beads having a diameter of 0.5 mm or less are preferably used.
  • the barium titanate powder used in the above production method is not particularly limited, but barium titanate powder having an average primary particle size of 10 to LOOOnm can be preferably used. More preferred is an average primary particle size of 10-200 nm!
  • the average primary particle diameter is an arithmetic average value of particle diameters obtained by observing particles with an electron microscope.
  • the dispersibility and dispersion stability of the barium titanate powder in a polar solvent are good, and no residue remains when the barium titanate dispersion composition is coated and baked.
  • a barium titanate dispersion composition can be provided.
  • % means “mass 0/0”
  • parts means “parts by weight”.
  • Molecular weight” in Tables 1 and 2 below represents a weight average molecular weight. The weight average molecular weight is Water 2690 (manufactured by Waters) and is measured using PLgel MIXED—D (manufactured by Polymer Laboratories).
  • V is a value determined as a weight average molecular weight in terms of polystyrene.
  • the average primary particle size of barium titanate is the arithmetic average value of the particle size obtained by observing particles with an electron microscope.
  • barium titanate with an average primary particle size of 20 nm, 12-hydroxystearic acid 6 parts by weight of carboxy group-terminated poly-prolatatone compound having a weight average molecular weight of 1000 obtained by ring-opening polymerization of ⁇ -force prolatatone and 54 parts by weight of propyl acetate with a paint shaker.
  • barium titanate dispersion composition 1.
  • barium titanate dispersion composition 2 40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6-group of carboxy group-terminated poly-force prolatatonic compounds having a weight-average molecular weight of 2000 and ring-opening polymerization of ⁇ -force prolatatone using 12-hydroxystearic acid as an initiator Part by mass and 54 parts by mass of propyl acetate were ground with a paint shaker using ⁇ 0.3 mm zirca beads to obtain a barium titanate dispersion composition 2.
  • Part by mass and 54 parts by mass of propyl acetate were ground with a paint shaker with ⁇ 0.3 mm zirca beads to obtain a barium titanate dispersion composition 3.
  • barium titanate with an average primary particle size of 20 nm, a carboxy group having a weight average molecular weight of 2000 obtained by ring-opening polymerization of ⁇ -strength prolataton using a 12-hydroxystearic acid condensate (condensation degree 2) as an initiator 6 parts by weight of a terminal poly-strength prolatatatone compound and 54 parts by weight of propyl acetate were squeezed with Zircoyu beads having a diameter of 0.3 mm to obtain a barium titanate dispersion composition 4.
  • barium titanate with an average primary particle size of lOOnm 40 parts by weight of barium titanate with an average primary particle size of lOOnm, a carboxy-group-terminated poly-force prolatatonic compound with a weight average molecular weight of 2000 obtained by ring-opening polymerization of ⁇ -force prolatatone using 12-hydroxystearic acid as an initiator 8 parts by mass and 57.2 parts by mass of propyl acetate were kneaded with Zircoyu beads having a diameter of 3 mm with a paint shaker to obtain a barium titanate dispersion composition 6.
  • barium titanate dispersion composition 8 50 parts by mass of barium titanate with an average primary particle size of 20 nm, ⁇ -force prolatatatone ring-opening polymerization using bishydroxymethylpropionic acid as an initiator, and a force-average molecular weight of 2000. 5 parts by mass and 42.5 parts by mass of propyl acetate were kneaded with a paint shaker with ⁇ 0.3 mm zirco-yu beads to obtain a barium titanate dispersion composition 8.
  • barium titanate dispersion composition 9 40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6-group of carboxy group-terminated poly-force prolatatonic compounds having a weight-average molecular weight of 2000 and ring-opening polymerization of ⁇ -force prolatatone using 12-hydroxystearic acid as an initiator Part by mass and 54 parts by mass of methyl ethyl ketone were ground with a paint shaker and ⁇ 0.3 mm Zirco-Urea beads to obtain a barium titanate dispersion composition 9.
  • barium titanate dispersion composition 40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6-group of carboxy group-terminated poly-force prolatatonic compounds having a weight-average molecular weight of 2000 and ring-opening polymerization of ⁇ -force prolatatone using 12-hydroxystearic acid as an initiator Part by weight, 54 parts by weight of toluene
  • the mixture was kneaded with Zirca beads having a diameter of 0.3 mm in a car to obtain a barium titanate dispersion composition 10.
  • barium titanate with an average primary particle size of 20 nm 6-group of carboxy group-terminated polyforce prolatatonic compounds with a weight average molecular weight of 6000, which is obtained by ring-opening polymerization of ⁇ -force prolatatone using 12-hydroxystearic acid as an initiator.
  • Part by mass and 54 parts by mass of propyl acetate were ground with a paint shaker using ⁇ 0.3 mm zircon beads to obtain a barium titanate dispersion composition 11.
  • barium titanate with an average primary particle size of 20 nm 40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6 parts by weight of a polycarboxylic acid dispersant (G 700, manufactured by Kyoeisha Chemical Co., Ltd.), and 54 parts by weight of propyl acetate are combined with a paint shaker. The mixture was kneaded with 3 mm zirconia beads to obtain Barium Titanate Dispersion Composition 12.
  • barium titanate dispersion composition 13 40 parts by mass of barium titanate with an average primary particle size of 20 nm, 6 parts by mass of acrylic dispersant (malimarim AKM-0531, manufactured by NOF Corporation) having maleic anhydride at the adsorption site, and 54 parts by mass of propyl acetate A paint shaker was used to knead with Zirco Your beads having a diameter of 0.3 mm to obtain a barium titanate dispersion composition 13.
  • barium titanate dispersion composition 14 40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6 parts by weight of a condensate with an average molecular weight of 2000 condensed with 12-hydroxystearic acid as a dispersant, and 54 parts by weight of propyl acetate The mixture was kneaded with ⁇ 0.3 mm Zirco Your beads to obtain a barium titanate dispersion composition 14.
  • the fluidity of the barium titanate dispersion compositions 1 to 14 was determined based on whether the obtained barium titanate dispersion composition was liquid or gel (purine).
  • the particle size (d50) of the barium titanate dispersion compositions 1 to 10 and 14 having a liquid flowability was measured with a nanotrack particle size measuring device (UPA-EX150, manufactured by Nikkiso Co., Ltd.). .
  • the barium titanate dispersion compositions of Examples:! To 10 are excellent in fluidity and also excellent in dispersibility of barium titanate because of their small particle size. Yes. Moreover, even if the barium titanate dispersion composition of the example was coated and baked to form a coating film, no residue was generated.
  • the barium titanate dispersion composition of the present invention has the problems of dispersibility and dispersion stability of the barium titanate powder in a polar solvent, and the case where the barium titanate dispersion composition is coated and fired. Both of the residue problems can be solved.
  • the barium titanate dispersion composition of the present invention can be used to form a dielectric layer of a multilayer ceramic capacitor that requires a small and large capacity.

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Abstract

Disclosed is a barium titanate dispersion composition exhibiting good dispersibility of a barium titanate powder in a polar solvent. This barium titanate dispersion composition leaves no residuals when the barium titanate dispersion composition using a polar solvent is coated and sintered. Specifically disclosed is a barium titanate dispersion composition which is obtained by dispersing a barium titanate powder in a dispersion medium while using a terminally carboxylated polylactone compound as a dispersing agent. The terminally carboxylated polylactone compound is obtained by ring-opening polymerizing a lactone compound while using, as an initiator, at least one substance selected from hydroxycarboxylic acids and condensation products of hydroxycarboxylic acids. The weight average molecular weight of the terminally carboxylated polylactone compound is 500-5000.

Description

明 細 書  Specification
チタン酸バリウム分散組成物  Barium titanate dispersion composition
技術分野  Technical field
[0001] 本発明は、チタン酸バリウム分散組成物に関し、より詳しくは、積層セラミックコンデン サ一の誘電体の用途等に使用されるチタン酸バリウム分散組成物に関する。  TECHNICAL FIELD [0001] The present invention relates to a barium titanate dispersion composition, and more particularly to a barium titanate dispersion composition used for dielectric use of a multilayer ceramic capacitor.
背景技術  Background art
[0002] 光ファイバに代表されるブロードバンドや衛星等の通信インフラの拡充に伴い、さま ざまなメディアを通じて、文字、映像、音楽といった多種多様のコンテンツが配信され ている。従来、これらは PCのネットワークやテレビ等を主力としていた力 最近では、 場所や時間の制約がなぐ情報機器としての普及量が圧倒的に多い携帯電話向け のモバイルコンテンツにも注力されるようになって!/、る。  [0002] With the expansion of communication infrastructure such as broadband and satellite represented by optical fiber, a wide variety of contents such as text, video, and music are distributed through various media. Conventionally, these have been mainly focused on PC networks and TVs. Recently, mobile content for mobile phones, which are overwhelmingly popular as information devices with no restrictions on location and time, has been focused on. /!
[0003] 一方、受信側の携帯電話には、上記のコンテンツ受信の他にも、動画の双方向通信 やゲーム対戦などが期待されており、それを実現するために、大量の情報データを 即時に処理できる能力が要求されている。しかし、高度な情報処理能力が付加され れば、必然的に携帯電話を構成する部品数は増加し、消費電力に見合った大容量 のバッテリーを搭載しなければならなくなる。現在でも、カメラ、テレビ、 GPSなどの非 常に多くの機能を有し、高機能化もさることながら、軽量'省スペースで洗練されたデ ザインが強く求められる携帯電話にとって、限られたスペースの中にいかにして増加 する部品を配置するかは、極めて大きな問題である。  [0003] On the other hand, in addition to receiving the above-mentioned contents, the mobile phone on the receiving side is expected to have two-way video communication and game play. To realize this, a large amount of information data is instantly received. The ability to process is required. However, if advanced information processing capabilities are added, the number of parts that make up a mobile phone will inevitably increase, and a large-capacity battery that matches the power consumption will have to be installed. Even today, it has a lot of functions such as cameras, TVs, GPS, etc., and it is not only limited in space, but also for high-functionality mobile phones that require a lightweight, space-saving and sophisticated design. How to place the increasing number of parts inside is a very big problem.
[0004] そこで、この問題を解決するために、個々の部品を軽量 '省スペース化するという最も 基本的な技術の開発が継続して行われている。例えば、デジタル回路等で発生する 高周波ノイズの除去に利用されるコンデンサ一は、容量が増加すると体積も増加する 傾向があり、また、個数が多くなるほど、その分の体積と重量が増加する。最近では、 上記用途で積層セラミックスコンデンサーが多用されることから、積層セラミックスコン デンサ一の小型大容量ィ匕が進められて 、る。  [0004] Therefore, in order to solve this problem, the development of the most basic technology for reducing the weight of individual parts and saving space has been continuously performed. For example, a capacitor used for removing high-frequency noise generated in a digital circuit or the like tends to increase in volume as the capacity increases, and the volume and weight increase as the number increases. Recently, multilayer ceramic capacitors are frequently used in the above-mentioned applications, and therefore, small and large capacity capacitors for multilayer ceramic capacitors are being promoted.
[0005] 積層セラミックスコンデンサ一は、セラミックの誘電体層を電極で挟んだ複合層を多 層設けたもので、高い誘電率を有するチタン酸バリウムをベースとした誘電体層が利 用される。そして、誘電体層の形成を容易にする方法として、チタン酸バリウムを含有 する分散組成物をコーティングし、その後焼成して誘電体層を得る方法が行われて いる。 [0005] A multilayer ceramic capacitor is provided with a plurality of composite layers in which a ceramic dielectric layer is sandwiched between electrodes. A dielectric layer based on barium titanate having a high dielectric constant is useful. Used. As a method for facilitating the formation of the dielectric layer, a method of coating a dispersion composition containing barium titanate and then firing it to obtain a dielectric layer has been performed.
[0006] 積層セラミックコンデンサーの小型大容量ィ匕のためには、電極 誘電体複合層の薄 膜化'高積層化が必要であり、現在は、 1 m以下の厚さで誘電体層が形成され、容 量に応じて数十〜数千層程度積層したものが製造されている。この誘電体層をコー ティング法で形成させようとすると、チタン酸バリウムを微粒ィ匕し、さらに分散媒体中に 安定的に分散させることが必要となる。また、コーティング被膜表面の平滑性を持た せるために十分な流動性を有し、最終的な組成物として、極性有機溶剤系のコーテ イング剤として利用されて 、るため、極性有機溶剤系で利用できなければならな 、。  [0006] In order to reduce the size and capacity of multilayer ceramic capacitors, it is necessary to reduce the thickness of the electrode dielectric composite layer and increase the number of layers. At present, the dielectric layer is formed with a thickness of 1 m or less. Depending on the capacity, tens to thousands of layers are laminated. In order to form this dielectric layer by a coating method, it is necessary to finely disperse barium titanate and to disperse it stably in a dispersion medium. In addition, it has sufficient fluidity to give the coating film surface smoothness, and is used as a polar organic solvent-based coating agent as a final composition. I must be able to do it.
[0007] 従来より、無機材料の粉末を分散させる分散剤がいろいろ提案されている。  [0007] Conventionally, various dispersants for dispersing powders of inorganic materials have been proposed.
例えば、無機顔料を分散させる分散剤としてヒドロキシカルボン酸を縮合して得られ る酸価 10〜： LOOの縮合ヒドロキシカルボン酸又はその塩を使用する技術 (例えば、 特許文献 1参照）、縮合度 2以上のポリヒドロキシカルボン酸と多価アルコールのエス テルィ匕物を使用する技術 (例えば、特許文献 2参照）が提案されている。  For example, a technique using a condensed hydroxycarboxylic acid of LOO or a salt thereof obtained by condensing hydroxycarboxylic acid as a dispersant for dispersing an inorganic pigment: LOO (for example, see Patent Document 1), degree of condensation 2 A technique using the above-described ester of a polyhydroxycarboxylic acid and a polyhydric alcohol (for example, see Patent Document 2) has been proposed.
[0008] しかし、これらの分散剤は極性溶媒に対する溶解性が低いため、チタン酸バリウムを これらの分散剤を使用して極性溶媒中に分散させた場合、初期の分散性及び分散 安定性 (これらを合わせて分散性と呼ぶことがある）が充分でな 、と 、う問題を有する  However, since these dispersants have low solubility in polar solvents, when disperse barium titanate in polar solvents using these dispersants, initial dispersibility and dispersion stability (these Are sometimes referred to as dispersibility).
[0009] また、無機顔料を分散させる分散剤として、ポリアリルァミンのポリエステル等の誘導 体を使用する技術 (例えば、特許文献 3参照)が提案されている。 [0009] In addition, a technique using a derivative such as polyallylamine polyester as a dispersant for dispersing an inorganic pigment has been proposed (for example, see Patent Document 3).
この分散剤を使用してチタン酸バリウムを極性溶媒に分散させた場合は、分散性は 良好である力 分散剤がヘテロ原子を有しているため焼成時に残渣が残る問題を有 するものであった。  When this dispersant is used to disperse barium titanate in a polar solvent, the dispersibility is good. Since the dispersant has heteroatoms, there is a problem that residues remain during firing. It was.
[0010] このように無機顔料を分散させる技術はいろいろ提案されているが、極性溶媒中での チタン酸バリウム粉末の分散性及び分散安定性の問題、並びに、チタン酸バリウム分 散組成物をコーティングし、焼成した場合の残渣の問題の両方を満足させるものが 得られていない。 [0011] 特許文献 1 :特公昭 54— 34009号公報 [0010] Although various techniques for dispersing inorganic pigments have been proposed in this way, the problem of dispersibility and dispersion stability of barium titanate powder in a polar solvent, and coating with a barium titanate dispersion composition However, a product that satisfies both of the problems of residue when fired has not been obtained. [0011] Patent Document 1: Japanese Patent Publication No. 54-34009
特許文献 2：特開平 06 - 15157号公報  Patent Document 2: Japanese Patent Laid-Open No. 06-15157
特許文献 3 :特開平 09— 169821号公報  Patent Document 3: Japanese Patent Application Laid-Open No. 09-169821
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0012] 本発明が解決しょうとする課題は、極性溶媒中でのチタン酸バリウム粉末の分散性が 良好で、且つ極性溶媒に適用したチタン酸バリウム分散組成物をコーティングし、焼 成した場合に残渣がないチタン酸バリウム分散組成物を提供することにある。 [0012] The problem to be solved by the present invention is that the dispersibility of the barium titanate powder in the polar solvent is good and the barium titanate dispersion composition applied to the polar solvent is coated and baked. The object is to provide a barium titanate dispersion composition free of residues.
課題を解決するための手段  Means for solving the problem
[0013] 本発明者らは、上記の課題を解決するために鋭意検討した結果、チタン酸バリウム 粉末の分散剤として、特定のカルボキシ基末端ポリラタトンィ匕合物、すなわち、ヒドロ キカルボン酸ゃヒドロキシカルボン酸の縮合物を開始剤としてラタトンィ匕合物を開環 重合して得られるカルボキシ基末端ポリラタトンィ匕合物を使用することにより、上記課 題を解決し得ることを見いだし、本発明を完成するに到った。 As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that a specific carboxyl group-terminated polylatatonic compound, ie, hydroxycarboxylic acid hydroxycarboxylic acid, as a dispersant for barium titanate powder. It was found that the above problems can be solved by using a carboxy group-terminated polylatatin compound obtained by ring-opening polymerization of a ratatony compound using the above condensate as an initiator, and the present invention has been completed. It was.
[0014] すなわち、本発明は、（1)カルボキシ基末端ポリラタトン化合物を分散剤として、平均 一次粒子径 10〜： LOOOnmのチタン酸バリウム粉末を、分散媒体中に分散させてなる チタン酸バリウム分散組成物であって、 [0014] That is, the present invention provides (1) a barium titanate dispersion composition obtained by dispersing barium titanate powder having an average primary particle diameter of 10 to LOOOnm in a dispersion medium using a carboxy group-terminated polylatatone compound as a dispersant. A thing,
前記カルボキシ基末端ポリラタトンィ匕合物力 ヒドロキシカルボン酸及びヒドロキシカ ルボン酸の縮合物力もなる群力 選択される少なくとも 1種を開始剤としてラタトンィ匕 合物を開環重合して得られるものであり、かつ  The carboxy group-terminated polylatatin compound compound is obtained by ring-opening polymerization of a ratatoni compound using at least one selected as an initiator and a group force that also has a condensate force of hydroxycarboxylic acid and hydroxycarboxylic acid, and
前記カルボキシ基末端ポリラタトンィ匕合物の重量平均分子量が 500〜5000であるチ タン酸バリウム分散組成物に関する。  The present invention relates to a barium titanate dispersion composition having a weight average molecular weight of 500 to 5,000 for the carboxy group-terminated polylatatone compound.
[0015] また、本発明は、（2)上記分散剤が、 12—ヒドロキシステアリン酸、 12—ヒドロキシス テアリン酸の縮合物及びビスヒドロキシメチルプロピオン酸力 なる群力 選択される 少なくとも 1種を開始剤として力プロラタトンを開環重合して得られるカルボキシ基末 端ポリ力プロラタトン化合物であり、かつ [0015] In the present invention, (2) at least one of the above dispersants is selected from the group power consisting of 12-hydroxystearic acid, condensate of 12-hydroxystearic acid and bishydroxymethylpropionic acid. A carboxy group terminal poly force prolatatone compound obtained by ring-opening polymerization of force prolatatone as an agent, and
前記カルボキシ基末端ポリ力プロラタトン化合物の重量平均分子量が 500〜5000で あることを特徴とする上記（1)項に記載のチタン酸バリウム分散組成物に関する。 [0016] また、本発明は、（3)前記開始剤が、 12—ヒドロキシステアリン酸、縮合度が 2の 12— ヒドロキシステアリン酸の縮合物及びビスヒドロキシメチルプロピオン酸カもなる群から 選択される少なくとも 1種であり、かつ The barium titanate dispersion composition described in (1) above, wherein the weight average molecular weight of the carboxy group-terminated poly force prolatatone compound is 500 to 5,000. [0016] In the present invention, (3) the initiator is selected from the group consisting of 12-hydroxystearic acid, a condensate of 12-hydroxystearic acid having a condensation degree of 2, and bishydroxymethylpropionic acid. At least one, and
前記カルボキシ基末端ポリ力プロラタトン化合物の重量平均分子量が 1000〜3000 であることを特徴とする上記（2)項に記載のチタン酸バリウム分散組成物に関する。  The barium titanate dispersion composition described in (2) above, wherein the weight average molecular weight of the carboxy group-terminated poly force prolatatone compound is 1000 to 3000.
[0017] また、本発明は、（4)上記分散媒体は、極性溶媒である上記（1)、（2)又は (3)項に 記載のチタン酸バリゥム分散組成物に関する。 [0017] The present invention also relates to (4) the barium titanate dispersion composition described in (1), (2) or (3) above, wherein the dispersion medium is a polar solvent.
更に、本発明は、（5)上記（1)、（2)、（3)又は (4)項に記載のチタン酸バリウム分散 組成物の製造方法であって、  Furthermore, the present invention is (5) a method for producing a barium titanate dispersion composition according to the above (1), (2), (3) or (4),
平均一次粒子径 10〜： LOOOnmのチタン酸バリウム粉末、カルボキシ基末端ポリラクト ン化合物及び分散媒体を含む原料組成物を練肉する工程を有し、  Average primary particle size 10 to: having a step of kneading a raw material composition containing LOOOnm barium titanate powder, a carboxy-terminated polylacton compound and a dispersion medium,
前記カルボキシ基末端ポリラタトンィ匕合物力 ヒドロキシカルボン酸及びヒドロキシカ ルボン酸の縮合物力もなる群力 選択される少なくとも 1種を開始剤としてラタトンィ匕 合物を開環重合して得られるものであり、かつ  The carboxy group-terminated polylatatin compound compound is obtained by ring-opening polymerization of a ratatoni compound using at least one selected as an initiator and a group force that also has a condensate force of hydroxycarboxylic acid and hydroxycarboxylic acid, and
前記カルボキシ基末端ポリラタトンィ匕合物の重量平均分子量が 500〜5000であるチ タン酸バリウム分散組成物の製造方法に関する。  The present invention relates to a method for producing a barium titanate dispersion composition in which the weight average molecular weight of the carboxy group-terminated polylatatin compound is 500 to 5,000.
[0018] 以下、本発明のチタン酸バリウム分散組成物について更に詳細に説明する。  [0018] Hereinafter, the barium titanate dispersion composition of the present invention will be described in more detail.
本発明のチタン酸バリウム分散組成物において、チタン酸バリウム粉末の含有量は、 特に限定されないが、チタン酸バリウム分散組成物 100質量部中に 1〜70質量部が 好ましぐ 10〜50質量部がより好ましい。チタン酸バリウム粉末の含有量が 1質量部 より少ない場合は一回のコーティングで得られる被膜におけるチタン酸バリウム量が 不足する場合があり、一方 70質量部より多い場合は、チタン酸バリウム粉末の分散 性が低下する場合がある。  In the barium titanate dispersion composition of the present invention, the content of the barium titanate powder is not particularly limited, but 1 to 70 parts by mass is preferable in 100 parts by mass of the barium titanate dispersion composition 10 to 50 parts by mass Is more preferable. When the content of barium titanate powder is less than 1 part by mass, the amount of barium titanate in the film obtained by a single coating may be insufficient. On the other hand, when the content is more than 70 parts by mass, the barium titanate powder is dispersed. May decrease.
[0019] 本発明において、チタン酸バリウム粉末を分散させる分散剤は、ラタトンィ匕合物を開 環重合して得られるカルボキシ基末端ポリラタトンィ匕合物であり、重量平均分子量 50 0〜5000のものである。開環重合においては、ヒドロキシカルボン酸及びヒドロキシカ ルボン酸の縮合物力 なる群力 選択される少なくとも 1種を開始剤として用いる。  [0019] In the present invention, the dispersant for dispersing the barium titanate powder is a carboxy group-terminated polylatatonic compound obtained by ring-opening polymerization of a latatin compound, and has a weight average molecular weight of 500 to 5,000. is there. In the ring-opening polymerization, at least one selected from the group power as a condensate of hydroxycarboxylic acid and hydroxycarboxylic acid is used as an initiator.
[0020] 上記ヒドロキシカルボン酸の具体例としては、リシノレイン酸、リシノール酸、 12—ヒド ロキシステアリン酸、ひまし油脂肪酸、水添ひまし油脂肪酸、 δーヒドロキシ吉草酸、 ε—ヒドロキシカプロン酸、 2 ヒドロキシナフタレン一 3—カルボン酸、 2 ヒドロキシ ナフタレン 6—力ルボン酸、 2, 2 ジメチロールプロピオン酸、 2, 2 ジメチロール 吉草酸、 2, 2—ジメチロールペンタン酸、リンゴ酸、酒石酸、乳酸、グリコール酸、グ ルコン酸、ヒドロキシビバリン酸、 1 1 ォキシへキサデカン酸、 2—ォキシドデカン酸、 サリチル酸、ビスヒドロキシメチルプロピオン酸等が例示でき、チタン酸バリウム粉末の 分散性の点から、炭素数が 8以上の直鎖状のヒドロキシカルボン酸、水酸基を 2っ以 上有するヒドロキシカルボン酸が好ましぐ 12—ヒドロキシステアリン酸、ビスヒドロキシ メチルプロピオン酸がより好まし 、。 [0020] Specific examples of the hydroxycarboxylic acid include ricinoleic acid, ricinoleic acid, and 12-hydride. Roxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, 2-hydroxynaphthalene 1-carboxylic acid, 2 hydroxynaphthalene 6-strong rubonic acid, 2, 2 dimethylolpropionic acid, 2 , 2 Dimethylol Valeric acid, 2, 2-Dimethylolpentanoic acid, Malic acid, Tartaric acid, Lactic acid, Glycolic acid, Gluconic acid, Hydroxybivalic acid, 1 1 Oxyhexadecanoic acid, 2-Oxidodecanoic acid, Salicylic acid, Bishydroxy Examples thereof include methyl propionic acid and the like. From the viewpoint of dispersibility of the barium titanate powder, linear hydroxycarboxylic acids having 8 or more carbon atoms and hydroxycarboxylic acids having 2 or more hydroxyl groups are preferred. More preferred are stearic acid and bishydroxymethylpropionic acid.
[0021] また、上記ヒドロキシカルボン酸の縮合物としては、上記ヒドロキシカルボン酸の 1種 又は 2種以上を従来公知の方法で脱水縮合したものが例示できる。  [0021] Examples of the condensate of the hydroxycarboxylic acid include those obtained by dehydrating and condensing one or more of the hydroxycarboxylic acids by a conventionally known method.
[0022] 好ましくは、チタン酸バリウム粉末の分散性の点から、炭素数が 8以上の直鎖状のヒド ロキシカルボン酸の縮合物が好ましぐ 12—ヒドロキシステアリン酸の縮合物がより好 ましい。  [0022] Preferably, a linear hydroxycarboxylic acid condensate having 8 or more carbon atoms is preferred from the viewpoint of dispersibility of the barium titanate powder, and a 12-hydroxystearic acid condensate is more preferred. Yes.
[0023] また、炭素数が 8以上の直鎖状のヒドロキシカルボン酸の縮合物を用いる場合は、極 性溶剤の溶解性の点から縮合度が 3以下、より好ましくは 2である。  [0023] When a linear hydroxycarboxylic acid condensate having 8 or more carbon atoms is used, the degree of condensation is 3 or less, more preferably 2 in view of the solubility of the polar solvent.
[0024] また上記ラタトンィ匕合物としては、 ε—力プロラタトン、 δ—バレロラタトン、 13—メチル  [0024] In addition, as the above-mentioned ratataton compound, ε-force prolatathone, δ-valerolatataton, 13-methyl
δ バレロラタトン、 13 プロピオラタトン、 γ ブチロラタトン、 4ーメチルカプロラ タトン、 2—メチルカプロラタトン等のラタトン類が例示でき、チタン酸バリウム粉末の分 散性の点から、 ε—力プロラタトン、 4—メチルカプロラタトン、 2—メチルカプロラタトン 等の力プロラタトンを使用するのが好ましい。これらラタトンィ匕合物は単独で用いても よぐ 2種以上を併用してもよい。  δ valerolatatone, 13 propiolatataton, γ butyrolatataton, 4-methylcaprolataton, 2-methylcaprolataton, and other latatones can be exemplified, and from the dispersibility of barium titanate powder, It is preferable to use force prolatatones such as 2-methylcaprolataton. These ratatoi compounds may be used alone or in combination of two or more.
[0025] ラタトンィ匕合物を開環重合して得られるカルボキシ基末端ポリラタトンィ匕合物の重量 平均分子量は 500〜5000の範囲であり、好ましくは 1000〜3000の範囲である。力 ルポキシ基末端ポリラタトンィ匕合物の重量平均分子量は 500より小さくても、 5000よ り大きくても分散性が低下する傾向がある。なお、本発明において、重量平均分子量 は、カラムクロマトグラフィー法によって測定することができる。一例としては、 Water 2690 (ゥォーターズ社製）で、？1^61 5 μ ΐη MIXED - D (Polymer Laboratori es社製)を使用して行な 、ポリスチレン換算の重量平均分子量として求めることがで きる。 [0025] The weight average molecular weight of the carboxy group-terminated polylatathony compound obtained by ring-opening polymerization of the ratatoni compound is in the range of 500 to 5000, preferably in the range of 1000 to 3000. Even if the weight average molecular weight of the force l-oxyl-terminated polylatatonic compound is less than 500 or more than 5000, the dispersibility tends to decrease. In the present invention, the weight average molecular weight can be measured by a column chromatography method. One example is Water 2690 (Wotars). 1 ^ 61 5 μ ΐη MIXED-D (Polymer Laboratori can be obtained as polystyrene-equivalent weight average molecular weight.
[0026] 前記カルボキシ基末端ポリラタトンィ匕合物は、従来公知の方法で製造でき、例えば、 窒素雰囲気中下で、ヒドロキシカルボン酸及びヒドロキシカルボン酸の縮合物からな る群力も選択される少なくとも 1種と、ラタトンィ匕合物とを、触媒の存在下、 90〜210°C で加熱して、ラタトン類を開環重合することにより得ることができる。  [0026] The carboxy group-terminated polylatatonic compound can be produced by a conventionally known method, for example, at least one selected from the group force consisting of hydroxycarboxylic acid and a condensate of hydroxycarboxylic acid in a nitrogen atmosphere. And a rataton compound can be obtained by heating at 90 to 210 ° C. in the presence of a catalyst to perform ring-opening polymerization of the ratatones.
[0027] なお、上記触媒としては、アルカリ金属、アルカリ土類金属、アルカリ金属やアルカリ 土類金属の水素化物やアルコキシド、錯体などのァ-オン重合触媒、 AlEtや ZnEt  [0027] The above-mentioned catalysts include alkali metals, alkaline earth metals, alkali metal and alkaline earth metal hydrides, alkoxides, complexes, and other ion-on polymerization catalysts, AlEt and ZnEt.
3 などの有機金属化合物などの従来公知の触媒を用いることができる。  Conventionally known catalysts such as organometallic compounds such as 3 can be used.
2  2
[0028] また、カルボキシ基末端ポリラタトンィ匕合物の使用量は、チタン酸バリウム 100質量部 に対して、 1〜： LOO質量部が好ましぐ 3〜20質量部がより好ましいが、チタン酸バリ ゥムの表面積や種類等により適宜決められる。  [0028] The amount of the carboxy group-terminated polylatatonic compound used is preferably 1 to: 3 to 20 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of barium titanate. It is determined as appropriate depending on the surface area and type of rum.
[0029] なお、上記使用量が 1質量部より少ないと、チタン酸バリウム粉末の分散性が低下す る傾向があり、使用量が 100質量部より大きいと焼成後の塗膜の収縮が大きくなる、 焼成時に必要なエネルギー量が増加する等の問題を有する。 [0029] If the amount used is less than 1 part by mass, the dispersibility of the barium titanate powder tends to decrease, and if the amount used is greater than 100 parts by mass, the shrinkage of the coating film after firing increases. There are problems such as an increase in the amount of energy required during firing.
[0030] 本発明において、チタン酸バリウム分散組成物を構成する分散媒体としては、前記力 ルポキシ基末端ポリラタトンィ匕合物を溶解することができる有機溶剤が使用できる。 具体例としては、トルエン等の芳香族系溶剤、酢酸プロピル、酢酸プチル、酢酸ェチ ル等のエステル系溶剤、メチルェチルケトン等のケトン系溶剤、ポリエチレングリコー ルモノメチルエーテル等のエーテル系溶媒等の極性溶媒が例示できる。 [0030] In the present invention, as a dispersion medium constituting the barium titanate dispersion composition, an organic solvent capable of dissolving the above-described force-oxy group-terminated polylatatonic compound can be used. Specific examples include aromatic solvents such as toluene, ester solvents such as propyl acetate, butyl acetate and ethyl acetate, ketone solvents such as methyl ethyl ketone, and ether solvents such as polyethylene glycol monomethyl ether. The polar solvent can be illustrated.
[0031] 尚、カルボキシ基末端ポリラタトン化合物の溶解性が低下しな!、範囲であれば、カル ボキシ基末端ポリラタトンィ匕合物を溶解することができない溶媒も併用することができ る。 [0031] It should be noted that the solubility of the carboxy group-terminated polylatathone compound does not decrease! If it is in the range, a solvent that cannot dissolve the carboxy group-terminated polylatatone compound can be used in combination.
[0032] 本発明のチタン酸バリウム分散組成物には、上記構成材料以外に必要に応じて、バ インダー榭脂、レべリング剤、消泡剤、界面活性剤等の添加剤を適宜添加することが できる。  [0032] To the barium titanate dispersion composition of the present invention, additives such as a binder resin, a leveling agent, an antifoaming agent, and a surfactant are appropriately added in addition to the above-described constituent materials as necessary. be able to.
[0033] 次に、上記構成材料を含有するチタン酸バリウム分散組成物の製造法について説明 する。 上記チタン酸バリウム分散組成物の製造法としては、前記チタン酸バリウム粉末、前 記カルボキシ基末端ポリラタトン化合物及び前記分散媒体を含む原料組成物を練肉 する工程を有する方法等を挙げることができる。具体的には、前記チタン酸バリウム 粉末と、前記カルボキシ基末端ポリラタトン化合物と、前記分散媒体と、必要に応じて 添加剤とを撹拌混合し、ジルコユアビーズセラミックスビーズ、ガラスビーズ等のビー ズを粉砕メディアとして用いたメディアミル、サンドミル、ボールミル等で練肉すること により得ることができる。上記ビーズとしては、直径 0. 5mm以下のビーズを使用する ことが好ましい。 [0033] Next, a method for producing a barium titanate dispersion composition containing the above constituent materials will be described. Examples of the method for producing the barium titanate dispersion composition include a method including a step of kneading the raw material composition containing the barium titanate powder, the carboxy group-terminated polylatatone compound, and the dispersion medium. Specifically, the barium titanate powder, the carboxy group-terminated polylatatone compound, the dispersion medium, and an additive as necessary are stirred and mixed, and beads such as zirconia beads ceramic beads and glass beads are added. It can be obtained by kneading with a media mill, sand mill, ball mill or the like used as the grinding media. As the above beads, beads having a diameter of 0.5 mm or less are preferably used.
[0034] 上記製造法に使用されるチタン酸バリウム粉末は、特に限定されないが、平均一次 粒子径が 10〜： LOOOnmのチタン酸バリウム粉末を好適に使用できる。平均一次粒 子径が 10〜200nmのものがより好まし!/、。  [0034] The barium titanate powder used in the above production method is not particularly limited, but barium titanate powder having an average primary particle size of 10 to LOOOnm can be preferably used. More preferred is an average primary particle size of 10-200 nm!
上記平均一次粒子径は、電子顕微鏡による粒子の観察によって求められる粒子径 の算術平均値である。  The average primary particle diameter is an arithmetic average value of particle diameters obtained by observing particles with an electron microscope.
発明の効果  The invention's effect
[0035] 本発明によれば、極性溶媒中でのチタン酸バリウム粉末の分散性及び分散安定性 が良好で、且つ、チタン酸バリウム分散組成物をコーティングし、焼成した場合の残 渣が残らないチタン酸バリウム分散組成物を提供することができる。  [0035] According to the present invention, the dispersibility and dispersion stability of the barium titanate powder in a polar solvent are good, and no residue remains when the barium titanate dispersion composition is coated and baked. A barium titanate dispersion composition can be provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0036] 以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例 のみに限定されるものではない。なお、特に断りのない限り、「％」は「質量0 /0」を意味 し、「部」は「質量部」を意味するものとする。また下記表 1及び表 2における「分子量」 は、重量平均分子量を表す。重量平均分子量は、 Water 2690 (ウォーターズ社製 )で、 PLgel MIXED— D (Polymer Laboratories社製）を使用して行な[0036] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass 0/0", "parts" means "parts by weight". “Molecular weight” in Tables 1 and 2 below represents a weight average molecular weight. The weight average molecular weight is Water 2690 (manufactured by Waters) and is measured using PLgel MIXED—D (manufactured by Polymer Laboratories).
V、ポリスチレン換算の重量平均分子量として求めた値である。またチタン酸バリウム の平均一次粒子径は、電子顕微鏡による粒子の観察によって求められる粒子径の 算術平均値である。 V is a value determined as a weight average molecular weight in terms of polystyrene. The average primary particle size of barium titanate is the arithmetic average value of the particle size obtained by observing particles with an electron microscope.
[0037] (実施例 1)  [0037] (Example 1)
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン酸 を開始剤とし ε—力プロラタトンを開環重合させた重量平均分子量 1000のカルボキ シ基末端ポリ力プロラタトンィ匕合物の 6質量部、酢酸プロピルの 54質量部をペイント シエイカーで Φ 0. 3mmのジルコ-ァビーズにて練肉し、チタン酸バリウム分散組成 物 1を得た。 40 parts by mass of barium titanate with an average primary particle size of 20 nm, 12-hydroxystearic acid 6 parts by weight of carboxy group-terminated poly-prolatatone compound having a weight average molecular weight of 1000 obtained by ring-opening polymerization of ε-force prolatatone and 54 parts by weight of propyl acetate with a paint shaker. -Meated with a beads to obtain a barium titanate dispersion composition 1.
[0038] (実施例 2) [0038] (Example 2)
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン酸 を開始剤とし ε—力プロラタトンを開環重合させた重量平均分子量 2000のカルボキ シ基末端ポリ力プロラタトンィ匕合物の 6質量部、酢酸プロピルの 54質量部をペイント シエイカーで Φ 0. 3mmのジルコ-ァビーズにて練肉し、チタン酸バリウム分散組成 物 2を得た。  40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6-group of carboxy group-terminated poly-force prolatatonic compounds having a weight-average molecular weight of 2000 and ring-opening polymerization of ε-force prolatatone using 12-hydroxystearic acid as an initiator Part by mass and 54 parts by mass of propyl acetate were ground with a paint shaker using Φ 0.3 mm zirca beads to obtain a barium titanate dispersion composition 2.
[0039] (実施例 3) [0039] (Example 3)
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン酸 を開始剤とし ε一力プロラタトンを開環重合させた重量平均分子量 4000のカルボキ シ基末端ポリ力プロラタトンィ匕合物の 6質量部、酢酸プロピルの 54質量部をペイント シエイカーで Φ 0. 3mmのジルコ-ァビーズにて練肉し、チタン酸バリウム分散組成 物 3を得た。  40 parts by mass of barium titanate with an average primary particle size of 20 nm, 6-group of carboxy group-terminated poly-prolatathony compound having a weight-average molecular weight of 4000 obtained by ring-opening polymerization of ε-strength prolatatone using 12-hydroxystearic acid as an initiator. Part by mass and 54 parts by mass of propyl acetate were ground with a paint shaker with Φ 0.3 mm zirca beads to obtain a barium titanate dispersion composition 3.
[0040] (実施例 4) [0040] (Example 4)
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン酸 の縮合物 (縮合度 2)を開始剤とし ε一力プロラタトンを開環重合させた重量平均分 子量 2000のカルボキシ基末端ポリ力プロラタトン化合物の 6質量部、酢酸プロピルの 54質量部ペイントシエイカ一で Φ 0. 3mmのジルコユアビーズにて練肉し、チタン酸 バリウム分散組成物 4を得た。  40 parts by mass of barium titanate with an average primary particle size of 20 nm, a carboxy group having a weight average molecular weight of 2000 obtained by ring-opening polymerization of ε-strength prolataton using a 12-hydroxystearic acid condensate (condensation degree 2) as an initiator 6 parts by weight of a terminal poly-strength prolatatatone compound and 54 parts by weight of propyl acetate were squeezed with Zircoyu beads having a diameter of 0.3 mm to obtain a barium titanate dispersion composition 4.
[0041] (実施例 5) [Example 5]
平均一次粒子径 50nmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン酸 を開始剤とし ε—力プロラタトンを開環重合させた重量平均分子量 2000のカルボキ シ基末端ポリ力プロラタトンィ匕合物の 4質量部、酢酸プロピルの 56質量部をペイント シエイカーで Φ 0. 3mmのジルコ-ァビーズにて練肉し、チタン酸バリウム分散組成 物 5を得た。 [0042] (実施例 6) 40 parts by weight of barium titanate with an average primary particle size of 50 nm, 4 of a carboxy group-terminated poly-prolatatonic compound having a weight average molecular weight of 2000 and ring-opening polymerization of ε-force prolataton using 12-hydroxystearic acid as an initiator. Part by mass and 56 parts by mass of propyl acetate were ground with Φ 0.3 mm zircon beads using a paint shaker to obtain a barium titanate dispersion composition 5. [Example 6]
平均一次粒子径 lOOnmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン 酸を開始剤とし ε—力プロラタトンを開環重合させた重量平均分子量 2000のカルボ キシ基末端ポリ力プロラタトンィ匕合物の 2. 8質量部、酢酸プロピルの 57. 2質量部を ペイントシエイカ一で Φ Ο. 3mmのジルコユアビーズにて練肉し、チタン酸バリウム分 散組成物 6を得た。  40 parts by weight of barium titanate with an average primary particle size of lOOnm, a carboxy-group-terminated poly-force prolatatonic compound with a weight average molecular weight of 2000 obtained by ring-opening polymerization of ε-force prolatatone using 12-hydroxystearic acid as an initiator 8 parts by mass and 57.2 parts by mass of propyl acetate were kneaded with Zircoyu beads having a diameter of 3 mm with a paint shaker to obtain a barium titanate dispersion composition 6.
[0043] (実施例 7) [0043] (Example 7)
平均一次粒子径 20nmのチタン酸バリウムの 10質量部、 12—ヒドロキシステアリン酸 を開始剤とし ε—力プロラタトンを開環重合させた重量平均分子量 2000のカルボキ シ基末端ポリ力プロラタトンィ匕合物の 1. 5質量部、酢酸プロピルの 88. 5質量部をぺ イントシエイカ一で Φ 0. 3mmのジルコ-ァビーズにて練肉し、チタン酸バリウム分散 組成物 7を得た。  10 parts by weight of barium titanate with an average primary particle size of 20 nm, 1 of a carboxy group-terminated polyforce prolatatone compound having a weight average molecular weight of 2000 obtained by ring-opening polymerization of ε-force prolatatone using 12-hydroxystearic acid as an initiator 5 parts by mass and 88.5 parts by mass of propyl acetate were milled with a 0.3 mm diameter zirca bead using a paint shaker to obtain a barium titanate dispersion composition 7.
[0044] (実施例 8) [0044] (Example 8)
平均一次粒子径 20nmのチタン酸バリウムの 50質量部、ビスヒドロキシメチルプロピ オン酸を開始剤とし ε —力プロラタトンを開環重合させた重量平均分子量 2000の力 ルボキシ基末端ポリ力プロラタトン化合物の 7. 5質量部、酢酸プロピルの 42. 5質量 部をペイントシエイカ一で Φ 0. 3mmのジルコユアビーズにて練肉し、チタン酸バリウ ム分散組成物 8を得た。  50 parts by mass of barium titanate with an average primary particle size of 20 nm, ε-force prolatatatone ring-opening polymerization using bishydroxymethylpropionic acid as an initiator, and a force-average molecular weight of 2000. 5 parts by mass and 42.5 parts by mass of propyl acetate were kneaded with a paint shaker with Φ 0.3 mm zirco-yu beads to obtain a barium titanate dispersion composition 8.
[0045] (実施例 9) [Example 9]
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン酸 を開始剤とし ε—力プロラタトンを開環重合させた重量平均分子量 2000のカルボキ シ基末端ポリ力プロラタトンィ匕合物の 6質量部、メチルェチルケトンの 54質量部をペイ ントシエイカ一で Φ 0. 3mmのジルコユアビーズにて練肉し、チタン酸バリウム分散組 成物 9を得た。  40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6-group of carboxy group-terminated poly-force prolatatonic compounds having a weight-average molecular weight of 2000 and ring-opening polymerization of ε-force prolatatone using 12-hydroxystearic acid as an initiator Part by mass and 54 parts by mass of methyl ethyl ketone were ground with a paint shaker and Φ0.3 mm Zirco-Urea beads to obtain a barium titanate dispersion composition 9.
[0046] (実施例 10) [Example 10]
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン酸 を開始剤とし ε—力プロラタトンを開環重合させた重量平均分子量 2000のカルボキ シ基末端ポリ力プロラタトンィ匕合物の 6質量部、トルエンの 54質量部をペイントシエイ カーで Φ 0. 3mmのジルコ-ァビーズにて練肉し、チタン酸バリウム分散組成物 10を 得た。 40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6-group of carboxy group-terminated poly-force prolatatonic compounds having a weight-average molecular weight of 2000 and ring-opening polymerization of ε-force prolatatone using 12-hydroxystearic acid as an initiator Part by weight, 54 parts by weight of toluene The mixture was kneaded with Zirca beads having a diameter of 0.3 mm in a car to obtain a barium titanate dispersion composition 10.
[0047] (比較例 1) [0047] (Comparative Example 1)
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、 12—ヒドロキシステアリン酸 を開始剤とし ε—力プロラタトンを開環重合させた重量平均分子量 6000のカルボキ シ基末端ポリ力プロラタトンィ匕合物の 6質量部、酢酸プロピルの 54質量部をペイント シエイカーで Φ 0. 3mmのジルコ-ァビーズにて練肉し、チタン酸バリウム分散組成 物 11を得た。  40 parts by mass of barium titanate with an average primary particle size of 20 nm, 6-group of carboxy group-terminated polyforce prolatatonic compounds with a weight average molecular weight of 6000, which is obtained by ring-opening polymerization of ε-force prolatatone using 12-hydroxystearic acid as an initiator. Part by mass and 54 parts by mass of propyl acetate were ground with a paint shaker using Φ 0.3 mm zircon beads to obtain a barium titanate dispersion composition 11.
[0048] (比較例 2) [0048] (Comparative Example 2)
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、ポリカルボン酸系分散剤（G 700、共栄社化学 (株)製)の 6質量部、酢酸プロピルの 54質量部をペイントシエイカ 一で Φ 0. 3mmのジルコ-ァビーズにて練肉し、チタン酸バリウム分散組成物 12を 得た。  40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6 parts by weight of a polycarboxylic acid dispersant (G 700, manufactured by Kyoeisha Chemical Co., Ltd.), and 54 parts by weight of propyl acetate are combined with a paint shaker. The mixture was kneaded with 3 mm zirconia beads to obtain Barium Titanate Dispersion Composition 12.
[0049] (比較例 3) [0049] (Comparative Example 3)
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、無水マレイン酸を吸着部位 に持つアクリル系分散剤（マリマリム AKM— 0531、 日本油脂社製)の 6質量部、酢 酸プロピルの 54質量部をペイントシエイカ一で Φ 0. 3mmのジルコユアビーズにて練 肉し、チタン酸バリウム分散組成物 13を得た。  40 parts by mass of barium titanate with an average primary particle size of 20 nm, 6 parts by mass of acrylic dispersant (malimarim AKM-0531, manufactured by NOF Corporation) having maleic anhydride at the adsorption site, and 54 parts by mass of propyl acetate A paint shaker was used to knead with Zirco Your beads having a diameter of 0.3 mm to obtain a barium titanate dispersion composition 13.
[0050] (比較例 4) [0050] (Comparative Example 4)
平均一次粒子径 20nmのチタン酸バリウムの 40質量部、分散剤として 12-ヒドロキシ ステアリン酸を縮合させた平均分子量 2000の縮合物の 6質量部、酢酸プロピルの 5 4質量部をペイントシエイカ一で Φ 0. 3mmのジルコユアビーズにて練肉し、チタン酸 バリウム分散組成物 14を得た。  40 parts by weight of barium titanate with an average primary particle size of 20 nm, 6 parts by weight of a condensate with an average molecular weight of 2000 condensed with 12-hydroxystearic acid as a dispersant, and 54 parts by weight of propyl acetate The mixture was kneaded with Φ 0.3 mm Zirco Your beads to obtain a barium titanate dispersion composition 14.
[0051] <性能評価 > [0051] <Performance evaluation>
(流動性）  (Liquidity)
チタン酸バリウム分散組成物 1〜14の流動性については、得られたチタン酸バリウム 分散組成物が液状かゲル状 (プリン状)のものであるか否かで判断した。  The fluidity of the barium titanate dispersion compositions 1 to 14 was determined based on whether the obtained barium titanate dispersion composition was liquid or gel (purine).
[0052] (評価基準） 〇：液状のもの [0052] (Evaluation criteria) ○: Liquid
X：ゲル状のもの  X: Gel
[0053] <分散粒径 > [0053] <Dispersed particle size>
流動性が液状であるチタン酸バリウム分散組成物 1〜10、 14のチタン酸バリウムの粒 径 (d50)をナノトラック粒径測定装置 (UPA— EX150、 日機装 (株)社製)で測定し た。  The particle size (d50) of the barium titanate dispersion compositions 1 to 10 and 14 having a liquid flowability was measured with a nanotrack particle size measuring device (UPA-EX150, manufactured by Nikkiso Co., Ltd.). .
[0054] [表 1] [0054] [Table 1]
Figure imgf000013_0001
Figure imgf000013_0001
[0055] [表 2] [0055] [Table 2]
Figure imgf000014_0001
Figure imgf000014_0001
[0056] 表 1及び 2から分力るように、実施例:!〜 10のチタン酸バリウム分散組成物は流動性 に優れ、また粒径が小さいことからチタン酸バリウムの分散性にも優れている。また、 実施例のチタン酸バリウム分散組成物をコーティングし、焼成してコーティング被膜を 形成しても残渣は生じな力つた。  [0056] As shown in Tables 1 and 2, the barium titanate dispersion compositions of Examples:! To 10 are excellent in fluidity and also excellent in dispersibility of barium titanate because of their small particle size. Yes. Moreover, even if the barium titanate dispersion composition of the example was coated and baked to form a coating film, no residue was generated.
産業上の利用可能性  Industrial applicability
[0057] 本発明のチタン酸バリウム分散組成物は、極性溶媒中でのチタン酸バリウム粉末の 分散性及び分散安定性の問題、並びに、チタン酸バリウム分散組成物をコーティン グし、焼成した場合の残渣の問題の両方を解決することができるものである。本発明 のチタン酸バリウム分散組成物は、小型大容量ィ匕が求められる積層セラミックスコン デンサ一の誘電体層を形成するために使用することができる。  [0057] The barium titanate dispersion composition of the present invention has the problems of dispersibility and dispersion stability of the barium titanate powder in a polar solvent, and the case where the barium titanate dispersion composition is coated and fired. Both of the residue problems can be solved. The barium titanate dispersion composition of the present invention can be used to form a dielectric layer of a multilayer ceramic capacitor that requires a small and large capacity.

Claims

請求の範囲 The scope of the claims
[1] カルボキシ基末端ポリラタトンィ匕合物を分散剤として、チタン酸バリウム粉末を、分散 媒体中に分散させてなるチタン酸バリウム分散組成物であって、  [1] A barium titanate dispersion composition obtained by dispersing a barium titanate powder in a dispersion medium using a carboxy group-terminated polylatatonic compound as a dispersant,
前記カルボキシ基末端ポリラタトンィ匕合物力 ヒドロキシカルボン酸及びヒドロキシカ ルボン酸の縮合物力もなる群力 選択される少なくとも 1種を開始剤としてラタトンィ匕 合物を開環重合して得られるものであり、かつ  The carboxy group-terminated polylatatin compound compound is obtained by ring-opening polymerization of a ratatoni compound using at least one selected as an initiator and a group force that also has a condensate force of hydroxycarboxylic acid and hydroxycarboxylic acid, and
前記カルボキシ基末端ポリラタトンィ匕合物の重量平均分子量が 500〜5000であるチ タン酸バリウム分散組成物。  A barium titanate dispersion composition, wherein the carboxy group-terminated polylatatonic compound has a weight average molecular weight of 500 to 5,000.
[2] 前記分散剤が、 12—ヒドロキシステアリン酸、 12—ヒドロキシステアリン酸の縮合物及 びビスヒドロキシメチルプロピオン酸力 なる群力 選択される少なくとも 1種を開始剤 として力プロラタトンを開環重合して得られるカルボキシ基末端ポリ力プロラタトンィ匕合 物であり、かつ [2] The dispersing agent is a ring-opening polymerization of force prolatatone using at least one selected from the group force of 12-hydroxystearic acid, condensate of 12-hydroxystearic acid and bishydroxymethylpropionic acid as an initiator. A carboxy-terminated poly-force prolatatonic compound obtained by
前記カルボキシ基末端ポリ力プロラタトン化合物の重量平均分子量が 500〜5000で あることを特徴とする請求項 1記載のチタン酸バリウム分散組成物。  The barium titanate dispersion composition according to claim 1, wherein the weight average molecular weight of the carboxy group-terminated poly force prolatatone compound is 500 to 5,000.
[3] 前記開始剤が、 12—ヒドロキシステアリン酸、縮合度が 2の 12—ヒドロキシステアリン 酸の縮合物及びビスヒドロキシメチルプロピオン酸カゝらなる群カゝら選択される少なくと も 1種であり、かつ [3] The initiator is at least one selected from the group consisting of 12-hydroxystearic acid, a 12-hydroxystearic acid condensate having a condensation degree of 2, and bishydroxymethylpropionic acid. Yes, and
前記カルボキシ基末端ポリ力プロラタトン化合物の重量平均分子量が 1000〜3000 であることを特徴とする請求項 2記載のチタン酸バリウム分散組成物。  3. The barium titanate dispersion composition according to claim 2, wherein the weight average molecular weight of the carboxy group-terminated poly force prolatathone compound is 1000 to 3000.
[4] 前記分散媒体は、極性溶媒である請求項 1、 2又は 3記載のチタン酸バリウム分散組 成物。 [4] The barium titanate dispersion composition according to claim 1, 2 or 3, wherein the dispersion medium is a polar solvent.
[5] 請求項 1、 2、 3又は 4記載のチタン酸バリウム分散組成物の製造方法であって、 平均一次粒子径 10〜： LOOOnmのチタン酸バリウム粉末、カルボキシ基末端ポリラクト ン化合物及び分散媒体を含む原料組成物を練肉する工程を有し、  [5] The method for producing a barium titanate dispersion composition according to claim 1, 2, 3 or 4, wherein the barium titanate powder has an average primary particle diameter of 10 to: LOOOnm, a carboxy group-terminated polylacton compound, and a dispersion medium Having a step of kneading a raw material composition containing
前記カルボキシ基末端ポリラタトンィ匕合物力 ヒドロキシカルボン酸及びヒドロキシカ ルボン酸の縮合物力もなる群力 選択される少なくとも 1種を開始剤としてラタトンィ匕 合物を開環重合して得られるものであり、かつ  The carboxy group-terminated polylatatin compound compound is obtained by ring-opening polymerization of a ratatoni compound using at least one selected as an initiator and a group force that also has a condensate force of hydroxycarboxylic acid and hydroxycarboxylic acid, and
前記カルボキシ基末端ポリラタトンィ匕合物の重量平均分子量が 500〜5000である チタン酸バリウム分散組成物の製造方法。 The weight average molecular weight of the carboxy group-terminated polylatatonic compound is 500 to 5,000. Method for producing barium titanate dispersion composition.
PCT/JP2007/056611 2006-03-29 2007-03-28 Barium titanate dispersion composition WO2007114152A1 (en)

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