JP2007061792A - Inorganic pigment dispersing agent - Google Patents
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Abstract
Description
本発明は、無機顔料を水等に分散させてスラリーを得る際に好適に用いられる無機顔料用分散剤、及びそれを含有する無機顔料分散組成物に関する。 The present invention relates to an inorganic pigment dispersant that is suitably used when a slurry is obtained by dispersing an inorganic pigment in water or the like, and an inorganic pigment dispersion composition containing the dispersant.
無機顔料を水系媒体中に分散し、スラリー化するに際しては、ポリアクリル酸塩系分散剤が使用されている。例えば、ファインセラミクスの原料であるアルミナ等の無機顔料をポリアクリル酸塩系分散剤により水に分散して得られるスラリーは、基板に塗布し、乾燥、焼成する事により、平滑性のあるファインセラミクス部品を得ることができる。 In dispersing an inorganic pigment in an aqueous medium to form a slurry, a polyacrylate dispersant is used. For example, a slurry obtained by dispersing an inorganic pigment such as alumina, which is a raw material of fine ceramics, in water with a polyacrylate dispersant, is applied to a substrate, dried, and fired to obtain smooth fine ceramics. Parts can be obtained.
近年、上記のスラリーは、１〜４週間程度保存した後に使用するケースが出てきている。ところがファインセラミクスの高機能化、微細化に伴い、無機顔料は微粒に、また、そのスラリーは乾燥効率の向上等、生産性を高めるためさらに高濃度になってきている。しかしながら、微粒化された無機顔料の高濃度スラリーは、従来の分散剤ではスラリーの長期保存安定化は困難である。 In recent years, the above-mentioned slurry has been used after being stored for about 1 to 4 weeks. However, as fine ceramics become more functional and finer, inorganic pigments are becoming finer and the slurry is becoming higher in concentration in order to increase productivity, such as improvement in drying efficiency. However, a high-concentration slurry of finely divided inorganic pigment is difficult to stabilize for long-term storage with a conventional dispersant.
例えば特許文献１においてリン酸エステル含有の分散剤が開示されているが、このような分散剤では、スラリーの長期保存安定性が満足できるレベルには至っていない。
本発明の課題は、微粒化された無機顔料の高濃度スラリーにおいて長期分散安定性に優れる無機顔料用分散剤、及びそれを含有する無機顔料分散組成物を提供することにある。 The subject of this invention is providing the dispersing agent for inorganic pigments which is excellent in long-term dispersion stability in the high concentration slurry of the atomized inorganic pigment, and the inorganic pigment dispersion composition containing the same.
本発明は、下記一般式（１）で表されるモノマー１と、下記一般式（２）で表されるモノマー２と、下記一般式（３）で表されるモノマー３を含むモノマー成分の共重合体（以下本発明の共重合体という）を含有する無機顔料用分散剤、及びこの分散剤と、無機顔料とを含有する無機顔料分散組成物を提供する。 The present invention relates to a monomer component comprising a monomer 1 represented by the following general formula (1), a monomer 2 represented by the following general formula (2), and a monomer 3 represented by the following general formula (3). Disclosed are a dispersant for inorganic pigments containing a polymer (hereinafter referred to as a copolymer of the present invention), and an inorganic pigment dispersion composition containing the dispersant and an inorganic pigment.
〔式中、Ｒ1は、水素原子又はメチル基、Ｍ1は水素原子又は陽イオン基を示す。〕 [Wherein, R 1 represents a hydrogen atom or a methyl group, and M 1 represents a hydrogen atom or a cationic group. ]
〔式中、Ｒ2は水素原子又はメチル基、Ｒ3は炭素数２〜１２のアルキレン基、ｍ1は１〜３０の数、Ｍ2及びＭ3はそれぞれ独立に、水素原子又は陽イオン基を示す。〕 [Wherein, R 2 is a hydrogen atom or a methyl group, R 3 is an alkylene group having 2 to 12 carbon atoms, m 1 is a number of 1 to 30, M 2 and M 3 are each independently a hydrogen atom or a cationic group. Indicates. ]
〔式中、Ｒ4及びＲ5はそれぞれ独立に、水素原子又はメチル基、Ｒ6及びＲ7はそれぞれ独立に、炭素数２〜１２のアルキレン基、ｍ2及びｍ3はそれぞれ独立に、１〜３０の数、Ｍ4は水素原子又は陽イオン基を示す。〕 [Wherein R 4 and R 5 are each independently a hydrogen atom or a methyl group, R 6 and R 7 are each independently an alkylene group having 2 to 12 carbon atoms, m 2 and m 3 are each independently 1 The number of ˜30, M 4 represents a hydrogen atom or a cationic group. ]
本発明の無機顔料用分散剤は、無機顔料のスラリーにおいて低粘度化が可能であり、また、低粘度化スラリーの長期分散安定性にも優れる。 The dispersant for inorganic pigments of the present invention can reduce the viscosity of the inorganic pigment slurry, and is excellent in long-term dispersion stability of the low viscosity slurry.
本発明の共重合体は、前記モノマー１と、モノマー２と、モノマー３を含むモノマー成分を共重合することにより得られる。 The copolymer of the present invention is obtained by copolymerizing the monomer component including the monomer 1, the monomer 2, and the monomer 3.
モノマー１は前記一般式（１）で表されるモノマー成分であり、具体例としては、アクリル酸、メタクリル酸又はこれらの塩等が挙げられ、１種又は２種以上を用いることができる。 The monomer 1 is a monomer component represented by the general formula (1). Specific examples thereof include acrylic acid, methacrylic acid, and salts thereof, and one or more of them can be used.
モノマー２は前記一般式（２）で表されるモノマー成分であり、一般式（２）において、Ｒ3は炭素数２〜１０のアルキレン基が好ましく、炭素数２〜５のアルキレン基が更に好ましい。ｍ1は１〜２０の数が好ましく、１〜１０の数が更に好ましく、１〜５の数が特に好ましい。 The monomer 2 is a monomer component represented by the general formula (2). In the general formula (2), R 3 is preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 2 to 5 carbon atoms. . m 1 is preferably a number of 1 to 20, more preferably a number of 1 to 10, and particularly preferably a number of 1 to 5.
モノマー２の具体例として、２−ヒドロキシエチルメタクリレートモノリン酸エステル、２−ヒドロキシエチルアクリレートモノリン酸エステル、ポリアルキレングリコールモノメタクリレートモノリン酸エステル、ポリアルキレングリコールモノアクリレートモノリン酸エステル又はこれらの塩等が挙げられる。中でも、製造の容易さ及び製造物の品質安定性の観点から、２−ヒドロキシエチルメタクリレートモノリン酸エステル又はその塩が好ましい。 Specific examples of monomer 2 include 2-hydroxyethyl methacrylate monophosphate, 2-hydroxyethyl acrylate monophosphate, polyalkylene glycol monomethacrylate monophosphate, polyalkylene glycol monoacrylate monophosphate, or salts thereof. . Among these, 2-hydroxyethyl methacrylate monophosphate or a salt thereof is preferable from the viewpoint of ease of production and quality stability of the product.
モノマー３は前記一般式（３）で表されるモノマー成分であり、一般式（３）において、Ｒ6及びＲ7はそれぞれ炭素数２〜１０のアルキレン基が好ましく、炭素数２〜５のアルキレン基が更に好ましい。ｍ2及びｍ3はそれぞれ１〜２０の数が好ましく、１〜１０の数が更に好ましく、１〜５の数が特に好ましい。 The monomer 3 is a monomer component represented by the general formula (3). In the general formula (3), R 6 and R 7 are each preferably an alkylene group having 2 to 10 carbon atoms, and an alkylene having 2 to 5 carbon atoms. Groups are more preferred. m 2 and m 3 are each preferably a number of 1 to 20, more preferably a number of 1 to 10, and particularly preferably a number of 1 to 5.
モノマー３の具体例として、２−ヒドロキシエチルメタクリレートジリン酸エステル、２−ヒドロキシエチルアクリレートジリン酸エステル又はこれらの塩等が挙げられる。中でも、製造の容易さ及び製造物の品質安定性の観点から、２−ヒドロキシエチルメタクリレートジリン酸エステル又はその塩が好ましい。 Specific examples of the monomer 3 include 2-hydroxyethyl methacrylate diphosphate, 2-hydroxyethyl acrylate diphosphate or a salt thereof. Among these, 2-hydroxyethyl methacrylate diphosphate or a salt thereof is preferable from the viewpoint of ease of production and product quality stability.
モノマー１、モノマー２及びモノマー３において、Ｍ1、Ｍ2、Ｍ3及びＭ4で示される陽イオン基としては、アルカリ金属、アルカリ土類金属、４級アンモニウム、アンモニウム及び有機アミンからなる群から選ばれる少なくとも１種の陽イオン基が好ましい。アルカリ金属としては、ナトリウム、カリウム、リチウム等が挙げられる。アルカリ土類金属としては、マグネシウム、カルシウム、バリウム等が挙げられる。４級アンモニウムとしては、水酸化テトラメチルアンモニウム、水酸化トリエチルメチルアンモニウム等が挙げられる。有機アミンとしては、ジエタノールアミン、トリエタノールアミン、エチレンジアミン、ジエチレントリアミン、トリエチルアミン、トリブチルアミン等が挙げられる。これらの中で好ましいものは、無機顔料の高濃度スラリーを低粘度化し、低粘度化スラリーを長期分散安定化する観点において、アルカリ金属であり、ナトリウム、カリウムがより好ましい。また、アンモニウムは電子材料等の灰分の残存を嫌う用途への使用に好ましい。 In monomer 1, monomer 2 and monomer 3, the cationic groups represented by M 1 , M 2 , M 3 and M 4 are selected from the group consisting of alkali metals, alkaline earth metals, quaternary ammonium, ammonium and organic amines. At least one selected cationic group is preferred. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include magnesium, calcium, and barium. Examples of the quaternary ammonium include tetramethylammonium hydroxide and triethylmethylammonium hydroxide. Examples of the organic amine include diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylamine, and tributylamine. Among these, preferred are alkali metals, and sodium and potassium are more preferred from the viewpoint of lowering the viscosity of a high-concentration slurry of inorganic pigment and stabilizing the low-viscosity slurry for a long period of time. Ammonium is preferred for use in applications where ash content remains, such as electronic materials.
本発明の共重合体の中和度又はアルカリ過剰度は、特に規定されないが、通常５０〜１２０％であり、７０〜１１０％が好ましく、８０〜１１０％がより好ましい。 The degree of neutralization or alkali excess of the copolymer of the present invention is not particularly limited, but is usually 50 to 120%, preferably 70 to 110%, more preferably 80 to 110%.
尚、中和度又はアルカリ過剰度とは、［Ａ（塩を構成し得るフリーの塩基の当量＋塩を構成している酸基の当量）／Ｂ（塩を構成し得るフリーの酸基の当量＋塩を構成している酸基の当量）］×１００（％）で表される。Ａ／Ｂが１以下であれば中和度と表現し、Ａ／Ｂ＝１であれば中和度１００％を示す。Ａ／Ｂが１より大きいものはアルカリ過剰度と表現し、１００％より大きい値を示す。 The degree of neutralization or the excess of alkali means [A (equivalent of free base capable of constituting a salt + equivalent of acid group constituting a salt) / B (free acid group capable of constituting a salt). Equivalent + equivalent of acid group constituting the salt)] × 100 (%). When A / B is 1 or less, the degree of neutralization is expressed, and when A / B = 1, the degree of neutralization is 100%. A / B greater than 1 is expressed as alkali excess and shows a value greater than 100%.
本発明の共重合体を構成する全モノマー成分中の、モノマー２とモノマー３の合計割合は、無機顔料の高濃度化スラリーを低粘度化させる観点から、３〜２５モル％が好ましく、３〜２０モル％が更に好ましく、４〜１８モル％が特に好ましい。 The total ratio of the monomer 2 and the monomer 3 in all the monomer components constituting the copolymer of the present invention is preferably 3 to 25 mol% from the viewpoint of reducing the viscosity of the highly concentrated slurry of the inorganic pigment, 20 mol% is still more preferable, and 4-18 mol% is especially preferable.
また本発明の共重合体を構成するモノマー２とモノマー３の割合は、無機顔料の高濃度化スラリーを低粘度化させる観点から、モル比でモノマー２／モノマー３＝９９／１〜４０／６０が好ましく、９９／１〜７０／３０が更に好ましい。 Further, the ratio of the monomer 2 and the monomer 3 constituting the copolymer of the present invention is such that monomer 2 / monomer 3 = 99/1 to 40/60 in terms of molar ratio from the viewpoint of reducing the viscosity of the highly concentrated slurry of the inorganic pigment. Is preferable, and 99/1 to 70/30 is more preferable.
なお本発明において、全モノマー成分中の、モノマー２とモノマー３の合計量、モノマー２とモノマー３の割合は、例えば、以下の方法で算出することができる。 In the present invention, the total amount of monomer 2 and monomer 3 and the ratio of monomer 2 and monomer 3 in all monomer components can be calculated by the following method, for example.
31Ｐ−ＮＭＲ測定によりモノマー２、モノマー３中にそれぞれ含まれるリン酸モノエステル、リン酸ジエステルを定量して算出する（内部標準試料としてトリメチルフォスフェートを使用）。ここで、測定装置はＵＮＩＴＹ ＩＮＯＶＡ ３００（ＶＡＲＩＡＮ社）を用い、測定条件は、パルス幅９０°パルス（１７．２μｓ）、待ち時間３０ｓとする。 The phosphoric acid monoester and phosphoric acid diester contained in monomer 2 and monomer 3 are respectively determined by 31 P-NMR measurement and calculated (using trimethyl phosphate as an internal standard sample). Here, the measurement apparatus uses UNITY INOVA 300 (Varian), and the measurement conditions are a pulse width of 90 ° pulse (17.2 μs) and a waiting time of 30 s.
モノマー２及びモノマー３は、これらを含む混合モノマーとして、例えば、一般式（４）で表される有機ヒドロキシ化合物と無水リン酸（Ｐ2Ｏ5）及び水を所定の仕込み比で反応させることで、反応生成物として製造することができる。 The monomer 2 and the monomer 3 are mixed monomers containing them, for example, by reacting the organic hydroxy compound represented by the general formula (4) with phosphoric anhydride (P 2 O 5 ) and water at a predetermined charging ratio. Can be produced as a reaction product.
〔式中、Ｒ8は水素原子又はメチル基、Ｒ9は炭素数２〜１２のアルキレン基、ｍ4は１〜３０の数を示す。〕
また、モノマー２及びモノマー３は、これらを含む混合モノマーとして市販品を使用することもでき、例えば、ホスマーＭ、ホスマーＰＥ、ホスマーＰ（ユニケミカル）、ＪＡＭＰ５１４、ＪＡＭＰ５１４Ｐ、ＪＭＰ１００（何れも城北化学）、ライトエステルＰ−１Ｍ、ライトアクリレートＰ−１Ａ（いずれも共栄社化学）、ＭＲ２００（大八化学）、カヤマー（日本化薬）、Ethyleneglycol methacrylate phosphate（アルドリッチ試薬）などとして入手できる。
[Wherein R 8 represents a hydrogen atom or a methyl group, R 9 represents an alkylene group having 2 to 12 carbon atoms, and m 4 represents a number of 1 to 30. ]
Moreover, the monomer 2 and the monomer 3 can also use a commercial item as a mixed monomer containing these, for example, Phosmer M, Phosmer PE, Phosmer P (Unichemical), JAMP514, JAMP514P, JMP100 (all are Johoku Chemical) , Light ester P-1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich Reagent), etc. are available.
本発明の共重合体の製造においては、上記モノマー１、２及び３の他に、これらと共重合可能なその他のモノマーを用いることもできる。共重合可能な他のモノマーとしては、アリルスルホン酸、メタリルスルホン酸、あるいはこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩又はアミン塩が挙げられる。また、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸等のアクリル酸系モノマー、あるいはこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩、メチルエステル、エチルエステルや、無水マレイン酸等の無水化合物などが挙げられる。更に、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、２−（メタ）アクリルアミド−２−メタスルホン酸、２−（メタ）アクリルアミド−２−エタンスルホン酸、２−（メタ）アクリルアミド−２−プロパンスルホン酸、スチレン、スチレンスルホン酸などが挙げられる。全モノマー成分中、モノマー１、２及び３の合計割合は、本発明の分散剤としての性能を達成する観点から、９０〜１００モル％、更に９５〜１００モル％、特に１００モル％が好ましい。 In the production of the copolymer of the present invention, in addition to the monomers 1, 2 and 3, other monomers copolymerizable with these can also be used. Examples of other copolymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts, or amine salts thereof. In addition, acrylic monomers such as crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters, anhydrous Examples thereof include anhydrous compounds such as maleic acid. Furthermore, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, Examples include 2- (meth) acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. In the total monomer components, the total proportion of monomers 1, 2 and 3 is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 100 mol% from the viewpoint of achieving the performance as the dispersant of the present invention.
本発明の共重合体の製造法は特に限定されないが、例えばモノマー１、２及び３を、連鎖移動剤及び重合開始剤の存在下で溶液重合する方法が好ましい。連鎖移動剤としては、チオール系連鎖移動剤、ハロゲン化炭化水素系連鎖移動剤等が挙げられ、チオール系連鎖移動剤が好ましい。重合開始剤としては、過硫酸のアンモニウム塩又はアルカリ金属塩あるいは過酸化水素、２，２’−アゾビス（２−アミジノプロパン）ジヒドロクロライド、２，２’−アゾビス（２−メチルプロピオンアミド）ジハイドレート等の水溶性アゾ化合物を用いることができる。また、重合開始剤と併用して、亜硫酸水素ナトリウム、アミン化合物などの促進剤を使用することもできる。使用される溶媒としては、水、あるいは水と、メチルアルコール、エチルアルコール、イソプロピルアルコール、アセトン、メチルエチルケトン等とを含有する含水溶媒系の溶媒が挙げられる。取り扱いと反応設備から考慮すると、水が好ましい。 The method for producing the copolymer of the present invention is not particularly limited, but for example, a method in which monomers 1, 2, and 3 are solution polymerized in the presence of a chain transfer agent and a polymerization initiator is preferable. Examples of chain transfer agents include thiol chain transfer agents and halogenated hydrocarbon chain transfer agents, and thiol chain transfer agents are preferred. As a polymerization initiator, persulfuric acid ammonium salt or alkali metal salt or hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) dihydrate, etc. These water-soluble azo compounds can be used. In addition, an accelerator such as sodium bisulfite and an amine compound can be used in combination with the polymerization initiator. Examples of the solvent to be used include water or a water-containing solvent type solvent containing water and methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, and the like. In view of handling and reaction equipment, water is preferred.
本発明の共重合体の重量平均分子量（Ｍｗ）は、無機顔料のスラリーを長期分散安定化させる観点から、１２０００〜８００００が好ましく、１５０００〜７００００がより好ましく、２００００〜６００００が特に好ましい。 The weight average molecular weight (Mw) of the copolymer of the present invention is preferably 12000 to 80000, more preferably 15000 to 70000, and particularly preferably 20000 to 60000, from the viewpoint of long-term dispersion stabilization of the inorganic pigment slurry.
尚、ここで共重合体の重量平均分子量は、実施例に記載された測定法により測定された値である。 In addition, the weight average molecular weight of a copolymer here is the value measured by the measuring method described in the Example.
本発明の分散剤中の本発明の共重合体の含有量は、無機顔料の高濃度スラリーを低粘度化できる範疇において、９７〜１００重量％が好ましく、９８〜１００重量％がより好ましく、９９〜１００重量％が特に好ましい。本発明の分散剤中には、本発明の共重合体以外に未反応のモノマー１、モノマー２、モノマー３等を含有していてもよい。 The content of the copolymer of the present invention in the dispersant of the present invention is preferably from 97 to 100% by weight, more preferably from 98 to 100% by weight, in the category capable of reducing the viscosity of the high-concentration slurry of inorganic pigment. ˜100% by weight is particularly preferred. The dispersant of the present invention may contain unreacted monomer 1, monomer 2, monomer 3 and the like in addition to the copolymer of the present invention.
本発明で分散する無機顔料の平均粒径は０．１〜０．５μｍが好ましく、０．１〜０．４μｍが更に好ましい。尚、無機顔料の平均粒径はレーザー回折／散乱式粒度分布測定装置（例えば、株式会社堀場製作所製ＬＡ−９２０）により求めることができる。 The average particle diameter of the inorganic pigment dispersed in the present invention is preferably 0.1 to 0.5 μm, and more preferably 0.1 to 0.4 μm. In addition, the average particle diameter of an inorganic pigment can be calculated | required with the laser diffraction / scattering type particle size distribution measuring apparatus (For example, LA-920 by Horiba, Ltd.).
本発明において対象となる無機顔料は、リン酸カルシウム、リン酸亜鉛、クレー、ベントナイト、サチンホワイト、亜鉛華、ベンガラ、フェライト、酸化チタン、アルミナ、酸化マグネシウム、炭酸カルシウム、タルク、ホワイトカーボン、ゼオライト、各種チタン酸塩、各種珪酸塩、カーボンブラック、炭化珪素のような炭化物、窒化アルミニウムのような窒化物等が挙げられ、ファインセラミクスの原料から選ばれる少なくとも１種が好ましく、チタン酸バリウム等のチタン酸塩や、アルミナが更に好ましい。 Inorganic pigments of interest in the present invention are calcium phosphate, zinc phosphate, clay, bentonite, satin white, zinc white, bengara, ferrite, titanium oxide, alumina, magnesium oxide, calcium carbonate, talc, white carbon, zeolite, various titanium Examples include acid salts, various silicates, carbon black, carbides such as silicon carbide, nitrides such as aluminum nitride, and preferably at least one selected from raw materials of fine ceramics, and titanates such as barium titanate. Alumina is more preferable.
尚、ファインセラミクスとは基本的に無機化合物からなり、鉱物を原料として１０００℃以上の高温反応にて製造するものである。具体的にはセメント、ガラス、陶磁器、耐火物、研磨材といった構造材料、またＩＣパッケージ、配線基板、センサー、磁性体、コンデンサー、光ファイバーといった電磁気・光学用部材が挙げられる。 Fine ceramics are basically composed of an inorganic compound, and are produced by a high-temperature reaction at 1000 ° C. or higher using a mineral as a raw material. Specific examples include structural materials such as cement, glass, ceramics, refractories, and abrasives, and electromagnetic / optical members such as IC packages, wiring boards, sensors, magnetic bodies, capacitors, and optical fibers.
本発明の分散剤は特にフェライト製造工程用又はチタン酸バリウム等の電磁気・光学用部材ファインセラミクス無機顔料用の分散剤として有効である。 The dispersant of the present invention is particularly effective as a dispersant for a ferrite production process or an electromagnetic / optical member fine ceramic inorganic pigment such as barium titanate.
本発明の分散剤は、電磁気・光学用部材ファインセラミクス用等の無機顔料分散組成物を得る際に有効に用いることができ、特に電子材料ファインセラミック用として用いることが好ましい。 The dispersant of the present invention can be effectively used in obtaining an inorganic pigment dispersion composition for electromagnetic ceramics and optical member fine ceramics, and is particularly preferably used for electronic material fine ceramics.
本発明の無機顔料分散組成物は、本発明の分散剤を用いて無機顔料の粉体、粉体の原鉱石又は粗粒子を水系媒体中に分散させることにより、得ることができる。水系媒体としては、水、あるいは水とエチルアルコール、エチレングリコール等の水溶性有機溶媒との混合溶液が挙げられ、好ましくは水である。 The inorganic pigment dispersion composition of the present invention can be obtained by dispersing an inorganic pigment powder, powder ore or coarse particles in an aqueous medium using the dispersant of the present invention. Examples of the aqueous medium include water or a mixed solution of water and a water-soluble organic solvent such as ethyl alcohol or ethylene glycol, preferably water.
本発明の無機顔料分散組成物中の無機顔料の含有量は、特に規定はないが、６５〜８５重量％が好ましい。また、無機顔料分散組成物中の本発明の分散剤の含有量は特に規定されないが、無機顔料１００重量部に対して通常０．０１〜１０重量部が好ましく、０．０５〜５重量部がさらに好ましく、０．０５〜３重量部が特に好ましい。 The content of the inorganic pigment in the inorganic pigment dispersion composition of the present invention is not particularly specified, but is preferably 65 to 85% by weight. In addition, the content of the dispersant of the present invention in the inorganic pigment dispersion composition is not particularly specified, but is usually preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight with respect to 100 parts by weight of the inorganic pigment. Further preferred is 0.05 to 3 parts by weight.
本発明の分散剤を使用して、無機顔料分散組成物を得る方法としては、通常のスラリー化方法が用いられる。例えば本発明の分散剤を溶解した水溶液に無機顔料を添加して撹拌、混合する方法、無機顔料に水と本発明の分散剤を加えて撹拌、混合する方法等が挙げられる。撹拌、混合する方法としては、例えば高速ディスパー、ホモミキサー、ボールミル、ビーズミル等一般に用いられる湿式粉砕機を使用することができる。 As a method for obtaining an inorganic pigment dispersion composition using the dispersant of the present invention, a usual slurrying method is used. Examples thereof include a method of adding an inorganic pigment to an aqueous solution in which the dispersant of the present invention is dissolved and stirring and mixing, a method of adding water and the dispersant of the present invention to an inorganic pigment, and stirring and mixing. As a method of stirring and mixing, for example, a generally used wet pulverizer such as a high-speed disper, a homomixer, a ball mill, or a bead mill can be used.
以下の例において、無機顔料用分散剤の物性は以下の方法で測定した。 In the following examples, the physical properties of the dispersant for inorganic pigment were measured by the following methods.
＜重量平均分子量＞
ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により、下記条件で測定した。
カラム：ＴＳＫ ＰＷＸＬ＋Ｇ4000ＰＷＸＬ＋Ｇ2500ＰＷＸＬ（いずれも東ソー株式会社製）
カラム温度：４０℃
検出器：ＲＩ又はＵＶ（２１０ｎｍ）
溶離液：０．２ｍｏｌ／Ｌ リン酸緩衝液／アセトニトリル（９／１）
流速：１．０ｍＬ／ｍｉｎ
注入量：０．１ｍＬ
標準：ポリエチレングリコール
製造例１
攪拌機、温度計、還流冷却管、窒素導入管、滴下ロートを備えた反応容器にイオン交換水３０ｇを仕込み、窒素気流下で１００℃に加熱後、この温度を維持しながら、８０重量％アクリル酸水溶液１２１．７ｇと２−ヒドロキシエチルメタクリレートモノリン酸エステル２８．４ｇと２−ヒドロキシエチルメタクリレートジリン酸エステル５．２ｇを混合したもの、７重量％２−メルカプトエタノール水溶液８４．３ｇ、及び３重量％過硫酸ナトリウム水溶液２８．６ｇをそれぞれ別の滴下ロートから２．５時間かけて滴下し重合反応を行った。滴下終了後、１００℃で３時間熟成したが、熟成時間内中３重量％過硫酸ナトリウム７．１ｇを１分間かけて滴下し、重合反応を完結させた。次に脱臭として３５重量％過酸化水素水溶液を１００℃で３０分かけて１０．９ｇ滴下し、その後１００℃で１時間熟成した。熟成終了後、冷却し、約６０℃を保持しながらｐＨが６．５〜８．５となるように３０重量％水酸化ナトリウム水溶液で中和して（中和度９９％）、Ｍｗが４８３００の分散剤（以下分散剤１という）を得た。
<Weight average molecular weight>
It measured by GPC (gel permeation chromatography) on the following conditions.
Column: TSK PWXL + G4000PWXL + G2500PWXL (both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI or UV (210 nm)
Eluent: 0.2 mol / L phosphate buffer / acetonitrile (9/1)
Flow rate: 1.0 mL / min
Injection volume: 0.1 mL
Standard: Polyethylene glycol Production Example 1
A reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was charged with 30 g of ion-exchanged water, heated to 100 ° C. under a nitrogen stream, and maintained at this temperature while maintaining 80% by weight acrylic acid. A mixture of 121.7 g of an aqueous solution, 28.4 g of 2-hydroxyethyl methacrylate monophosphate and 5.2 g of 2-hydroxyethyl methacrylate diphosphate, 84.3 g of a 7 wt% 2-mercaptoethanol aqueous solution, and 3 wt% excess A sodium sulfate aqueous solution (28.6 g) was dropped from another dropping funnel over 2.5 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 3 hours, and 7.1 g of 3% by weight sodium persulfate was added dropwise over the course of 1 minute to complete the polymerization reaction. Next, 10.9 g of a 35 wt% aqueous hydrogen peroxide solution was added dropwise at 100 ° C. over 30 minutes for deodorization, and then aged at 100 ° C. for 1 hour. After completion of aging, the mixture is cooled and neutralized with a 30% by weight aqueous sodium hydroxide solution (neutralization degree 99%) so that the pH is 6.5 to 8.5 while maintaining about 60 ° C., and the Mw is 48300. A dispersant (hereinafter referred to as Dispersant 1) was obtained.
製造例２〜１０及び比較製造例１〜４
表１に示すモノマーを用い、製造例１と同様にして分散剤２〜１０及び比較分散剤１〜４の合成を行った。
Production Examples 2 to 10 and Comparative Production Examples 1 to 4
Using the monomers shown in Table 1, the dispersants 2 to 10 and the comparative dispersants 1 to 4 were synthesized in the same manner as in Production Example 1.
分散剤１〜１０及び比較分散剤１〜４のモノマー組成、重量平均分子量（Ｍｗ）、中和度又はアルカリ過剰度を表１にまとめて示した。 The monomer composition, weight average molecular weight (Mw), degree of neutralization or alkali excess of dispersants 1-10 and comparative dispersants 1-4 are summarized in Table 1.
実施例１
５００ｍＬのディスポビーカーに平均粒径が０．１４μｍのアルミナ１２０．００ｇ、イオン交換水３１．４５ｇ、及び分散剤１〜１０又は比較分散剤１〜４（イオン交換水で希釈して固形分３０重量％に調整したもの）２．４０ｇを仕込んだ後、特殊機化工業株式会社製のホモディスパーで攪拌（２５００ｒ／ｍｉｎ×３分間）し、７８重量％のスラリーを調製した。得られたスラリーを株式会社東京計器製のＢ型粘度測定装置を用いて２５℃におけるＢ粘度をローターの回転速度６０ｒ／ｍｉｎで１分後に測定した。ローターとしては、粘度５００ｍＰａ・ｓ未満の場合はローターNo.２、粘度５００〜２０００ｍＰａ・ｓの場合はローターNo.３、粘度２０００ｍＰａ・ｓを越える場合はローターNo.４を用いた。
Example 1
In a 500 mL disposable beaker, 120.00 g of alumina having an average particle size of 0.14 μm, 31.45 g of ion-exchanged water, and dispersants 1 to 10 or comparative dispersants 1 to 4 (diluted with ion-exchanged water to have a solid content of 30 wt. After preparing 2.40 g, the mixture was stirred with a homodisper manufactured by Tokushu Kika Kogyo Co., Ltd. (2500 r / min × 3 minutes) to prepare a 78 wt% slurry. The obtained slurry was measured for B viscosity at 25 ° C. using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. after 1 minute at a rotational speed of the rotor of 60 r / min. As the rotor, rotor No. 2 was used when the viscosity was less than 500 mPa · s, rotor No. 3 was used when the viscosity was 500 to 2000 mPa · s, and rotor No. 4 was used when the viscosity exceeded 2000 mPa · s.
また、上記スラリーを２５０ｍＬのポリビンで２５℃にて３０日間静置した後、３０〜４０回程度振とうし、その後、同様に上記の条件でＢ粘度を測定した。これらの結果を表２に示す。 The slurry was allowed to stand at 250C for 30 days with 250 mL of polybin, and then shaken about 30 to 40 times. Thereafter, the B viscosity was similarly measured under the above conditions. These results are shown in Table 2.
尚、スラリーは、Ｂ粘度（製造直後及び３０日後）が２５０ｍＰａ・ｓ以下であり、経時増粘をしていないものが良好である。 The slurry has a B viscosity (immediately after production and after 30 days) of 250 mPa · s or less, and a slurry that is not thickened with time is good.
実施例２
５００ｍＬのディスポビーカーに平均粒径が０．２１μｍのカルサイト系軽質炭酸カルシウム１７５．００ｇ、イオン交換水８０．３６ｇ、及び分散剤１〜１０又は比較分散剤１〜４（イオン交換水で希釈して固形分３０重量％に調整したもの）５．８３ｇを仕込んだ後、特殊機化工業株式会社製のホモディスパーで攪拌（２５００ｒ／ｍｉｎ×２分間）し、６７重量％の一次分散スラリーを調製した。次いで、このスラリーに１ｍｍガラスビーズを全仕込み量の１．５倍（重量比）の割合で仕込み、さらにホモディスパーで約２０℃に保冷しながら攪拌（７６００ｒ／ｍｉｎ×１５分間）し、二次分散スラリーを調製した。
Example 2
In a 500 mL disposable beaker, 175.00 g of calcite-based light calcium carbonate with an average particle size of 0.21 μm, 80.36 g of ion-exchanged water, and dispersants 1-10 or comparative dispersants 1-4 (diluted with ion-exchanged water) Prepared to a solid content of 30% by weight), and then stirred with a homodisper manufactured by Tokushu Kika Kogyo Co., Ltd. (2500 r / min × 2 minutes) to prepare a 67% by weight primary dispersion slurry. did. Next, 1 mm glass beads were charged into this slurry at a ratio of 1.5 times (weight ratio) of the total charged amount, and further stirred while being kept at about 20 ° C. with a homodisper (7600 r / min × 15 minutes). A dispersion slurry was prepared.
ガラスビーズを濾別した後、得られた二次分散スラリーを株式会社東京計器製のＢ型粘度測定装置を用いて２５℃におけるＢ粘度をローターの回転速度６０ｒ／ｍｉｎで１分後に測定した。ローターとしては、粘度に応じて実施例１と同様のものを用いた。 After the glass beads were filtered off, the obtained secondary dispersion slurry was measured for B viscosity at 25 ° C. using a B-type viscosity measuring device manufactured by Tokyo Keiki Co., Ltd. after 1 minute at a rotational speed of the rotor of 60 r / min. As the rotor, the same rotor as in Example 1 was used depending on the viscosity.
また、このスラリーを２５０ｍＬのポリビンで２５℃にて３０日間静置した後、３０〜４０回程度振とうし、その後、同様に上記の条件でＢ粘度を測定した。これらの結果を表３に示す。 The slurry was allowed to stand at 250C for 30 days with 250 mL of polybin, and then shaken about 30 to 40 times. Thereafter, the B viscosity was similarly measured under the above conditions. These results are shown in Table 3.
尚、スラリーは、Ｂ粘度（製造直後及び３０日後）が４００ｍＰａ・ｓ以下であり、経時増粘をしていないものが良好である。 The slurry has a B viscosity (immediately after production and after 30 days) of 400 mPa · s or less, and a slurry that is not thickened with time is good.
Claims (4)
The inorganic pigment dispersion composition containing the dispersing agent in any one of Claims 1-3, and an inorganic pigment.
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| JP2011168700A (en) * | 2010-02-18 | 2011-09-01 | Uni-Chemical Co Ltd | Method for producing composition containing phosphate group-containing vinyl-based polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5887161A (en) * | 1981-11-18 | 1983-05-24 | Dainippon Toryo Co Ltd | Resin composition |
| JPS6028818A (en) * | 1983-07-28 | 1985-02-14 | Lion Corp | Dispersing agent for calcium carbonate |
| JP2000104005A (en) * | 1998-09-28 | 2000-04-11 | Dainippon Printing Co Ltd | Pigment dispersant, photosensitive coloring composition and composition for light protecting layer |
| JP2000327386A (en) * | 1999-05-14 | 2000-11-28 | Taiheiyo Cement Corp | Cement dispersant and hydraulic composition including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5887161A (en) * | 1981-11-18 | 1983-05-24 | Dainippon Toryo Co Ltd | Resin composition |
| JPS6028818A (en) * | 1983-07-28 | 1985-02-14 | Lion Corp | Dispersing agent for calcium carbonate |
| JP2000104005A (en) * | 1998-09-28 | 2000-04-11 | Dainippon Printing Co Ltd | Pigment dispersant, photosensitive coloring composition and composition for light protecting layer |
| JP2000327386A (en) * | 1999-05-14 | 2000-11-28 | Taiheiyo Cement Corp | Cement dispersant and hydraulic composition including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011168700A (en) * | 2010-02-18 | 2011-09-01 | Uni-Chemical Co Ltd | Method for producing composition containing phosphate group-containing vinyl-based polymer |
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