TW201629120A - Non-aqueous dispersant and non-aqueous dispersion composition - Google Patents
Non-aqueous dispersant and non-aqueous dispersion composition Download PDFInfo
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Abstract
Description
本發明係關於一種非水性分散劑及含有該非水性分散劑的非水性分散體組合物，非水性分散劑可用於有機或無機粉體等分散體在非水性溶劑中的分散。更詳細而言，本發明係關於一種非水性分散劑及含有該非水性分散劑的非水性分散體組合物，該非水性分散劑能夠以少量的添加量使分散體以高濃度分散於非水性溶劑中，同時賦予優異的分散穩定性。The present invention relates to a non-aqueous dispersant and a non-aqueous dispersion composition containing the non-aqueous dispersant, which can be used for dispersion of a dispersion of an organic or inorganic powder or the like in a non-aqueous solvent. More specifically, the present invention relates to a non-aqueous dispersant and a non-aqueous dispersion composition containing the non-aqueous dispersant capable of dispersing the dispersion in a non-aqueous solvent at a high concentration in a small amount of addition. At the same time, it imparts excellent dispersion stability.
使有機粉體或無機粉體等分散體分散於非水性溶劑中的非水性分散體組合物被用於各種工業領域中。作為有機粉體，例如可列舉出有機顏料，含有有機顏料的非水性分散體組合物被用於塗料、印刷油墨、噴墨用油墨、濾色片用抗蝕劑及書寫用具油墨等。此外，作為無機粉體，例如可列舉出陶瓷粉體或金屬粉體，含有陶瓷粉體的非水性分散體組合物除了用於多層陶瓷電容器的電介質層、半導體基板、各種感測器及液晶顯示元件等電子部件以外，還用於研磨材料或耐火材料等。此外，含有金屬粉體的非水性分散體組合物作為形成電極的電子材料，例如作為導電膏或導電性油墨而被廣泛利用。A non-aqueous dispersion composition in which a dispersion such as an organic powder or an inorganic powder is dispersed in a non-aqueous solvent is used in various industrial fields. Examples of the organic powder include an organic pigment, and a non-aqueous dispersion composition containing an organic pigment is used for a coating material, a printing ink, an ink for inkjet, a resist for a color filter, and a writing instrument ink. Further, examples of the inorganic powder include a ceramic powder or a metal powder, and a non-aqueous dispersion composition containing a ceramic powder is used for a dielectric layer, a semiconductor substrate, various sensors, and a liquid crystal display for a multilayer ceramic capacitor. In addition to electronic components such as components, it is also used for abrasive materials or refractory materials. Further, the non-aqueous dispersion composition containing a metal powder is widely used as an electronic material for forming an electrode, for example, as a conductive paste or a conductive ink.
近年來，在電子部件用途中，期望部件的小型化、高容量化及高效率化等產品特性的改進，為了滿足這些要求，謀求原料陶瓷粉體或金屬粉體等分散體的微粒化、非水性分散體組合物中的分散體的高濃度化。在製備非水性分散體組合物時，由於有機粉體或無機粉體在單獨狀態下分散性不充分的情況較多，因此以提高非水性分散體組合物的流動性及儲藏穩定性為目的，通常使用分散劑。作為該分散劑，迄今為止，人們提出了許多高分子類分散劑，例如聚丙烯酸或它們的共聚物、聚氧化烯衍生物與馬來酸酐的共聚物等。In recent years, in the use of electronic components, improvement in product characteristics such as miniaturization, high capacity, and high efficiency of components has been desired. In order to meet these requirements, it is desired to atomize and disperse a dispersion such as a raw material ceramic powder or a metal powder. The concentration of the dispersion in the aqueous dispersion composition is increased. In the preparation of the non-aqueous dispersion composition, since the organic powder or the inorganic powder is insufficient in dispersibility in a single state, it is intended to improve the fluidity and storage stability of the non-aqueous dispersion composition. A dispersing agent is usually used. As the dispersant, many polymer dispersants such as polyacrylic acid or a copolymer thereof, a copolymer of a polyoxyalkylene derivative and maleic anhydride, and the like have been proposed.
但隨著微粒化，在以往的高分子類分散劑中，分散劑在粒子間貫通吸附，容易產生橋接凝聚，由此產生初期分散性降低的問題。此外，由於分散體的表面積增加，分散體的表面自由能增大，分散體系容易變得不穩定。因此，即使能夠暫時分散，若試圖減少分散體的表觀表面積，則分散體再次凝聚，難以穩定保持分散狀態。初期分散性及分散穩定性伴隨分散體的微粒化而降低，由此產生非水性分散體組合物變稠或分散體沉積等問題。在產生了這些問題的非水性分散體組合物中，不僅引起生產性、加工特性及操作性的降低，還導致最終製品的質量降低。However, in the conventional polymer-based dispersant, the dispersant penetrates and adsorbs between the particles, and bridge aggregation is likely to occur, which causes a problem that the initial dispersibility is lowered. Further, since the surface area of the dispersion increases, the surface free energy of the dispersion increases, and the dispersion system tends to become unstable. Therefore, even if it is possible to temporarily disperse, if an attempt is made to reduce the apparent surface area of the dispersion, the dispersion re-agglomerates and it is difficult to stably maintain the dispersed state. The initial dispersibility and the dispersion stability are lowered by the atomization of the dispersion, thereby causing problems such as thickening of the non-aqueous dispersion composition or deposition of the dispersion. In the non-aqueous dispersion composition in which these problems occur, not only the productivity, processing characteristics, and workability are lowered, but also the quality of the final product is lowered.
因此，對於分散劑，要求能夠獲得以高濃度含有分散體且低黏度的非水性分散體組合物的同時，分散體經長時間而不會沉積，能夠穩定分散的性能。Therefore, it is required that the dispersant can obtain a non-aqueous dispersion composition containing a dispersion at a high concentration and having a low viscosity, and the dispersion can be stably deposited without being deposited for a long period of time.
為了解決上述問題，在專利文獻1中，提出了一種聚氧亞乙基單苯醚與環式羧酸的酯化物，但其對含有微粒分散體的非水性分散體組合物而言並不能充分滿足效果。此外，在專利文獻2中，分別提出了親油性高的聚氧亞丙基單甲基丙烯酸醚與偏苯三酸酐的酯化物，但對所述組合物的效果並不完全令人滿意。In order to solve the above problem, Patent Document 1 proposes an esterified product of a polyoxyethylene monophenyl ether and a cyclic carboxylic acid, but it is insufficient for a nonaqueous dispersion composition containing a fine particle dispersion. Satisfy the effect. Further, in Patent Document 2, an esterified product of polyoxypropylene monomethacrylate and trimellitic anhydride having high lipophilicity has been proposed, but the effect on the composition is not completely satisfactory.
〔先前技術文獻〕 〔專利文獻〕 專利文獻1：特開昭62-106838號公報 專利文獻2：特開2007-144402號公報[Prior Art Document] [Patent Document] Patent Document 1: JP-A-62-106838 (Patent Document 2) JP-A-2007-144402
〔發明所欲解決之課題〕[The subject to be solved by the invention]
綜上所述，本發明的目的在於解決所述技術問題，具體為提供一種非水性分散劑，其能夠使粒徑為1μm以下的微粒分散體以高濃度分散於非水性溶劑中，同時能夠賦予其優異的分散穩定性。In view of the above, an object of the present invention is to solve the above problems, and in particular to provide a non-aqueous dispersant capable of dispersing a fine particle dispersion having a particle diameter of 1 μm or less in a non-aqueous solvent at a high concentration while imparting Its excellent dispersion stability.
〔解決課題之手段〕[Means for solving the problem]
為了解決所述技術問題，本申請發明人等經過認真研究，結果發現由具有特定結構的聚醚與三羧酸酐形成的聚醚酯化合物能夠解決所述技術問題。In order to solve the technical problem, the inventors of the present application have earnestly studied, and as a result, have found that a polyether ester compound formed of a polyether having a specific structure and a tricarboxylic anhydride can solve the technical problem.
即，本發明為下述[1]~[3]。That is, the present invention is the following [1] to [3].
[1]下述式(1)所示的非水性分散劑，。[1] a non-aqueous dispersant represented by the following formula (1), .
式(1)中，R為碳原子數1~22的直鏈或支鏈狀的烴基；A1 O為氧亞乙基(Oxyethylene group)、m為A1 O所示的氧亞乙基的平均加成莫耳數，為1~30；A2 O為碳原子數3~4的氧亞烷基(Oxyalkylene group)，n為A2 O所示的氧亞烷基的平均加成莫耳數，為1~30；m與n滿足0.1≤m/n≤10且5≤m＋n≤40的關係；a為芳香環的數量，為1~2；M表示氫原子、銨(ammonium)或烷醇銨(alkanolammonium)。In the formula (1), R is a linear or branched hydrocarbon group having 1 to 22 carbon atoms; A 1 O is an oxyethylene group; and m is an oxyethylene group represented by A 1 O. The average addition mole number is 1~30; A 2 O is an oxyalkylene group having 3 to 4 carbon atoms, and n is the average addition mole of oxyalkylene group represented by A 2 O The number is 1~30; m and n satisfy the relationship of 0.1≤m/n≤10 and 5≤m+n≤40; a is the number of aromatic rings, which is 1~2; M represents hydrogen atom, ammonium or alkane Alkanolmmonium.
[2]根據[1]所述的非水性分散劑，其特徵在於，A2 O為碳原子數為3的氧亞丙基(Oxypropylene group)。[2] The non-aqueous dispersing agent according to [1], wherein A 2 O is an oxypropylene group having 3 carbon atoms.
[3]一種非水性分散體組合物，其含有由[1]或[2]所述的非水性分散劑、非水性溶劑及由所述非水性分散劑分散的分散體。[3] A non-aqueous dispersion composition comprising the non-aqueous dispersant according to [1] or [2], a non-aqueous solvent, and a dispersion dispersed by the non-aqueous dispersant.
〔發明效果〕[effect of the invention]
根據本發明，能夠使粒徑為1μm以下的有機粉體或無機粉體等微粒分散體以高濃度分散於非水性溶劑中，同時能夠賦予其優異的分散穩定性。According to the present invention, the fine particle dispersion such as the organic powder or the inorganic powder having a particle diameter of 1 μm or less can be dispersed in a non-aqueous solvent at a high concentration, and excellent dispersion stability can be imparted thereto.
以下對本發明的非水性分散劑及非水性分散體組合物的實施方式依次進行說明。Hereinafter, embodiments of the non-aqueous dispersing agent and the non-aqueous dispersion composition of the present invention will be sequentially described.
(非水性分散劑)(non-aqueous dispersant)
本發明的非水性分散劑含有下述式(1)所示的聚醚與三羧酸酐形成的聚醚酯化合物，此外，式(1)所示的聚醚與三羧酸酐形成的酯化合物在下文中也僅稱為「聚醚酯類化合物」。。The non-aqueous dispersing agent of the present invention contains a polyether ester compound formed of a polyether represented by the following formula (1) and a tricarboxylic acid anhydride, and an ester compound formed of the polyether represented by the formula (1) and a tricarboxylic anhydride is under This article is also referred to as "polyether ester compound". .
R為碳原子數1~22的直鏈或支鏈的烴基。作為 R，可列舉出甲基、乙基、丙基、丁基、己基、庚基、辛基、月桂基、肉豆蔻基、棕櫚基、硬脂基、山崳基(behenyl group)等直鏈狀飽和烴基，異丙基、異丁基、叔丁基、異戊基、異辛基、2-乙基己基、異壬基、3,5,5-三甲基己基、異癸基、異硬脂基、2-辛基癸基、2-辛基十二烷基、2-己基癸基等支鏈狀飽和烴基，烯丙基、(甲基)丙烯酸基、棕櫚醯基、油烯基、亞油基等不飽和烴基等。這些基團可以使用一種或兩種以上混合使用。從對非水性溶劑的溶解性及初期分散性的角度考慮，較佳為碳原子數4~18的直鏈或支鏈狀飽和烴基或不飽和烴基，更進一步較佳為碳原子數4~18的支鏈狀飽和烴基。R is a linear or branched hydrocarbon group having 1 to 22 carbon atoms. Examples of R include a linear chain such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, an octyl group, a lauryl group, a myristyl group, a palmity group, a stearyl group, or a behenyl group. Saturated hydrocarbon group, isopropyl, isobutyl, tert-butyl, isopentyl, isooctyl, 2-ethylhexyl, isodecyl, 3,5,5-trimethylhexyl, isodecyl, iso Branched saturated hydrocarbon group such as stearyl, 2-octyldecyl, 2-octyldodecyl or 2-hexyldecyl, allyl, (meth)acrylic, palmitoyl, oleyl An unsaturated hydrocarbon group such as a linoleic group or the like. These groups may be used alone or in combination of two or more. From the viewpoint of solubility in a nonaqueous solvent and initial dispersibility, a linear or branched saturated hydrocarbon group or an unsaturated hydrocarbon group having 4 to 18 carbon atoms is preferred, and a carbon number of 4 to 18 is further more preferred. Branched saturated hydrocarbon group.
A1 O及A2 O為聚氧亞烷基，能夠在吸附於分散體時，藉由作為位阻排斥(steric repulsion)部位進行作用，而使分散體良好分散，同時能夠提高對非水性溶劑的溶解性。A 1 O and A 2 O are polyoxyalkylene groups, which can act as a steric repulsion site when adsorbed to the dispersion, so that the dispersion is well dispersed and the non-aqueous solvent can be improved. Solubility.
A1 O為碳原子數為2的氧亞乙基，A2 O為碳原子數為3~4的氧亞烷基，較佳碳原子數為3的氧亞丙基。m表示氧亞乙基的平均加成莫耳數，n表示碳原子數3~4的氧亞烷基的平均加成莫耳數，m為1~30，n為1~30。A 1 O is an oxyethylene group having 2 carbon atoms, and A 2 O is an oxyalkylene group having 3 to 4 carbon atoms, preferably an oxypropylene group having 3 carbon atoms. m represents the average addition mole number of the oxyethylene group, and n represents the average addition mole number of the oxyalkylene group having 3 to 4 carbon atoms, m is 1 to 30, and n is 1 to 30.
從初期分散性及分散穩定性的角度考慮，更較佳m為3以上，特別較佳為4以上。此外，m更較佳為25以下，特別較佳為20以下。More preferably, m is 3 or more, and particularly preferably 4 or more, from the viewpoint of initial dispersibility and dispersion stability. Further, m is more preferably 25 or less, and particularly preferably 20 or less.
此外，從初期分散性及分散穩定性的角度考慮，特別較佳n為3以上。此外，n更較佳為25以下，進一步較佳為20以下，特別較佳為15以下。Further, it is particularly preferable that n is 3 or more from the viewpoint of initial dispersibility and dispersion stability. Further, n is more preferably 25 or less, still more preferably 20 or less, and particularly preferably 15 or less.
A1 O所示的氧亞乙基的平均加成莫耳數m與A2 O所示的氧亞烷基的平均加成莫耳數n存在0.1≤m/n≤10且5≤m＋n≤40的關係。A present average addition molar number of oxyethylene groups A and m oxyalkylene average addition molar number n shown in FIG 1 O 2 O 0.1≤m / n≤10 and 5≤m + n≤ 40 relationship.
m/n表示聚醚酯類化合物中，聚醚鏈的親水性強的A1 O與親油性強的A2 O的平衡性。若m/n小於0.1，親油性過高，因此在非水性溶劑中聚醚鏈擴張，聚醚鏈容易纏繞，因此有初期分散性或分散穩定性降低的可能。此外，若m/n超過10，則親水性過高，因此在非水性溶劑中的溶解性降低，因此聚醚鏈收縮，位阻排斥效果降低，有初期分散性降低的可能。m/n represents the balance between the hydrophilicity of the polyether chain A 1 O and the lipophilic A 2 O in the polyether ester compound. When m/n is less than 0.1, the lipophilicity is too high, so that the polyether chain is expanded in the nonaqueous solvent, and the polyether chain is easily entangled, so that the initial dispersibility or the dispersion stability may be lowered. Further, when m/n exceeds 10, the hydrophilicity is too high, so the solubility in a non-aqueous solvent is lowered. Therefore, the polyether chain shrinks, the steric hindrance effect is lowered, and the initial dispersibility may be lowered.
從上述角度考慮，m/n更較佳為0.2以上，進一步較佳為0.5以上，特別較佳為0.7以上。此外，m/n更較佳為8以下，特別較佳為7以下。From the above viewpoints, m/n is more preferably 0.2 or more, further preferably 0.5 or more, and particularly preferably 0.7 or more. Further, m/n is more preferably 8 or less, and particularly preferably 7 or less.
m＋n代表聚醚鏈長度，滿足5≤m＋n≤40。若m＋n小於5，則，難以獲得充分的位阻排斥效果，此外，若超過40，則聚醚鏈容易相互纏繞，有初期分散性降低的可能。從初期分散性及分散穩定性的角度考慮，m＋n特別較佳為6以上。此外，m＋n更較佳為35以下，進一步較佳為30以下，特別較佳為25以下。m+n represents the length of the polyether chain and satisfies 5≤m+n≤40. When m+n is less than 5, it is difficult to obtain a sufficient steric repulsion effect, and if it exceeds 40, the polyether chains are likely to be entangled with each other, and the initial dispersibility may be lowered. From the viewpoint of initial dispersibility and dispersion stability, m+n is particularly preferably 6 or more. Further, m+n is more preferably 35 or less, still more preferably 30 or less, and particularly preferably 25 or less.
a表示芳香環的數量，為1~2。聚醚酯類化合物中的芳香環來自三羧酸酐，鍵合於芳香環的羧基作為吸附於分散體的吸附部位而起作用。在同一個芳香環上具有羧基，將更易於在分散體上吸附，故而從初期分散性的角度來看，較佳a=1。a represents the number of aromatic rings, which is 1 to 2. The aromatic ring in the polyether ester compound is derived from a tricarboxylic acid anhydride, and a carboxyl group bonded to the aromatic ring functions as an adsorption site adsorbed to the dispersion. It is preferable to have a carboxyl group on the same aromatic ring to adsorb on the dispersion, so that a = 1 is preferable from the viewpoint of initial dispersibility.
a=1情況下的化學式如式(1A)所示，a=2情況下的化學式如式(1B)所示。 。The chemical formula in the case of a = 1 is as shown in the formula (1A), and the chemical formula in the case of a = 2 is as shown in the formula (1B). .
M為氫原子或銨或烷醇銨，較佳為氫原子或烷醇銨，更進一步較佳為氫原子。M is a hydrogen atom or ammonium or an alkanolammonium, preferably a hydrogen atom or an alkanolammonium, and still more preferably a hydrogen atom.
接著，對式(1)所示的聚醚酯類化合物的製法進行說明。Next, a method for producing the polyether ester compound represented by the formula (1) will be described.
式(1)所示的聚醚酯類化合物可藉由製備聚醚的第一製程、以及使在第一製程中得到的聚醚與三羧酸酐反應的第二製程而製備。The polyether ester compound represented by the formula (1) can be produced by a first process for preparing a polyether, and a second process for reacting a polyether obtained in the first process with a tricarboxylic anhydride.
對第一製程進行說明。Explain the first process.
可以藉由在具有碳原子數為1~22的直鏈或支鏈狀烴基的醇上，加成環氧烷(Alkylene oxide)而製備聚醚。The polyether can be produced by adding an alkylene oxide to an alcohol having a linear or branched hydrocarbon group having 1 to 22 carbon atoms.
作為用於環氧烷的加成反應的催化劑，可列舉出鹼催化劑，例如可使用鹼金屬或鹼土類金屬的氧化物或氫氧化物、醇化物、三乙胺等烷胺類、三乙醇胺等烷醇胺。此外，除了所述的鹼催化劑之外，可以使用三氟化硼或四氯化錫等路易士酸催化劑。相對於加成反應完成後的質量，催化劑的用量通常為0.01~5.0質量%。Examples of the catalyst for the addition reaction of an alkylene oxide include an alkali catalyst. For example, an oxide or hydroxide of an alkali metal or an alkaline earth metal, an alkylamine such as an alcoholate or triethylamine, or a triethanolamine can be used. Alkanolamine. Further, in addition to the above-mentioned base catalyst, a Lewis acid catalyst such as boron trifluoride or tin tetrachloride may be used. The amount of the catalyst is usually from 0.01 to 5.0% by mass based on the mass after completion of the addition reaction.
環氧烷的加成反應可藉由以下方式進行：例如，在氬氣或氮氣等不活潑氣體氣氛下，以50~200℃、0.02~1.0MPa，一邊持續加壓一邊添加環氧烷。The addition reaction of the alkylene oxide can be carried out by, for example, adding an alkylene oxide while continuously pressurizing at 50 to 200 ° C and 0.02 to 1.0 MPa in an inert gas atmosphere such as argon or nitrogen.
接著，對第二製程進行說明。Next, the second process will be described.
作為在第二製程中使用的三羧酸酐，可列舉出偏苯三酸酐、1,2,3-苯三羧酸酐、1,2,5-萘三羧酸酐、1,4,5-萘三羧酸酐、2,3,6-萘三羧酸酐、1,2,8-萘三羧酸酐的芳香族三羧酸酐。Examples of the tricarboxylic acid anhydride used in the second process include trimellitic anhydride, 1,2,3-benzenetricarboxylic anhydride, 1,2,5-naphthalenetricarboxylic anhydride, and 1,4,5-naphthalenetricarboxylic anhydride. An aromatic tricarboxylic anhydride of 2,3,6-naphthalenetricarboxylic anhydride or 1,2,8-naphthalenetricarboxylic anhydride.
在第二製程中的反應比例，在以單烷基聚醚的羥基的莫耳數為(H)，以三羧酸酐的莫耳數為(T)時，較佳為0.7＜(H)/(T)＜1.2，更進一步較佳為(H)/(T)=1。The reaction ratio in the second process is preferably (0.7) when the number of moles of the hydroxyl group of the monoalkyl polyether is (H) and the number of moles of the tricarboxylic anhydride is (T). (T) < 1.2, and further preferably (H) / (T) = 1.
在第二製程中可以使用催化劑。作為催化劑可列舉出叔胺化合物，例如可列舉出三乙胺、三乙烯二胺、N,N-二甲基苄胺、N-甲基嗎啉、1,8-二氮雜雙環-[5.4.0]-7-十一碳烯、1,5-二氮雜雙環-[4.3.0]-5-壬烯等。A catalyst can be used in the second process. The catalyst may, for example, be a tertiary amine compound, and examples thereof include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, and 1,8-diazabicyclo-[5.4. .0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-decene, and the like.
在第一製程、第二製程可以在無溶劑下進行，也可以使用適當的脫水有機溶劑。在反應中使用的溶劑，可在反應完成後藉由蒸餾等操作去除，或者可直接作為製品的一部分而使用。反應溫度為80~180℃，較佳為90~160℃、更進一步較佳為100~140℃。The first process and the second process may be carried out without a solvent, and a suitable dehydrated organic solvent may also be used. The solvent used in the reaction may be removed by distillation or the like after completion of the reaction, or may be used as a part of the product. The reaction temperature is 80 to 180 ° C, preferably 90 to 160 ° C, and more preferably 100 to 140 ° C.
本發明的聚醚酯類化合物可藉由胺進行中和。作為胺，可列舉出氨、甲胺、二甲胺、乙胺等烷胺或單乙醇胺、二乙醇胺、三乙醇胺等烷醇胺，可使用從它們中選出的一種或兩種以上。The polyether ester compound of the present invention can be neutralized by an amine. The amine may, for example, be an alkylamine such as ammonia, methylamine, dimethylamine or ethylamine or an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine, and one or two or more selected from them may be used.
(非水性分散體組合物)(non-aqueous dispersion composition)
本發明的非水性分散體組合物含有非水性分散劑、分散體及非水性溶劑。The non-aqueous dispersion composition of the present invention contains a non-aqueous dispersant, a dispersion, and a non-aqueous solvent.
在此，將非水性分散劑、分散體及非水性溶劑的總質量記為100質量%。Here, the total mass of the non-aqueous dispersant, the dispersion, and the non-aqueous solvent is referred to as 100% by mass.
在該情況下，非水性分散劑的含量較佳為0.05~20質量%。若非水性分散劑的含量不足0.05質量%，則可能無法獲得充分的初期分散性及分散穩定性，含量即使超過20質量%，也可能無法獲得與含量相稱的效果。從初期分散性及分散穩定性的角度考慮，非水性分散劑的含量較佳為0.1~15質量%，更進一步較佳為0.5~10質量%。In this case, the content of the non-aqueous dispersant is preferably from 0.05 to 20% by mass. When the content of the non-aqueous dispersant is less than 0.05% by mass, sufficient initial dispersibility and dispersion stability may not be obtained, and even if the content exceeds 20% by mass, an effect commensurate with the content may not be obtained. The content of the non-aqueous dispersant is preferably from 0.1 to 15% by mass, and more preferably from 0.5 to 10% by mass, from the viewpoint of initial dispersibility and dispersion stability.
作為本發明的非水性分散體組合物中含有的分散體，可列舉出有機粉體或無機粉體。The dispersion contained in the non-aqueous dispersion composition of the present invention may, for example, be an organic powder or an inorganic powder.
作為有機粉體例如可列舉出偶氮類、二偶氮類、縮合偶氮類、硫靛類、陰丹酮類(indanthrone)、喹吖啶酮類、蒽醌類、苯並咪唑酮類、苝類、酞菁類、蒽吡啶類及二噁嗪類等有機顏料。Examples of the organic powder include azo, diazo, condensed azo, thiopurine, indanthrone, quinacridone, anthraquinone, and benzimidazolone. Organic pigments such as terpenoids, phthalocyanines, anthraquinones and dioxazines.
作為無機粉體，例如可列舉出鐵、鋁、鉻、鎳、鈷、鋅、鎢、銦、錫、鈀、鋯、鈦、銅、銀、金、鉑等金屬粉體、兩種以上的金屬或金屬與非金屬組成的合金粉體、對金屬粉體或合金粉體進行複合化的複合粉體、兩種以上的無機粉體或無機粉體與其他粉體混合的混合粉體。Examples of the inorganic powder include metal powders such as iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, and platinum, and two or more kinds of metals. Or an alloy powder composed of a metal and a non-metal, a composite powder in which a metal powder or an alloy powder is composited, two or more inorganic powders, or a mixed powder in which an inorganic powder and another powder are mixed.
另外，作為無機粉體，可列舉出矽酸鹽礦物、其他的矽酸化合物、碳酸化合物、硫酸化合物、氫氧化合物、氧化物、氮化物、碳化物、鈦酸化合物等各粉體。例如，可列舉出高嶺土、黏土、滑石、雲母、膨潤土、白雲石、矽酸鈣、矽酸鋁、矽酸鎂、碳酸鈣、碳酸鎂、碳酸鋇、硫酸鈣、硫酸鋇、硫酸鋁、氫氧化鋁、氫氧化鐵、氧化鋯、氧化鎂、氧化鋁、氧化鈦、氧化鐵、氧化鋅、三氧化銻、氧化銦、氧化銦錫、碳化矽、碳化鎢、氮化鋁、氮化矽、氮化硼、鈦酸鋇、鈦酸鈣、鈦酸鍶、碳黑、玻璃纖維、碳纖維、碳奈米纖維、碳奈米管(單壁碳奈米管、雙壁碳奈米管、多壁碳奈米管)等各粉體。Further, examples of the inorganic powder include various powders such as a citrate mineral, another phthalic acid compound, a carbonic acid compound, a sulfuric acid compound, a hydroxide, an oxide, a nitride, a carbide, and a titanate compound. For example, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate, aluminum citrate, magnesium citrate, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, and hydroxide can be cited. Aluminum, iron hydroxide, zirconia, magnesia, alumina, titania, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, antimony carbide, tungsten carbide, aluminum nitride, tantalum nitride, nitrogen Boron, barium titanate, calcium titanate, barium titanate, carbon black, glass fiber, carbon fiber, carbon nanofiber, carbon nanotube (single-walled carbon nanotube, double-walled carbon nanotube, multi-wall carbon) Nano tube) and other powders.
作為分散體，較佳為鎳、鈷、鈀、銅、銀、金、鉑等金屬粉體，氧化鋯、氧化鎂、氧化鋁、氧化鐵、氧化鋅、氧化銦錫等氧化物的粉體，鈦酸鋇、鈦酸鈣、鈦酸鍶等鈦氧化合物的粉體。The dispersion is preferably a metal powder such as nickel, cobalt, palladium, copper, silver, gold or platinum, or a powder of an oxide such as zirconium oxide, magnesium oxide, aluminum oxide, iron oxide, zinc oxide or indium tin oxide. A powder of a titanium oxide compound such as barium titanate, calcium titanate or barium titanate.
從有用性的角度考慮，分散體的平均粒徑較佳為0.01~1μm，更進一步較佳為0.01~0.7μm，特別較佳為0.01~0.5μm。此外，分散體的平均粒徑可藉由使用SEM(掃描型電子顯微鏡)或TEM(透射型電子顯微鏡)的電子顯微鏡法或Microtrack法(雷射繞射・散射法)進行測定。The average particle diameter of the dispersion is preferably from 0.01 to 1 μm, more preferably from 0.01 to 0.7 μm, particularly preferably from 0.01 to 0.5 μm, from the viewpoint of usefulness. Further, the average particle diameter of the dispersion can be measured by an electron microscope method using a SEM (scanning electron microscope) or a TEM (transmission electron microscope) or a Microtrack method (laser diffraction/scattering method).
在將非水性分散劑、分散體及非水性溶劑的總量記為100質量%的情況下，分散體的含量在非水性分散體組成中通常為10~90質量%，較佳為30~85質量%，更進一步較佳為55~80質量%。When the total amount of the non-aqueous dispersant, the dispersion, and the non-aqueous solvent is 100% by mass, the content of the dispersion is usually 10 to 90% by mass, preferably 30 to 85, in the non-aqueous dispersion composition. The mass % is more preferably 55 to 80% by mass.
作為在本發明的非水性分散體組合物中使分散體分散的分散介質的非水性溶劑(有機溶劑)，例如可列舉出甲苯或二甲苯等芳香族烴類溶劑，環己烷等烴類溶劑，丙酮、甲乙酮、甲基異丁基酮及環己酮等酮類溶劑，醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯及γ-丁內酯等酯類溶劑，乙二醇單***、乙二醇單異丙醚、乙二醇單正丁醚、二乙二醇單***、二乙二醇單正丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單正丙醚、二丙二醇單正丁醚等二醇醚類溶劑，乙二醇單***乙酸酯、乙二醇單異丙基乙酸酯、乙二醇單正丁醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單正丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單正丙醚乙酸酯、丙二醇單正丁醚乙酸酯、二丙二醇單***乙酸酯、二丙二醇單正丙醚乙酸酯、及二丙二醇單正丁醚乙酸酯等二醇醚酯類溶劑，松油醇、二氫松油醇、乙酸松油酯及二氫乙酸松油酯等萜類溶劑，甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇及叔丁醇等醇類溶劑，可使用從這些非水性溶劑中選出的一種或兩種以上。Examples of the nonaqueous solvent (organic solvent) of the dispersion medium in which the dispersion is dispersed in the non-aqueous dispersion composition of the present invention include aromatic hydrocarbon solvents such as toluene and xylene, and hydrocarbon solvents such as cyclohexane. a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, an ester solvent such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate or γ-butyrolactone, Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether and other glycol ether solvents, ethylene glycol monoethyl ether acetate, ethylene Alcohol monoisopropyl acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate a glycol ether ester solvent such as dipropylene glycol monoethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, and dipropylene glycol mono-n-butyl ether acetate, terpineol, dihydroterpineol, and terpineol acetate And an anthracene solvent such as terpineol dihydroacetate, an alcohol solvent such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol, which can be selected from these nonaqueous solvents. One or two or more.
從提高分散體的分散性及與本發明中聚醚酯類化合物的相溶性的角度考慮，非水性溶劑較佳溶解度參數(SP值)為8.5~12.5(cal/cm3 )1/2 的。此外，非水性溶劑的溶解度參數(SP值)可藉由Hansen公式計算，其詳細內容記載於《SP值 基礎・應用與計算方法》(山本秀樹著，資訊機構社刊，2006年發行)，根據該記載求出。The non-aqueous solvent preferably has a solubility parameter (SP value) of 8.5 to 12.5 (cal/cm 3 ) 1/2 from the viewpoint of improving the dispersibility of the dispersion and the compatibility with the polyether ester compound of the present invention. In addition, the solubility parameter (SP value) of the non-aqueous solvent can be calculated by the Hansen formula, and the details are described in "SP Value Foundation, Application and Calculation Method" (Yamamoto Hideki, Information Agency, published in 2006), according to This record is obtained.
若具體例示溶解度參數(SP值)在所述範圍的非水性溶劑，可列舉出甲苯、甲乙酮、甲基異丁基酮、環己酮、醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、乙二醇單***、乙二醇單正丁醚、二乙二醇單***、二乙二醇單正丁醚、丙二醇單甲醚、丙二醇單正丁醚、乙二醇單***乙酸酯、乙二醇單正丁醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單正丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單正丁醚乙酸酯、松油醇、二氫松油醇、乙酸松油酯、二氫乙酸松油酯、異丙醇、正丁醇。可單獨使用從這些非水性溶劑中選出的一種，也可使用兩種以上的混合物。Specific examples of the nonaqueous solvent having a solubility parameter (SP value) in the above range include toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, n-propyl acetate, and isopropyl acetate. N-butyl acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, ethylene glycol single Ethyl acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono-n-butyl Ether acetate, terpineol, dihydroterpineol, terpineol acetate, terpineol dihydroacetate, isopropanol, n-butanol. One selected from these nonaqueous solvents may be used alone, or a mixture of two or more kinds may be used.
此外，即使是溶解度參數(SP值)在8.5~12.5(cal/cm3 )1/2 範圍外的非水性溶劑，也可藉由組合兩種以上的非水性溶劑，將SP值調整至所述範圍。Further, even in a non-aqueous solvent having a solubility parameter (SP value) in the range of 8.5 to 12.5 (cal/cm 3 ) 1/2 , the SP value may be adjusted to the above by combining two or more kinds of non-aqueous solvents. range.
混合溶劑的SP值可實驗性求出，或者，作為簡便的方法，可以藉由各非水性溶劑的莫耳比與SP值的積的總和而計算。在本發明的非水性分散體組合物中，可使用以這些方法調整過SP值的混合溶劑。The SP value of the mixed solvent can be experimentally determined, or can be calculated as a simple method by the sum of the product of the molar ratio of each nonaqueous solvent and the SP value. In the non-aqueous dispersion composition of the present invention, a mixed solvent in which the SP value is adjusted by these methods can be used.
在非水性分散體組合物中，非水性溶劑的含量通常為5~50質量%，較佳為10~40質量%，更進一步較佳為10~30質量%。The content of the nonaqueous solvent in the nonaqueous dispersion composition is usually from 5 to 50% by mass, preferably from 10 to 40% by mass, and still more preferably from 10 to 30% by mass.
在不損害其目的的範圍內，可在本發明的非水性分散體組合物中加入其他表面活性劑、黏合劑、增塑劑及消泡劑等各種添加劑。Various additives such as other surfactants, binders, plasticizers, and antifoaming agents may be added to the non-aqueous dispersion composition of the present invention insofar as the object is not impaired.
本發明的非水性分散體組合物，可以公知的非水性分散體組合物的製備方法為基準進行製備。例如，可列舉出在溶解有分散體的非水性溶劑中添加分散體後，在室溫下進行攪拌混合的方法，在分散體中添加非水性溶劑及分散劑後，在室溫下進行攪拌混合的方法等。The non-aqueous dispersion composition of the present invention can be produced on the basis of a known method for preparing a non-aqueous dispersion composition. For example, a method in which a dispersion is added to a non-aqueous solvent in which a dispersion is dissolved and then stirred and mixed at room temperature is added, and a non-aqueous solvent and a dispersing agent are added to the dispersion, followed by stirring and mixing at room temperature. Method etc.
作為用於攪拌、混合或分散的分散機器，可使用公知的分散機。例如，可列舉出輥磨機、球磨機、珠磨機、砂磨機、均化器、分散器、自轉公轉型混合器等。此外，也可在超聲波發生浴槽中進行分散處理。實施例 As the dispersion machine for stirring, mixing or dispersing, a known dispersing machine can be used. For example, a roll mill, a ball mill, a bead mill, a sand mill, a homogenizer, a disperser, a self-rotating public-transition mixer, etc. are mentioned. Further, the dispersion treatment may be performed in the ultrasonic generation bath. Example
然後，藉由實施例及比較例對本發明進行更進一步的詳細說明。Then, the present invention will be further described in detail by way of examples and comparative examples.
(合成例1：聚醚酯類化合物1的合成)(Synthesis Example 1: Synthesis of Polyether Ester Compound 1)
向設有攪拌機、壓力計、溫度計、安全閥、氣體吹入管、排氣管、冷卻盤管及蒸汽套的不銹鋼製5升容積的耐壓容器中，加入288g(2mol)3,5,5-三甲基-1-己醇(商品名：NONANOL，KHneochem株式會社製)及2g氫氧化鉀，在氮置換後，一邊攪拌一邊升溫至120℃。在攪拌下、120℃、0.05~0.50MPa(表壓)的條件下，藉由氣體吹入管從另外準備的耐壓容器中將705g(16mol)環氧乙烷用氮氣一邊加壓一邊添加。在添加完成後，在相同條件下使其反應至內壓一定。然後，在所述方法中，添加349g(6mol)環氧丙烷，在添加完成後，在相同條件下使其反應至內壓一定。然後，從耐壓容器中取出反應物，用鹽酸中和至pH6~7，為了去除所含有的水分，進行100℃、1小時的減壓處理，最後藉由過濾去除鹽，得到1270g聚醚。所得到的聚醚的羥值為84，從羥值求出的分子量為668。Add 288g (2mol) 3,5,5- to a stainless steel 5-liter volume pressure vessel equipped with a mixer, pressure gauge, thermometer, safety valve, gas injection pipe, exhaust pipe, cooling coil and steam jacket. Trimethyl-1-hexanol (trade name: NONOOL, manufactured by KHneochem Co., Ltd.) and 2 g of potassium hydroxide were heated to 120 ° C while stirring with nitrogen. Under stirring, at 120 ° C and 0.05 to 0.50 MPa (gauge pressure), 705 g (16 mol) of ethylene oxide was added while being pressurized with nitrogen gas from a separately prepared pressure-resistant container by a gas injection tube. After the addition was completed, it was allowed to react under the same conditions until the internal pressure was constant. Then, in the method, 349 g (6 mol) of propylene oxide was added, and after the completion of the addition, the reaction was carried out under the same conditions until the internal pressure was constant. Then, the reactant was taken out from the pressure-resistant container, neutralized with hydrochloric acid to pH 6 to 7, and the water contained therein was removed at 100 ° C for 1 hour, and finally, the salt was removed by filtration to obtain 1270 g of a polyether. The obtained polyether had a hydroxyl value of 84 and a molecular weight determined from a hydroxyl value of 668.
然後，在設有攪拌裝置、溫度計、氣體吹入管的玻璃製0.5升容積的反應容器中，加入267g(0.4mol)上述得到的聚醚及77g(0.4mol)偏苯三酸酐(關東化學(株)製)，在120℃下反應4小時。藉由酸值的測定確認98%以上的酸酐半酯化，結束反應。由此，得到聚醚酯類化合物1。Then, 267 g (0.4 mol) of the above-obtained polyether and 77 g (0.4 mol) of trimellitic anhydride (manufactured by Kanto Chemical Co., Ltd.) were placed in a glass-made reaction vessel equipped with a stirrer, a thermometer, and a gas injection tube. The reaction was carried out at 120 ° C for 4 hours. It was confirmed by the measurement of the acid value that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. Thus, a polyether ester compound 1 was obtained.
此外，將合成例1中的3,5,5-三甲基-1-己醇、環氧乙烷及環氧丙烷適當變更為其他化合物，以合成例1為基準進行操作，由此合成表1的聚醚酯類化合物2~7及式(2)的聚醚酯類化合物8。In addition, 3,5,5-trimethyl-1-hexanol, ethylene oxide, and propylene oxide in Synthesis Example 1 were appropriately changed to other compounds, and the synthesis was carried out based on Synthesis Example 1, thereby synthesizing the table. Polyether ester compound 2 to 7 of 1 and polyether ester compound 8 of formula (2).
合成的聚醚酯類化合物1~7示於表1，化合物8示於式(2)。 [表1]
R為碳原子數10~16的直鏈狀/支鏈狀烴基的混合物。R is a mixture of linear/branched hydrocarbon groups having 10 to 16 carbon atoms.
(實施例1~5、比較例1~3)(Examples 1 to 5, Comparative Examples 1 to 3)
將聚醚酯類化合物1~8用作分散劑，按下述方式配製非水性分散體組合物。Using the polyether ester compounds 1 to 8 as a dispersing agent, a non-aqueous dispersion composition was prepared in the following manner.
在50mL螺紋管中，稱量20.0g鈦酸鋇粉體(平均粒徑：0.05μm，藉由使用SEM的電子顯微鏡法測定)、5.0g丙二醇單甲醚乙酸酯及1.4g分散劑，使用自轉公轉型混合機進行5分鐘攪拌，進行預分散。然後，使用0.5mm的氧化鋯珠，藉由使用珠磨機進行4小時分散，得到漿液狀的非水性分散體組合物。此外，丙二醇單甲醚乙酸酯的SP值為8.7(cal/cm3 )1/2 。In a 50 mL screw tube, 20.0 g of barium titanate powder (average particle diameter: 0.05 μm, determined by electron microscopy using SEM), 5.0 g of propylene glycol monomethyl ether acetate, and 1.4 g of a dispersing agent were weighed. The self-rotating public-transition mixer was stirred for 5 minutes to carry out pre-dispersion. Then, using 0.5 mm zirconia beads, dispersion was carried out for 4 hours using a bead mill to obtain a slurry-like non-aqueous dispersion composition. Further, the SP value of propylene glycol monomethyl ether acetate was 8.7 (cal/cm 3 ) 1/2 .
將使用聚醚酯類化合物1~5得到的非水性分散體組合物作為實施例1~5，將使用聚醚酯類化合物6~8得到的非水性分散體組合物作為比較例1~3。The non-aqueous dispersion composition obtained using the polyether ester compounds 1 to 5 was used as Examples 1 to 5, and the non-aqueous dispersion compositions obtained using the polyether ester compounds 6 to 8 were used as Comparative Examples 1 to 3.
(分散試驗)(dispersion test)
使用實施例1~5及比較例1~3的非水性分散體組合物，進行分散試驗。The dispersion test was carried out using the nonaqueous dispersion compositions of Examples 1 to 5 and Comparative Examples 1 to 3.
對於各非水性分散體組合物，使用動態黏彈性裝置(Paar Physica MCR-300，Anton Paar社製)測定溫度20℃、剪切速度為0.1~100(1/s)的剪切黏度。剪切速度為1(1/s)時的剪切黏度如表2所示。For each non-aqueous dispersion composition, a shear viscosity of a temperature of 20 ° C and a shear rate of 0.1 to 100 (1/s) was measured using a dynamic viscoelastic device (Paar Physica MCR-300, manufactured by Anton Paar Co., Ltd.). The shear viscosity at a shear rate of 1 (1/s) is shown in Table 2.
此外，以相同條件測定在室溫靜置一週的各非水性分散體組合物的剪切黏度。剪切速度為1(1/s)時的剪切黏度一併示於表2。 [表2]
添加了本發明的聚醚酯類化合物1~5的實施例1~5的非水性分散體組合物，均在剛製備後顯示了良好的分散性，即使在一週後，也幾乎看不到經時的黏度變化。The non-aqueous dispersion compositions of Examples 1 to 5 to which the polyether ester compounds 1 to 5 of the present invention were added exhibited good dispersibility immediately after preparation, and even after one week, almost no Viscosity change at the time.
另一方面，添加了m/n在範圍外的聚醚酯類化合物6及7、或是添加了具有與本發明式(1)所示的聚醚酯類化合物中的環氧烷的加成方式相反結構的聚醚酯類化合物8的比較例1~3的非水性分散體組合物，不僅剛製備後的剪切黏度高，並且經時的黏度變化大，因此可知不僅剛製備後的分散性差，分散穩定性也差。On the other hand, polyether ester compounds 6 and 7 having m/n outside the range or addition of alkylene oxide having a polyether ester compound represented by formula (1) of the present invention are added. In the non-aqueous dispersion composition of Comparative Examples 1 to 3 of the polyether ester compound 8 having the opposite structure, not only the shear viscosity immediately after the preparation was high, but also the viscosity change over time was large, so that it was found that not only the dispersion immediately after preparation Poor performance and poor dispersion stability.
(實施例6~9、比較例4~6)(Examples 6 to 9 and Comparative Examples 4 to 6)
將聚醚酯類化合物1~4、6、7、8用作分散劑，按下述配製非水性分散體組合物。此外，將使用聚醚酯類化合物1~4得到的非水性分散體組合物作為實施例6~9，將使用聚醚酯類化合物6~8得到的非水性分散體組合物作為比較例4~6。The polyether ester compounds 1 to 4, 6, 7, and 8 were used as a dispersing agent, and a non-aqueous dispersion composition was prepared as follows. Further, the non-aqueous dispersion composition obtained using the polyether ester compounds 1 to 4 was used as Examples 6 to 9, and the non-aqueous dispersion composition obtained using the polyether ester compounds 6 to 8 was used as Comparative Example 4~ 6.
在50mL螺紋管中，稱量20.0g鈦酸鋇粉體(平均粒徑：0.05μm，藉由使用SEM的電子顯微鏡法測定)、5.0g甲苯/乙醇混合溶劑(1/1、質量比)及1.4g分散劑，使用自轉公轉型混合機進行5分鐘攪拌，進行預分散。然後，使用0.5mm的氧化鋯珠，藉由使用珠磨機進行4小時分散，得到漿液狀的非水性分散體組合物。此外，甲苯/乙醇混合溶劑(1/1，質量比)的SP值為11.4(cal/cm3 )1/2 。In a 50 mL screw pipe, 20.0 g of barium titanate powder (average particle diameter: 0.05 μm, determined by electron microscopy using SEM), 5.0 g of a toluene/ethanol mixed solvent (1/1, mass ratio), and 1.4 g of dispersant was pre-dispersed by stirring for 5 minutes using a self-rotating public conversion mixer. Then, using 0.5 mm zirconia beads, dispersion was carried out for 4 hours using a bead mill to obtain a slurry-like non-aqueous dispersion composition. Further, the SP value of the toluene/ethanol mixed solvent (1/1, mass ratio) was 11.4 (cal/cm 3 ) 1/2 .
(分散試驗)(dispersion test)
使用實施例6~9及比較例4~6的非水性分散體組合物，進行分散試驗。The dispersion test was carried out using the nonaqueous dispersion compositions of Examples 6 to 9 and Comparative Examples 4 to 6.
對於各非水性分散體組合物，使用動態黏彈性裝置(Paar Physica MCR-300，Anton Paar社製)測定溫度20℃、剪切速度為0.1~100(1/s)的剪切黏度。將剪切速度為1(1/s)時的剪切黏度示於表3。For each non-aqueous dispersion composition, a shear viscosity of a temperature of 20 ° C and a shear rate of 0.1 to 100 (1/s) was measured using a dynamic viscoelastic device (Paar Physica MCR-300, manufactured by Anton Paar Co., Ltd.). The shear viscosity at a shear rate of 1 (1/s) is shown in Table 3.
此外，以相同條件測定在室溫靜置一週的各非水性分散體組合物的剪切黏度。將剪切速度為1(1/s)時的剪切黏度一併示於表3。 [表3]
添加有本發明的聚醚酯類化合物1~4的實施例6~9的非水性分散體組合物，均在剛製備後顯示良好分散性，即使一週後也幾乎沒發現經時的黏度變化。The non-aqueous dispersion compositions of Examples 6 to 9 to which the polyether ester compounds 1 to 4 of the present invention were added exhibited good dispersibility immediately after preparation, and almost no change in viscosity over time was observed even after one week.
另一方面，添加了m/n在範圍外的聚醚酯類化合物6及7、或是添加了具有與本發明式(1)所示的聚醚酯類化合物中的環氧烷的加成方式相反結構的聚醚酯類化合物8的比較例4~6的非水性分散體組合物，不僅剛製備後的剪切黏度高，並且經時的黏度變化大，因此可知不僅剛製備後的分散性差，分散穩定性也差。On the other hand, polyether ester compounds 6 and 7 having m/n outside the range or addition of alkylene oxide having a polyether ester compound represented by formula (1) of the present invention are added. In the non-aqueous dispersion composition of Comparative Examples 4 to 6 of the polyether ester compound 8 having the opposite structure, not only the shear viscosity immediately after the preparation was high, but also the viscosity change over time was large, so that it was found that not only the dispersion immediately after preparation Poor performance and poor dispersion stability.
(實施例10~12、比較例7~9)(Examples 10 to 12, Comparative Examples 7 to 9)
將聚醚酯類化合物1、3、4、6、7、8用作分散劑，按下述配製非水性分散體組合物。此外，將使用聚醚酯類化合物1、3、4得到的非水性分散體組合物作為實施例10~12，將使用聚醚酯類化合物6~8得到的非水性分散體組合物作為比較例7~9。Using the polyether ester compounds 1, 3, 4, 6, 7, 8 as a dispersing agent, a non-aqueous dispersion composition was prepared as follows. Further, the non-aqueous dispersion composition obtained using the polyether ester compounds 1, 3 and 4 was used as Examples 10 to 12, and the non-aqueous dispersion composition obtained using the polyether ester compounds 6 to 8 was used as a comparative example. 7~9.
在50mL螺紋管中，稱量20.0g鈦酸鋇粉體(平均粒徑：0.1μm，藉由使用SEM的電子顯微鏡法測定)、5.0g甲苯/乙醇混合溶劑(3/7、質量比)及0.4g分散劑，使用自轉公轉型混合機進行5分鐘攪拌，進行預分散。然後，使用1.0mm的氧化鋯珠，藉由使用珠磨機進行3小時分散，得到漿液狀的非水性分散體組合物。此外，甲苯/乙醇混合溶劑(3/7，質量比)的SP值為12.0(cal/cm3 )1/2 。20.0 g of barium titanate powder (average particle diameter: 0.1 μm, determined by electron microscopy using SEM), 5.0 g of a toluene/ethanol mixed solvent (3/7, mass ratio), and 50 mL of a threaded tube 0.4 g of a dispersing agent was stirred for 5 minutes using a self-rotating public-transition mixer to carry out pre-dispersion. Then, 1.0 mm of zirconia beads were used and dispersed by using a bead mill for 3 hours to obtain a slurry-like non-aqueous dispersion composition. Further, the SP value of the toluene/ethanol mixed solvent (3/7, mass ratio) was 12.0 (cal/cm 3 ) 1/2 .
(分散試驗)(dispersion test)
使用實施例10~12及比較例7~9的非水性分散體組合物，進行分散試驗。The dispersion test was carried out using the nonaqueous dispersion compositions of Examples 10 to 12 and Comparative Examples 7 to 9.
對於各非水性分散體組合物，使用動態黏彈性裝置(Paar Physica MCR-300，Anton Paar社製)測定溫度20℃、剪切速度為0.1~100(1/s)的剪切黏度。將剪切速度為1(1/s)時的剪切黏度示於表4。For each non-aqueous dispersion composition, a shear viscosity of a temperature of 20 ° C and a shear rate of 0.1 to 100 (1/s) was measured using a dynamic viscoelastic device (Paar Physica MCR-300, manufactured by Anton Paar Co., Ltd.). The shear viscosity at a shear rate of 1 (1/s) is shown in Table 4.
此外，以相同條件測定在室溫靜置一週的各非水性分散體組合物的剪切黏度。將剪切速度為1(1/s)時的剪切黏度一併示於表4。 [表4]
添加有本發明的聚醚酯類化合物1、3及4的實施例10~12的非水性分散體組合物，均在剛製備後顯示良好的分散性，即使一週後也幾乎沒發現經時的黏度變化。The non-aqueous dispersion compositions of Examples 10 to 12 to which the polyether ester-based compounds 1, 3 and 4 of the present invention were added exhibited good dispersibility immediately after preparation, and even after one week, almost no time-lapse was observed. Viscosity changes.
另一方面，添加了m/n在範圍外的聚醚酯類化合物6及7、或是添加了具有與本發明式(1)所示的聚醚酯類化合物中的環氧烷的加成方式相反結構的聚醚酯類化合物8的比較例7~9的非水性分散體組合物，不僅剛製備後的剪切黏度高，並且經時的黏度變化大，因此可知不僅剛製備後的分散性差，分散穩定性也差。On the other hand, polyether ester compounds 6 and 7 having m/n outside the range or addition of alkylene oxide having a polyether ester compound represented by formula (1) of the present invention are added. In the non-aqueous dispersion composition of Comparative Examples 7 to 9 of the polyether ester compound 8 having the opposite structure, not only the shear viscosity immediately after the preparation was high, but also the viscosity change over time was large, so that it was found that not only the dispersion immediately after preparation Poor performance and poor dispersion stability.
(實施例13~15、比較例10~12)(Examples 13 to 15 and Comparative Examples 10 to 12)
將聚醚酯類化合物1、3、4、6、7、8用作分散劑，按下述配製非水性分散體組合物。此外，將使用聚醚酯類化合物1、3、4得到的非水性分散體組合物作為實施例13~15，將使用聚醚酯類化合物6~8得到的非水性分散體組合物作為比較例10~12。Using the polyether ester compounds 1, 3, 4, 6, 7, 8 as a dispersing agent, a non-aqueous dispersion composition was prepared as follows. Further, the non-aqueous dispersion composition obtained using the polyether ester compounds 1, 3 and 4 was used as Examples 13 to 15, and the non-aqueous dispersion composition obtained using the polyether ester compounds 6 to 8 was used as a comparative example. 10~12.
在50mL螺紋管中，稱量20.0g氧化鋁粉體(平均粒徑：0.4μm，使用雷射繞射法測定)、5.0g甲苯/乙醇混合溶劑(1/1、質量比)及0.2g分散劑，使用自轉公轉型混合機進行5分鐘攪拌，進行預分散。然後，使用1.0mm的氧化鋯珠，藉由使用珠磨機進行3小時分散，得到漿液狀的非水性分散體組合物。Weigh 20.0g of alumina powder (average particle size: 0.4μm, measured by laser diffraction method), 5.0g of toluene/ethanol mixed solvent (1/1, mass ratio) and 0.2g dispersion in a 50mL threaded pipe The agent was stirred for 5 minutes using a self-rotating public conversion mixer to carry out pre-dispersion. Then, 1.0 mm of zirconia beads were used and dispersed by using a bead mill for 3 hours to obtain a slurry-like non-aqueous dispersion composition.
(分散試驗)(dispersion test)
使用實施例13~15及比較例10~12的非水性分散體組合物，進行分散試驗。The dispersion test was carried out using the nonaqueous dispersion compositions of Examples 13 to 15 and Comparative Examples 10 to 12.
對於各非水性分散體組合物，使用動態黏彈性裝置(Paar Physica MCR-300，Anton Paar社製)，測定溫度20℃、剪切速度為0.1~100(1/s)的剪切黏度。將剪切速度為1(1/s)時的剪切黏度示於表5。For each non-aqueous dispersion composition, a dynamic viscoelastic device (Paar Physica MCR-300, manufactured by Anton Paar Co., Ltd.) was used, and the shear viscosity at a temperature of 20 ° C and a shear rate of 0.1 to 100 (1/s) was measured. The shear viscosity at a shear rate of 1 (1/s) is shown in Table 5.
此外，以相同條件測定在室溫靜置一週的各非水性分散體組合物的剪切黏度。將剪切速度為1(1/s)時的剪切黏度一併示於表5。 [表5]
添加有本發明的聚醚酯類化合物1、3及4的實施例13~15的非水性分散體組合物，均在剛製備後顯示良好的分散性，即使一週後也顯示良好的分散穩定性。The non-aqueous dispersion compositions of Examples 13 to 15 to which the polyether ester-based compounds 1, 3 and 4 of the present invention were added exhibited good dispersibility immediately after preparation, and showed good dispersion stability even after one week. .
另一方面，添加了m/n在範圍外的聚醚酯類化合物6及7、或是添加了具有與本發明式(1)所示的聚醚酯類化合物中的環氧烷的加成方式相反結構的聚醚酯類化合物8的比較例10~12的非水性分散體組合物，不僅剛製備後的剪切黏度高，並且經時的黏度變化大，因此可知不僅剛製備後的分散性差，分散穩定性也差。On the other hand, polyether ester compounds 6 and 7 having m/n outside the range or addition of alkylene oxide having a polyether ester compound represented by formula (1) of the present invention are added. In the non-aqueous dispersion composition of Comparative Examples 10 to 12 of the polyether ester compound 8 having the opposite structure, not only the shear viscosity immediately after the preparation was high, but also the viscosity change over time was large, so that it was found that not only the dispersion immediately after preparation Poor performance and poor dispersion stability.
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| CN111902882B (en) * | 2018-03-28 | 2022-08-26 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| KR20210110285A (en) * | 2018-12-25 | 2021-09-07 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive pastes, electronic components, and multilayer ceramic capacitors |
| JPWO2020137290A1 (en) * | 2018-12-25 | 2021-11-04 | 住友金属鉱山株式会社 | Conductive pastes, electronic components, and multilayer ceramic capacitors |
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| JPS6161623A (en) * | 1984-08-31 | 1986-03-29 | Dainippon Ink & Chem Inc | Pigment dispersant |
| JPS61183390A (en) * | 1985-02-08 | 1986-08-16 | Nippon Oil & Fats Co Ltd | Additive for aqueous slurry of solid fuel |
| JPS61185326A (en) * | 1985-02-08 | 1986-08-19 | Nippon Oil & Fats Co Ltd | Dispersant for inorganic powder in oil |
| SU1510720A3 (en) | 1985-11-02 | 1989-09-23 | Хюльс Аг. (Фирма) | Coal suspension |
| GB0124967D0 (en) | 2001-10-17 | 2001-12-05 | Unilever Plc | Cosmetic and personal care compositions |
| JP5135760B2 (en) * | 2005-11-02 | 2013-02-06 | 東洋インキＳｃホールディングス株式会社 | Dispersant and production method thereof |
| WO2011148520A1 (en) * | 2010-05-26 | 2011-12-01 | 第一工業製薬株式会社 | Dispersant and dispersion composition |
| JP5727215B2 (en) | 2010-12-22 | 2015-06-03 | 第一工業製薬株式会社 | Dispersant and dispersion composition |
| JP6277719B2 (en) * | 2013-01-09 | 2018-02-14 | 日油株式会社 | Non-aqueous dispersant and non-aqueous dispersion composition |
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- 2016-01-27 JP JP2016013097A patent/JP6604475B2/en active Active
- 2016-02-05 CN CN201610082936.2A patent/CN105860054B/en active Active
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| TWI814910B (en) * | 2018-09-27 | 2023-09-11 | 日商住友金屬鑛山股份有限公司 | Conductive paste, electronic components, and laminated ceramic capacitors |
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| KR20160097154A (en) | 2016-08-17 |
| CN105860054B (en) | 2020-10-09 |
| KR102535901B1 (en) | 2023-05-23 |
| TWI689530B (en) | 2020-04-01 |
| JP2016147261A (en) | 2016-08-18 |
| CN105860054A (en) | 2016-08-17 |
| JP6604475B2 (en) | 2019-11-13 |
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