TW201024329A - Polymeric dispersant and pigment composition thereof - Google Patents
Polymeric dispersant and pigment composition thereof Download PDFInfo
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201024329 六、發明說明: 【發明所屬之技術領域】 本發明關於一種分散劑’特別關於一種高分子型分 散劑。 【先前技術】 有機顏料不同於染料,為不可溶解之固態粒子,藉由 分散於不同溶劑或樹脂中而後應用之,具有較佳的熱安定 罄 性,耐久性及耐紫外光性,應用於塗料可以提高色彩經時 鮮豔度等,且可以保護所塗佈的系統表面。由以上可知, 顏料在各方面皆優於染料,但由於顏料粒子於製作過程中 易聚集,且顆粒尺寸較大’導致顏料顆粒過大造成顏料用 量的降低色彩鮮豔度、色飽和度及不利於穩定分散。因此, 分散劑被進一步用來促進顏料粒子之微細化分散、奈米 化、及高安定化。目前使用於液晶顯示器(LCD)彩色濾光片 之色聚分散除要求分散安定外’並需透光率高且其彩色光 p且解析度要佳,然而其關鍵也在於分散劑,分散劑必須針 對分散系統設計錯定(anchoring)端對顏料可有強的吸附作 用’/谷合(solvation)端則應有適當的溶合(s〇ivati〇n)效果。 許多過去的聚合分散劑使用隨機式共聚物(rad〇in c〇p〇lymer),但這些是相對較沒有效果的材料。美國專利第 5,852,123號揭露一種分散劑其包含接枝共聚物,其具有聚 ,物的主幹和接枝於主幹上之巨型單體侧鏈,且連接巨型 單體或主幹上之極性基,其設計為吸附在顏料粒子的表面 上,且連接共聚物分散劑於顏料表面。然而,此類分散劑 201024329 會使顏料粒子太靠近而凝聚在一起,導致顏料分散液和塗 料之安定性和流變性變差’並降低顏色的強度。 基於上述,設計一嶄新的分散劑,使顏料的分散效果 達到最佳化,實為分散劑技術極需研究之重點。 【發明内容】 本發明係提供一種分散劑,其係由一具有末端胺基之 化合物(例如聚醚二胺(poly(oxyalkylene) diamine)或聚醚三 Φ 胺(poly(oxyalkylene) triamine)和二異氰酸鹽 (diisocyanate)(具有二個異氰酸鹽官能基(isocyanate)之化合 物)反應合成之高分子型分散劑,可作為分散劑或穩定劑, 製成穩定的顏料組合物(分散液或色漿)。該分散劑亦包含 尿素基(Urea)鏈段’可與顏料表面改質之官能基型成氫鍵, 進行貼附使分散劑包覆於顏料外層,此外,該分散劑包含 油溶性的鏈段(例如oxypropylene鏈段),可利用此鏈段之 • 親油性質,使分散劑溶於壓克力單體溶劑中•並利用分散 劑溶合鏈端之立體障礙效應穩定其顏料粒子分散於壓克力 單體中,避免顏料聚集,該分散劑可且可添加至高濃度, 所得之分散液仍能保持在低黏度。 根據本發明一較佳實施例’該向分子型分散劑可由一 具有末端胺基之化合物與一二異氰酸鹽(diisocyanate)經聚 合反應而得’其中該具有末端胺基之化合物包含二胺 (diamine)化合物、三胺化合物、或其混合。 根據本發明其他較佳實施例,本發明亦提供一種顏料 組合物,該顏料組合物包含:一顏料;以及一高分子型分 4 201024329 散劑,其係由一具有末端胺基之化合物與一二異氰酸鹽 (diisocyanate)經聚合反應而得,其中該具有末端胺基之化 合物包含二胺(diamine)化合物、三胺化合物(triamine)、或 其混合。 以下猎由數個實施例’以更進一步說明本發明之方 法、特徵及優點,但並非用來限制本發明之範圍,本發明 之範圍應以所附之申請專利範圍為準。 【實施方式】 • 本發明所述之高分子型分散劑,其係由一具有末端胺 基之化合物與一二異氰酸鹽(diisocyanate)經聚合反應而 得。其中’該具有末端胺基之化合物可包含二胺(diamine) 化合物、三胺化合物、或其混合(二胺及三胺化合物同時 參與聚合反應)。該具有末端胺基之化合物與該二異氰酸 鹽之聚合反應溫度可為室溫(25-30。〇,亦可為室溫以下 (例如0-25°C) ’其中該具有末端胺基之化合物與該二異氰 酸鹽之反應莫耳比為2: 1至5: 4。此外,該具有末端胺 ❿ 基之化合物除包含二胺(diamine)化合物、三胺化合物、或 其混合外,可更包含一單胺(monoamine)化合物參與和該 二異氰酸鹽之聚合反應。 該二異氰酸鹽可包含二苯基甲烷二異氰酸酯 (4,4_methylene bis phenyl diisocyanate,MDI)、曱苯二異 氰酸酯(toluene diisocyanate,TDI)、異佛爾酮二異氰酸酯 (isophorone diisocyanate,IPDI)、或其混合。 該二胺(diamine)化合物可包含聚醚二胺、或烯烴二 胺,例如聚丙基醚雙胺(polyoxypropylene diamine)、聚乙 5 201024329 基醚雙胺(polyoxyethylene diamine)、聚(乙基醚-丙基鍵) 雙胺(poly(oxyethylene-oxypropylene)diamine)、或其混201024329 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a dispersant', particularly to a polymeric dispersant. [Prior Art] Organic pigments are different from dyes and are insoluble solid particles. They are dispersed in different solvents or resins and then applied. They have better thermal stability, durability and UV resistance. It can improve the color vividness of the color, etc., and can protect the surface of the coated system. It can be seen from the above that the pigment is superior to the dye in all aspects, but because the pigment particles are easy to aggregate during the production process, and the particle size is large, the pigment particles are too large, resulting in a decrease in the amount of the pigment, color saturation, color saturation and stability. dispersion. Therefore, the dispersant is further used to promote fine dispersion, nanocrystallization, and high stability of the pigment particles. At present, the color dispersion of liquid crystal display (LCD) color filters requires dispersion and stability, and the light transmittance is high, and the color light and resolution are good. However, the key is the dispersant, and the dispersant must For the dispersion system design, the anchoring end can have a strong adsorption effect on the pigment'/the solvation end should have an appropriate smelting effect. Many of the past polymeric dispersants used random copolymers (rad〇in c〇p〇lymer), but these are relatively ineffective materials. U.S. Patent No. 5,852,123 discloses a dispersant comprising a graft copolymer having a backbone of a polymer and a megamonomer side chain grafted onto the backbone and linking the megamons or polar groups on the backbone, It is designed to adsorb on the surface of the pigment particles and to connect the copolymer dispersant to the surface of the pigment. However, such a dispersant 201024329 causes the pigment particles to be too close together to cause aggravation of the stability and rheology of the pigment dispersion and the coating, and to reduce the strength of the color. Based on the above, a new dispersant is designed to optimize the dispersion of the pigment, which is the focus of the dispersant technology. SUMMARY OF THE INVENTION The present invention provides a dispersant which is composed of a compound having a terminal amine group (for example, poly(oxyalkylene) diamine) or poly(oxyalkylene) triamine and A polymeric dispersant prepared by the reaction of a diisocyanate (a compound having two isocyanate functional groups), which can be used as a dispersing agent or a stabilizer to form a stable pigment composition (dispersion liquid) Or a color paste. The dispersant further comprises a urea-based (Urea) segment which can form a hydrogen bond with a functional group modified by the surface of the pigment, and is attached so that the dispersant coats the outer layer of the pigment, and further, the dispersant comprises Oil-soluble segments (such as oxypropylene segments) can utilize the lipophilic nature of the segment to dissolve the dispersant in the acrylic monomer solvent and stabilize the steric barrier effect of the dispersing agent by melting the chain ends. The pigment particles are dispersed in the acrylic monomer to avoid pigment aggregation, the dispersant can be added to a high concentration, and the resulting dispersion can still be maintained at a low viscosity. According to a preferred embodiment of the invention, the molecular form is The agent may be obtained by polymerizing a compound having a terminal amino group with a diisocyanate, wherein the compound having a terminal amine group comprises a diamine compound, a triamine compound, or a mixture thereof. According to another preferred embodiment of the present invention, the present invention also provides a pigment composition comprising: a pigment; and a polymer type 4 201024329 powder, which is composed of a compound having a terminal amine group and a disaccharide The diisocyanate is obtained by polymerization, wherein the compound having a terminal amine group comprises a diamine compound, a triamine compound, or a mixture thereof. The following is further carried out by several embodiments' The method, the features and the advantages of the present invention are not intended to limit the scope of the present invention, and the scope of the present invention shall be determined by the scope of the appended claims. , which is obtained by polymerizing a compound having a terminal amino group with a diisocyanate, wherein 'the terminal amine group The compound may comprise a diamine compound, a triamine compound, or a mixture thereof (diamine and triamine compounds simultaneously participate in the polymerization reaction). The polymerization temperature of the compound having a terminal amine group and the diisocyanate may be Room temperature (25-30. 〇, may also be below room temperature (eg 0-25 ° C) 'where the reaction of the compound having a terminal amine group with the diisocyanate is 2: 1 to 5 Further, the compound having a terminal amine thiol group may further comprise a monoamine compound and the diisocyanate in addition to a diamine compound, a triamine compound, or a mixture thereof. Polymerization. The diisocyanate may comprise 4,4-methylene bis phenyl diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), or It's mixed. The diamine compound may comprise a polyether diamine, or an olefin diamine, such as polyoxypropylene diamine, polyethylethylene diamine, poly(ethyl ether-propyl) Poly(oxyethylene-oxypropylene) diamine, or a mixture thereof
合。此外,該二胺(diamine)化合物亦可為 RHehe. In addition, the diamine compound may also be R
以及R係為獨立的氳、曱基、或乙基。該二胺(diamine) 化合物之分子量可在200至4000g/mol之間。 該三胺(triamine)化合物可包含包含聚_三胺、或烯烴 三胺,例如為聚丙基ϋ三胺(polyoxypropylene triamine)。 在本發明一較佳實施例中,該三胺(triamine)化合物包含 6 201024329And R is an independent oxime, sulfhydryl, or ethyl group. The diamine compound may have a molecular weight of between 200 and 4000 g/mol. The triamine compound may comprise a poly-triamine, or an olefin triamine, such as a polyoxypropylene triamine. In a preferred embodiment of the invention, the triamine compound comprises 6 201024329
R ch2-(och2ch)^nh2R ch2-(och2ch)^nh2
R CH2 ,其中X、Y、及z 係大於或等於1,以及R係為獨立的氫、甲基、或乙基。 該三胺(triamine)化合物之分子量可介於400至5000g/mol 之間。 此外,上述之單胺(monoamine)可包含R CH2 wherein X, Y, and z are greater than or equal to 1, and R is independently hydrogen, methyl, or ethyl. The triamine compound may have a molecular weight of between 400 and 5000 g/mol. In addition, the above monoamine may comprise
R R ,其中X、Y、及Z係大於或等 ❹於1,以及R係為獨立的氫、曱基、或乙基。 本發明所使用之具有末端胺基之化合物(單胺、二 胺、或三胺高分子),亦可為已有商業化之產品,例如由 Huntsman Chemical Co.所製造販售的一系列含胺基化合 物,如Jeffamine D2000[聚丙二醇雙(2-氨基丙基醚)(poly (propylene glycol) bis (2-amino propyl ether)) » Mw 2000] ' Jeffamine D4000[聚丙二醇雙(2-氨基丙基醚)(poly (propylene glycol) bis (2-amino propyl ether)),Mw 4000] 及Jeffamine ED2001[(聚丙二醇嵌段-聚乙二醇嵌段-聚丙 7 201024329 二醇般段)雙(2-氨基丙基醚)(poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether)),Mw 2000]等;其他還有 如T3000[三官能聚丙二醇2-氨基丙基醚(tri-functional poly(propylene glycol)2-amino propyl ether),Mw 3000]、 T5000[三官能聚丙二醇2-氨基丙基醚(tri-functional poly(propylene glycol)2-aminopropyl ether),Mw 5000] 等。Jeffamine系列之結構式係列舉如下: ❿ JEFFAMIME MOMMMNES (M seiies)R R , wherein the X, Y, and Z systems are greater than or equal to 1, and the R is an independent hydrogen, sulfhydryl, or ethyl group. The compound having a terminal amine group (monoamine, diamine, or triamine polymer) used in the present invention may also be a commercially available product such as a series of amines sold by Huntsman Chemical Co. Base compound, such as Jeffamine D2000 [poly (propylene glycol) bis (2-amino propyl ether) » Mw 2000] ' Jeffamine D4000 [polypropylene glycol bis (2-aminopropyl) (poly(propylene glycol) bis (2-amino propyl ether), Mw 4000] and Jeffamine ED2001 [(polypropylene glycol block-polyethylene glycol block-polypropylene 7 201024329 diol-like segment) double (2- Poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), Mw 2000]; others such as T3000 [trifunctional polypropylene glycol Tri-functional poly(propylene glycol 2-amino propyl ether), Mw 3000], T5000 [tri-functional poly(propylene glycol 2-aminopropyl ether) Ether), Mw 5000] and so on. The structural series of the Jeffamine series are as follows: ❿ JEFFAMIME MOMMMNES (M seiies)
mmAMim Y/x mol mrn MW M-600 9/1 600 M-1000 3/19 1000 M-1000 29/6 2000 M-2070 貨31 2000 ❹ 8 201024329 JEFWAMSNE MAMINES (D Seiles)mmAMim Y/x mol mrn MW M-600 9/1 600 M-1000 3/19 1000 M-1000 29/6 2000 M-2070 Cargo 31 2000 ❹ 8 201024329 JEFWAMSNE MAMINES (D Seiles)
JEFFAMIim D-230 D-400 D-2000 U^4〇f〇〇 % MW 〜2 5 230 -6.1 430 〜3 3 2,000 4,000 JEFFAMINE DIAMINES {MM Series)JEFFAMIim D-230 D-400 D-2000 U^4〇f〇〇 % MW ~2 5 230 -6.1 430 ~3 3 2,000 4,000 JEFFAMINE DIAMINES {MM Series)
JEFIAMIHE X 誦 EDR-14S 2.0 60D EDR-176 3:.0 900JEFIAMIHE X 诵 EDR-14S 2.0 60D EDR-176 3:.0 900
JEFFAMINE DIAMINES {ED Series)JEFFAMINE DIAMINES {ED Series)
;X y ch3 ch3 JEiTAMINE y x+z MW HK-511 2,0 〜1.2 220 ED-600 4.0 〜3.6 600 ED900 42.5 ~6,0 900 ED2003 '〜39 ^6,0 2000 201024329;X y ch3 ch3 JEiTAMINE y x+z MW HK-511 2,0 ~1.2 220 ED-600 4.0 ~3.6 600 ED900 42.5 ~6,0 900 ED2003 '~39 ^6,0 2000 201024329
JEFFAAfIXE TRL4MIKES (T Series)JEFFAAfIXE TRL4MIKES (T Series)
JEFFAMINE R XI (X+I+z) MW T-403 C.2H5 X 5-6 440 T-3000 H 0 50 3000 T-5000 H 0 85 5000 JEFFAMINER ScciMidary Armies H \Λ ch3 ch3 jmVAMINE SD-231 衍生起始輪 D-230 腳 315 SD-401 D-400 515 SD-2001 D-2000 205.0 SD-404 T-403 565JEFFAMINE R XI (X+I+z) MW T-403 C.2H5 X 5-6 440 T-3000 H 0 50 3000 T-5000 H 0 85 5000 JEFFAMINER ScciMidary Armies H \Λ ch3 ch3 jmVAMINE SD-231 Starting wheel D-230 foot 315 SD-401 D-400 515 SD-2001 D-2000 205.0 SD-404 T-403 565
JEFF^MINE DIAMINESJEFF^MINE DIAMINES
JEFFAMINE x MW POP-2000 -33 2,000 10 201024329 此外,根據本發明一較佳實施例,本發明亦提供一 種顏料組合物,其包含:一顏料;以及上述之高分子型 分散劑。其中該顏料可為一綠色顏料。該高分子型分散 劑之含量可不小於於10wt%,以該顏料組合物之固含量 為基準。 以下藉由下列實施例來說明本發明所述之高分子型 分散劑及包含其之顏料組合物,用以進一步闡明本發明 之技術特徵。 高分子型分散劑之製備 實施例1 將聚丙基醚雙胺(Poly(oxypropylene) diamine、 Jeffamine amine POP2000、分子量 2000)放入 100t:真 空烘箱8小時除水,並將二苯基曱烷二異氰酸酯 (4,4’ -Methylenebis(phenyl isocyanate、MDI)利用減壓蒸 館純化。將]V[DI(2 g,8 mmol)置於一四頸瓶中,加入20 Φ g Toluene(約為MDI的10倍)溶解,接著在氮氣狀態下, 以機械授拌至MDI溶解,使溶液呈現homogeneous狀 態。接著,取 32g 的 POP2000(溶於 150 g Toluene),一 次加入MDI溶液中,在氮氣及室溫下反應十分鐘,即可 收集產物。在此實施例中,POP2000與MDI的莫耳數比 2: 1。將產物倒於鋁盤或玻璃盤上,置於循環烘箱80°C除 去Toluene,可得到產物p〇p2000-MDI(A)(線狀高分 子),為淡黃色黏稠液體。上述之聚合反應流程如反應式 (I)所示: 201024329JEFFAMINE x MW POP-2000 -33 2,000 10 201024329 Further, according to a preferred embodiment of the present invention, the present invention also provides a pigment composition comprising: a pigment; and the above-mentioned polymer type dispersant. Wherein the pigment can be a green pigment. The polymer type dispersant may be contained in an amount of not less than 10% by weight based on the solid content of the pigment composition. Hereinafter, the polymer type dispersant of the present invention and the pigment composition containing the same will be described by way of the following examples to further clarify the technical features of the present invention. Preparation Example of Polymer Dispersant Example 1 Poly(oxypropylene) diamine (Poly(oxypropylene) diamine, Jeffamine amine POP2000, molecular weight 2000) was placed in a 100 t vacuum oven for 8 hours to remove water, and diphenylnonane diisocyanate was added. (4,4'-Methylenebis(phenyl isocyanate, MDI) was purified by vacuum distillation. Place [V[DI(2 g, 8 mmol) in a four-necked flask and add 20 Φ g Toluene (about MDI 10 times) dissolved, then under nitrogen, mechanically mixed to MDI to dissolve, so that the solution appeared in a homogeneous state. Then, take 32g of POP2000 (dissolved in 150g Toluene), once added to MDI solution, under nitrogen and room temperature The product can be collected by reacting for ten minutes. In this embodiment, the molar ratio of POP2000 to MDI is 2: 1. The product is poured on an aluminum pan or a glass plate, and placed in a circulating oven at 80 ° C to remove Toluene. The product p〇p2000-MDI(A) (linear polymer) is obtained as a pale yellow viscous liquid. The above polymerization reaction scheme is as shown in the reaction formula (I): 201024329
N=C=0 MDI ch3 ch3 aN=C=0 MDI ch3 ch3 a
NH2CHCH2-f〇CHCH2}-NH2 + 0=C=N POP2000NH2CHCH2-f〇CHCH2}-NH2 + 0=C=N POP2000
Η Ο Η Η Ο H -► HzN^-R-N-C-N-R-N-C-N-R'jj-NHs R'= -^chgh2-(-ochch2^ r= i\=y~CH2\_)^Η Ο Η Η Ο H -► HzN^-R-N-C-N-R-N-C-N-R'jj-NHs R'= -^chgh2-(-ochch2^ r= i\=y~CH2\_)^
a = 33 n>1 反應式(I) 實施例2-4 如實施例1所述之方式進行,但POP2000與MDI 的莫耳數比由2:1分別調至3:2、4:3、及5:4,分別得到 產物 POP2000_MDI(B)_(D)。 表1列出依實施例1-4所使用POP2000與MDI的 莫耳數比,及所得之產物。 表1 產物 POP2000 與 MDI 的莫耳數比 實施例1 POP2000-MDI(A) 2:1 實施例2 POP2000-MDI(B) 3:2 實施例3 POP2000-MDI(C) 4.:3 實施例4 POP2000-MDI(D) 5:4 12 201024329 實施例5 將MDI(2 g,8 mmol)置於一四頸瓶中,加入20 g Toluene(約為MDI的10倍)溶解,接著在氮氣狀態下, 以機械授拌至MDI溶解,使溶液呈現homogeneous狀 態。接著,取16g的POP2000及3.2gPOP400(聚丙基醚 雙胺(Poly(oxypropylene) diamine、Jeffamine amine ?0?400、分子量 400)溶於38 8 1[〇11^116,一次加入]\401 ® 溶液中,在氮氣及室溫下反應十分鐘,即可收集產物。 在此實施例中,聚丙基醚雙胺(POP2000及POP400總合) 與MDI的莫耳數比為2 : 1,以及POP2000與POP400 的莫耳數比為1 : 1。將產物倒於鋁盤或玻璃盤上,置於 循環烘箱 80°C除去 Toluene,可得到產物 POP2000-P〇P400-MDI(A)(線狀高分子),為淡黃色黏稠 液體。 實施例6-9 如實施例1所述之方式進行,但POP2000與POP400 的莫耳數比由1:1分別調至7:1、3:1、5:3、及3:5,分別 得到產物P〇P2000-POP400-MDI(B)-(E)。聚丙基醚雙胺 (POP2000及POP400總合)與MDI的莫耳數比為仍維持 為 2 : 1。 表2列出依實施例5-9所使用POP2000&POP400與 MDI的莫耳數比、POP2000與POP400的莫耳數比、及 13 201024329 所得之產物。 表2 產物 POP2000&POP4 00與MDI的莫 耳數比 POP2000 與 POP400 的 莫耳數比 實施 例5 POP2000-POP400-MDI(A) 2:1 1:1 實施 例6 POP2000-POP400-MDI(B) 2:1 7:1 實施 例7 POP2000-POP400-MDI(C) 2:1 3:1 實施 例8 POP2000-POP400-MDIP) 2:1 5:3 實施 例9 POP2000-PQP400-MDI(E) 2:1 3:5 實施例10 將MDI(2 g,8 mmol)置於一四頸瓶中,加入20 g Toluene溶解,接著在氮氣狀態下,以機械攪拌至MDI 溶解,使溶液呈現homogeneous狀態。接著,取29.1 g 的 POP2000(溶於 150 g Toluene)及 0.6gT403(聚丙基醚三 胺(polyoxypropylene triamine、Jeffamine amine T403、分 子量440)溶於28g Toluene,一次加入MDI溶液中,在 氮氣及室溫下反應十分鐘,即可收集產物。在此實施例 14 201024329 中,聚醚胺(POP2000與T403)與Mm的莫耳數比2 ··卜 POP2000與T403的莫耳數比為1〇:卜將產物倒於鋁盤 或玻璃盤上,置於循環烘箱8(TC除去T〇luene,可得到 產物POP2000-T403-MDI(A)(樹枝狀高分子)’為淡黃色 黏稠液體。上述之聚合反應流程如反應式(Π)所示: ch3 ch3a = 33 n>1 Reaction Formula (I) Example 2-4 was carried out as described in Example 1, but the molar ratio of POP2000 to MDI was adjusted from 2:1 to 3:2, 4:3, respectively. And 5:4, the product POP2000_MDI(B)_(D) was obtained. Table 1 lists the molar ratios of POP2000 to MDI used in Examples 1-4, and the resulting products. Table 1 Moir number ratio of product POP2000 to MDI Example 1 POP2000-MDI (A) 2:1 Example 2 POP2000-MDI (B) 3:2 Example 3 POP2000-MDI (C) 4.: 3 Example 4 POP2000-MDI(D) 5:4 12 201024329 Example 5 MDI (2 g, 8 mmol) was placed in a four-necked flask, dissolved in 20 g of Toluene (about 10 times MDI), followed by nitrogen. Next, mechanically stir to MDI to dissolve, so that the solution is in a homogeneous state. Next, 16 g of POP2000 and 3.2 g of POP400 (Poly(oxypropylene) diamine, Jeffamine amine?0?400, molecular weight 400) were dissolved in 38 8 1 [〇11^116, once added]\401 ® solution. The product can be collected by reacting under nitrogen at room temperature for ten minutes. In this example, the molar ratio of polypropyl ether diamine (POP2000 and POP400 total) to MDI is 2:1, and POP2000 and The molar ratio of POP400 is 1:1. The product is poured on an aluminum pan or a glass plate, and placed in a circulating oven at 80 ° C to remove Toluene, to obtain the product POP2000-P〇P400-MDI (A) (linear polymer) ), is a pale yellow viscous liquid. Examples 6-9 were carried out as described in Example 1, but the molar ratio of POP2000 to POP400 was adjusted from 1:1 to 7:1, 3:1, 5:3, respectively. And 3:5, respectively, the product P〇P2000-POP400-MDI(B)-(E). The molar ratio of polypropyl ether diamine (POP2000 and POP400 total) to MDI is still maintained at 2:1. Table 2 lists the molar ratios of POP2000 & POP400 to MDI used in Examples 5-9, the molar ratio of POP2000 to POP400, and the product obtained in 13 201024329. Table 2 Product PO P2000 & POP4 00 and MDI molar ratio POP2000 and POP400 molar ratio Example 5 POP2000-POP400-MDI (A) 2:1 1:1 Example 6 POP2000-POP400-MDI (B) 2:1 7:1 Example 7 POP2000-POP400-MDI(C) 2:1 3:1 Example 8 POP2000-POP400-MDIP) 2:1 5:3 Example 9 POP2000-PQP400-MDI(E) 2:1 3 :5 Example 10 MDI (2 g, 8 mmol) was placed in a four-necked flask, dissolved in 20 g of Toluene, and then mechanically stirred until the MDI was dissolved under nitrogen to bring the solution to a homogeneous state. Next, take 29.1 g of POP2000 (dissolved in 150 g of Toluene) and 0.6 g of T403 (polyoxypropylene triamine, Jeffamine amine T403, molecular weight 440) dissolved in 28 g of Toluene, once added to the MDI solution, under nitrogen and at room temperature. The product can be collected by reacting for ten minutes. In this example 14, 201024329, the molar ratio of polyetheramine (POP2000 and T403) to Mm is 2, and the molar ratio of POP2000 to T403 is 1〇: Pour the product onto an aluminum pan or glass plate and place it in a circulating oven 8 (TC removes T〇luene to obtain product POP2000-T403-MDI(A) (dendrimer)' as a pale yellow viscous liquid. The reaction scheme is as shown in the reaction formula (Π): ch3 ch3
NH2CHCH2+OCHCH2 如NH2 + 0=C=N a PDP2000 ch3 CH2(〇〇H2Gi-|-NH2 CH2~~CZ/)~ N=c=。 ΜΏΙ ch3 02H5-C-CH2-0H2{OCH2CH)-NH2 CHsCOCHjCHl-NHs (x+y+z=5-6) CH; 丁403 mNH2CHCH2+OCHCH2 such as NH2 + 0 = C = N a PDP2000 ch3 CH2 (〇〇H2Gi-|-NH2 CH2~~CZ/)~ N=c=. ΜΏΙ ch3 02H5-C-CH2-0H2{OCH2CH)-NH2 CHsCOCHjCHl-NHs (x+y+z=5-6) CH; Ding 403 m
Η Ο Η Η Ο H I II 1 1 Η ί N一 —R—n—G_N Η Ο Η Η Ο H j n I t m ! -R-N-C-N 一 R—N-C—N-R、 -NH2 Η Ο Η Η Ο H i i\ \ I U ! FT—fsl—C-N_R_N-C—N—HI Ο Η Ο HI HI II 1 1 Η ί N-R-n-G_N Η Η Η Ο Ο H jn I tm ! -RNCN A R-NC-NR, -NH2 Η Ο Η Η Ο H ii\ \ IU ! FT—fsl—C-N_R_N-C—N—
Η Ο Η Η Ο H -FT-N-C-N - R_N-C_N-R 十剛2 N~C~N-R~N-〇-N 4—R'-M-C-N-R-N-C-N-R,-4—NH2 I 11 I f I) ] \ ! 1! i * jl «Η Ο Η Η Ο H -FT-NCN - R_N-C_N-R 十刚2 N~C~NR~N-〇-N 4—R'-MCNRNCNR,-4—NH2 I 11 I f I) ] \ ! 1! i * jl «
Η Ο Η Η Ο H V Η Ο Η Η Ο H 15 201024329 ch3 ch3 R'= +CHCH2 和 CHCH:15 Ο Η Η Ο H V Η Ο Η Ο Ο H 15 201024329 ch3 ch3 R'= +CHCH2 and CHCH:
RR
CH2(〇CH2CH ch3 CH3 ^ C2H5 *~Ό ~ 0H2~ C H2 (ΟΟΗ2〇Η^· DH2{DCH2〇H^ml ❹ a= 33 n> 1 ,x+y+2=5-6 反應式(II) 實施例11-12 如實施例10所述之方式進行,但POP2000與T403 的莫耳數比由10:1分別調至15:1、及30:1,分別得到產 物 POP2000_T403-MDI(B)-(C)。聚醚胺(POP2000 及 T403 總合)與MDI的莫耳數比為仍維持為2 : 1。 表3列出依實施例10-12所使用POP2000及T403 的莫耳數比、聚醚胺(POP2000及T403總合)與MDI的 莫耳數比、及所得之產物。 16 201024329 表3 產物 POP2000&T403 POP2000 與 與MDI的莫耳 T403 的莫 數比 耳數比 實施例 POP2000-T403-MDI(A) 2:1 10:1 10 實施例 POP2000-T403-MDI(B) 2:1 15:1 11 實施例 POP2000-T403-MDI(Q 2:1 30:1 10 實施例13-15 如實施例10所述之方式進行,但聚醚胺(POP2000 及T403總合)與MDI的莫耳數比由2:1分別調至3:2、 4:3 及 5:4,分別得到產物 POP2000-T403-MDI(D)-(F)。 φ POP2〇00與T4〇3的莫耳數比為仍維持為10 : 1。 表4列出依實施例10及13-15所使用ΡΟΡ2000及 Τ403的莫耳數比、聚醚胺(ΡΟΡ2000及Τ403總合)與MDI 的莫耳數比、及所得之產物。 17 201024329 表4 產物 POP2000&T403 與MDI的莫耳 數比 POP2000 與 T403 的莫 耳數比 實施例 10 POP2000-T403-MDI(A) 2:1 10:1 實施例 13 POP2000-T403-MDIP) 3:2 10:1 實施例 14 POP2000-T403-MDI(E) 4:3 10:1 實施例 15 POP2000-T403-MDI(F) 5:4 10:1 顏料组合物之製備 實施例15 φ 取lg POP2000-MDI(A)(實施例1所得之分散劑)溶 於17g HDDA(1,6己二醇二丙烯酸酯)中,置於塑膠研磨 瓶中,再加入綠色顏料2g及1.0mm錄珠70g。接著,利 用機械攪拌器,在轉速2000rpm下,研磨20分鐘,即得 顏料組合物(A)。最後,對所得之顏料分散溶液(A)進行 黏度及分子粒徑的分析,其結果如表5所示。 比較實施例1 如實施例15所述之方式進行,但不加入任何之分散 18 201024329 劑’得到顏料組合物(B)。對所得之顏料分散溶液出)進 行黏度及分子粒徑的分析,其結果如表5所示。 實施例16-29 如貫施例15所述之方式進行,但將所使用之分散劑 由 POP2000-MDI(A)分別替換為 p〇p2〇〇〇-MDI(B)-(D)、 POP2000-POP400-MDI(A)-(D) 、 以 及 POP2000-T403-MDI(A)-(F),分別得到顏料組合物 • (C)-(O)。對所得之顏料分散溶液(c)-(O)進行黏度及分子 粒徑的分析,其結果如表5所示 表5 顏 料 組 合 物 分散劑 聚醚胺與MDI的莫耳比 黏度(cP)(在不 同轉速(rpm) 下) 10 50 100 無 - 690 190 120 A POP2000-M DI(A) 2:1 40 30 20 C POP2000-M DI(B) 3:2 100 40 30 D POP2000-M DI(C) 4:3 120 50 40 E POP2000-M DI(D) 5:4 ~~*-------------1 120 50 40 19 201024329 顏 料 組 合 物 分散劑 聚醚胺與 MDI的莫耳 比 POP2000 與 POP400 的莫耳比 分子粒徑 (nm)&所佔體 積分率(vol%) 黏度(cP)(在不 同轉速(rpm) 下) 10 50 100 F POP200G-POP4 00-MDI(A) 2:1 1:1 1420-2080(91) 280-410(9) 40 30 30 G POP2000-POP4 00-MDI(B) 2:1 7:1 600-870(98) 160-200(2) 270 100 70 POP2000-POP4 00-MDI(C) 2:1 3:1 570-^60(97) 120-170(3) 50 30 30 I POP2000-POP4 00-MDI(D) 2:1 5:3 530-810(96) 110-150(4) 110 50 40 顏 料 組 合 物 分散劑 聚醚胺與 MDI的莫耳 比 POP2000 與 T403 的莫耳比 分子粒徑 (rnn)&所佔體 積分物〇1%) 黏度(cPX在不同 #it(rptn)T) 10 50 100 J ❿ POP2000-T403- MDI(A) 2:1 10:1 600-780(96) 170-210(4) 50 50 50 K POP2000-T403- MDI(B) 2:1 15:1 820-1220(92) 180-270(8) 150 70 50 L POP2000-T403- MDI(C) 2:1 30:1 320-490(93) 60-70(7) 270 110 80 Μ POP2000-T403- MDIP) 3:2 10:1 230-320(36) 90-130(16) 30-40(48) <36 20 201024329 N POP2000-T403- MDI(E) 4:3 10:1 750-1180(94) 130-190(6) 40 20 20 〇 POP2000-T403- MDI(F) 5:4 10:1 420-620(70) 90-120(30) <36 由表5中可知,加入本發明所述之分散劑的顏料組 合物明顯比未加入本發明所述之分散劑的顏料組合物具 有大幅降低的黏度,此外,該顏料組合物之料徑也可以 # 利用不同之分散劑加以調控。 綜上所述,本發明係提供一種分散劑,其係由一具 有末端胺基之化合物(例如聚醚二胺(poly(oxyalkylene) diamine)或聚醚三胺(poly(oxyalkylene) triamine)和二異 氰酸鹽(diisocyanate)(具有二個異氰酸鹽官能基 (isocyanate)之化合物)反應合成之高分子型分散劑,可作 為分散劑或穩定劑,製成穩定的顏料組合物(分散液)。 參該分散劑包含油溶性的鍵段(例如oxypropylene鍵段), 可利用此鏈段之親油性質(作為溶媒端(salvati〇n segment)) ’使分散劑溶於壓克力單體溶劑中。此外,該 分散劑亦包含脲基(Urea)鏈段(作為錨定點(anchoring point)) ’可與顏料表面改質之官能基型成氫鍵,進行貼 附並穩定其顏料粒子。該分散劑可避免顏料聚集,且可 添加至高濃度(>l〇wt%),所得之分散液仍能保持在低黏 度。 雖然本發明已以實施例揭露如上,然其並非用以限 201024329 定本發明,任何熟習此技藝者,在不脫離本發明之精神 和範圍内,當可作些許之更動與潤飾,因此本發明之保 護範圍當視後附之申請專利範圍所界定者為準。CH2(〇CH2CH ch3 CH3 ^ C2H5 *~Ό ~ 0H2~ C H2 (ΟΟΗ2〇Η^· DH2{DCH2〇H^ml ❹ a= 33 n> 1 ,x+y+2=5-6 Reaction formula (II Example 11-12 was carried out as described in Example 10, but the molar ratio of POP2000 to T403 was adjusted from 10:1 to 15:1 and 30:1, respectively, to obtain the product POP2000_T403-MDI(B). - (C). The molar ratio of polyetheramine (total of POP2000 and T403) to MDI is still maintained at 2: 1. Table 3 lists the molar ratios of POP2000 and T403 used in Examples 10-12. , the molar ratio of polyetheramine (collective of POP2000 and T403) to MDI, and the obtained product. 16 201024329 Table 3 Mobi-numbered ratio of product POP2000 & T403 POP2000 to Mot T403 with MDI Example POP2000 -T403-MDI(A) 2:1 10:1 10 Example POP2000-T403-MDI(B) 2:1 15:1 11 Example POP2000-T403-MDI (Q 2:1 30:1 10 Example 13 -15 was carried out as described in Example 10, but the molar ratio of polyetheramine (POP2000 and T403 total) to MDI was adjusted from 2:1 to 3:2, 4:3 and 5:4, respectively. The product POP2000-T403-MDI(D)-(F) was obtained. The molar number of φ POP2〇00 and T4〇3 To maintain still 10: 1. Table 4 lists the molar ratios of ΡΟΡ2000 and Τ403 used in Examples 10 and 13-15, the molar ratio of polyetheramine (ΡΟΡ2000 and Τ403) and MDI, and The product obtained. 17 201024329 Table 4 Moir number ratio of product POP2000 & T403 to MDI Moir number ratio of POP2000 to T403 Example 10 POP2000-T403-MDI(A) 2:1 10:1 Example 13 POP2000-T403 -MDIP) 3:2 10:1 Example 14 POP2000-T403-MDI(E) 4:3 10:1 Example 15 POP2000-T403-MDI(F) 5:4 10:1 Preparation Example of Pigment Composition 15 φ lg POP2000-MDI (A) (dispersant obtained in Example 1) was dissolved in 17 g HDDA (1,6 hexanediol diacrylate), placed in a plastic grinding bottle, and then added green pigment 2g and 1.0 Mm recorded beads 70g. Subsequently, the pigment composition (A) was obtained by grinding at a rotation speed of 2000 rpm for 20 minutes using a mechanical stirrer. Finally, the obtained pigment dispersion solution (A) was analyzed for viscosity and molecular particle diameter, and the results are shown in Table 5. Comparative Example 1 The procedure described in Example 15 was carried out, but without any dispersion of 18 201024329 agent' to obtain a pigment composition (B). The obtained pigment dispersion solution was analyzed for viscosity and molecular particle diameter, and the results are shown in Table 5. Examples 16-29 were carried out as described in Example 15, except that the dispersant used was replaced by POP2000-MDI (A) to p〇p2〇〇〇-MDI(B)-(D), POP2000, respectively. - POP400-MDI(A)-(D), and POP2000-T403-MDI(A)-(F), respectively, to obtain a pigment composition • (C)-(O). The obtained pigment dispersion solutions (c)-(O) were analyzed for viscosity and molecular particle size, and the results are shown in Table 5. Table 5 The molar composition viscosity (cP) of the pigment composition dispersant polyetheramine and MDI ( At different speeds (rpm) 10 50 100 None - 690 190 120 A POP2000-M DI(A) 2:1 40 30 20 C POP2000-M DI(B) 3:2 100 40 30 D POP2000-M DI( C) 4:3 120 50 40 E POP2000-M DI(D) 5:4 ~~*-------------1 120 50 40 19 201024329 Pigment composition dispersant polyetheramine and MDI molar ratio POP2000 and POP400 molar ratio molecular size (nm) & volume fraction (vol%) viscosity (cP) (at different speeds (rpm)) 10 50 100 F POP200G-POP4 00 -MDI(A) 2:1 1:1 1420-2080(91) 280-410(9) 40 30 30 G POP2000-POP4 00-MDI(B) 2:1 7:1 600-870(98) 160- 200(2) 270 100 70 POP2000-POP4 00-MDI(C) 2:1 3:1 570-^60(97) 120-170(3) 50 30 30 I POP2000-POP4 00-MDI(D) 2: 1 5:3 530-810(96) 110-150(4) 110 50 40 pigment composition dispersant polyetheramine and MDI molar ratio POP2000 and T403 molar ratio molecular size (rnn) & Volume fraction 〇 1%) Viscosity (cPX at different #it(rptn)T) 10 50 100 J ❿ POP2000-T403- MDI(A) 2:1 10:1 600-780(96) 170-210(4) 50 50 50 K POP2000-T403 - MDI(B) 2:1 15:1 820-1220(92) 180-270(8) 150 70 50 L POP2000-T403- MDI(C) 2:1 30:1 320-490(93) 60-70 (7) 270 110 80 Μ POP2000-T403-MDIP) 3:2 10:1 230-320(36) 90-130(16) 30-40(48) <36 20 201024329 N POP2000-T403- MDI(E 4:3 10:1 750-1180(94) 130-190(6) 40 20 20 〇POP2000-T403- MDI(F) 5:4 10:1 420-620(70) 90-120(30) < As can be seen from Table 5, the pigment composition to which the dispersant of the present invention is added has significantly lower viscosity than the pigment composition to which the dispersant of the present invention is not added, and further, the diameter of the pigment composition Can also be adjusted with different dispersants. In summary, the present invention provides a dispersing agent which is composed of a compound having a terminal amine group (for example, poly(oxyalkylene) diamine or poly(oxyalkylene) triamine) and A polymeric dispersant prepared by the reaction of a diisocyanate (a compound having two isocyanate functional groups), which can be used as a dispersing agent or a stabilizer to form a stable pigment composition (dispersion liquid) The dispersant comprises an oil-soluble bond segment (for example, an oxypropylene bond segment), and the oleophilic property of the segment (as a salvati〇n segment) can be utilized to disperse the dispersant in the acrylic monomer. In addition, the dispersant also contains a Urea segment (as an anchoring point) which can form a hydrogen bond with a functional group modified by the surface of the pigment to attach and stabilize the pigment particles. The dispersant can avoid pigment aggregation and can be added to a high concentration (> l% wt%), and the resulting dispersion can still be maintained at a low viscosity. Although the present invention has been disclosed by way of example, it is not intended to be limited to 201024329. Fixed States that a person skilled in this art, without departing from the spirit and scope of the present invention, it is intended that the modifications and variations of the present invention is therefore defined by the security guard of the scope of the appended claims which are when the range of their equivalents.
22 201024329 【圖式簡單說明】 無。 【主要元件符號說明】 無022 201024329 [Simple description of the diagram] None. [Main component symbol description] No 0
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Cited By (4)
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TWI492965B (en) * | 2013-12-31 | 2015-07-21 | Ind Tech Res Inst | Polymer and dispersion |
TWI548673B (en) * | 2015-11-05 | 2016-09-11 | 財團法人工業技術研究院 | Polymer and dispersion |
US10059858B2 (en) | 2016-12-22 | 2018-08-28 | Industrial Technology Research Institute | Polymer and dispersion liquid |
TWI765572B (en) * | 2020-03-16 | 2022-05-21 | 財團法人工業技術研究院 | Pigment composite particle |
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US5212230A (en) * | 1991-03-28 | 1993-05-18 | Miles Inc. | Aqueous polyurea dispersions prepared by an emulsion polymerization process |
US5731397A (en) * | 1996-04-16 | 1998-03-24 | Huntman Petrochemical Corporation | Polyurea spray railcar lining systems |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI492965B (en) * | 2013-12-31 | 2015-07-21 | Ind Tech Res Inst | Polymer and dispersion |
TWI548673B (en) * | 2015-11-05 | 2016-09-11 | 財團法人工業技術研究院 | Polymer and dispersion |
US10213758B2 (en) | 2015-11-05 | 2019-02-26 | Industrial Technology Research Institute | Polymer and dispersion |
US10059858B2 (en) | 2016-12-22 | 2018-08-28 | Industrial Technology Research Institute | Polymer and dispersion liquid |
TWI765572B (en) * | 2020-03-16 | 2022-05-21 | 財團法人工業技術研究院 | Pigment composite particle |
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