TWI398493B - Surface denaturation disperse carbon black - Google Patents
Surface denaturation disperse carbon black Download PDFInfo
- Publication number
- TWI398493B TWI398493B TW96118164A TW96118164A TWI398493B TW I398493 B TWI398493 B TW I398493B TW 96118164 A TW96118164 A TW 96118164A TW 96118164 A TW96118164 A TW 96118164A TW I398493 B TWI398493 B TW I398493B
- Authority
- TW
- Taiwan
- Prior art keywords
- carbon black
- group
- denatured
- terminal
- polymer
- Prior art date
Links
Description
本發明係關於對例如矽油等非極性溶劑或異構烷烴系烴等的低極性溶劑、進一步對樹脂等顯示優良的分散性之表面變性分散性碳黑。The present invention relates to a surface-denatured dispersible carbon black which exhibits excellent dispersibility to a resin such as a non-polar solvent such as eucalyptus oil or an isoparaffin-based hydrocarbon or a low-polarity solvent.
碳黑自古即用於作為黑色著色顏料，近年作為噴墨印表機用等的黑色著色材，開發藉由表面改質而提升對極性溶劑之水之分散性之碳黑顏料。Carbon black has been used as a black coloring pigment since ancient times. In recent years, it has been developed as a black coloring material for inkjet printers, and carbon black pigment which improves the dispersibility of water in a polar solvent by surface modification.
又，對非極性溶劑或低極性溶劑之分散性之改善、提升之期望很強，例如，希望開發使用於塗料等之組合物、彩色濾光片用黑矩陣、顯示器裝置等之分散性碳黑。Further, there is a strong demand for improvement and improvement in dispersibility of a non-polar solvent or a low-polarity solvent. For example, it is desired to develop a dispersible carbon black for use in a composition such as a paint, a black matrix for a color filter, or a display device. .
例如，日本專利公開08－337624號公報，作為於用於油墨、影印機用碳粉、塗料、樹脂著色劑等之各種媒體中的分散性優良的碳黑接枝高分子，提案包含：含有矽膠成分之聚合物部分；及碳黑部分，分散於矽油中時的崩潰電壓為0.5kV/mm以上之碳黑接枝高分子。此係，藉由於碳黑接枝高分子之聚合部分含有矽膠成分之高分子鏈，即使在極性低的溶劑中亦可付與充分的分散性者。For example, Japanese Laid-Open Patent Publication No. 08-337624 discloses a carbon black graft polymer excellent in dispersibility in various media such as inks for toners, photoconductors, paints, and resin colorants. The polymer portion of the component; and the carbon black portion, the carbon black graft polymer having a breakdown voltage of 0.5 kV/mm or more when dispersed in the eucalyptus oil. In this case, since the polymer portion of the carbon black graft polymer contains a polymer chain of a silicone component, sufficient dispersibility can be imparted even in a solvent having a low polarity.
又，於日本專利公開09－272706號公報提案有一種反應性碳黑接枝高分子，其包含：片段(A)；及與片段(A)相異鏈構造之片段(B)，片段(A)係藉由使具有與碳黑表面的官能基之反應性之基(1)之聚合物，與碳黑表面的官能基反應而得之碳黑接枝高分子，片段(A)、(B)具有與目的媒體之母體具有反應性之基(2)。Further, Japanese Laid-Open Patent Publication No. 09-272706 proposes a reactive carbon black graft polymer comprising: a fragment (A); and a fragment (B) having an isomeric structure with the fragment (A), a fragment (A) a carbon black graft polymer obtained by reacting a polymer having a group (1) having reactivity with a functional group on the surface of carbon black with a functional group on the surface of carbon black, and a fragment (A), (B) ) has a basis (2) that is reactive with the parent of the intended medium.
但是，因以環氧基作為反應性基，為三員開環使用觸媒故有於分散體中殘留觸媒之問題。又，並沒有具體揭示將異氰酸基與異氰酸基經由反應性高分子鍵結之接枝碳黑。However, since an epoxy group is used as a reactive group, a catalyst is used for three members to open the ring, so that the catalyst remains in the dispersion. Further, the graft carbon black in which an isocyanate group and an isocyanate group are bonded via a reactive polymer is not specifically disclosed.
本發明者們對關於可對非極性溶劑或低極性溶劑、進一步於樹脂中顯示良好的分散性之碳黑的表面變性進行研究，結果發現，將碳黑的表面以具有長的側鏈之梳狀構造之高分子反應之表面變性碳黑，於該等溶液中可顯示優良的分散性。The present inventors studied the surface denaturation of carbon black which can exhibit good dispersibility in a non-polar solvent or a low-polar solvent, and further found that the surface of the carbon black is a comb having a long side chain. The surface-denatured carbon black of the polymer reaction of the structure has excellent dispersibility in these solutions.
本發明係基於上述見識完成者，本發明之目的係提供一種表面變性分散性碳黑，其係經由三異氰酸化合物將碳黑表面之官能基與單邊末端二醇變性高分子鍵結使表面變性，於非極性溶劑、低極性溶劑、樹脂中顯示優良的分散性者。The present invention is based on the above findings, and an object of the present invention is to provide a surface-denatured dispersible carbon black which is obtained by denaturation of a functional group of a carbon black surface with a unilateral terminal diol denatured polymer via a triisocyanate compound. Surface denaturation, showing excellent dispersibility in non-polar solvents, low-polar solvents, and resins.
為達成上述目的本發明之表面變性分散性碳黑，其特徵在於：碳黑的表面官能基，與於異構造之3末端具有異氰酸基之三異氰酸化合物之1個末端的異氰酸基鍵結，其他的2個末端異氰酸基與單邊末端二醇變性高分子之羥基鍵結。The surface-denatured dispersible carbon black of the present invention for achieving the above object is characterized by a surface functional group of carbon black and an isocyanic acid at one end of a triisocyanate compound having an isocyanate group at the 3 terminal end of the heterostructure. The acid group is bonded, and the other two terminal isocyanato groups are bonded to the hydroxyl group of the unilateral terminal diol denatured polymer.
本發明之表面變性分散性碳黑，係將三異氰酸化合物之3末端異氰酸基與碳黑的表面官能基及單邊末端二醇變性高分子之羥基鍵結，使三異氰酸化合物作為中間物質介在而使碳黑表面變性者，對矽油等非極性溶劑、異構烷烴系烴溶劑或樹脂媒體等的低極性溶劑具有優良的分散性。The surface-denatured dispersible carbon black of the present invention is obtained by bonding a 3-terminal isocyanate group of a triisocyanate compound to a surface functional group of carbon black and a hydroxyl group of a unilateral terminal diol denatured polymer to obtain triisocyanate. When the compound is used as an intermediate substance to denature the surface of the carbon black, it has excellent dispersibility for a low-polar solvent such as a non-polar solvent such as eucalyptus oil, an isoparaffin-based hydrocarbon solvent or a resin medium.
用於本發明之碳黑之種類並無特別限制，可使用爐黑、熱黑、槽黑等之任一，最好使用以電子顯微鏡測定之一次粒徑為0.01~0.3 μm之碳黑。以一次粒徑未滿0.01 μm之碳黑則作用於粒子間的凝聚力大而容易凝聚，另一方面，超過0.3 μm時以表面變性狀態之自重變大，容易在溶劑中沉降。The type of the carbon black to be used in the present invention is not particularly limited, and any of furnace black, hot black, and channel black may be used, and carbon black having a primary particle diameter of 0.01 to 0.3 μm as measured by an electron microscope is preferably used. Carbon black having a primary particle diameter of less than 0.01 μm acts on the cohesive force between the particles to be easily aggregated. On the other hand, when it exceeds 0.3 μm, the self-weight becomes large in the surface denaturation state, and it is easy to settle in a solvent.
本發明之表面變性分散性碳黑，係包含：碳黑的表面官能基，與於異構造之3末端具有異氰酸基之三異氰酸化合物之1個末端的異氰酸基胺酯鍵結，其他的2個末端異氰酸基與單邊末端二醇變性高分子之羥基胺酯鍵結之構造。The surface-denatured dispersible carbon black of the present invention comprises: a surface functional group of carbon black, and an isocyanatoamine ester bond at one end of a triisocyanate compound having an isocyanate group at the 3 terminal end of the heterostructure. The structure of the other two terminal isocyanato groups bonded to the hydroxylamine ester of the unilateral terminal diol denatured polymer.
於碳黑，根據其生成製程或氧化等後處理而存在各種表面官能基，官能基的種類或官能基的量可例如以下述之方法控制。In the carbon black, various surface functional groups exist depending on the post-treatment such as the formation process or oxidation, and the kind of the functional group or the amount of the functional group can be controlled, for example, by the following method.
(1)羥基、羧基、苯醌基係將碳黑曝於臭氧、氧、NOx 、Sox 等氣體氣氛之方法；以低溫氧電漿處理之方法；放入臭氧水、過氧化氫水、過氧2酸或其鹽類、次亞鹵素酸鹽、重鉻酸鹽、過錳酸鹽、硝酸等氧化劑水溶液攪拌混合之方法等之氣相氧化處理或液相氧化處理之方法。(1) a hydroxyl group, a carboxyl group, quinone group-based carbon black is exposed in the process gas atmosphere of ozone, oxygen, NO x, So x and the like; to the cryogenic oxygen plasma process; into ozone water, hydrogen peroxide, A method of gas phase oxidation treatment or liquid phase oxidation treatment of a method such as a method of stirring and mixing an aqueous solution of an oxidizing agent such as peroxydiacid or a salt thereof, a hypophosphite, a dichromate, a permanganate or a nitric acid.
(2)胺基，係以硝酸/硫酸混合系氧化生成硝基，以甲醛等還元劑還元之方法。(2) The amine group is a method in which a nitric acid/sulfuric acid mixture is oxidized to form a nitro group, and a reductive agent such as formaldehyde is used.
(3)碸基，係以濃硫酸碸化之方法。(3) The sulfhydryl group is a method of hydrating with concentrated sulfuric acid.
(4)環氧基，係使羥基、羧基與具有環氧基之鹵化物反應之方法。(4) An epoxy group is a method of reacting a hydroxyl group or a carboxyl group with a halide having an epoxy group.
對該等官能基，與於異構造之3末端具有異氰酸基之三異氰酸化合物反應，與1個末端異氰酸基鍵結。例如與羥基以胺酯基(OHOCN)，與胺基以尿素鍵結(NHCONH)鍵結。再者，官能基之生成，例如氧化處理時處理至pH成5以下為佳，只要是pH5以下的碳黑，則無須施以氧化處理，可直接使用。These functional groups are reacted with a triisocyanate compound having an isocyanate group at the 3-terminal end of the heterostructure, and bonded to one terminal isocyanate group. For example, an amine group (OHOCN) with a hydroxyl group and a urea bond (NHCONH) with an amine group. Further, the formation of the functional group, for example, the treatment at the time of the oxidation treatment to a pH of 5 or less is preferable, and if it is a carbon black having a pH of 5 or less, it is not necessary to be subjected to an oxidation treatment, and it can be used as it is.
作為三異氰酸化合物，只要是異三聚氰酸酯構造、雙縮脲構造、加成構造等，於3末端全部具有異氰酸基者即可無特別限制地使用，例如，作為具有異三聚氰酸酯構造可例示三井武田化學(股)製D－177N、D－170N、D－170HN、D－172N等。The triisocyanate compound is not particularly limited as long as it has an isocyanurate structure, a biuret structure, an addition structure, or the like, and all of the three ends have an isocyanate group, for example, The structure of the cyanurate can be exemplified by D-177N, D-170N, D-170HN, D-172N, etc. manufactured by Mitsui Takeda Chemical Co., Ltd.
將該反應，對作為碳黑粒子表面之官能基之羥基，與作為在異構造之3末端具有異三聚氰酸酯之三異氰酸具有異氰酸基之己烷異氰酸化合物(三異氰酸六亞甲基異三聚氰酸酯，三井武田化學(股)製D－177N)反應，1個末端異氰酸基與碳黑粒子表面的羥基鍵結時之反應式示於下述化學式1。The reaction, a hydroxyl group as a functional group on the surface of the carbon black particles, and a hexane isocyanate compound having an isocyanate group as a triisocyanate having an isomeric cyanurate at the 3 terminal of the heterostructure (3) Reaction of hexamethylene isocyanurate isocyanate, D-177N manufactured by Mitsui Takeda Chemical Co., Ltd., and the reaction formula of one terminal isocyanate group bonded to the hydroxyl group on the surface of carbon black particles is shown below. Chemical formula 1.
碳黑依需要施以適宜氧化處理調整表面官能基量、特別是羥基或羧基等含有氫的官能基量，放入酯或酮等的非反應性溶劑，加入於異構造之3末端具有異氰酸基之三異氰酸化合物以攪拌脫泡機攪拌混合，進一步以三輥磨等充分混煉，使三異氰酸化合物之1個末端異氰酸基與碳黑的表面官能基鍵結。The carbon black is subjected to an appropriate oxidation treatment to adjust the amount of the surface functional group, particularly a hydroxyl group-containing functional group such as a hydroxyl group or a carboxyl group, and is added to a non-reactive solvent such as an ester or a ketone, and is added to the heterostructure to have an isocyanate at the 3 terminal end. The acid-based triisocyanate compound is stirred and mixed by a stirring defoaming machine, and further kneaded by a three-roll mill or the like to bond one terminal isocyanate group of the triisocyanate compound to the surface functional group of carbon black.
本發明之表面變性分散性碳黑，係三異氰酸之1個末端異氰酸基與碳黑粒子表面之官能基鍵結，剩下的其他2個末端異氰酸基與單邊末端二醇變性高分子之羥基鍵結表面變性者。The surface denaturing and dispersible carbon black of the present invention is a terminal isocyanate group of triisocyanate bonded to a functional group on the surface of the carbon black particle, and the remaining two terminal isocyanato groups and a unilateral terminal The alcohol-denatured polymer has a hydroxyl-bonded surface-denatured person.
作為單邊末端二醇變性高分子，以側鏈長的梳狀構造之高分子為佳，例如可例示其主骨架為聚丙烯酸－2－乙基己基酯、聚丙烯酸辛酯等之高分子，將使用丙烯－1,2－二醇聚(2－乙基己基羰基乙烯)硫化物(綜研化學(股)製UT－1001)之情形例示於下述化學式2。The unilateral terminal diol-denatured polymer is preferably a polymer having a comb structure having a side chain length, and examples thereof include a polymer having a main skeleton of polyethyl-2-ethylhexyl acrylate or polyoctyl acrylate. A case where propylene-1,2-diol poly(2-ethylhexylcarbonylethylene) sulfide (UT-1001 manufactured by Seiko Kogyo Co., Ltd.) is used is exemplified in the following Chemical Formula 2.
如化學式2，本發明之表面變性分散性碳黑，係使碳黑的表面官能基(羥基)，與三異氰酸化合物之1個末端的異氰酸基鍵結，其他的2個末端異氰酸基與單邊末端二醇變性高分子之羥基鍵結表面改質者，藉由使三異氰酸化合物作為中間物質介在將碳黑與單邊末端二醇變性高分子鍵結者。The chemically modified surface-dispersible carbon black of the present invention has a surface functional group (hydroxyl group) of carbon black bonded to an isocyanate group at one terminal of a triisocyanate compound, and the other two terminal ends are different. The surface of the hydroxy-bonded surface of the cyanate group and the uni-terminal terminal diol denatured polymer is modified by using a triisocyanate compound as an intermediate substance to bond the carbon black to the unilateral terminal diol.
如此地表面變性之碳黑，對矽油或具有異構造之烴溶劑等之非極性溶劑或低極性溶劑具有優良的分散性，又對於樹脂亦顯示優良的分散性。The surface-denatured carbon black has excellent dispersibility for non-polar solvents or low-polar solvents such as eucalyptus oil or a hydrocarbon solvent having a different structure, and exhibits excellent dispersibility for the resin.
該表面變性分散性碳黑，係將碳黑放入酯或酮等的非反應性溶劑，加入於異構造之3末端具有異氰酸基之三異氰酸化合物以攪拌脫泡機攪拌混合，進一步以三輥磨等充分混煉，使三異氰酸化合物之1個末端異氰酸基與碳黑的表面官能基鍵結。The surface-denatured dispersible carbon black is obtained by adding carbon black to a non-reactive solvent such as an ester or a ketone, and adding a triisocyanate compound having an isocyanate group at the 3 terminal of the heterostructure to be stirred and mixed by a stirring defoaming machine. Further, the mixture is sufficiently kneaded by a three-roll mill or the like to bond one terminal isocyanate group of the triisocyanate compound to the surface functional group of the carbon black.
接著，加入單邊末端二醇變性高分子以攪拌脫泡機攪拌脫泡後，藉由三輥磨等充分混煉混合物。之後，於混煉物加入溶劑稀釋之後以超音波均質儀、高壓均質儀、加工均質儀、球磨、珠磨等使之混合分散，以25~100℃的溫度熱處理適宜時間，介由使三異氰酸化合物之未反應之2個末端異氰酸基與單邊末端二醇變性高分子之羥基作胺酯鍵結而表面變性。Next, the unilateral terminal diol denatured polymer is added, stirred and defoamed by a stirring defoaming machine, and then the mixture is sufficiently kneaded by a three-roll mill or the like. After that, the mixture is diluted with a solvent, and then mixed and dispersed by an ultrasonic homogenizer, a high-pressure homogenizer, a processing homogenizer, a ball mill, a bead mill, etc., and heat-treated at a temperature of 25 to 100 ° C for a suitable time. The unreacted two terminal isocyanato groups of the cyanic acid compound are bonded to the hydroxyl group of the unilateral terminal diol denatured polymer as an amine ester to be surface-denatured.
此時，添加少量加成反應促進觸媒或脫水縮合劑為佳，胺酯反應會較容易進行。作為加成反應促進觸媒、脫水縮合劑，可例示二丁基二月桂酸錫、濃硫酸、N,N’－二環己基碳二亞胺、N,N’－二異丙基碳二亞胺、N－乙基－(3－二甲基胺基丙基)碳二亞胺、1－羥基苯併***、氰基磷酸二乙酯、1－乙氧羰基－2－乙氧基－1,2－二氫醌、氯甲酸異丁酯、三苯基氯甲烷、新戊氧基甲基氯、氯化鉿等，其他具有N＝N鍵結之化合物或酸酐亦可得同樣的效果。At this time, it is preferred to add a small amount of the addition reaction to promote the catalyst or the dehydrating condensing agent, and the amine ester reaction is easier to carry out. Examples of the addition reaction-promoting catalyst and the dehydrating condensing agent include dibutyltin dilaurate, concentrated sulfuric acid, N,N'-dicyclohexylcarbodiimide, and N,N'-diisopropylcarbodiimide. Amine, N-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole, diethyl cyanophosphate, 1-ethoxycarbonyl-2-ethoxy- 1,2-dihydroanthracene, isobutyl chloroformate, triphenylchloromethane, neopentyloxymethyl chloride, cesium chloride, etc., other compounds having an N=N bond or an acid anhydride can also have the same effect. .
以下，將本發明之實施例與比較例對比具體說明。Hereinafter, the examples of the present invention will be specifically described in comparison with comparative examples.
將東海碳(股)製碳黑TB#7550F於2N的過硫酸鈉水溶液中氧化，藉由乾燥、粉碎、分級得到於粒子表面具有酸性官能基之氧化碳黑粉末(羥基0.74 μ eq/m2 、羧基4.8 μ eq/m2 )。The Tokai carbon (TB) carbon black TB#7550F was oxidized in a 2N aqueous solution of sodium persulfate, and dried, pulverized, and classified to obtain an oxidized carbon black powder having an acidic functional group on the surface of the particles (hydroxyl 0.74 μ eq/m 2 ) Carboxy group 4.8 μ eq/m 2 ).
於該氧化碳黑25.0g添加異構烷烴系烴溶劑(艾克森美孚公司製ISOPAR G)39.5g濕潤，接著加入三異氰酸化合物之三異氰酸六亞甲基異三聚氰酸酯(三井武田化學(股)製D－177N)4.725g，作為單邊末端二醇變性高分子之丙烯－1,2－二醇聚(2－乙基己基羰基乙烯)硫化物(綜研化學(股)製UT－1001：分子量3500)17.5g混合，使用攪拌脫泡機((股)SHINKI製去泡鍊太郎)進行攪拌2分鐘，脫泡2分鐘實施前混煉。將該前混煉物進一步以三輥((股)井上製作所製S－4 3/4×11)混煉30分鐘，添加KISHIDA化學(股)製月桂酸二丁酯0.47225g以10wt%的濃度溶解於異構烷烴系烴溶劑(ISOPAR G)，進一步以3輥混煉30分鐘。此時，由於異構烷烴系烴溶劑會少量揮發，故適宜添加異構烷烴系烴溶劑。25.0 g of the oxidized carbon black was added with 39.5 g of an isoparaffin-based hydrocarbon solvent (ISOPAR G manufactured by ExxonMobil), followed by the addition of a triisocyanate hexamethylene isocyanurate trisocyanate (Mitsubishi Takeda Chemical Co., Ltd. D-177N) 4.725g, propylene-1,2-diol poly(2-ethylhexylcarbonylvinyl) sulfide as a unilateral terminal diol denatured polymer UT-1001: MW-1001: molecular weight: 3,500), 17.5 g of the mixture was mixed, and the mixture was stirred for 2 minutes using a stirring defoaming machine (manufactured by SHINKI), and defoamed for 2 minutes to carry out pre-kneading. The pre-kneaded product was further kneaded in a three-roll (S-4 3/4×11 manufactured by In-situ Co., Ltd.) for 30 minutes, and KISHIDA Chemical Co., Ltd. was used to prepare 0.47225 g of dibutyl laurate to a concentration of 10% by weight. Dissolved in an isoparaffinic hydrocarbon solvent (ISOPAR G) and further kneaded in a 3 roll for 30 minutes. In this case, since the isoparaffinic hydrocarbon solvent is volatilized in a small amount, an isoparaffinic hydrocarbon solvent is suitably added.
於上述混煉物加入異構烷烴系烴溶劑以使全量成為250g，使用超音波均質儀((股)日本精機製作所Ultrasonic Generator)處理10分鐘，進行機械分散。之後，以高壓均質儀((股)東海製NANOMIZER TL－1500)，由50MPa至150MPa進一步進行機械分散。To the above-mentioned kneaded product, an isoparaffinic hydrocarbon solvent was added to make the total amount to 250 g, and the mixture was treated with an ultrasonic homogenizer (Ulrasonic Generator, Japan) for 10 minutes to carry out mechanical dispersion. Thereafter, mechanical dispersion was further carried out from 50 MPa to 150 MPa by a high pressure homogenizer (NANOMIZER TL-1500, manufactured by Tokai).
將上述分散體於1公升分離瓶以70℃邊充分攪拌加熱處理6小時。The above dispersion was heat-treated at 70 ° C for 6 hours in a 1 liter separation bottle.
加熱處理終了後，再次加入異構烷烴系烴溶劑使全量為250g，得到10wt%自己分散於異構烷烴系烴溶劑之表面變性碳黑分散體1。After the end of the heat treatment, the isoparaffinic hydrocarbon solvent was again added to make the total amount 250 g, and 10 wt% of the surface denatured carbon black dispersion 1 dispersed in the isoparaffinic hydrocarbon solvent was obtained.
使用與實施例1相同的碳黑以臭氧氣相氧化，製作pH2.5的氧化碳黑(羥基1.0 μ eq/m2 、羧基3.2 μ eq/m2 )。The same carbon black as in Example 1 was subjected to ozone gas phase oxidation to prepare carbon black (pH 1.0 μ eq/m 2 , carboxyl group 3.2 μ eq/m 2 ) having a pH of 2.5.
使用該碳黑，藉由與實施例1相同的方法，得到表面變性碳黑分散體2。Using the carbon black, a surface-denatured carbon black dispersion 2 was obtained by the same method as in Example 1.
於碳黑使用槽黑(Degussa公司製Special Black4(pH2.3)：羥基0.16 μ eq/m2 、羧基4.2 μ eq/m2 )以外，藉由與實施例1相同的方法，得到表面變性碳黑分散體3。Surface denatured carbon was obtained by the same method as in Example 1 except that the black was used for the carbon black (Special Black 4 (pH 2.3) manufactured by Degussa Co., Ltd.: hydroxyl group: 0.16 μ eq/m 2 , carboxyl group: 4.2 μ eq/m 2 ). Black dispersion 3.
作為分散之溶劑，代替異構烷烴系烴溶劑使用PGMEA(丙二醇甲醚醋酸酯)以外，藉由與實施例1相同的方法，得到表面變性碳黑分散體4。The surface-denatured carbon black dispersion 4 was obtained in the same manner as in Example 1 except that PGMEA (propylene glycol methyl ether acetate) was used instead of the isoparaffinic hydrocarbon solvent.
與實施例4同樣地，代替異構烷烴系烴溶劑使用PGMEA，為捕捉未反應之異氰酸基，於70℃保持步驟中，對碳黑添加成20wt%之5g脂肪族系酯醇(四日市合成(股)製YGNOL EHP01)以外，藉由與實施例1相同的方法，得到表面變性碳黑分散體5。In the same manner as in Example 4, PGMEA was used instead of the isoparaffinic hydrocarbon solvent, and in order to capture the unreacted isocyanate group, the carbon black was added in an amount of 20% by weight to 5 g of the aliphatic ester alcohol in the holding step at 70 ° C (Four City) A surface-denatured carbon black dispersion 5 was obtained in the same manner as in Example 1 except for the synthesis (manufactured by YGNOL EHP01).
作為分散之溶劑，代替異構烷烴系烴溶劑使用矽油(信越化學工業(股)製KF96L－1cs)，作為反應性高分子代替單邊末端二醇變性高分子使用單邊末端二醇變性矽膠高分子((股)CHISSO製FM－DA21：分子量5000)16.25g以外，藉由與實施例1相同的方法，得到表面變性碳黑分散體6。As a solvent for dispersion, an eucalyptus oil (KF96L-1cs manufactured by Shin-Etsu Chemical Co., Ltd.) is used instead of the isoparaffin-based hydrocarbon solvent, and a unilateral terminal diol-denatured phthalocyanine is used as a reactive polymer instead of a unilateral terminal diol denatured polymer. A surface-denatured carbon black dispersion 6 was obtained in the same manner as in Example 1 except that the molecule (FM-DA21 manufactured by CHISSO: molecular weight: 5000) was 16.25 g.
與實施例4同樣地，作為分散之溶劑使用PGMEA以外，藉由與實施例1相同的方法，得到表面變性碳黑分散體，混合添加甲基丙烯酸樹脂31.3g作為樹脂，ILGACURE907(Ciba Speciality Chemicals製)4.7g作為光聚合起始劑，製作樹脂組合物1。In the same manner as in Example 4, a surface-denatured carbon black dispersion was obtained in the same manner as in Example 1 except that PGMEA was used as a solvent for dispersion, and 31.3 g of a methacrylic resin was mixed and added as a resin, and ILGACURE 907 (manufactured by Ciba Speciality Chemicals) 4.7 g was used as a photopolymerization initiator to prepare a resin composition 1.
於實施例1，使用未施以氧化處理之碳黑(東海碳(股)製TB#7550，pH6~7(羥基0.13 μ eq/m2 、羧基0.37 μ eq/m2 ))以外，藉由與實施例1相同的方法，得到表面變性碳黑分散體7。In Example 1, except that carbon black (Tunghai carbon (TB) TB#7550, pH 6-7 (hydroxyl 0.13 μ eq/m 2 , carboxyl group 0.37 μ eq/m 2 )) which was not subjected to oxidation treatment was used, In the same manner as in Example 1, a surface-denatured carbon black dispersion 7 was obtained.
於實施例1，未使用三異氰酸化合物以外，藉由與實施例1相同的方法，得到表面變性碳黑分散體8。The surface-denatured carbon black dispersion 8 was obtained in the same manner as in Example 1 except that the triisocyanate compound was not used.
於實施例7，使用未施以氧化處理之碳黑(東海碳(股)製TB#7550F)以外，藉由與實施例7相同的方法，製作樹脂組合物2。In the same manner as in Example 7, except that carbon black (TB#7550F manufactured by Tokai Carbon Co., Ltd.) which was not subjected to oxidation treatment was used, the resin composition 2 was produced in the same manner as in Example 7.
關於所得分散體1~8，使用外差式雷射都卜勒方式粒度分布測定裝置(漢威公司製9340－UPA150)測定分散體中的碳黑凝聚體之平均粒徑，又藉由振動式黏度計(山一電機(股)製VM－100A－L)測定分散體之黏度。將測定結果之經時變化示於表1。又，關於樹脂組合物1、2，滴到硬質玻璃上，使用棒塗佈機(日本CEDARS SERVICE公司製Rod.No.6)製作厚度13.7 μm之膜，使之硬化，將外觀評價，以膜厚Macbeth黑色度計(Macbeth公司製TR－927)測定黑色度，以超絕緣計(東亞DKK(股)製SM－8220)測定表面電阻，示於表2。With respect to the obtained dispersions 1 to 8, the average particle diameter of the carbon black aggregates in the dispersion was measured using a heterodyne laser Doppler particle size distribution measuring apparatus (manufactured by Hanwei Co., Ltd. 9340-UPA150), and vibration type A viscosity meter (Mountain-Motor Co., Ltd. VM-100A-L) was used to measure the viscosity of the dispersion. The change over time of the measurement results is shown in Table 1. In addition, the resin compositions 1 and 2 were dropped on a hard glass, and a film having a thickness of 13.7 μm was formed using a bar coater (Rod. No. 6 manufactured by CEDARS SERVICE Co., Ltd., Japan), and the film was cured to evaluate the appearance. The blackness was measured by a thick Macbeth blackness meter (TR-927 manufactured by Macbeth Co., Ltd.), and the surface resistance was measured by a super insulation meter (SM-8220 manufactured by Toago DKK Co., Ltd.), which is shown in Table 2.
如表1~2所示，分散體1~7較分散體8分散性優良，又由於分散體3較分散體1、2、4、5碳黑粒徑大故分散性稍微較差。但是分散體3與分散體7均並非無法使用之範圍，藉由多進行過濾處理等即足以使用。又，分散體4及5由於在物性上幾乎看不到有所差異，因此將未反應的異氰酸基以醇終結，並不會急劇地提升分散性及保存安定性。又，樹脂組合物1分散性優良，但是樹脂組合物2可看到碳黑的凝聚沉澱，黑色度及表面電阻亦以樹脂組合物1較佳。As shown in Tables 1 and 2, the dispersions 1 to 7 were superior in dispersibility to the dispersion 8, and the dispersion 3 was slightly inferior in dispersibility due to the larger particle size of the dispersions 1, 2, 4, and 5 carbon black. However, both the dispersion 3 and the dispersion 7 are not incapable of use, and it is sufficient to use by performing a filtration treatment or the like. Further, since the dispersions 4 and 5 hardly differ in physical properties, the unreacted isocyanate group is terminated with an alcohol, and the dispersibility and storage stability are not drastically improved. Further, the resin composition 1 is excellent in dispersibility, but the resin composition 2 can be observed to form agglomerated precipitates of carbon black, and the blackness and surface resistance are also preferably the resin composition 1.
本發明之表面變性分散性碳黑，使用作為液晶顯示用黑矩陣或電子紙用顯示媒體等之黑色顏料極為有用。The surface-denatured dispersible carbon black of the present invention is extremely useful as a black pigment such as a black matrix for liquid crystal display or a display medium for electronic paper.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW96118164A TWI398493B (en) | 2007-05-22 | 2007-05-22 | Surface denaturation disperse carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW96118164A TWI398493B (en) | 2007-05-22 | 2007-05-22 | Surface denaturation disperse carbon black |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200846421A TW200846421A (en) | 2008-12-01 |
| TWI398493B true TWI398493B (en) | 2013-06-11 |
Family
ID=44823156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW96118164A TWI398493B (en) | 2007-05-22 | 2007-05-22 | Surface denaturation disperse carbon black |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI398493B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09118821A (en) * | 1995-10-26 | 1997-05-06 | Sumitomo Bakelite Co Ltd | Production of composite material of thermosetting resin and composite material of thermosetting resin |
-
2007
- 2007-05-22 TW TW96118164A patent/TWI398493B/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09118821A (en) * | 1995-10-26 | 1997-05-06 | Sumitomo Bakelite Co Ltd | Production of composite material of thermosetting resin and composite material of thermosetting resin |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200846421A (en) | 2008-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101344666B1 (en) | Dispersible surface-modified carbon black | |
| JP5057262B2 (en) | Method for producing surface-modified carbon black | |
| JP5093733B2 (en) | Method for producing surface-treated carbon black aqueous dispersion | |
| JP5585957B2 (en) | Polyurethane resin-added pigment, method for producing polyurethane resin-added pigment, pigment dispersion composition, and inkjet ink composition | |
| KR101877083B1 (en) | Process for producing pigment dispersion composition | |
| JP5678389B2 (en) | Method for producing aqueous dispersion of polyurethane resin-added pigment, aqueous dispersion of polyurethane resin-added pigment, and ink composition | |
| JP5488900B2 (en) | Pigment dispersion composition and inkjet ink composition | |
| WO2011152353A1 (en) | Polyurethane resin adhesion pigment, pigment dispersion composition and inkjet ink composition | |
| JP5120747B2 (en) | Surface-modified carbon black, method for producing the same, and dispersion thereof | |
| JP6325513B2 (en) | Method for producing modified polymer particles containing pigment | |
| JP2013520545A (en) | Method for preparing encapsulated solid particles | |
| JP2007297436A (en) | Surface modified carbon black, its dispersion and manufacturing method of the same | |
| TWI398493B (en) | Surface denaturation disperse carbon black | |
| JP5187679B2 (en) | Hydrophilic resin-dispersed carbon black and method for producing aqueous dispersion thereof | |
| JP5057265B2 (en) | Surface modified dispersible carbon black | |
| JP2007291194A (en) | Surface-modified carbon black, dispersion thereof, and method for producing the same | |
| JP2002256198A (en) | Water-based pigment dispersion, water-based ink and image-forming method using the same | |
| JP2011137058A (en) | Method for producing aqueous dispersion for inkjet recording |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |