TW200846421A - Surface modified dispersive carbon black - Google Patents

Abstract

The present invention provides a surface modified dispersive carbon black, in which the surface is modified by bonding functional groups of the carbon black surface to a single side terminal glycol modified polymer through an isocyanuric acid compound, so as to exhibit excellent dispersivity in non-polar solvents, low-polar solvents and resins. This invention is characterized in that the surface functional groups of the carbon black are bonded to one of three isocyanato groups of the isocyanuric acid compound, the other two isocyanato groups being bonded to a hydroxyl group of the single side terminal glycol modified polymer.

Description

200846421 IX. Description of the Invention: [Technical Fields of the Invention] Non-polar solvents such as eucalyptus oil or isoparaffin-based resins, etc. (4) Excellent dispersibility of the present invention relates to low-polarity solvents such as hydrocarbons, surface-induced denaturation Dispersive carbon black. [Prior Art]

Carbon black has been used as a black coloring material for black coloring pigments and watches since ancient times. Heart - Dispersibility of water as a solvent for the ink:: Black: The surface of the r is modified to enhance the opposite polarity to the non-polar It is desirable to change the dispersibility of the low-polarity solvent. For example, it is desired to develop a dispersible carbon black such as a black matrix for a composition color filter or a display device used for a paint or the like. For example, Japanese Patent Publication No. 08-337624 discloses a carbon black graft polymer excellent in dispersibility in various media such as inks for toners, photocopiers, paints, and resin colorants, and includes: Shi Xijiao into the stomach ♦ 5 substances 1, and stone black parts, the breakdown voltage when dispersed in Shixia oil is a carbon black graft polymer of 〇.5kV/mm or more. 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. Further, a reactive carbon black graft polymer comprising: a fragment (A); and a fragment (B) having a hetero-bond structure with the fragment (A), a fragment (A), is proposed in Japanese Patent Laid-Open Publication No. 09-272706 The carbon black is grafted high by reacting a polymer having a group (1) having reactivity with 2122-8880-PF 5 200846421 b b group on the surface of the carbon black, and reacting with a functional group which blocks the black surface Molecules, fragments (A), (B) have a group (2) reactive with the parent of the intended medium. SUMMARY OF THE INVENTION However, since an epoxy group is used as a reactive group, a catalyst is used for three-member open-loop opening, so that a catalyst remains in the dispersion. Further, there is no specific disclosure of the grafted carbon in which an isocyanate group and an isocyanate group are bonded via a reactive polymer. The inventors have shown good results in a non-polar solvent or a low-polar solvent, and further in a resin. The surface denaturation of the dispersive carbon black was investigated, and it was found that 'the surface denatured carbon black which reacts the surface of the carbon black with a comb structure having a long side chain, and exhibits excellent dispersion in the solutions. Sex.

The present invention is based on the above findings, and the object of the present invention is to provide a surface-denatured dispersible carbon black which is obtained by bonding a functional group of a black surface to a unilateral terminal diol denatured polymer via a triisocyanate compound. table

Denatured, in non-polar (four), low-polar solvents, resin-dispersive. J is a surface-based dispersible carbon black of the present invention which achieves the above object, and is characterized by a surface functional group of carbon black, a tri-isocyano group having a fl acid group at the three ends of the 盥/, /, π呉 structure. The acid compound ^ 0 y is a terminally blocked isocyanate group, and its two terminal isocyanato groups are bonded to a single _. , pingqiong, sterol, alcohol, denatured polymer, hydroxyl

2122-8880-PF 6 200846421 The surface denaturing and dispersible carbon of the present invention is Q ^ ^ Η ^ is a diisocyanate compound of 3 end of the scorpion knocking base and carbon black 柹 ancient eight; eve ~ f back s month 匕The base and the early terminal diol are bonded to each other, and the triisocyanate compound is used as an intermediate substance to impart a low polarity to the surface of the carbon black, such as a non-polar solvent such as a material, a fluorochemical solvent, or a resin medium. The solvent has excellent dispersibility [Embodiment]

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 it is preferable to use the electron microscopic measurement for the field use; and the secondary particle size is /3 (four). Carbon black. When the stone with a sub-particle size of less than 01/zm is anti-black, the cohesive force between the particles is large and it is easy to agglomerate. On the other hand, when it exceeds 〇·3 # m, the self-weight of the surface denaturing state becomes large, and it is easy to settle in a solvent. . - The surface-denatured dispersible carbon black of the present invention comprises: a surface B of carbon black, which is an isocyanate group having an isocyanate group at the 3 end of the heterostructure, and an isocyanate group at one end of the product. The amine s is bonded, and the other two terminal isocyanato groups are bonded to the hydroxylamine ester of the unilateral terminal diol denatured polymer. The carbon black is present on various surfaces according to its post-production process or oxidation treatment. The functional group, the kind of the functional group or the amount of the functional group can be controlled, for example, by the method described below. (1) a method of exposing carbon black to a gas atmosphere such as ozone, oxygen, N〇x, etc. via a base, a carboxyl group or a benzoquinone system; a method of treating with a low-temperature oxygen plasma; and adding hydrogen peroxide water of hexa-oxygen Peroxy 2 acid or its salts, hypohalites,

2122-8880-PF 7 200846421 A method of gas phase oxidation treatment or liquid phase oxidation treatment of a method such as dichromate, perchlorate or decanoic acid. (2) The amine group is a method in which a nitric acid/sulfuric acid mixed system is used to oxidize to form a nitro group, and a reductive agent such as 骏jun et al. ' (3) Hard base, which is a method of hardening with concentrated sulfuric acid. (4) An epoxy group is a method of reacting a hydroxyl group or a carboxyl group with a halide having an epoxy group. φ These functional groups are reacted with a diisocyanate 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 (0H0CN) with a hydroxyl group and a urea bond (NHC〇NH) with an amine group are bonded. Further, the formation of the functional group, for example, the oxidation treatment is preferably carried out until pI1 is 5 or less, and if it is carbon black having a pH of 5 or less, it can be used as it is without being subjected to oxidation treatment. The triisocyanate compound may be used without any particular limitation as long as it has an isocyanurate structure, a double-cylinder structure, an addition structure, or the like, and has an isocyanate group at the three ends, for example, The iso-cyanate structure can be exemplified by Mitsui Takeda Chemical Co., Ltd., D-177N, D-ΠΟΝ, D-170HN, D-172N, and the like. 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) The reaction formula of hexamethylene isocyanate isocyanate is carried out by the reaction of the hydroxy group on the surface of the carbon black particles with the reaction of one terminal isocyanate group and D-177N. The following chemical formula 1.

2122-8880-PF 8 200846421 (Chemical Formula 1) ^^)-0H + η

η carbon black OH οm , Ji I person CB ^OCN-CCH^-N N-(CH2)6-NC〇n

0 people

(CH^-NCO carbon black is added to a non-reactive solvent such as an ester or a ketone, and is added to a heterostructure according to an appropriate oxidation treatment to adjust the amount of the surface functional group, particularly a hydroxyl group or a carboxyl group. The triisocyanate compound having an isocyanate group at the end of 3 is stirred and mixed by a stirring defoaming machine, and further refined by a three-roll mill or the like to obtain a terminal isocyanate group and carbon black of the diisocyanate compound. Surface functional group bonding.

The surface denaturing and dispersible carbon black of the present invention is a functional group of a monoisocyanic group of triisocyanate bonded to a surface of the carbon black particle, and the remaining two terminal isocyanato groups are unilaterally- The early end of the cake is known as the hydroxy-bonded surface of the denatured polymer. The case where the oxime is a polymer having a high degree of denaturation of the terminal diol is exemplified, for example, a high alcohol ♦ (2 & hexyl carbonyl ethene) UT-1001 such as hexyl ester or octyl acrylate is exemplified below. The comb structure with a side chain length is a polyacrylic acid 2-ethyl group, and propylene-1, two materials will be used (made by Xiayan Chemical Co., Ltd.)

2122-8880-PP 9 200846421 (Chemical Formula 2)

OH again -〇Oi-(CH2)6~N N-{CH2)^NC〇 + HO~CH~CH2-S-(CH2

(CH^-NCO

CHnCI-I -CH)n c=o I <^2 >-CH ! (CH2)3 ch3 OH 111 OCN- G (CH2)6 - 〒人1|| 一 〇人 isK^o

IiO 1 !1 (CH 2)6-NCO — ?H—CH 2 - s - (CH ‘ CH〇

(CH2)6-NCCr Ml HO-CH)nc=oi ch2 ch3gh0-ch *1 carbon black (CH2)3 ch3 As in Chemical Formula 2, the surface denaturing dispersible carbon black of the present invention is a surface functional group of carbon black ( a hydroxyl group, bonded to the isocyanate group at the i-terminal of the triisocyanate compound, and the other two terminal isocyanate groups and the hydroxy bond surface of the unilateral terminal diol denatured polymer are surface-modified by Combining triisocyanate

The substance acts as an intermediate substance to bond the carbon black to the unilateral terminal diol denatured polymer. 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. The surface-denatured dispersible carbon black is obtained by adding carbon black to a non-reactive solvent such as ester or 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 the terminal isocyanate groups of the triisocyanate compound to the surface functional groups of carbon. 2122-8880-PF 10 200846421 Next, after adding the unilateral terminal diol denatured polymer to the defoaming machine for defoaming, the mixture is sufficiently kneaded by a three-roll mill or the like. Thereafter, after the mixture is diluted with a solvent, the mixture is dispersed by an ultrasonic homogenizer, a high-pressure homogenizer, a processing homogenizer, a ball mill, a bead mill, etc., to 2^(10). The temperature of c is heat-treated for a suitable period of time, and the surface is denatured by bonding the unreacted two terminal isocyanato groups of the triisocyanate compound to the amine group of the unilateral terminal diol denatured polymer.

At this time, it is easier to add a small amount of addition reaction to promote the contact or dehydration condensing agent. As an addition reaction-promoting catalyst and a dehydrating condensing agent, it can be exemplified by dibutyl-moon society deficiency 4 J丞 January, only tin sulphate, concentrated sulfuric acid, N,N,-dicyclohexylcarbodiimide, N,N ,--昱 and feces # 一吴丙奴二胺胺,Ν-ethyl-(3-dimethylaminopropyl) carbodiimide, j 铋 铋 ^ ^ Basic and two. Sit, diethyl cyanoacrylate, 1-ethoxy oxycarbyl - 2 - ethane - fluorenyl-1,2-dihydroanthracene, isobutyl chloroformate, triphenylmethane, neopentyl Methyl hydrazine, methyl hydrazine, ruthenium chloride, etc., other compounds having a ruthenium bond, or bismuth phthalic anhydride can also have the same effect. EXAMPLES Hereinafter, examples of the present invention will be specifically described in comparison with comparative examples. Example 1 The carbon dioxide black of the East China Sea carbon (4) was oxidized in an aqueous solution of sodium persulfate. The oxidized carbon black powder having an acidic functional group on the surface of the particles was obtained by drying, pulverizing and classifying, U" dance": .74 I. Based on the emulsified carbon black 25. Og added isoparaffin, the company is made from (10), moist, and then added three different

2122-8880-PF 11 200846421 hexamethylene isocyanuric acid triacetate (D-nTNMJZSg manufactured by Mitsui Takeda Chemical Co., Ltd.) as a unilateral terminal diol denatured polymer propylene-U- The diol poly(2-ethylhexylethylene) sulfide (UT-UHH: molecular weight 3500) was mixed with 17.5g, and the defoaming machine was used. The mixture was stirred for 2 minutes, and defoamed for 2 minutes to carry out pre-kneading. The pre-kneaded product was further kneaded for 30 minutes in a three-roll (8-4 3/4 <11) manufactured by Inoue Co., Ltd., and added. 1[18][111] october (shares) #制月酸酸丁丁〇.47225g dissolved in isocratic = smog solvent (ISOPAR G) at a concentration of 10wt%, further kneaded in 3 rolls for 3 minutes . At this time, since the isothermal hydrocarbon-based smog solvent is slightly volatilized, it is suitable to add an isoparaffinic hydrocarbon solvent. To the above-mentioned kneaded product, an isoparaffinic hydrocarbon solvent was added to make a total amount of 250 g, and the mixture was treated for 1 minute using an ultrasonic homogenizer (Ultra Seiki Co., Ltd.) to carry out mechanical dispersion. Thereafter, mechanical dispersion was further carried out from 5 MPa to 15 MPa using a pressure homogenizer (NAN 〇MIZER TL_i5 (10) manufactured by Tokai Co., Ltd.). The above dispersion was placed in a 1 liter separation bottle at 7 (the TC side was stirred and heated for 6 hours, added, and treated), and then the isomeric hydrocarbon-burning hydrocarbon solvent was added again to make the total amount 25Og. Wt% self-dispersed in surface-denatured carbon black dispersion 1 of an isoparaffinic hydrocarbon solvent. Example 2 Carbon black was prepared by gas phase oxidation using the same carbon black as in Example 1 to prepare PH2·5 (base group 1) · 〇# eq/m2, enemy base 3.2 private eq/m^). 2122-8880-pp 12 200846421 / m Using the carbon black, a surface-denatured carbon black dispersion was obtained by the same method as in the example. 2. Example 3 The use of channel black (Special Black 4 (PH2.3): hydroxy hydrazine 16 #eq/m 2 , carboxyl 42 / / eq / m 2 ) & In the same manner, a surface-denatured carbon black dispersion 3 was obtained. Example 4 A solvent obtained by dispersing was used in the same manner as in Example except that PGMEA (propylene glycol methyl ether acetate) was used instead of the isoparaffinic hydrocarbon solvent. Surface-denatured carbon black dispersion 4. Example 5 In the same manner as in Example 4, the isomeric hydrocarbon-based hydrocarbon solvent was replaced. In addition to the unreacted isocyanate group, the PGMEA is added to a carbon black of 20 w1:% of 5 g of an aliphatic ester alcohol (four-day synthesis (share) φ system YGN0L EHP01) in a 7 〇〇c holding step. The surface-denatured carbon black dispersion 5 was obtained by the same method as in Example 1. Example 6 As a solvent for dispersion, instead of the isomeric hydrocarbon-based hydrocarbon solvent, Shiyue Oil (KF96L-lcs manufactured by Shin-Etsu Chemical Co., Ltd.) was used. In the same manner as in Example 1, except that the reactive polymer was used in place of the unilateral terminal diol denatured polymer, which was 16.25 g of a unilateral terminal diol-modified phthalocyanine polymer (FM-DA21: molecular weight: 5000). A method of obtaining a surface-denatured carbon black dispersion 6 〇 2122-8880-PP 13 200846421 % Example 7 In the same manner as in Example 4, a surface was obtained in the same manner as in Example 1 except that pgmea was used as a solvent for dispersion. The denatured carbon black dispersion 'mixed and added mercapto acrylate resin 31·3 g as a resin, ILGACURE 907 (manufactured by Ciba Speciality Chemicals), 4 7 g, as a photopolymerization initiator, to prepare a resin composition 1. Example 8 Using carbon black not oxidized (Tunghai carbon (TB) TB#7550, pH 6~7 (hydroxy 〇·13/z eq/m2, carboxy 〇·37 from //m2) by using the example In the same manner, a surface-denatured carbon black dispersion 7 was obtained. Comparative Example 1 In the same manner as in Example 1, except that a triisocyanate compound was not used, a surface-denatured carbon black dispersion 8 was obtained. Example 2 φ The resin composition 2 was produced in the same manner as in Example 7 except that carbon black (Tunghai carbon (TB) 750#F) which was not subjected to oxidation treatment was used. With respect to the obtained dispersions 1 to 8, the average particle diameter of the carbon black aggregates in the dispersion was measured by using a heterodyne laser Doppler particle size distribution measuring apparatus (934 〇 υ υ Α Α Α 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 The viscosity of the dispersion was measured by a vibrating viscometer (VM-1G0A-L manufactured by Yamaichi Electric Co., Ltd.). The time-dependent changes in the measurement results are shown in Table i. In addition, the resin composition was dropped onto a hard: glass, and a film having a thickness of 13·7 μm was produced using a bar coater (R〇d N〇2122-8880-PF 14 200846421 6 manufactured by CEDARS SERVICE, Japan). To make it harden, the appearance is evaluated, and the blackness is measured by a Macbeth blackness meter (Tr-927 manufactured by Macbeth Co., Ltd.), and the super insulation meter (East Asia MK (share) floc, t~士二 SM- 8220) The surface resistance was measured, not shown in Table 2. Lu made direct average particle size (nm) Viscosity (cP) Average particle size after 1 week (nm) Viscosity (cP) Average particle size after 2 weeks (nm) Viscosity (cP) Average particle size after 3 weeks (nm) Viscosity ( cP) Average particle size (nm) after 4 weeks Viscosity (cP) Dispersion 1 146 1.45 196 1.19 161 1.23 154 1.24 1521.22

2601.21 156 1.48 166 1.30 168 1.31 170 L31 dispersion 3 dispersion dispersion 5 dispersion 6 dispersion 7 dispersion 8 304 Ί ί Λ 201 212 190 490 2045 1.14 丄51 1.52 1.56 1.34 0.80 359 1 r\ Λ 208 215 195 516 2225 1. 08 —~ 丄40 1.41 L37 1.29 0.90 456 220 218 202 513 2190 _1.42 1.43 1.45 1.31 0. 93 434 232 223 208 521 2188 1.16 丄44 1.45 1.51 1.34 0. 94 445 240 230 212 527 2195 1 · 14 ^— 丄46 1.46 1.50 1.37 0. 92 Table 2 Appearance of resin composition Dispersibility Good film thickness (from m) 13. 2 Blackness (0. D.) 3. 6 Surface resistance (Ω / □) 4. Lxl〇8

As shown in Tables 1 to 2, the dispersoid J dispersion dispersion 8 was excellent in dispersibility, and the dispersion 3 was slightly inferior in dispersibility due to the larger particle size of the dispersions 1 and 4 and 5 carbon black. However, both the dispersion 3 and the batch μ 77 regime 7 are not unusable. The range of 2122-8880-PF 15 200846421 is sufficient for 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 =, black coagulation and precipitation, blackness and surface resistance are also in the resin composition.

1 is preferred. J industry profitability

The surface-denatured dispersible carbon black of the present invention is used as a black pigment for a black matrix or an electronic paper display medium, etc., and is not required by the staff. [Simple description of the drawing] None 】 Main component symbol description]

2122-8880~pp 16

Claims (1)

200846421 % X. Patent Application Range: 1. A surface-denatured dispersible carbon black characterized by a surface functional group of carbon black and a triisocyanate compound having an isocyanate group at the 3 terminal end of the heterostructure. The terminal isocyanate-bonded, and the other two terminal isocyanato groups are bonded to the hydroxyl group of the unilateral terminal diol denatured polymer. 2122-8880-PF 17 200846421 VII. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: Benefit 2122-8880-PF 4