JP2000212468A - Surface treated carbon black, its production and aqueous dispersion containing it - Google Patents
Surface treated carbon black, its production and aqueous dispersion containing itInfo
- Publication number
- JP2000212468A JP2000212468A JP1507799A JP1507799A JP2000212468A JP 2000212468 A JP2000212468 A JP 2000212468A JP 1507799 A JP1507799 A JP 1507799A JP 1507799 A JP1507799 A JP 1507799A JP 2000212468 A JP2000212468 A JP 2000212468A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- treated carbon
- surface treatment
- general formula
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 103
- 239000006185 dispersion Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims abstract description 26
- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000004381 surface treatment Methods 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000012756 surface treatment agent Substances 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 239000012736 aqueous medium Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 125000003277 amino group Chemical group 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000011324 bead Substances 0.000 description 8
- 239000008213 purified water Substances 0.000 description 8
- 125000004151 quinonyl group Chemical group 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 6
- 239000000976 ink Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- -1 dimethylamino, diethylamino, dibutylamino Chemical group 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 241000872198 Serjania polyphylla Species 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UTDLLFNRQRIZTJ-UHFFFAOYSA-N C1=CC2=C(C=CC(=C2C(=C1)O)N)S(=O)(=O)[O-].[NH4+] Chemical compound C1=CC2=C(C=CC(=C2C(=C1)O)N)S(=O)(=O)[O-].[NH4+] UTDLLFNRQRIZTJ-UHFFFAOYSA-N 0.000 description 1
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000008135 aqueous vehicle Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- KIAOUBCOZQOKRD-UHFFFAOYSA-M potassium;4-amino-5-hydroxynaphthalene-1-sulfonate Chemical compound [K+].C1=CC(O)=C2C(N)=CC=C(S([O-])(=O)=O)C2=C1 KIAOUBCOZQOKRD-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は表面処理されたカーボン
ブラック及びそれを含む水性分散体に関する。The present invention relates to a surface-treated carbon black and an aqueous dispersion containing the same.
【０００２】[0002]
【従来の技術】カーボンブラックは、着色顔料や遮光材
料として印刷インキ、塗料、プラスチック形成材料など
幅広い分野で使用されている。従来、これらの用途にお
いてはカーボンブラックを有機媒体に分散して使用する
ことが一般的であったが、最近では環境問題や人体への
影響という観点から水性化への転換が急速に進行しつつ
ある。しかしながら、カーボンブラックの多くは本来親
油性であり、水性ビヒクルに対する顔料分散性などの適
性が大幅に劣るため、通常の分散方法では満足な分散体
は得られない。そこで、従来より各種の添加剤、例えば
界面活性剤などの分散剤や水性顔料分散樹脂を用いてカ
ーボンブラックの表面を修飾し、水中分散性を付与させ
るといった方法が検討されてきた。しかし、カーボンブ
ラック粒子表面の修飾が不十分である場合には粒子同士
が容易に再凝集し分散安定性が損なわれる、また、分散
剤と分散樹脂との相溶性が悪い場合にはインキや塗料の
性能低下を招くといった問題があった。その上、用途に
合わせて分散樹脂を変更すればそれに伴い分散剤を選択
しなければならず、汎用性に欠けるといった問題もあっ
た。2. Description of the Related Art Carbon black is used in a wide range of fields such as printing inks, paints, and plastic forming materials as coloring pigments and light-shielding materials. Conventionally, in these applications, carbon black was generally used by dispersing it in an organic medium. Recently, however, the conversion to water-based has been rapidly progressing from the viewpoint of environmental problems and impact on the human body. is there. However, many carbon blacks are inherently lipophilic, and their suitability such as pigment dispersibility in an aqueous vehicle is significantly inferior. Therefore, a satisfactory dispersion cannot be obtained by a usual dispersion method. Therefore, conventionally, a method of modifying the surface of carbon black with various additives, for example, a dispersant such as a surfactant or an aqueous pigment-dispersed resin to impart dispersibility in water has been studied. However, when the surface of the carbon black particles is insufficiently modified, the particles easily re-aggregate and the dispersion stability is impaired, and when the compatibility between the dispersant and the dispersing resin is poor, inks and paints are used. However, there is a problem that the performance is deteriorated. In addition, if the dispersing resin is changed according to the application, a dispersing agent must be selected accordingly, and there is a problem that versatility is lacking.
【０００３】一方、カーボンブラックに水中分散性を付
与するための種々の試みがなされ、その一つとしてカー
ボンブラックの酸化処理による親水化処理がある。酸化
処理方法としてはオゾン処理、プラズマ処理などの気相
酸化法と硝酸や過酸化水素水、過塩素酸ソーダなどを用
いる液相酸化法が考案されている。一般的な酸化処理条
件を比較すると気相酸化より液相酸化の方が効果が高
く、液相酸化の中でも、硝酸の方が過酸化水素水と比較
し表面酸性度の増加の程度が大きく、親水性をより一層
向上させることが知られている。しかし、液相酸化は処
理後の精製が困難という欠点を持つ。特に硝酸酸化で得
られたカーボンブラックについては変異原性の問題が指
摘されている。一方、気相酸化は、精製工程を必要とし
ない利点があるが、先述の通り酸性度が低いために十分
な親水性が得られないという欠点を持つ。[0003] On the other hand, various attempts have been made to impart dispersibility in water to carbon black, and one of them is a hydrophilic treatment by oxidizing carbon black. As the oxidation treatment method, a gas phase oxidation method such as ozone treatment and plasma treatment, and a liquid phase oxidation method using nitric acid, hydrogen peroxide solution, sodium perchlorate, and the like have been devised. Comparing general oxidation treatment conditions, liquid-phase oxidation is more effective than gas-phase oxidation, and among liquid-phase oxidations, nitric acid has a greater degree of increase in surface acidity than hydrogen peroxide solution, It is known that the hydrophilicity is further improved. However, liquid phase oxidation has the disadvantage that purification after treatment is difficult. In particular, the problem of mutagenicity has been pointed out for carbon black obtained by nitric acid oxidation. On the other hand, gas phase oxidation has the advantage of not requiring a purification step, but has the drawback that sufficient hydrophilicity cannot be obtained due to low acidity as described above.
【０００４】その他の方法として、フッ素ガスを用いた
親水化処理法が考案されているが、保存中の性能安定性
に問題を有している。[0004] As another method, a hydrophilization treatment method using fluorine gas has been devised, but has a problem in performance stability during storage.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、水性媒体に
対し、これらの欠点がない優れた分散性及び分散安定性
を有する表面処理カーボンブラックならびにその製造方
法及びそれを含む水性分散体を提供することにある。DISCLOSURE OF THE INVENTION The present invention provides a surface-treated carbon black having excellent dispersibility and dispersion stability which does not have these drawbacks in an aqueous medium, a method for producing the same, and an aqueous dispersion containing the same. Is to do.
【０００６】[0006]
【課題を解決するための手段】すなわち本発明は、下記
一般式（１）で表される表面処理剤でカーボンブラック
粒子の表面を処理したことを特徴とする表面処理カーボ
ンブラックである。 一般式（１）That is, the present invention is a surface-treated carbon black characterized by treating the surface of carbon black particles with a surface-treating agent represented by the following general formula (1). General formula (1)
【０００７】[0007]
【化３】 Embedded image
【０００８】〔式中、Ｒ1 、Ｒ2 はそれぞれ水素原子ま
たは炭素数１〜４のアルキル基を表し（Ｒ1 、Ｒ2 が一
体となって環を形成してもよい。）、Ｍは水素原子、ア
ルカリ金属原子、アンモニウムまたはアミンを表し、
ｍ、ｎは０〜３の整数を表し、１≦ｍ＋ｎ≦３であ
る。〕 さらに本発明は、表面処理前のカーボンブラックの全表
面官能基量が０．２ミリ当量／ｇ以上であることを特徴
とする上記の表面処理カーボンブラックである。さらに
本発明は、上記の発明いずれか記載の表面処理カーボン
ブラックを含む水性分散体である。[In the formula, R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (R 1 and R 2 may be combined to form a ring), and M is Represents a hydrogen atom, an alkali metal atom, ammonium or an amine,
m and n represent an integer of 0 to 3, and 1 ≦ m + n ≦ 3. Further, the present invention is the above-mentioned surface-treated carbon black, wherein the total surface functional group content of the carbon black before the surface treatment is 0.2 meq / g or more. Furthermore, the present invention is an aqueous dispersion containing the surface-treated carbon black according to any one of the above-mentioned inventions.
【０００９】さらに本発明は、カーボンブラックを一般
式（１）で表される表面処理剤を含む溶液中において粉
砕機または分散機によるせん断応力またはメディアによ
る衝撃力によって微分散させながら表面処理することを
特徴とする表面処理カーボンブラックの製造方法であ
る。さらに本発明は、微分散させる工程中またはその前
後に４０℃〜１００℃で加熱処理を行うことを特徴とす
る上記の表面処理カーボンブラックの製造方法である。Further, the present invention provides a method for surface-treating carbon black in a solution containing a surface-treating agent represented by the general formula (1) while finely dispersing the solution by a shearing force by a pulverizer or a disperser or an impact force by a medium. A method for producing a surface-treated carbon black characterized by the following. Furthermore, the present invention is the above-mentioned method for producing a surface-treated carbon black, wherein a heat treatment is performed at 40 ° C. to 100 ° C. during or before and after the step of finely dispersing.
【００１０】[0010]
【発明の実施の形態】以下本発明について詳細に説明す
る。本発明に用いるカーボンブラックとしては、特に種
類や製造履歴に制約されることはなく、市販のオイルフ
ァーネスブラック、ガスファーネスブラック、サーマル
ブラック、アセチレンブラック、チャンネルブラックな
ど各種のものを用いることができる。また、通常行われ
ているオゾン処理、プラズマ処理、液相酸化処理された
カーボンブラックも使用できる。さて、カーボンブラッ
クは、その製造過程において、粒子表面にカルボキシル
基（−ＣＯＯＨ）、フェノール性水酸基（−ＯＨ）、キ
ノン基（＞Ｃ＝Ｏ）といった表面官能基が一般に生成さ
れる。これらの官能基の定量は、カルボキシル基（−Ｃ
ＯＯＨ）およびフェノール性水酸基（−ＯＨ）について
は滴定法によって、また、キノン基（＞Ｃ＝Ｏ）につい
ては水素化硼素ナトリウムの水素吸収法によってそれぞ
れ求めることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The carbon black used in the present invention is not particularly limited by the type and production history, and various types such as commercially available oil furnace black, gas furnace black, thermal black, acetylene black, and channel black can be used. In addition, carbon black subjected to ordinary ozone treatment, plasma treatment, and liquid phase oxidation treatment can also be used. Now, in the process of producing carbon black, surface functional groups such as a carboxyl group (—COOH), a phenolic hydroxyl group (—OH), and a quinone group (> C ＝ O) are generally generated on the particle surface. The quantification of these functional groups is based on the carboxyl group (-C
OOH) and phenolic hydroxyl group (-OH) can be determined by a titration method, and quinone group (> C = O) can be determined by a hydrogen absorption method of sodium borohydride.
【００１１】本発明に用いるカーボンブラックにおける
上記の表面官能基の全量、すなわち、全表面官能基量は
０．２〜８．０ミリ当量／ｇが好ましく、１．０〜６．
０ミリ当量／ｇが特に好ましい。全表面官能基量が０．
２ミリ当量／ｇより少ないと、表面処理剤の吸着あるい
は反応点が少ないために十分な表面処理効果を得ること
ができない。一方、全表面官能基量が８．０ミリ当量／
ｇより多いカーボンブラックを用いた場合は、表面処理
の顕著な効果が現れにくい。また、全表面官能基量に占
める各官能基の比率については特に制限はないが、カル
ボキシル基の含有量の多い方が好ましい。The total amount of the above surface functional groups in the carbon black used in the present invention, that is, the total amount of the surface functional groups is preferably from 0.2 to 8.0 meq / g, more preferably from 1.0 to 6.
0 meq / g is particularly preferred. The total surface functional group content is 0.
If the amount is less than 2 meq / g, a sufficient surface treatment effect cannot be obtained because the surface treatment agent is adsorbed or the reaction site is small. On the other hand, the total surface functional group content was 8.0 meq /
When more than g of carbon black is used, a remarkable effect of the surface treatment is hardly exhibited. Further, the ratio of each functional group to the total surface functional group amount is not particularly limited, but it is preferable that the content of the carboxyl group is large.
【００１２】本発明に用いるカーボンブラックの粒径
は、通常のインキや塗料に用いるカーボンブラックの粒
径範囲と同様に０．０１〜１０μｍが好ましく、０．０
１〜０．５μｍが特に好ましい。ただし、ここで言う粒
径とは電子顕微鏡などで測定された平均一次粒子径を示
し、この物性値は一般にカーボンブラックの物理的特性
を表すのに用いられている。本発明における表面処理剤
は一般式（１）で表され、分子中、α−ナフトールスル
ホン酸（塩）の水酸基に対してペリ位にアミノ基が置換
したα−ナフトール-モノ〜トリ-スルホン酸（塩）であ
る。 一般式（１）The particle size of the carbon black used in the present invention is preferably 0.01 to 10 μm, similarly to the range of the particle size of the carbon black used for ordinary inks and coatings.
1 to 0.5 μm is particularly preferred. However, the particle size referred to here indicates an average primary particle size measured by an electron microscope or the like, and the physical property values are generally used to represent physical properties of carbon black. The surface treating agent in the present invention is represented by the general formula (1), and α-naphthol-mono to tri-sulfonic acid in which the amino group is substituted at the peri-position to the hydroxyl group of α-naphtholsulfonic acid (salt) in the molecule. (Salt). General formula (1)
【００１３】[0013]
【化４】 Embedded image
【００１４】〔式中、Ｒ1 、Ｒ2 はそれぞれ水素原子ま
たは炭素数１〜４のアルキル基を表し（Ｒ1 、Ｒ2 が一
体となって環を形成してもよい。）、Ｍは水素原子、ア
ルカリ金属原子、アンモニウムまたはアミンを表し、
ｍ、ｎは０〜３の整数を表し、１≦ｍ＋ｎ≦３であ
る。〕 一般式（１）で表される表面処理剤に含有されるアミノ
基としては、１級アミノ基（−ＮＨ2 ）およびメチルア
ミノ基、エチルアミノ基、ブチルアミノ基などの２級ア
ミノ基、ジメチルアミノ基、ジエチルアミノ基、ジブチ
ルアミノ基、ピペリジノ基などの３級アミノ基を例示で
きる。これらのアミノ基は、カーボンブラックの表面官
能基のうち酸性を示すカルボキシル基（−ＣＯＯＨ）お
よびフェノール性水酸基（−ＯＨ）に対して酸−塩基相
互作用によって吸着し、特に１級アミノ基（−ＮＨ2 ）
については、酸−塩基相互作用のみならず、キノン基
（＞Ｃ＝Ｏ）とのアゾメチン結合（＞Ｃ＝Ｎ−）形成に
よって大きな表面処理効果が得られると考えられる。[Wherein, R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (R 1 and R 2 may form a ring together), and M is Represents a hydrogen atom, an alkali metal atom, ammonium or an amine,
m and n represent an integer of 0 to 3, and 1 ≦ m + n ≦ 3. The amino group contained in the surface treatment agent represented by the general formula (1) includes a primary amino group (—NH 2 ) and a secondary amino group such as a methylamino group, an ethylamino group, and a butylamino group; Examples include tertiary amino groups such as dimethylamino, diethylamino, dibutylamino, and piperidino. These amino groups are adsorbed to the carboxyl group (—COOH) and the phenolic hydroxyl group (—OH), which are acidic among the surface functional groups of carbon black, by an acid-base interaction. NH 2 )
It is thought that a large surface treatment effect can be obtained not only by acid-base interaction but also by formation of an azomethine bond (> C = N-) with a quinone group (> C = O).
【００１５】一般式（１）で表される表面処理剤に含有
されるスルホン酸（塩）基は、式中のＭが水素の場合は
スルホン酸を表し、Ｍがアルカリ金属、アンモニウムま
たはアミンの場合はスルホン酸塩を表す。一般式（１）
中のＭが水素原子、すなわちスルホン酸の場合、表面処
理剤に含まれるアミノ基と相互作用し、表面処理剤同士
が分子間会合を起こしてカーボンブラックの表面官能基
へのアミノ基の吸着または反応が阻害され、十分な表面
処理効果が得られない場合がある。このような場合、表
面処理の工程前または工程中に、スルホン酸をアルカリ
金属、アンモニアまたはアミンによって中和して用いる
ことにより目的とする表面処理カーボンブラックを得る
ことができる。一般式（１）におけるスルホン酸（塩）
基はアニオン性であり表面処理カーボンブラックに親水
性を付与している。The sulfonic acid (salt) group contained in the surface treatment agent represented by the general formula (1) represents a sulfonic acid when M is hydrogen, and M represents an alkali metal, ammonium or amine. In the case, it represents a sulfonate. General formula (1)
When M in the formula is a hydrogen atom, that is, a sulfonic acid, the M interacts with an amino group contained in the surface treatment agent, and the surface treatment agents cause intermolecular association to adsorb the amino group to the surface functional group of the carbon black. In some cases, the reaction is inhibited, and a sufficient surface treatment effect cannot be obtained. In such a case, the target surface-treated carbon black can be obtained by neutralizing the sulfonic acid with an alkali metal, ammonia or an amine before or during the surface treatment step. Sulfonic acid (salt) in general formula (1)
The groups are anionic and impart hydrophilicity to the surface-treated carbon black.
【００１６】本発明で用いる表面処理剤の具体例として
は、１−アミノ−８−ヒドロキシナフタレン−２、４−
ジスルホン酸、１−アミノ−８−ヒドロキシナフタレン
−３、６−ジスルホン酸、１−アミノ−８−ヒドロキシ
ナフタレン−４−スルホン酸、またはこれらのアルカリ
金属塩、アンモニウム塩、アミン塩などを挙げることが
できる。また、これらの表面処理剤は単独あるいは２種
類以上混合して用いてもよい。本発明における表面処理
剤の添加量は、カーボンブラック１ｇに対して０．０１
〜１０ｍモルが好ましく、０．１〜５ｍモルが特に好ま
しい。添加量が０．０１ｍモルより少ない場合は、カー
ボンブラック粒子表面への表面処理剤の吸着量あるいは
反応量が少ないために満足な表面処理効果が得られな
い。一方、添加量が１０ｍモルより多い場合は、顕著な
表面処理の効果が現れにくい。Specific examples of the surface treatment agent used in the present invention include 1-amino-8-hydroxynaphthalene-2,4-
Examples thereof include disulfonic acid, 1-amino-8-hydroxynaphthalene-3, 6-disulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid, and alkali metal salts, ammonium salts, and amine salts thereof. it can. These surface treatment agents may be used alone or in combination of two or more. The amount of the surface treatment agent added in the present invention is 0.01 to 1 g of carbon black.
It is preferably from 10 to 10 mmol, particularly preferably from 0.1 to 5 mmol. If the addition amount is less than 0.01 mmol, a satisfactory surface treatment effect cannot be obtained because the adsorption amount or reaction amount of the surface treatment agent on the surface of the carbon black particles is small. On the other hand, if the added amount is more than 10 mmol, a remarkable effect of the surface treatment is hardly exhibited.
【００１７】本発明における表面処理カーボンブラック
は、上記のような表面処理剤をカーボンブラックと混合
撹拌することによって得られる。好ましくは、表面処理
剤を含む溶液中、粉砕機または分散機を用いてせん断応
力またはメディアの衝撃力によりカーボンブラックを微
分散させながら表面処理操作を行うのがよい。カーボン
ブラックの分散操作なしに表面処理を行った場合、カー
ボンブラック粒子の凝集体表面のみに処理効果を与える
のに対し、カーボンブラック粒子の凝集体を微分散させ
ながら処理を行った場合、より微細な粒子表面に表面処
理効果を与え、従って、水性媒体に対する分散性を向上
させることができる。The surface-treated carbon black of the present invention can be obtained by mixing and stirring the above-mentioned surface treating agent with carbon black. Preferably, the surface treatment operation is performed while finely dispersing the carbon black in a solution containing the surface treatment agent by using a pulverizer or a disperser by a shear stress or an impact force of a medium. When the surface treatment is performed without the dispersion operation of carbon black, the treatment effect is given only to the surface of the aggregate of the carbon black particles, whereas when the treatment is performed while the aggregate of the carbon black particles is finely dispersed, the finer The surface treatment effect can be given to the surface of the fine particles, so that the dispersibility in an aqueous medium can be improved.
【００１８】本発明において用いることができる粉砕機
または分散機としては、せん断応力によりカーボンブラ
ック粒子を微分散させる３本ロールミルや２本ロールミ
ル、ガラスビーズやジルコニアビーズなどのメディアの
衝撃力によりカーボンブラック粒子を微分散させるボー
ルミル、アトライター、サンドミル、コボールミル、バ
スケットミル、振動ミル、ペイントコンディショナーな
どや、せん断応力、キャビテーション、衝突力、ポテン
シャルコアなどを発生させるような回転羽根によって微
分散させるディスパー、ホモジナイザー、クレアミック
ス（エム・テクニック株式会社登録商標）などや、カー
ボンブラック粒子同士またはカーボンブラック粒子とビ
ヒクルや分散機壁面の衝突力やせん断力によって微分散
させるニーダー、エクストルーダー、ジェットミルなど
や、超音波により微分散させる超音波分散機などを挙げ
ることができる。Examples of the pulverizer or disperser that can be used in the present invention include a three-roll mill or two-roll mill for finely dispersing carbon black particles by shear stress, and carbon black by the impact force of media such as glass beads and zirconia beads. Dispersers and homogenizers that finely disperse particles by ball mills, attritors, sand mills, co-ball mills, basket mills, vibration mills, paint conditioners, etc., and rotating blades that generate shear stress, cavitation, collision force, potential core, etc. , CLEARMIX (registered trademark of M Technique Co., Ltd.), and a kneader that finely disperses carbon black particles by collision force or shear force between carbon black particles or between vehicle and dispersing machine wall, Custo ruder, or a jet mill, and the like ultrasonic disperser for finely dispersed by ultrasound.
【００１９】本発明において、表面処理剤を含む溶液
中、カーボンブラックを微分散させる工程中またはその
前後に加熱処理を行っても良い。加熱処理温度に特に限
定はないが、４０℃〜１００℃であることが好ましい。
本発明の表面処理カーボンブラックの製造工程において
用いる溶剤は、水、有機溶剤およびそれらの混合液であ
る。表面処理剤を溶解するものであれば特に限定はない
が、作業性、環境安全性を考慮し、水または水と相溶す
る有機溶剤の混合液が好ましい。水と相溶する有機溶剤
としては、例えば、メチルアルコール、エチルアルコー
ル、イソプロピルアルコールなどの低級アルコール類、
Ｎ,Ｎ-ジメチルホルムアミド、ジメチルアセトアミドな
どのアミド類、アセトン、ジアセトンアルコールなどの
ケトン類、テトラヒドロフラン、ジオキサンなどのエー
テル類、Ｎ−メチル−２−ピロリドンなどを挙げること
ができるがこれに限定されるものではない。In the present invention, heat treatment may be performed before or after the step of finely dispersing the carbon black in the solution containing the surface treating agent. Although the heat treatment temperature is not particularly limited, it is preferably from 40C to 100C.
The solvent used in the production process of the surface-treated carbon black of the present invention is water, an organic solvent, and a mixture thereof. There is no particular limitation as long as it dissolves the surface treatment agent, but in view of workability and environmental safety, water or a mixed solution of an organic solvent compatible with water is preferable. Examples of the organic solvent compatible with water include methyl alcohol, ethyl alcohol, lower alcohols such as isopropyl alcohol,
Examples include, but are not limited to, amides such as N, N-dimethylformamide and dimethylacetamide, ketones such as acetone and diacetone alcohol, ethers such as tetrahydrofuran and dioxane, and N-methyl-2-pyrrolidone. Not something.
【００２０】なお、表面処理が終了した後に、カーボン
ブラックに含有する余剰の表面処理剤を、溶剤によって
精製、洗浄することが好ましいが、そのまま使用するこ
とも可能である。本発明の表面処理カーボンブラックを
含む水性分散体は、表面処理カーボンブラックを水性媒
体や樹脂を含む媒体中に分散することによって得られ
る。ここで水性媒体とは、水または水と相溶する有機溶
剤の混合液を表す。係る有機溶剤としては、例えば、メ
チルアルコール、エチルアルコール、イソプロピルアル
コールなどの低級アルコール類、Ｎ,Ｎ-ジメチルホルム
アミド、ジメチルアセトアミドなどのアミド類、アセト
ン、ジアセトンアルコールなどのケトン類、テトラヒド
ロフラン、ジオキサンなどのエーテル類、Ｎ−メチル−
２−ピロリドンなどを挙げることができる。また樹脂と
しては、通常の水性塗料用に用いられるアクリル樹脂、
ウレタン樹脂、ポリオキシアルキレン樹脂、ビニル系樹
脂、エポキシ樹脂、アミノ樹脂、ポリビニルアセタール
樹脂、ポリビニルブチラール樹脂、スチレン系樹脂、フ
ェノキシ樹脂、ポリエステル樹脂などの水溶性または水
分散性の樹脂を挙げることができ、これらを単独あるい
は２種類以上混合して用いることができる。これらの樹
脂は水溶液型、エマルション型などその形態に特に制限
はない。また、分散性または分散安定性の向上を目的と
して界面活性剤などの分散剤、消泡剤や防腐剤などの各
種添加剤を用いてもよい。After the surface treatment is completed, it is preferable to purify and wash the surplus surface treating agent contained in the carbon black with a solvent, but it is also possible to use it as it is. The aqueous dispersion containing the surface-treated carbon black of the present invention can be obtained by dispersing the surface-treated carbon black in an aqueous medium or a medium containing a resin. Here, the aqueous medium refers to water or a mixed solution of an organic solvent compatible with water. Examples of such organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; amides such as N, N-dimethylformamide and dimethylacetamide; ketones such as acetone and diacetone alcohol; tetrahydrofuran; dioxane; Ethers, N-methyl-
2-pyrrolidone and the like can be mentioned. As the resin, acrylic resin used for ordinary water-based paint,
Water-soluble or water-dispersible resins such as urethane resins, polyoxyalkylene resins, vinyl resins, epoxy resins, amino resins, polyvinyl acetal resins, polyvinyl butyral resins, styrene resins, phenoxy resins, and polyester resins can be given. These can be used alone or in combination of two or more. These resins are not particularly limited in form such as an aqueous solution type and an emulsion type. Further, for the purpose of improving dispersibility or dispersion stability, a dispersant such as a surfactant and various additives such as an antifoaming agent and a preservative may be used.
【００２１】本発明の表面処理カーボンブラックを水性
媒体や樹脂を含む媒体中に分散する方法は特に制限はな
く、前述の表面処理カーボンブラックの製造工程で例示
した各種分散機または粉砕機を用いることができる。本
発明の表面処理カーボンブラックは、表面処理剤のアミ
ノ基がカーボンブラック粒子表面の官能基へ酸−塩基的
な相互作用により吸着する。特に１級アミノ基（−ＮＨ
2 ）については、酸−塩基相互作用以外にキノン基（＞
Ｃ＝Ｏ）とアゾメチン結合（＞Ｃ＝Ｎ−）を形成する。
いずれの場合も、表面処理剤のスルホン酸（塩）基部分
がカーボンブラック粒子表面に配位することによって水
性媒体への分散性が向上するものと考えられる。本発明
における表面処理剤の作用機構は次のように推定され
る。表面処理剤のアミノ基はカーボンブラック粒子表面
の官能基と造塩するか、またはアゾメチン結合を形成す
る。また、表面処理剤のスルホン酸（塩）基部分は水性
媒体への分散性に寄与する。水酸基は下記一般式（２）
および（３）に表したようにアミノ基の窒素原子と水素
結合することにより、カーボンブラックと表面処理剤の
造塩体またはアゾメチン結合を熱力学的に安定化させる
ことによりカーボンブラックと表面処理剤とを強固に結
合させる機能を持つ。The method for dispersing the surface-treated carbon black of the present invention in an aqueous medium or a medium containing a resin is not particularly limited, and various dispersing machines or pulverizers exemplified in the above-mentioned process for producing the surface-treated carbon black may be used. Can be. In the surface-treated carbon black of the present invention, the amino group of the surface-treating agent is adsorbed to the functional group on the surface of the carbon black particles by an acid-base interaction. Particularly, a primary amino group (—NH
2 ) In addition to the acid-base interaction, a quinone group (>
C = O) to form an azomethine bond (> C = N-).
In any case, it is considered that the sulfonic acid (salt) group portion of the surface treatment agent coordinates to the surface of the carbon black particles to improve the dispersibility in an aqueous medium. The mechanism of action of the surface treatment agent in the present invention is presumed as follows. The amino group of the surface treating agent forms a salt with a functional group on the surface of the carbon black particles or forms an azomethine bond. The sulfonic acid (salt) group portion of the surface treatment agent contributes to dispersibility in an aqueous medium. The hydroxyl group is represented by the following general formula (2)
And hydrogen bonding to the nitrogen atom of the amino group as shown in (3), thereby stabilizing the salt-form or azomethine bond between the carbon black and the surface treating agent thermodynamically, thereby forming the carbon black and the surface treating agent. And has the function of firmly combining
【００２２】一般式（２）General formula (2)
【００２３】[0023]
【化５】 Embedded image
【００２４】〔式中、Ｒ1 、Ｒ2、Ｍ、ｍ、ｎは上記と
同じ意味を表す。〕 一般式（３）[Wherein, R 1 , R 2 , M, m, and n have the same meaning as described above. General formula (3)
【００２５】[0025]
【化６】 Embedded image
【００２６】〔式中、Ｒ1 、Ｒ2、Ｍ、ｍ、ｎは上記と
同じ意味を表す。〕 すなわち、本発明における表面処理剤の分子構造上の最
も重要な点は、ナフタレン環のペリ位にアミノ基と水酸
基とが置換していることである。それによって表面処理
剤がカーボンブラック粒子表面に強固に吸着または化学
結合することができると考えられる。それゆえ、α−ナ
フトールの水酸基のペリ位にアミノ基が置換したα−ナ
フトール-モノ〜トリ-スルホン酸（塩）類であることに
優れた分散効果の要因があるのであって、ナフタレン環
上のそれ以外の位置にたとえ他の置換基があっても水酸
基中水素原子による六員環構造形成の範疇を越えるもの
ではない。すなわち、その六員環上の水素結合力を電子
論的に多少強めることはあるが、本質的な点ではなく、
同一線上に包含されるものである。以上述べた作用機構
により、本発明の表面処理カーボンブラックを含む水性
分散体は、優れた分散安定性を有し、高漆黒性、高光
沢、高濃度な塗布膜を得ることができる。Wherein R 1 , R 2 , M, m and n have the same meaning as described above. That is, the most important point in the molecular structure of the surface treatment agent in the present invention is that an amino group and a hydroxyl group are substituted at the peri-position of the naphthalene ring. Thereby, it is considered that the surface treating agent can be strongly adsorbed or chemically bonded to the surface of the carbon black particles. Therefore, α-naphthol-mono to tri-sulfonic acids (salts) in which an amino group is substituted at the peri position of the hydroxyl group of α-naphthol have an excellent dispersing effect. Even if other substituents are present at other positions, the above does not exceed the category of forming a six-membered ring structure by a hydrogen atom in the hydroxyl group. That is, although the hydrogen bonding force on the six-membered ring may be somewhat enhanced electronically, it is not an essential point,
They are included on the same line. By the action mechanism described above, the aqueous dispersion containing the surface-treated carbon black of the present invention has excellent dispersion stability, and can provide a coating film with high jet-blackness, high gloss, and high concentration.
【００２７】なお、本発明の表面処理カーボンブラック
及びそれを含む水性分散体は、印刷インキ、塗料、化粧
品、筆記用インキ、トナー、電子写真用材料、インクジ
ェットなどの記録材料、プラスチックなどの着色剤など
広範囲の分野に利用可能である。The surface-treated carbon black of the present invention and the aqueous dispersion containing the same may be used as printing inks, paints, cosmetics, writing inks, toners, electrophotographic materials, recording materials such as ink jets, and colorants such as plastics. It can be used in a wide range of fields.
【００２８】[0028]
【実施例】本発明を実施例を用いて説明する。例中、
「部」「％」は、それぞれ「重量部」「重量％」であ
る。実施例で用いたカーボンブラックの各表面官能基量
は、下記の方法により測定し、それらを合計し全表面官
能基量を求めた。その結果を表１に示した。 （１）カルボキシル基（−ＣＯＯＨ）量の測定 乾燥カーボンブラック１ｇを１ｍｇ単位で秤量し、０．
１規定の炭酸水素ナトリウム水溶液５０ｍｌ中で４時間
振盪して反応させた後、濾過し、濾液の上澄み液２０ｍ
ｌを採取して０．０１規定の塩酸水溶液で滴定する。カ
ルボキシル基量は、カーボンブラック１ｇ中のミリ当量
（ｍｅｑ．／ｇ）として下式に従って求めた。 カルボキシル基量＝（50／20×0.01×( 滴定量−空滴定
量) ）／カーボンブラック試料重量 （２）水酸基（−ＯＨ）量の測定 乾燥カーボンブラック１ｇを１ｍｇ単位で秤量し、０．
１規定の水酸化ナトリウム水溶液５０ｍｌ中で４時間振
盪して反応させた後、濾過し、濾液の上澄み液２０ｍｌ
を採取して０．０１規定の塩酸水溶液で滴定する。これ
より、水酸基量とカルボキシル基量の合計量を、カーボ
ンブラック１ｇ中のミリ当量（ｍｅｑ．／ｇ）として下
式に従って求めた。 ( カルボキシル基＋水酸基) 量＝（50／20×0.01×( 滴
定量−空滴定量) ）／カーボンブラック試料重量 この合計量から先に求めたカルボキシル基量を差し引い
て、水酸基量を求めた。 （３）キノン基（＞Ｃ＝Ｏ）量 乾燥カーボンブラック３ｇを１ｍｇ単位で秤量し、水素
化ホウ素ナトリウム１００ｍｇの０．１規定の水酸化ナ
トリウム水溶液に溶解したもの５０ｍｌ中で２時間反応
させた後、６規定の硫酸水溶液を加えた時に発生する水
素ガス量を測定する。空試験も行い発生する水素ガス量
を求める。キノン基量は、カーボンブラック１ｇ中のミ
リ当量（ｍｅｑ．／ｇ）として下式に従って求めた。キ
ノン基量＝反応した水素化ホウ素ナトリウム量／カーボ
ンブラック試料重量DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to embodiments. In the example,
“Parts” and “%” are “parts by weight” and “% by weight”, respectively. The amount of each surface functional group of the carbon black used in the examples was measured by the following method, and they were summed to obtain the total amount of surface functional groups. The results are shown in Table 1. (1) Measurement of Carboxyl Group (—COOH) Amount 1 g of dry carbon black was weighed in units of 1 mg, and 0.1 g was measured.
The reaction was carried out by shaking for 4 hours in 50 ml of a 1N aqueous sodium hydrogen carbonate solution, followed by filtration, and the supernatant of the filtrate was 20 m
1 is collected and titrated with a 0.01 N hydrochloric acid aqueous solution. The amount of carboxyl group was determined as a milliequivalent (meq./g) in 1 g of carbon black according to the following formula. Carboxyl group amount = (50/20 × 0.01 × (titration−empty titration)) / carbon black sample weight (2) Measurement of hydroxyl group (—OH) amount
The reaction was carried out by shaking for 4 hours in 50 ml of a 1N aqueous sodium hydroxide solution, followed by filtration, and 20 ml of the supernatant of the filtrate.
And titrated with a 0.01 N aqueous hydrochloric acid solution. From this, the total amount of the hydroxyl group amount and the carboxyl group amount was determined as the milliequivalent (meq./g) in 1 g of carbon black according to the following equation. (Carboxyl group + hydroxyl group) amount = (50/20 × 0.01 × (titration-empty titration)) / carbon black sample weight The amount of carboxyl groups previously determined was subtracted from the total amount to determine the amount of hydroxyl groups. (3) Quinone group (> C = O) amount 3 g of dry carbon black was weighed in 1 mg units, and dissolved in 50 ml of a solution of 100 mg of sodium borohydride in a 0.1 N aqueous solution of sodium hydroxide for 2 hours. Thereafter, the amount of hydrogen gas generated when a 6 N aqueous sulfuric acid solution is added is measured. A blank test is also performed to determine the amount of hydrogen gas generated. The quinone group content was determined as the milliequivalent (meq./g) in 1 g of carbon black according to the following formula. Quinone group content = reacted sodium borohydride content / carbon black sample weight
【００２９】[0029]
【表１】 [Table 1]
【００３０】また、実施例により得られた表面処理カー
ボンブラックの分散性の評価については下記の方法で行
った。表面処理カーボンブラック２０部、精製水８０部
からなる組成物にジルコニアビーズを加え、ペイントシ
ェーカー（レッドデビル社製）で３０分分散し、水性分
散体を作成した。得られた分散体の粘度は超音波型粘度
計（ＶＭ−１Ａ−Ｌ山一電機株式会社製）で測定した。
粒度分布はレーザー粒径解析装置（ＭＩＣＲＯＴＲＡＣ
ＵＰＡ 日機装株式会社製）で測定し、平均粒径を求
めた。また、５０℃において１週間経時させた時の分散
体中の沈降物の状態を調べ、○×△で評価した。○は沈
殿物無し。△は若干の沈殿物有り。×は多量の沈殿物が
あることを表す。評価結果は表２に示した。 実施例１ カーボンブラックＡ ２５．０部、１−アミノ−８−ヒ
ドロキシナフタレン−４−スルホン酸７．５部、精製水
６７．５部からなる組成物にジルコニアビーズを加え、
ペイントシェーカー（レッドデビル社製）にて９０分分
散し、５０℃で４時間加熱処理した。The following method was used to evaluate the dispersibility of the surface-treated carbon blacks obtained in the examples. Zirconia beads were added to a composition consisting of 20 parts of surface-treated carbon black and 80 parts of purified water, and dispersed with a paint shaker (manufactured by Red Devil Co.) for 30 minutes to prepare an aqueous dispersion. The viscosity of the obtained dispersion was measured with an ultrasonic viscometer (VM-1A-L, manufactured by Yamaichi Electric Co., Ltd.).
The particle size distribution is measured using a laser particle size analyzer (MICROTRAC).
UPA manufactured by Nikkiso Co., Ltd.) to determine the average particle size. Further, the state of the sediment in the dispersion when the dispersion was aged at 50 ° C. for one week was examined and evaluated by ○ × △. ○ indicates no precipitate. △ indicates slight precipitation. X indicates that there is a large amount of precipitate. The evaluation results are shown in Table 2. Example 1 Zirconia beads were added to a composition consisting of 25.0 parts of carbon black A, 7.5 parts of 1-amino-8-hydroxynaphthalene-4-sulfonic acid, and 67.5 parts of purified water.
The mixture was dispersed in a paint shaker (manufactured by Red Devil Co.) for 90 minutes and heat-treated at 50 ° C. for 4 hours.
【００３１】その後、濾別して１０５℃で５時間乾燥
し、精製水を溶媒として８時間のソックスレー抽出を行
い余剰の１−アミノ−８−ヒドロキシナフタレン−４−
スルホン酸を除去したのち、再度１０５℃で５時間乾
燥、粉砕して本発明の表面処理カーボンブラックを得
た。 実施例２ カーボンブラックＡ ２５．０部、１−アミノ−８−ヒ
ドロキシナフタレン−４−スルホン酸アンモニウム塩
８．０部、精製水６７．０部からなる組成物にジルコニ
アビーズを加え、ペイントシェーカー（レッドデビル社
製）で９０分分散し、７０℃で２時間加熱処理した。そ
の後、実施例１と同様の操作を行い表面処理カーボンブ
ラックを得た。Thereafter, the mixture was filtered, dried at 105 ° C. for 5 hours, and subjected to Soxhlet extraction for 8 hours using purified water as a solvent to obtain excess 1-amino-8-hydroxynaphthalene-4-.
After removing the sulfonic acid, it was dried and crushed again at 105 ° C. for 5 hours to obtain the surface-treated carbon black of the present invention. Example 2 Zirconia beads were added to a composition consisting of 25.0 parts of carbon black A, 8.0 parts of 1-amino-8-hydroxynaphthalene-4-sulfonic acid ammonium salt and 67.0 parts of purified water, and a paint shaker ( (Red Devil Co., Ltd.) for 90 minutes and heat-treated at 70 ° C. for 2 hours. Thereafter, the same operation as in Example 1 was performed to obtain a surface-treated carbon black.
【００３２】実施例３ カーボンブラックＡ ２５．０部、１−アミノ−８−ヒ
ドロキシナフタレン−３、６−ジスルホン酸ジナトリウ
ム塩５．０部、精製水７０．０部からなる組成物にジル
コニアビーズを加え、ペイントシェーカー（レッドデビ
ル社製）で９０分分散し、４０℃で４時間加熱処理し
た。その後、実施例１と同様の操作を行い表面処理カー
ボンブラックを得た。 実施例４ カーボンブラックＢ ２５．０部、１−アミノ−８−ヒ
ドロキシナフタレン−２、４−ジスルホン酸ジナトリウ
ム塩５．０部、精製水７０．０部からなる組成物にジル
コニアビーズを加え、ペイントシェーカー（レッドデビ
ル社製）で９０分分散した。その後、実施例１と同様の
操作を行い表面処理カーボンブラックを得た。Example 3 Zirconia beads were added to a composition consisting of 25.0 parts of carbon black A, 5.0 parts of 1-amino-8-hydroxynaphthalene-3, disodium salt of 6-disulfonate and 70.0 parts of purified water. Was added, and the mixture was dispersed for 90 minutes using a paint shaker (manufactured by Red Devil Co.) and heat-treated at 40 ° C. for 4 hours. Thereafter, the same operation as in Example 1 was performed to obtain a surface-treated carbon black. Example 4 Zirconia beads were added to a composition consisting of 25.0 parts of carbon black B, 5.0 parts of 1-amino-8-hydroxynaphthalene-2, disodium 4-disulfonate 5.0 parts and 70.0 parts of purified water, The mixture was dispersed for 90 minutes using a paint shaker (manufactured by Red Devil). Thereafter, the same operation as in Example 1 was performed to obtain a surface-treated carbon black.
【００３３】実施例５ カーボンブラックＢ ２５．０部、１−アミノ−８−ヒ
ドロキシナフタレン−４−スルホン酸カリウム塩８．２
部、精製水６６．８部からなる組成物にジルコニアビー
ズを加え、ペイントシェーカー（レッドデビル社製）で
９０分分散し、７０℃で２時間加熱処理した。その後、
実施例１と同様の操作を行い表面処理カーボンブラック
を得た。 実施例６ カーボンブラックＣを用いた以外は、実施例３と同様の
操作により表面処理カーボンブラックを得た。Example 5 25.0 parts of carbon black B, 1-amino-8-hydroxynaphthalene-4-sulfonic acid potassium salt 8.2
Zirconia beads were added to a composition consisting of 66.8 parts of purified water and 66.8 parts of purified water, dispersed for 90 minutes with a paint shaker (manufactured by Red Devil Co.), and heated at 70 ° C. for 2 hours. afterwards,
The same operation as in Example 1 was performed to obtain a surface-treated carbon black. Example 6 A surface-treated carbon black was obtained in the same manner as in Example 3, except that carbon black C was used.
【００３４】比較例１、２、３ 未処理のカーボンブラックＡ、Ｂ、Ｃを比較例とした。
実施例１、２、３と比較例１を比べると、本発明の表面
処理剤を用いてカーボンブラックを処理することにより
水中での分散性および分散安定性が著しく向上している
ことがわかる。実施例４、５と比較例２、あるいは実施
例６と比較例３を比べても同様の効果が確認できる。Comparative Examples 1, 2, and 3 Untreated carbon blacks A, B, and C were used as comparative examples.
Comparing Examples 1, 2, and 3 with Comparative Example 1, it can be seen that the dispersibility and dispersion stability in water are significantly improved by treating the carbon black with the surface treating agent of the present invention. Similar effects can be confirmed by comparing Examples 4 and 5 with Comparative Example 2, or by comparing Example 6 with Comparative Example 3.
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【発明の効果】本発明の表面処理カーボンブラックは、
カーボンブラック粒子表面の官能基へ表面処理剤中のア
ミノ基が吸着あるいは化学結合し、さらに表面処理剤中
の水酸基の作用でカーボンブラックと表面処理剤の造塩
体またはアゾメチン結合が熱力学的に安定化されること
によってカーボンブラックと表面処理剤とが強固に結合
し、しかも、スルホン酸（塩）基部分がカーボンブラッ
ク粒子表面に配位することで水性媒体への優れた分散性
を得ることができた。また、カーボンブラックを微分散
させながら表面処理操作を行うことによって、より微細
なカーボンブラック粒子表面が処理され優れた分散効果
が得られた。The surface-treated carbon black of the present invention is
The amino groups in the surface treatment agent are adsorbed or chemically bonded to the functional groups on the surface of the carbon black particles, and the salt formation or azomethine bond between the carbon black and the surface treatment agent is thermodynamically affected by the action of the hydroxyl group in the surface treatment agent. By being stabilized, carbon black and the surface treating agent are firmly bonded, and the sulfonic acid (salt) group is coordinated to the surface of the carbon black particles to obtain excellent dispersibility in an aqueous medium. Was completed. In addition, by performing the surface treatment operation while finely dispersing the carbon black, finer carbon black particle surfaces were treated, and an excellent dispersing effect was obtained.
Claims (5)
でカーボンブラック粒子の表面を処理したことを特徴と
する表面処理カーボンブラック。 一般式（１） 【化１】 〔式中、Ｒ1 、Ｒ2 はそれぞれ水素原子または炭素数１
〜４のアルキル基を表し（Ｒ1 、Ｒ2 が一体となって環
を形成してもよい。）、Ｍは水素原子、アルカリ金属原
子、アンモニウムまたはアミンを表し、ｍ、ｎは０〜３
の整数を表し、１≦ｍ＋ｎ≦３である。〕1. A surface-treated carbon black obtained by treating the surface of carbon black particles with a surface-treating agent represented by the following general formula (1). General formula (1) [Wherein, R 1 and R 2 each represent a hydrogen atom or a carbon atom 1
Represents an alkyl group of 1 to 4 (R 1 and R 2 may form a ring together), M represents a hydrogen atom, an alkali metal atom, ammonium or an amine, and m and n represent 0 to 3
And 1 ≦ m + n ≦ 3. ]
官能基量が０．２ミリ当量／ｇ以上であることを特徴と
する請求項１記載の表面処理カーボンブラック。2. The surface-treated carbon black according to claim 1, wherein the total surface functional group content of the carbon black before the surface treatment is 0.2 meq / g or more.
ンブラックを含む水性分散体。3. An aqueous dispersion containing the surface-treated carbon black according to claim 1 or 2.
れる表面処理剤を含む溶液中において粉砕機または分散
機によるせん断応力またはメディアによる衝撃力によっ
て微分散させながら表面処理することを特徴とする表面
処理カーボンブラックの製造方法。 一般式（１） 【化２】 〔式中、Ｒ1 、Ｒ2 はそれぞれ水素原子または炭素数１
〜４のアルキル基を表し（Ｒ1 、Ｒ2 が一体となって環
を形成してもよい。）、Ｍは水素原子、アルカリ金属原
子、アンモニウムまたはアミンを表し、ｍ、ｎは０〜３
の整数を表し、１≦ｍ＋ｎ≦３である。〕4. A surface treatment while finely dispersing carbon black in a solution containing a surface treatment agent represented by the general formula (1) by a shear stress by a pulverizer or a disperser or an impact force by a medium. Of producing surface-treated carbon black. General formula (1) [Wherein, R 1 and R 2 each represent a hydrogen atom or a carbon atom 1
Represents an alkyl group of 1 to 4 (R 1 and R 2 may form a ring together), M represents a hydrogen atom, an alkali metal atom, ammonium or an amine, and m and n represent 0 to 3
And 1 ≦ m + n ≦ 3. ]
０℃〜１００℃で加熱処理を行うことを特徴とする請求
項４記載の表面処理カーボンブラックの製造方法。5. During or after the step of finely dispersing,
The method for producing surface-treated carbon black according to claim 4, wherein the heat treatment is performed at 0 ° C to 100 ° C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1507799A JP2000212468A (en) | 1999-01-25 | 1999-01-25 | Surface treated carbon black, its production and aqueous dispersion containing it |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1507799A JP2000212468A (en) | 1999-01-25 | 1999-01-25 | Surface treated carbon black, its production and aqueous dispersion containing it |
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| Publication Number | Publication Date |
|---|---|
| JP2000212468A true JP2000212468A (en) | 2000-08-02 |
Family
ID=11878797
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
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| JP2007045703A (en) * | 2005-08-04 | 2007-02-22 | Degussa Ag | Carbon material |
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| US10017652B2 (en) | 2015-08-18 | 2018-07-10 | Kusumoto Chemicals, Ltd. | Additive for aqueous coating material for imparting distinctness of image to coating film |
| CN111564632A (en) * | 2020-05-20 | 2020-08-21 | 苏州柔能纳米科技有限公司 | Preparation method of electrode slurry for flexible battery |
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