JP4563065B2 - Dispersant for inorganic pigment - Google Patents
Dispersant for inorganic pigment Download PDFInfo
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- JP4563065B2 JP4563065B2 JP2004106157A JP2004106157A JP4563065B2 JP 4563065 B2 JP4563065 B2 JP 4563065B2 JP 2004106157 A JP2004106157 A JP 2004106157A JP 2004106157 A JP2004106157 A JP 2004106157A JP 4563065 B2 JP4563065 B2 JP 4563065B2
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- 239000002270 dispersing agent Substances 0.000 title claims description 39
- 239000001023 inorganic pigment Substances 0.000 title claims description 25
- 239000002253 acid Substances 0.000 claims description 39
- 239000000049 pigment Substances 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 23
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910001424 calcium ion Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000004927 clay Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 229940098895 maleic acid Drugs 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 3
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- HSNJERRVXUNQLS-UHFFFAOYSA-N 1-(4-tert-butylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C(C)(C)C)C=C1 HSNJERRVXUNQLS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本発明は、無機顔料を水等に分散させてスラリーを得る際に好適に用いられる無機顔料用分散剤及びそれを含有する顔料分散組成物に関する。 The present invention relates to an inorganic pigment dispersant suitably used when an inorganic pigment is dispersed in water or the like to obtain a slurry, and a pigment dispersion composition containing the dispersant.
無機顔料を水系媒体中に分散し、スラリー化するに際しては、ポリカルボン酸塩系分散剤が使用されている。例えば、アクリル酸とマレイン酸との共重合体の塩が知られているが、スラリーの高濃度化に伴い、十分な分散性能が得られなくなってきている。 In dispersing an inorganic pigment in an aqueous medium to form a slurry, a polycarboxylate-based dispersant is used. For example, a salt of a copolymer of acrylic acid and maleic acid is known, but as the concentration of the slurry is increased, sufficient dispersion performance cannot be obtained.
特許文献１ではアクリル酸とマレイン酸との共重合モル比の異なる２種の共重合体の組み合わせにより分散性能の向上を報告している。しかしながら例えば水性塗料用途等で無機顔料スラリーをスプレーのようにシェア（剪断）のかかる状態で塗布する場合と、ハケのようにシェアのかからない状態で塗布する場合、スラリー粘度が大きく異なり（チキソトロピー性が大きい）、作業性に支障を及ぼす点が指摘されていた。
本発明の課題は、シェアの影響による無機顔料スラリー粘度の変化が小さく、また粘度値も低くすることができる無機顔料用分散剤及びそれを含有する顔料分散組成物を提供することにある。 An object of the present invention is to provide a dispersant for an inorganic pigment that can change the viscosity of the inorganic pigment slurry due to the influence of the share and can also reduce the viscosity value, and a pigment dispersion composition containing the dispersant.
本発明は、下記の（Ａ）成分及び（Ｂ）成分を、（Ａ）／（Ｂ）＝５０／５０〜９６／４（重量比）の割合で含有する無機顔料用分散剤、及びこの無機顔料用分散剤を含有する顔料分散組成物を提供する。
（Ａ）成分：
構成モノマー単位比率が、不飽和一塩基酸／不飽和二塩基酸（モル比）＝９１／９〜７４／２６で、重量平均分子量（Ｍｗ）が２５０００〜６００００である、不飽和一塩基酸と不飽和二塩基酸との共重合体の塩
（Ｂ）成分：
構成モノマー単位比率が、不飽和一塩基酸／不飽和二塩基酸（モル比）＝６３／３７〜４７／５３で、重量平均分子量（Ｍｗ）が２５０００〜６００００である、不飽和一塩基酸と不飽和二塩基酸との共重合体の塩
The present invention provides an inorganic pigment dispersant containing the following components (A) and (B) in a ratio of (A) / (B) = 50/50 to 96/4 (weight ratio), and the inorganic Provided is a pigment dispersion composition containing a pigment dispersant.
(A) component:
An unsaturated monobasic acid having a constituent monomer unit ratio of unsaturated monobasic acid / unsaturated dibasic acid (molar ratio) = 91/9 to 74/26 and a weight average molecular weight (Mw) of 25,000 to 60,000 Salt (B) component of copolymer with unsaturated dibasic acid:
An unsaturated monobasic acid having a constituent monomer unit ratio of unsaturated monobasic acid / unsaturated dibasic acid (molar ratio) = 63/37 to 47/53 and a weight average molecular weight (Mw) of 25,000 to 60,000 Salts of copolymers with unsaturated dibasic acids
本発明の無機顔料用分散剤は、シェアの影響による無機顔料スラリー粘度の変化が小さく、また粘度値も低くすることができる。 The inorganic pigment dispersant of the present invention has a small change in the viscosity of the inorganic pigment slurry due to the influence of the shear, and can also have a low viscosity value.
本発明の（Ａ）成分、（Ｂ）成分それぞれの共重合体を構成する不飽和一塩基酸としては、アクリル酸、メタクリル酸、クロトン酸等が挙げられるが、アクリル酸、メタクリル酸が好ましい。また、不飽和二塩基酸としては、マレイン酸無水物、マレイン酸、イタコン酸、フマル酸等が挙げられるが、マレイン酸無水物、マレイン酸、イタコン酸が好ましい。 Examples of the unsaturated monobasic acid constituting the copolymer of each of the components (A) and (B) of the present invention include acrylic acid, methacrylic acid, crotonic acid and the like, but acrylic acid and methacrylic acid are preferred. Examples of the unsaturated dibasic acid include maleic anhydride, maleic acid, itaconic acid, fumaric acid and the like, and maleic anhydride, maleic acid and itaconic acid are preferred.
本発明の（Ａ）成分、（Ｂ）成分それぞれの共重合体の塩としては、アルカリ金属塩、アルカリ土類金属塩、４級アンモニウム塩、アンモニウム塩、有機アミン塩から選ばれる少なくとも１種が好ましい。 The salt of the copolymer of each of the component (A) and the component (B) of the present invention is at least one selected from alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, ammonium salts, and organic amine salts. preferable.
塩を構成するアルカリ金属としては、ナトリウム、カリウム、リチウム等が挙げられる。アルカリ土類金属としては、マグネシウム、カルシウム、バリウム等が挙げられる。４級アンモニウムとしては、水酸化テトラメチルアンモニウム、水酸化トリエチルメチルアンモニウム等が挙げられる。有機アミンとしては、ジエタノールアミン、トリエタノールアミン、エチレンジアミン、ジエチレントリアミン、トリエチルアミン、トリブチルアミン等が挙げられる。 Examples of the alkali metal constituting the salt include sodium, potassium, and lithium. Examples of the alkaline earth metal include magnesium, calcium, and barium. Examples of the quaternary ammonium include tetramethylammonium hydroxide and triethylmethylammonium hydroxide. Examples of the organic amine include diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylamine, and tributylamine.
これらの中で好ましいものは、顔料の高濃度スラリーを低粘度化し、低粘度化スラリーを長期分散安定化する観点において、アルカリ金属塩であり、ナトリウム塩、カリウム塩がより好ましい。また、アンモニウム塩は電子材料等の灰分の残存を嫌う用途への使用に好ましい。 Among these, preferred are alkali metal salts, and sodium salts and potassium salts are more preferable from the viewpoint of lowering the viscosity of a high-concentration slurry of pigment and stabilizing the low-viscosity slurry for a long period of time. Ammonium salts are preferred for use in applications where ash content remains, such as electronic materials.
本発明の（Ａ）成分、（Ｂ）成分それぞれの共重合体の塩の中和度又はアルカリ過剰度は、特に規定されないが、粉体成分の耐分解性、並びに耐着色性及び耐臭気性の観点から、通常それぞれ５０〜１２０％であり、６０〜１１０％が好ましく、７５〜１０５％がより好ましい。 The degree of neutralization or alkali excess of the salt of the copolymer of each of the components (A) and (B) of the present invention is not particularly defined, but the decomposition resistance, color resistance and odor resistance of the powder component In view of the above, it is usually 50 to 120%, preferably 60 to 110%, more preferably 75 to 105%.
尚、中和度又はアルカリ過剰度とは、［Ａ（塩を構成し得るフリーの塩基の当量＋塩を構成している酸基の当量）／Ｂ（塩を構成し得るフリーの酸基の当量＋塩を構成している酸基の当量）］×１００（％）で表される。Ａ／Ｂが１以下であれば中和度と表現し、Ａ／Ｂ＝１であれば中和度１００％を示す。Ａ／Ｂが１より大きいものはアルカリ過剰度と表現し、１００％より大きい値を示す。 The degree of neutralization or the excess of alkali means [A (equivalent of free base capable of constituting a salt + equivalent of acid group constituting a salt) / B (free acid group capable of constituting a salt). Equivalent + equivalent of acid group constituting the salt)] × 100 (%). When A / B is 1 or less, the degree of neutralization is expressed, and when A / B = 1, the degree of neutralization is 100%. A / B greater than 1 is expressed as alkali excess and shows a value greater than 100%.
また、（Ａ）成分、（Ｂ）成分それぞれの共重合体の塩の水溶液のｐＨは、粉体成分の耐分解性、並びに耐着色性及び耐臭気性の観点から、５〜９が好ましく、５．５〜８．５が更に好ましく、６〜８が特に好ましい。 Moreover, the pH of the aqueous solution of the copolymer salt of each of the component (A) and the component (B) is preferably 5 to 9 from the viewpoint of the decomposition resistance of the powder component, and the resistance to coloring and odor. 5.5 to 8.5 is more preferable, and 6 to 8 is particularly preferable.
本発明の（Ａ）成分は、構成モノマー単位比率が、不飽和一塩基酸／不飽和二塩基酸（モル比）＝９１／９〜７４／２６であり、９１／９〜８０／２０が好ましく、８７／１３〜８０／２０が更に好ましい。 In the component (A) of the present invention, the constituent monomer unit ratio is unsaturated monobasic acid / unsaturated dibasic acid (molar ratio) = 91/9 to 74/26, preferably 91/9 to 80/20. 87/13 to 80/20 are more preferable.
また、本発明の（Ｂ）成分は、構成モノマー単位比率が、不飽和一塩基酸／不飽和二塩基酸（モル比）＝６３／３７〜４７／５３であり、６１／３９〜４８／５２が好ましく、５９／４１〜５０／５０が更に好ましい。 In addition, the component (B) component of the present invention has a constituent monomer unit ratio of unsaturated monobasic acid / unsaturated dibasic acid (molar ratio) = 63/37 to 47/53, and 61/39 to 48/52. Is preferable, and 59/41 to 50/50 is more preferable.
本発明の（Ａ）成分、（Ｂ）成分それぞれの重量平均分子量（Ｍｗ）は、顔料の高濃度スラリーを低粘度化し、低粘度化スラリーを長期分散安定化し、高剪断下におけるスラリーの粘度を小さく維持する観点から、２５０００〜６００００であり、３５０００〜５００００が好ましく、４００００〜５００００が更に好ましい。 The weight average molecular weight (Mw) of each of the component (A) and the component (B) of the present invention is such that the high-concentration slurry of the pigment is reduced in viscosity, the low-viscosity slurry is dispersed and stabilized for a long time, and the viscosity of the slurry under high shear is reduced. From the viewpoint of keeping it small, it is 25000 to 60000, preferably 35000 to 50000, and more preferably 40000 to 50000.
尚、ここで重量平均分子量（Ｍｗ）は、実施例に記載された測定法により測定された値である。 Here, the weight average molecular weight (Mw) is a value measured by the measuring method described in Examples.
また本発明の（Ａ）成分、（Ｂ）成分それぞれの数平均分子量（Ｍｎ）は、顔料の高濃度スラリーを低粘度化し、低粘度化スラリーを長期分散安定化し、高剪断下におけるスラリーの粘度を小さく維持する観点から、２００００〜４００００であることが好ましく、２５０００〜３８０００が更に好ましく、２７０００〜３５０００が特に好ましい。また、（Ａ）成分（Ｂ）成分それぞれのＭｗ／Ｍｎは３以下が好ましく、１．２５〜３が更に好ましく、１．２５〜２．５が特に好ましい。 In addition, the number average molecular weight (Mn) of each of the component (A) and the component (B) of the present invention is such that the high-concentration slurry of the pigment has a low viscosity, the low-viscosity slurry is long-term dispersed and stabilized, and the viscosity of the slurry under high shear is high. Is preferably 20000 to 40000, more preferably 25000 to 38000, and particularly preferably 27000 to 35000. Further, the Mw / Mn of each of the component (A) and the component (B) is preferably 3 or less, more preferably 1.25 to 3, and particularly preferably 1.25 to 2.5.
本発明の分散剤は、シェアの影響によるスラリー粘度の変化が小さくなり、塗布方法の適応性（スプレーやハケのいずれの塗布方法でも対応可能）に優れる観点から、（Ａ）成分及び（Ｂ）成分を、（Ａ）／（Ｂ）＝５０／５０〜９６／４（重量比）の割合で含有するが、５５／４５〜８５／１５が好ましく、６０／４０〜８０／２０が更に好ましい。 In the dispersant of the present invention, the change in the slurry viscosity due to the influence of the share becomes small, and from the viewpoint of excellent adaptability of the coating method (which can be applied by any spraying or brushing coating method), the component (A) and the component (B) Although a component is contained in the ratio of (A) / (B) = 50 / 50-96 / 4 (weight ratio), 55 / 45-85 / 15 are preferable and 60 / 40-80 / 20 are still more preferable.
本発明の分散剤は、顔料の高濃度スラリーを低粘度化し、低粘度化スラリーを長期分散安定化し、高剪断下におけるスラリーの粘度を小さく維持する観点から、カルシウムイオン８０ｍｇ／Ｌ存在下でのクレー分散能は１５％以上５０％未満が好ましく、２０〜４５％が更に好ましい。また、マグネシウムイオン２１ｍｇ／Ｌ存在下でのクレー分散能は４６％以上６０％未満が好ましく、４６〜５９％が更に好ましい。カルシウムイオン捕捉能は２７０ｍｇＣａＣＯ3／ｇ以上３８０ｍｇＣａＣＯ3／ｇ未満が好ましく、２９０〜３７９ｍｇＣａＣＯ3／ｇが更に好ましい。 The dispersant of the present invention has a low viscosity of a high-concentration slurry of pigment, stabilizes the low-viscosity slurry for a long period of time, and maintains a low viscosity of the slurry under high shear, in the presence of 80 mg / L of calcium ions. The clay dispersibility is preferably 15% or more and less than 50%, more preferably 20 to 45%. The clay dispersibility in the presence of 21 mg / L of magnesium ions is preferably 46% or more and less than 60%, and more preferably 46 to 59%. Calcium ion capturing ability is preferably less than 270mgCaCO 3 / g or more 380mgCaCO 3 / g, more preferably 290~379mgCaCO 3 / g.
尚、本発明でいう「クレー分散能」及び「カルシウムイオン捕捉能」は、実施例に記載された測定法により測定されるものであり、無機顔料用分散剤の特性の指標として用いられる値である。 The “clay dispersibility” and “calcium ion scavenging ability” as used in the present invention are measured by the measurement methods described in the examples, and are values used as indicators of the properties of the dispersant for inorganic pigments. is there.
本発明の分散剤中の（Ａ）成分と（Ｂ）成分の合計含有量は、顔料の高濃度スラリーを低粘度化できる範疇において、９０〜１００重量％が好ましく、９５〜１００重量％が更に好ましい。本発明の分散剤は、（Ａ）成分及び（Ｂ）成分以外に未反応の不飽和一塩基酸、不飽和二塩基酸等を含有していてもよい。 The total content of the component (A) and the component (B) in the dispersant of the present invention is preferably 90 to 100% by weight, more preferably 95 to 100% by weight, in the category where the viscosity of the high concentration slurry of the pigment can be reduced. preferable. The dispersant of the present invention may contain unreacted unsaturated monobasic acid, unsaturated dibasic acid and the like in addition to the components (A) and (B).
本発明の（Ａ）成分及び（Ｂ）成分の製造法は特に限定されないが、例えば以下に示す方法で製造することができる。 Although the manufacturing method of (A) component and (B) component of this invention is not specifically limited, For example, it can manufacture by the method shown below.
不飽和二塩基酸及びイオン交換水を不飽和二塩基酸の濃度が３７重量％以上となるように反応容器に仕込み、７５℃に加熱後、ＮａＯＨ水溶液を不飽和二塩基酸の仕込量の２倍のモル数で仕込み、不飽和二塩基酸のＮａ塩とする。次に約１００℃まで加熱した後、この温度で不飽和一塩基酸水溶液を、不飽和一塩基酸／不飽和二塩基酸（モル比）が、上記範囲となるように、また過酸化水素水溶液を過酸化水素が不飽和一塩基酸と不飽和二塩基酸の全仕込みモル数に対して１７〜５０モル％となるように、それぞれを３〜５時間かけて滴下し重合反応を行う。滴下終了後、１００℃で１〜１０時間熟成する。反応終了後、約６０℃に冷却し、ｐＨが８〜９となるようにアルカリ水溶液を仕込み、不飽和一塩基酸−不飽和二塩基酸共重合体のＮａ塩とする。 An unsaturated dibasic acid and ion-exchanged water are charged into a reaction vessel so that the concentration of the unsaturated dibasic acid is 37% by weight or more, heated to 75 ° C., and then an aqueous NaOH solution is added to the amount of the unsaturated dibasic acid charged to 2. Charge in double moles to make Na salt of unsaturated dibasic acid. Next, after heating to about 100 ° C., the unsaturated monobasic acid aqueous solution is heated at this temperature so that the unsaturated monobasic acid / unsaturated dibasic acid (molar ratio) falls within the above range. Are added dropwise over 3 to 5 hours so that hydrogen peroxide is 17 to 50 mol% with respect to the total number of moles of unsaturated monobasic acid and unsaturated dibasic acid charged, and a polymerization reaction is carried out. After completion of dropping, the mixture is aged at 100 ° C. for 1 to 10 hours. After completion of the reaction, the reaction solution is cooled to about 60 ° C., and an alkaline aqueous solution is added so that the pH is 8 to 9, thereby obtaining an Na salt of an unsaturated monobasic acid-unsaturated dibasic acid copolymer.
本発明において対象となる無機顔料は、炭酸カルシウム、リン酸カルシウム、リン酸亜鉛、クレー、ベントナイト、サチンホワイト、亜鉛華、ベンガラ、フェライト、酸化チタン、アルミナ、酸化マグネシウム、タルク、ホワイトカーボン、セメント、石膏、カーボンブラック、チタン酸塩、珪酸塩等が挙げられ、炭酸カルシウムや、チタン酸バリウム等のチタン酸塩が好ましい。 Inorganic pigments of interest in the present invention are calcium carbonate, calcium phosphate, zinc phosphate, clay, bentonite, satin white, zinc white, bengara, ferrite, titanium oxide, alumina, magnesium oxide, talc, white carbon, cement, gypsum, Examples thereof include carbon black, titanate, and silicate, and calcium carbonate and titanate such as barium titanate are preferable.
具体的には、本発明の分散剤は、軽質炭酸カルシウム製造工程用、炭酸カルシウム湿式粉砕用、紙コーティング塗料用、フェライト製造工程用又はチタン酸バリウム等の電子材料用の分散剤として有効である。また、アルミナ等のセラミック用顔料に対しても有効である。 Specifically, the dispersant of the present invention is effective as a dispersant for light calcium carbonate production process, calcium carbonate wet grinding, paper coating paint, ferrite production process or electronic materials such as barium titanate. . It is also effective for ceramic pigments such as alumina.
本発明の分散剤は、塗工紙用、電子材料用又はセラミック用等の顔料分散組成物を得る際に有効に用いることができ、特に塗工紙用として用いることが好ましい。顔料分散組成物は、本発明の分散剤を用いて無機顔料の粉体、粉体の原鉱石又は粗粒子等を水系媒体中に分散させることにより得ることができる。水系媒体としては水、あるいは水と、エチルアルコール、エチレングリコール等の水溶性有機溶媒との混合溶液が挙げられ、好ましくは水である。 The dispersant of the present invention can be used effectively when obtaining a pigment dispersion composition for coated paper, electronic materials, ceramics, etc., and is particularly preferably used for coated paper. The pigment dispersion composition can be obtained by dispersing an inorganic pigment powder, powder ore or coarse particles in an aqueous medium using the dispersant of the present invention. Examples of the aqueous medium include water or a mixed solution of water and a water-soluble organic solvent such as ethyl alcohol or ethylene glycol, preferably water.
顔料分散組成物中の顔料の含有量は、特に規定されないが、乾燥効率を向上し、生産性を高める観点から、５０重量％以上が好ましく、５０〜８５重量％がより好ましく、６５〜８５重量％が特に好ましい。また、顔料分散組成物中の本発明の分散剤の含有量は特に規定されないが、無機顔料１００重量部に対して通常０．０１〜１０重量部が好ましく、０．０５〜６重量部がさらに好ましく、０．０５〜５重量部が特に好ましい。 The content of the pigment in the pigment dispersion composition is not particularly defined, but is preferably 50% by weight or more, more preferably 50 to 85% by weight, and more preferably 65 to 85% from the viewpoint of improving the drying efficiency and increasing the productivity. % Is particularly preferred. Further, the content of the dispersant of the present invention in the pigment dispersion composition is not particularly defined, but is usually preferably 0.01 to 10 parts by weight, more preferably 0.05 to 6 parts by weight with respect to 100 parts by weight of the inorganic pigment. 0.05 to 5 parts by weight is preferable.
本発明の分散剤を使用して、顔料分散組成物を得る方法としては、通常のスラリー化方法が用いられる。例えば分散剤を溶解した水溶液に顔料を添加して撹拌、混合する方法、顔料に水と分散剤を加えて撹拌、混合する方法等が挙げられる。撹拌、混合する方法としては、例えば高速ディスパー、ホモミキサー、ボールミル等一般に用いられる撹拌装置を使用することができる。 As a method for obtaining a pigment dispersion composition using the dispersant of the present invention, a usual slurrying method is used. For example, a method of adding a pigment to an aqueous solution in which a dispersant is dissolved and stirring and mixing, a method of adding water and a dispersant to the pigment, stirring and mixing, and the like can be mentioned. As a method of stirring and mixing, for example, a generally used stirring device such as a high-speed disper, a homomixer, or a ball mill can be used.
また、顔料の鉱石又は粗粒子を粉砕と同時にスラリー化する場合には、顔料の鉱石又は粗粒子に水と分散剤を添加して、粉砕と同時にスラリー化する方法等が挙げられる。粉砕と同時にスラリー化する方法としてはビーズミル等一般に用いられる湿式粉砕機を使用することが出来る。 In addition, when slurrying the pigment ore or coarse particles at the same time as pulverization, a method of adding water and a dispersant to the pigment ore or coarse particles and slurrying at the same time as the pulverization may be mentioned. A generally used wet pulverizer such as a bead mill can be used as a method of slurrying simultaneously with pulverization.
本発明において、シェアの影響によるスラリー粘度の変化を検討する方法としてＴＩ値（チキソトロピック・インデックス）がある。これは調製したスラリーを一定の温度でＢ型粘度計にてスラリー粘度を測定するが、その際粘度計のローター回転速度を６ｒｐｍと６０ｒｐｍでそれぞれ測定し、以下の式で算出するものである。 In the present invention, there is a TI value (thixotropic index) as a method for examining the change in slurry viscosity due to the influence of shear. In this method, the slurry viscosity of the prepared slurry is measured with a B-type viscometer at a constant temperature. At that time, the rotor rotational speed of the viscometer is measured at 6 rpm and 60 rpm, respectively, and the following formula is calculated.
ＴＩ値＝（６ｒｐｍで測定時の粘度）／（６０ｒｐｍで測定時の粘度）
６０ｒｐｍで測定時の粘度の方がシェアがかかる状態であり、ＴＩ値が小さい程シェアの影響によるスラリー粘度の変化が少なくなる。ＴＩ値は３以下が好ましく、１〜２．５が更に好ましい。
TI value = (viscosity when measured at 6 rpm) / (viscosity when measured at 60 rpm)
The viscosity at the time of measurement at 60 rpm is a state in which the shear is applied, and the smaller the TI value, the smaller the change in slurry viscosity due to the influence of the shear. The TI value is preferably 3 or less, more preferably 1 to 2.5.
本発明の顔料分散組成物においては、ＴＩ値が小さい、即ちスラリー粘度の変化が小さい。このような格別顕著に優れた効果を発現する理由は定かではないが、シェアの影響を受けることなくスラリー粘度の変化が小さいという観点においては、おそらく無機顔料に対し、（Ａ）成分は表面電位の付与による静電斥力の向上に、（Ｂ）成分は吸着力の向上にそれぞれ寄与していることに基づくものと考えられる。 In the pigment dispersion composition of the present invention, the TI value is small, that is, the change in slurry viscosity is small. The reason why such a remarkably excellent effect is manifested is not clear, but from the viewpoint that the change in slurry viscosity is small without being affected by the share, the component (A) is probably the surface potential for inorganic pigments. It is considered that the component (B) contributes to the improvement of the attractive force due to the improvement of the electrostatic repulsion by the application of.
以下の例において、無機顔料用分散剤の物性は以下の方法で測定した。 In the following examples, the physical properties of the dispersant for inorganic pigment were measured by the following methods.
＜重量平均分子量＞
ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により、下記条件で測定した。
カラム：ＴＳＫ ＰＷＸＬ＋Ｇ4000ＰＷＸＬ＋Ｇ2500ＰＷＸＬ（いずれも東ソー株式会社製）
カラム温度：４０℃
検出器：ＲＩ又はＵＶ（２１０ｎｍ）
溶離液：０．２ｍｏｌ／Ｌ リン酸緩衝液／アセトニトリル（９／１）
流速：１．０ｍＬ／ｍｉｎ
注入量：０．１ｍＬ
標準：ポリエチレングリコール
＜クレー分散能＞
下記の手順で行った。尚、塩化カルシウム・２水和物を用いた方法がカルシウムイオン８０ｍｇ／Ｌ存在下でのクレー分散能を、また塩化マグネシウム・６水和物を用いた方法がマグネシウムイオン２１ｍｇ／Ｌ存在下でのクレー分散能を示す。
1) グリシン６７．５６ｇ、塩化ナトリウム５２．６ｇ及び１Ｎ−ＮａＯＨ水溶液６０ｍＬにイオン交換水を加えて６００ｇとしたグリシン緩衝液を調製する。
2) 塩化カルシウム・２水和物０．３２６８ｇ又は塩化マグネシウム・６水和物０．１９３７ｇと、1)の調製液６０ｇにイオン交換水を加えて１０００ｇとし、分散液を調製する。
3) ０．１重量％（固形分換算）無機顔料用分散剤水溶液を２０ｇ調製する。
4) 試験管にＪＩＳ試験用粉体１，８種（関東ローム，微粒：日本粉体工業技術協会）のクレー０．３ｇを入れ、2)の調製液２７ｇと3)の調製液３ｇを添加する。
5) 試験管をパラフィルムで密封した後、試験管を振り、試験管の底に塊がなくなったのを確認してから、試験管を上下に２０回振る。
6) 5)の試験管を直射日光のあたらない所に２０時間静置する。
7) ２０時間後、分散液の上澄み５ｍＬをホールピペットで２０ｍＬのスクリュー管に採取する。
8) ＵＶ分光器で透過率（Ｔ％）を測定する（波長３８０ｎｍ、１ｃｍセル）。
１００からＴ％の値を差し引いた値をクレー分散能（濁度）とする。
<Weight average molecular weight>
It measured by GPC (gel permeation chromatography) on the following conditions.
Column: TSK PWXL + G4000PWXL + G2500PWXL (both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI or UV (210 nm)
Eluent: 0.2 mol / L phosphate buffer / acetonitrile (9/1)
Flow rate: 1.0 mL / min
Injection volume: 0.1 mL
Standard: Polyethylene glycol <Clay dispersibility>
The following procedure was followed. It should be noted that the method using calcium chloride dihydrate has the ability to disperse clay in the presence of 80 mg / L calcium ion, and the method using magnesium chloride hexahydrate has the ability to use 21 mg / L magnesium ion. Shows clay dispersibility.
1) Prepare a glycine buffer solution by adding ion exchange water to 60.56 g of glycine, 52.6 g of sodium chloride and 60 mL of 1N NaOH aqueous solution to make 600 g.
2) Add ion-exchanged water to 1000 g of calcium chloride dihydrate 0.3268 g or magnesium chloride hexahydrate 0.1937 g and 60 g of the prepared solution of 1) to prepare a dispersion.
3) Prepare 20 g of 0.1 wt% (solid content conversion) inorganic pigment dispersant aqueous solution.
4) Put 0.3g of JIS test powder 1,8 types (Kanto loam, fine particles: Japan Powder Industrial Technology Association) into the test tube, and add 2g of preparation liquid 27g and 3g of preparation liquid 3g. To do.
5) After sealing the test tube with parafilm, shake the test tube and check that there is no lump at the bottom of the test tube, then shake the test tube up and down 20 times.
6) Leave the test tube of 5) in a place not exposed to direct sunlight for 20 hours.
7) After 20 hours, collect 5 mL of the supernatant of the dispersion with a whole pipette into a 20 mL screw tube.
8) Measure the transmittance (T%) with a UV spectrometer (wavelength 380 nm, 1 cm cell).
The value obtained by subtracting the value of T% from 100 is defined as clay dispersibility (turbidity).
＜カルシウムイオン捕捉能＞
1) カルシウムイオン標準水溶液を調製する。
<Calcium ion scavenging ability>
1) Prepare a standard calcium ion solution.
０．０１ｍｏｌ／Ｌカルシウムイオン水溶液：塩化カルシウム二水和物１．４７０１ｇをイオン交換水１ｋｇに溶解したもの
０．００１ｍｏｌ／Ｌカルシウムイオン水溶液：上記０．０１ｍｏｌ／Ｌカルシウムイオン水溶液１００ｇにイオン交換水を加えて１ｋｇにしたもの
０．０００１ｍｏｌ／Ｌカルシウムイオン水溶液：上記０．００１ｍｏｌ／Ｌカルシウムイオン水溶液１０ｇにイオン交換水を加えて１００ｇにしたもの
2) １００ｍＬビーカーに無機顔料用分散剤を固形分換算で１０ｍｇ及び０．００１ｍｏｌ／Ｌのカルシウムイオン水溶液５０ｇを加える。
3) 1)の各水溶液５０ｇと2)の水溶液をマグネチックスターラーで撹拌する。
4) 3)の各水溶液にｐＨが９〜１１になるように４．８重量％ＮａＯＨ水溶液を加える。
5) 4)の各水溶液に、４Ｍ−ＫＣｌ水溶液を１ｍＬ加える。
6) オリオン社製イオンアナライザーＥＡ９２０を用いて、オリオン社製カルシウムイオン電極９３−２０によりカルシウムイオン量を測定する。
7) 検量線から無機顔料用分散剤により捕捉されたカルシウムイオン量を測定し、分散剤の固形分１ｇ当たりの捕捉量を炭酸カルシウム換算のｍｇ数で表し、その値をカルシウムイオン捕捉能とする。
0.01 mol / L calcium ion aqueous solution: a solution obtained by dissolving 1.4701 g of calcium chloride dihydrate in 1 kg of ion exchange water 0.001 mol / L calcium ion aqueous solution: ion exchange water to 100 g of the above 0.01 mol / L calcium ion aqueous solution Added to make 1 kg 0.0001 mol / L calcium ion aqueous solution: 100 g obtained by adding ion-exchanged water to 10 g of the above 0.001 mol / L calcium ion aqueous solution
2) Into a 100 mL beaker, add 10 mg of the inorganic pigment dispersant and 50 g of 0.001 mol / L calcium ion aqueous solution in terms of solid content.
3) Stir 50 g of each aqueous solution of 1) and the aqueous solution of 2) with a magnetic stirrer.
4) Add 4.8 wt% NaOH aqueous solution to each aqueous solution of 3) so that the pH is 9-11.
5) Add 1 mL of 4M-KCl aqueous solution to each aqueous solution of 4).
6) Using an Orion ion analyzer EA920, measure the amount of calcium ions with an Orion calcium ion electrode 93-20.
7) Measure the amount of calcium ions captured by the dispersant for inorganic pigment from the calibration curve, express the amount captured per gram of the solid content of the dispersant in mg in terms of calcium carbonate, and use that value as the calcium ion scavengeability. .
製造例１
攪拌機、温度計、還流冷却管、窒素導入管、滴下ロートを備えた反応容器に、マレイン酸無水物４９．０ｇ及びイオン交換水５４．３ｇを仕込み、７５℃に加熱後、３０重量％ＮａＯＨ水溶液１３３．３ｇを滴下し、マレイン酸Ｎａ塩水溶液とした。次に窒素気流下で１００℃まで加熱した後、この温度を維持しながら、８０重量％アクリル酸水溶液２２５．３ｇ及び３５重量％過酸化水素水溶液１０９．３ｇをそれぞれ別の滴下ロートから３時間かけて滴下し重合反応を行った。滴下終了後、１００℃で７時間熟成し重合反応を完結させた。反応終了後、冷却し、約６０℃を保持しながらｐＨが６〜８となるように３０重量％ＮａＯＨ水溶液で中和して、アクリル酸―マレイン酸共重合体のナトリウム塩を得た。これを共重合体Ａ１という。
Production Example 1
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was charged with 49.0 g of maleic anhydride and 54.3 g of ion-exchanged water, heated to 75 ° C., and then a 30 wt% NaOH aqueous solution. 133.3g was dripped and it was set as the maleic-acid sodium salt aqueous solution. Next, after heating to 100 ° C. under a nitrogen stream, while maintaining this temperature, 225.3 g of 80 wt% acrylic acid aqueous solution and 109.3 g of 35 wt% aqueous hydrogen peroxide solution were respectively added from another dropping funnel over 3 hours. The solution was added dropwise to carry out a polymerization reaction. After completion of the dropping, the mixture was aged at 100 ° C. for 7 hours to complete the polymerization reaction. After completion of the reaction, the reaction mixture was cooled and neutralized with a 30 wt% NaOH aqueous solution so as to have a pH of 6 to 8 while maintaining about 60 ° C. to obtain a sodium salt of an acrylic acid-maleic acid copolymer. This is called copolymer A1.
製造例２
表１に示すモノマーを用い、製造例１と同様にして共重合体Ａ２〜Ａ１３を得た。
Production Example 2
Using monomers shown in Table 1, copolymers A2 to A13 were obtained in the same manner as in Production Example 1.
製造例１〜２で得られた共重合体Ａ１〜Ａ１３のモノマー組成、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及びＭｗ／Ｍｎをまとめて表１に示す。尚、共重合体Ａ１〜Ａ８，Ａ１０，Ａ１１及びＡ１３が本発明の（Ａ）成分である。 Table 1 shows the monomer composition, weight average molecular weight (Mw), number average molecular weight (Mn), and Mw / Mn of the copolymers A1 to A13 obtained in Production Examples 1 and 2. The copolymers A1 to A8, A10, A11 and A13 are the component (A) of the present invention.
製造例３
攪拌機、温度計、還流冷却管、窒素導入管、滴下ロートを備えた反応容器に、マレイン酸無水物１４９．６ｇ及びイオン交換水２６１．８ｇを仕込み、７５℃に加熱後、３０重量％ＮａＯＨ水溶液２３１．４ｇを滴下し、マレイン酸Ｎａ塩水溶液とした。次に窒素気流下で１００℃まで加熱した後、この温度を維持しながら、８０重量％アクリル酸水溶液１７２．１ｇ及び３５重量％過酸化水素水溶液３０．３ｇをそれぞれ別の滴下ロートから３時間かけて滴下し重合反応を行った。滴下終了後、１００℃で７時間熟成し重合反応を完結させた。反応終了後、冷却し、約６０℃を保持しながらｐＨが６〜８となるように３０重量％ＮａＯＨ水溶液で中和して、アクリル酸―マレイン酸共重合体のナトリウム塩を得た。これを共重合体Ｂ１という。
Production Example 3
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was charged with 149.6 g of maleic anhydride and 261.8 g of ion-exchanged water, heated to 75 ° C., and then 30% by weight NaOH aqueous solution. 231.4g was dripped and it was set as the maleic acid Na salt aqueous solution. Next, after heating to 100 ° C. under a nitrogen stream, while maintaining this temperature, 172.1 g of 80 wt% aqueous acrylic acid solution and 30.3 g of 35 wt% aqueous hydrogen peroxide solution were respectively added from another dropping funnel over 3 hours. The solution was added dropwise to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 7 hours to complete the polymerization reaction. After completion of the reaction, the reaction mixture was cooled and neutralized with a 30 wt% NaOH aqueous solution so as to have a pH of 6 to 8 while maintaining about 60 ° C. to obtain a sodium salt of an acrylic acid-maleic acid copolymer. This is called copolymer B1.
製造例４
表２に示すモノマーを用い、製造例３と同様にして共重合体Ｂ２〜Ｂ１３を得た。
Production Example 4
Using monomers shown in Table 2, copolymers B2 to B13 were obtained in the same manner as in Production Example 3.
製造例３〜４で得られた共重合体Ｂ１〜Ｂ１３のモノマー組成、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及びＭｗ／Ｍｎをまとめて表２に示す。尚、共重合体Ｂ１〜Ｂ９及びＢ１３が本発明の（Ｂ）成分である。 Table 2 shows the monomer composition, weight average molecular weight (Mw), number average molecular weight (Mn), and Mw / Mn of the copolymers B1 to B13 obtained in Production Examples 3 to 4. The copolymers B1 to B9 and B13 are the component (B) of the present invention.
実施例１
製造例で得られた共重合体Ａ１〜Ａ１３と共重合体Ｂ１〜Ｂ１３とを、表３に示す割合で配合し、本発明の分散剤１〜８及び比較分散剤１〜６を得た。
Example 1
Copolymers A1 to A13 and Copolymers B1 to B13 obtained in Production Examples were blended in the ratios shown in Table 3 to obtain dispersants 1 to 8 and comparative dispersants 1 to 6 of the present invention.
得られた分散剤のカルシウムイオン又はマグネシウムイオン存在下でのクレー分散能、及びカルシウムイオン捕捉能をまとめて表３に示す。 Table 3 shows the clay dispersibility in the presence of calcium ions or magnesium ions and the calcium ion scavengeability of the obtained dispersant.
実施例２
ディスポビーカー３００ｍＬに平均粒径が０．４μｍの酸化チタン１４８ｇ、及びスラリー濃度が７５重量％になるようにイオン交換水と、分散剤１〜８又は比較分散剤１〜６（酸化チタン１００重量部に対して１重量部）を仕込んだ後、特殊機化工業株式会社製のホモディスパーで攪拌（２５００ｒｐｍ×２分間）し、スラリー（顔料分散組成物）を調製した。得られたスラリーを株式会社東京計器製のＢ型粘度装置を用いて２５℃におけるＢ粘度をローターの回転速度６ｒｐｍ、６０ｒｐｍでそれぞれ１分後に測定した。また得られた粘度値からＴＩ値を算出した。結果を表４に示す。実施例においては、ローターの回転速度６ｒｐｍ及び６０ｒｐｍで測定したときのスラリー粘度の値は共に低く、かつ、ＴＩ値が３以下であり、良好な顔料分散組成物が得られていることがわかる。
Example 2
Disposable beaker 300 mL, titanium oxide 148 g with an average particle size of 0.4 μm, and ion-exchanged water and dispersant 1-8 or comparative dispersant 1-6 (100 parts by weight of titanium oxide) so that the slurry concentration becomes 75% by weight. 1 part by weight) was added, and the mixture was stirred (2500 rpm × 2 minutes) with a homodisper manufactured by Tokushu Kika Kogyo Co., Ltd. to prepare a slurry (pigment dispersion composition). The obtained slurry was measured for B viscosity at 25 ° C. using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. at a rotor rotational speed of 6 rpm and 60 rpm after 1 minute. Further, the TI value was calculated from the obtained viscosity value. The results are shown in Table 4. In the examples, the values of the slurry viscosity when measured at a rotor rotational speed of 6 rpm and 60 rpm are both low, and the TI value is 3 or less, indicating that a good pigment dispersion composition is obtained.
Claims (5)
（Ａ）成分：
構成モノマー単位比率が、不飽和一塩基酸／不飽和二塩基酸（モル比）＝９１／９〜７４／２６で、重量平均分子量（Ｍｗ）が２５０００〜６００００である、不飽和一塩基酸と不飽和二塩基酸との共重合体の塩
（Ｂ）成分：
構成モノマー単位比率が、不飽和一塩基酸／不飽和二塩基酸（モル比）＝６３／３７〜４７／５３で、重量平均分子量（Ｍｗ）が２５０００〜６００００である、不飽和一塩基酸と不飽和二塩基酸との共重合体の塩 A dispersant for inorganic pigment containing the following component (A) and component (B) in a ratio of (A) / (B) = 50/50 to 96/4 (weight ratio), wherein component (A) And the number average molecular weight (Mn) of (B) component is 20000-40000, respectively, and the dispersing agent for inorganic pigments which is Mw / Mn <= 3 .
(A) component:
An unsaturated monobasic acid having a constituent monomer unit ratio of unsaturated monobasic acid / unsaturated dibasic acid (molar ratio) = 91/9 to 74/26 and a weight average molecular weight (Mw) of 25,000 to 60,000 Salt (B) component of copolymer with unsaturated dibasic acid:
An unsaturated monobasic acid having a constituent monomer unit ratio of unsaturated monobasic acid / unsaturated dibasic acid (molar ratio) = 63/37 to 47/53 and a weight average molecular weight (Mw) of 25,000 to 60,000 Salts of copolymers with unsaturated dibasic acids
The pigment dispersion composition containing the dispersing agent for inorganic pigments in any one of Claims 1-4 .
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5957913A (en) * | 1982-09-29 | 1984-04-03 | Okutama Kogyo Kk | Production of high concentration slurry of synthetic calcium carbonate having good fluidity |
| JPS59193964A (en) * | 1983-04-15 | 1984-11-02 | Sannopuko Kk | Dispersing agent for light calcium carbonate |
| JPS60137429A (en) * | 1983-12-26 | 1985-07-22 | Lion Corp | Dispersant for calcium carbonate |
| JPH08188986A (en) * | 1995-01-05 | 1996-07-23 | Lion Corp | Pigment dispersant for coatd paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5957913A (en) * | 1982-09-29 | 1984-04-03 | Okutama Kogyo Kk | Production of high concentration slurry of synthetic calcium carbonate having good fluidity |
| JPS59193964A (en) * | 1983-04-15 | 1984-11-02 | Sannopuko Kk | Dispersing agent for light calcium carbonate |
| JPS60137429A (en) * | 1983-12-26 | 1985-07-22 | Lion Corp | Dispersant for calcium carbonate |
| JPH08188986A (en) * | 1995-01-05 | 1996-07-23 | Lion Corp | Pigment dispersant for coatd paper |
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