JPWO2016098578A1 - Pigment dispersion resin and pigment dispersion paste - Google Patents
Pigment dispersion resin and pigment dispersion paste Download PDFInfo
- Publication number
- JPWO2016098578A1 JPWO2016098578A1 JP2016564768A JP2016564768A JPWO2016098578A1 JP WO2016098578 A1 JPWO2016098578 A1 JP WO2016098578A1 JP 2016564768 A JP2016564768 A JP 2016564768A JP 2016564768 A JP2016564768 A JP 2016564768A JP WO2016098578 A1 JPWO2016098578 A1 JP WO2016098578A1
- Authority
- JP
- Japan
- Prior art keywords
- group
- pigment
- meth
- acrylate
- pigment dispersion
- 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.)
- Granted
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 131
- 239000006185 dispersion Substances 0.000 title claims abstract description 87
- 229920005989 resin Polymers 0.000 title claims abstract description 86
- 239000011347 resin Substances 0.000 title claims abstract description 86
- 239000000178 monomer Substances 0.000 claims abstract description 88
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 114
- -1 phosphoryloxy group Chemical group 0.000 claims description 71
- 125000001624 naphthyl group Chemical group 0.000 claims description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 125000005110 aryl thio group Chemical group 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 12
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000003367 polycyclic group Chemical group 0.000 abstract 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- 239000010408 film Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000001054 red pigment Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000001055 blue pigment Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 2
- 239000005971 1-naphthylacetic acid Substances 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- MVBJSQCJPSRKSW-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]prop-2-enamide Chemical compound OCC(CO)(CO)NC(=O)C=C MVBJSQCJPSRKSW-UHFFFAOYSA-N 0.000 description 2
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 2
- 125000001326 naphthylalkyl group Chemical group 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- KEDYOSQUMIXMFM-UHFFFAOYSA-N 1-ethenylchrysene Chemical compound C1=CC2=C3C=CC=CC3=CC=C2C2=C1C(C=C)=CC=C2 KEDYOSQUMIXMFM-UHFFFAOYSA-N 0.000 description 1
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- VYHUMZYFJVMWRC-UHFFFAOYSA-N n-(2-hydroxyethyl)-n-methylprop-2-enamide Chemical compound OCCN(C)C(=O)C=C VYHUMZYFJVMWRC-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FIBUWQFQYAAXHD-UHFFFAOYSA-N n-cyclopropyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1CC1 FIBUWQFQYAAXHD-UHFFFAOYSA-N 0.000 description 1
- LCXIFAOALNZGDO-UHFFFAOYSA-N n-cyclopropylprop-2-enamide Chemical compound C=CC(=O)NC1CC1 LCXIFAOALNZGDO-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000005582 pentacene group Chemical group 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- XIQGQTYUPQAUBV-UHFFFAOYSA-N prop-2-enoic acid;prop-1-en-2-ylbenzene;styrene Chemical group OC(=O)C=C.C=CC1=CC=CC=C1.CC(=C)C1=CC=CC=C1 XIQGQTYUPQAUBV-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005579 tetracene group Chemical group 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
Abstract
本発明が解決すべき課題は、高顔料濃度においても、顔料の分散性に優れる顔料分散樹脂、及び安定性に優れる顔料分散ペーストを提供することである。本発明は、固形分の総量を基準として、多環芳香族炭化水素を有するモノマーを1〜70質量%含有し、さらに該多環芳香族炭化水素を有するモノマーが、特定の多環芳香族炭化水素を有する重合性不飽和モノマーであることを特徴とする顔料分散樹脂を提供する。The problem to be solved by the present invention is to provide a pigment dispersion resin excellent in pigment dispersibility and a pigment dispersion paste excellent in stability even at a high pigment concentration. The present invention contains 1 to 70% by mass of a monomer having a polycyclic aromatic hydrocarbon based on the total amount of solids, and the monomer having the polycyclic aromatic hydrocarbon is a specific polycyclic aromatic carbon Provided is a pigment-dispersed resin, which is a polymerizable unsaturated monomer having hydrogen.
Description
[関連出願の相互参照]
本出願は、2014年12月15日に出願された、日本国特許出願第2014−252648号明細書(その開示全体が参照により本明細書中に援用される)に基づく優先権を主張する。
本発明は、高顔料濃度においても、様々な顔料の分散に好適な顔料分散樹脂、該顔料分散樹脂を含有する顔料分散ペーストに関する。[Cross-reference of related applications]
This application claims priority based on Japanese Patent Application No. 2014-252648 filed on Dec. 15, 2014, the entire disclosure of which is incorporated herein by reference.
The present invention relates to a pigment dispersion resin suitable for dispersing various pigments even at a high pigment concentration, and a pigment dispersion paste containing the pigment dispersion resin.
従来、顔料を顔料分散樹脂、溶媒及び場合によっては分散助剤の混合物中に分散させたペースト状の顔料分散体が、塗料、着色フィルム、着色シート、印刷用インキ、化粧品、磁石改質材、LED封止材、各種ゴム製品、樹脂成形品などの分野で広く用いられている。 Conventionally, a pigment-like pigment dispersion in which a pigment is dispersed in a mixture of a pigment-dispersing resin, a solvent, and, in some cases, a dispersion aid, is a paint, a colored film, a colored sheet, a printing ink, a cosmetic, a magnet modifier, Widely used in fields such as LED sealing materials, various rubber products, and resin molded products.
これらの分野では、発色性、鮮映性、導電性、仕上がり性、などの性能向上がますます要求されており、そのため、優れた顔料分散能力と、形成された顔料分散体中の顔料粒子を再凝集させないだけの優れた顔料分散安定性を有する顔料分散樹脂の開発がなされつつある。 In these fields, there is an ever-increasing demand for performance improvements such as color developability, sharpness, conductivity, finish, etc. Therefore, excellent pigment dispersion ability and pigment particles in the formed pigment dispersion Development of pigment dispersion resins having excellent pigment dispersion stability that does not cause re-aggregation has been underway.
顔料分散樹脂の設計にあたっては、顔料への濡れ性と顔料分散樹脂の溶媒中での分散安定性を両立させることが重要である。濡れ性に関しては、顔料分散樹脂が低粘度、低分子量であること、さらに顔料表面の疎水部と顔料分散樹脂の疎水部との相互作用があることが有利であるといわれ、分散安定化に関しては、顔料表面での立体反発層の形成や顔料分散樹脂の連続相への溶解性が良いことが有利であるといわれている。 In designing the pigment dispersion resin, it is important to satisfy both the wettability to the pigment and the dispersion stability of the pigment dispersion resin in the solvent. Regarding wettability, it is said that the pigment-dispersed resin has a low viscosity and a low molecular weight, and that it is advantageous that there is an interaction between the hydrophobic part of the pigment surface and the hydrophobic part of the pigment-dispersed resin. It is said that it is advantageous that the solid repulsion layer is formed on the pigment surface and the solubility of the pigment-dispersed resin in the continuous phase is good.
また、顔料分散樹脂が塗膜やフィルムや印刷物などの最終製品そのものの性能に悪い影響を及ぼさないように、少量の顔料分散樹脂で上記の効果を発揮することも重要となっている。 It is also important that a small amount of the pigment-dispersed resin exerts the above-described effect so that the pigment-dispersed resin does not adversely affect the performance of the final product itself such as a coating film, film or printed matter.
例えば、特許文献1には、特定のカーボンブラックを顔料分散剤によって分散させ、該顔料分散剤が、スチレン−α−メチルスチレン−アクリル酸共重合体および/またはスチレン−無水マレイン酸共重合体であることを特徴とする導電性高濃度カーボンブラック分散体を開示している。しかしながら、顔料分散ペーストを長期に貯蔵性する場合は、顔料の安定性が劣り、顔料が再凝集することがあった。
また、特許文献2には、アミンとジカルボン酸無水物基含有ポリマーとの反応生成物を顔料の分散添加剤として使用することが開示されている。しかしながら、顔料分散樹脂の極性が高いため、塗膜やフィルムなどの最終製品において、耐水性や耐候性などの性能が悪化する場合があった。For example, Patent Document 1 discloses that specific carbon black is dispersed with a pigment dispersant, and the pigment dispersant is a styrene-α-methylstyrene-acrylic acid copolymer and / or a styrene-maleic anhydride copolymer. An electrically conductive high concentration carbon black dispersion is disclosed. However, when the pigment dispersion paste is stored for a long period of time, the pigment stability is inferior and the pigment may reaggregate.
Patent Document 2 discloses the use of a reaction product of an amine and a dicarboxylic anhydride group-containing polymer as a pigment dispersion additive. However, due to the high polarity of the pigment-dispersed resin, performance such as water resistance and weather resistance may deteriorate in the final product such as a coating film or film.
本発明の目的は、高顔料濃度においても、顔料の分散性に優れる顔料分散樹脂、及び安定性に優れる顔料分散ペーストを提供することである。 An object of the present invention is to provide a pigment dispersion resin excellent in pigment dispersibility and a pigment dispersion paste excellent in stability even at a high pigment concentration.
発明者等は、上記課題を解決するために鋭意検討した結果、多環芳香族炭化水素を有するモノマーを含有する顔料分散樹脂によって、上記課題の解決が達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors have found that the above problems can be solved by a pigment dispersion resin containing a monomer having a polycyclic aromatic hydrocarbon, and to complete the present invention. It came.
即ち、本発明は、以下の顔料分散樹脂、及び顔料分散ペーストを提供するものである。 That is, the present invention provides the following pigment dispersion resin and pigment dispersion paste.
項1.多環芳香族炭化水素を有するモノマー(A)を1〜70質量%含む原料モノマーの共重合体であることを特徴とする顔料分散樹脂。 Item 1. A pigment-dispersed resin, which is a copolymer of raw material monomers containing 1 to 70% by mass of a monomer (A) having a polycyclic aromatic hydrocarbon.
項2.多環芳香族炭化水素を有するモノマー(A)が、下記式(1)で表わされる多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)であることを特徴とする前記項1に記載の顔料分散樹脂。 Item 2. Item 1 above, wherein the monomer (A) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon represented by the following formula (1). The pigment-dispersed resin described in 1.
(式中、Rは水素原子又はメチル基を示し、Aは多環芳香族炭化水素基を示し、Wは存在しても存在しなくても良い。Wが存在する場合、Wは炭素原子、窒素原子及び/又は酸素原子の数が1〜20の有機基であり、Wが存在しない場合、WはAに直接結合する。)
項3.多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)が、下記式(2)で表わされるナフチル基を有する重合性不飽和モノマー又はその誘導体(A−2)であることを特徴とする前記項2に記載の顔料分散樹脂。(Wherein R represents a hydrogen atom or a methyl group, A represents a polycyclic aromatic hydrocarbon group, W may or may not be present. When W is present, W is a carbon atom, When the number of nitrogen atoms and / or oxygen atoms is 1-20, and W is not present, W is directly bonded to A.)
Item 3. The polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer having a naphthyl group represented by the following formula (2) or a derivative (A-2) thereof: Item 3. The pigment-dispersed resin according to Item 2.
(式中、Rは水素原子又はメチル基を示し、X及びYは同一であっても異なっていてもよく、水素原子、アルキル基、アルコキシ基、水酸基、スルホン酸基、カルボキシル基、アミノ基、ニトロ基、ハロゲン原子、アリールオキシ基、アルキルチオ基又はアリールチオ基のいずれかを示し、Wは存在しても存在しなくても良い。Wが存在する場合、Wは炭素原子、窒素原子及び/又は酸素原子の数が1〜20の有機基であり、Wが存在しない場合、Wはナフチル基に直接結合する。)
項4.ナフチル基を有する重合性不飽和モノマー又はその誘導体(A−2)が、下記式(3)で表わされるナフチル(メタ)アクリレート又はその誘導体(A−3)であることを特徴とする前記項3に記載の顔料分散樹脂。(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, Represents a nitro group, a halogen atom, an aryloxy group, an alkylthio group or an arylthio group, and W may or may not be present, and when W is present, W is a carbon atom, a nitrogen atom and / or When the number of oxygen atoms is an organic group of 1 to 20 and W is not present, W is directly bonded to the naphthyl group.)
Item 4. Item 3. The polymerizable unsaturated monomer having a naphthyl group or a derivative (A-2) thereof is a naphthyl (meth) acrylate represented by the following formula (3) or a derivative (A-3) thereof: The pigment-dispersed resin described in 1.
(式中、Rは水素原子又はメチル基を示し、X及びYは同一であっても異なっていてもよく、水素原子、アルキル基、アルコキシ基、水酸基、スルホン酸基、カルボキシル基、アルコキシカルボニルオキシ基、ホスホリルオキシ基、アミノ基、ニトロ基、ハロゲン原子、アリールオキシ基、アルキルチオ基又はアリールチオ基のいずれかを示す。Wが存在する場合、Wは炭素原子、窒素原子及び/もしくは酸素原子の数が1〜20の有機基又は単結合である。)
項5.ナフチル(メタ)アクリレート又はその誘導体(A−3)が、下記式(4)で表わされる4−置換−1−ナフチル(メタ)アクリレート(A−4)又はその誘導体であることを特徴とする前記項4に記載の顔料分散樹脂。(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, alkyl group, alkoxy group, hydroxyl group, sulfonic acid group, carboxyl group, alkoxycarbonyloxy group) Group, phosphoryloxy group, amino group, nitro group, halogen atom, aryloxy group, alkylthio group or arylthio group, when W is present, W is the number of carbon atoms, nitrogen atoms and / or oxygen atoms Is an organic group of 1 to 20 or a single bond.)
Item 5. Naphthyl (meth) acrylate or a derivative thereof (A-3) is 4-substituted-1-naphthyl (meth) acrylate (A-4) or a derivative thereof represented by the following formula (4): Item 5. A pigment-dispersed resin according to Item 4.
(式中、Rは水素原子又はメチル基を示し、Zは水酸基、炭素数1〜8のアルキル基、炭素数1〜8のアルコキシ基、又は炭素数1〜8のアルコキシカルボニルオキシ基、ホスホリルオキシ基を示す。)
項6.重合性不飽和モノマー成分の総量を基準として、スチレンを5〜65質量%含有することを特徴とする前記項2〜5のいずれか1項に記載の顔料分散樹脂。(In the formula, R represents a hydrogen atom or a methyl group, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, or phosphoryloxy. Group.)
Item 6. Item 6. The pigment-dispersed resin according to any one of Items 2 to 5, which contains 5 to 65% by mass of styrene based on the total amount of the polymerizable unsaturated monomer components.
項7.重合性不飽和モノマー成分の総量を基準として、さらに、ポリアルキレングリコールマクロモノマーを1〜30質量%含有することを特徴とする前記項2〜6のいずれか1項に記載の顔料分散樹脂。 Item 7. Item 7. The pigment-dispersed resin according to any one of Items 2 to 6, further comprising 1 to 30% by mass of a polyalkylene glycol macromonomer based on the total amount of the polymerizable unsaturated monomer component.
項8.さらに、少なくとも1種の(メタ)アクリルアミド化合物を含有することを特徴とする前記項2〜7のいずれか1項に記載の顔料分散樹脂。 Item 8. Item 8. The pigment-dispersed resin as described in any one of Items 2 to 7, further comprising at least one (meth) acrylamide compound.
項9.前記項1〜8のいずれか1項に記載の顔料分散樹脂及び顔料を含有することを特徴とする顔料分散ペースト。 Item 9. A pigment dispersion paste comprising the pigment dispersion resin and the pigment according to any one of items 1 to 8.
項10.前記項1〜8のいずれか1項に記載の顔料分散樹脂及び導電性顔料を含有することを特徴とする導電性顔料分散ペースト。 Item 10. 9. A conductive pigment dispersion paste comprising the pigment dispersion resin according to any one of items 1 to 8 and a conductive pigment.
項11.多環芳香族炭化水素を有するモノマー(A)を1〜70質量%含む原料モノマーを共重合する工程を含む、顔料分散樹脂の製造方法。 Item 11. The manufacturing method of pigment dispersion resin including the process of copolymerizing the raw material monomer which contains 1-70 mass% of monomers (A) which have a polycyclic aromatic hydrocarbon.
項12.多環芳香族炭化水素を有するモノマー(A)が、下記式(1)で表わされる多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)であることを特徴とする前記項11に記載の方法。 Item 12. Item 11 above, wherein the monomer (A) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon represented by the following formula (1). The method described in 1.
(式中、Rは水素原子又はメチル基を示し、Aは多環芳香族炭化水素基を示し、Wは存在しても存在しなくても良い。Wが存在する場合、Wは炭素原子、窒素原子及び/又は酸素原子の数が1〜20の有機基であり、Wが存在しない場合、WはAに直接結合する。)
項13.多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)が、下記式(2)で表わされるナフチル基を有する重合性不飽和モノマー又はその誘導体(A−2)であることを特徴とする前記項12に記載の方法。(Wherein R represents a hydrogen atom or a methyl group, A represents a polycyclic aromatic hydrocarbon group, W may or may not be present. When W is present, W is a carbon atom, When the number of nitrogen atoms and / or oxygen atoms is 1-20, and W is not present, W is directly bonded to A.)
Item 13. The polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer having a naphthyl group represented by the following formula (2) or a derivative (A-2) thereof: Item 13. The method according to Item 12.
(式中、Rは水素原子又はメチル基を示し、X及びYは同一であっても異なっていてもよく、水素原子、アルキル基、アルコキシ基、水酸基、スルホン酸基、カルボキシル基、アミノ基、ニトロ基、ハロゲン原子、アリールオキシ基、アルキルチオ基又はアリールチオ基のいずれかを示し、Wは存在しても存在しなくても良い。Wが存在する場合、Wは炭素原子、窒素原子及び/又は酸素原子の数が1〜20の有機基であり、Wが存在しない場合、Wはナフチル基に直接結合する。)
項14.ナフチル基を有する重合性不飽和モノマー又はその誘導体(A−2)が、下記式(3)で表わされるナフチル(メタ)アクリレート又はその誘導体(A−3)であることを特徴とする前記項13に記載の方法。(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, Represents a nitro group, a halogen atom, an aryloxy group, an alkylthio group or an arylthio group, and W may or may not be present, and when W is present, W is a carbon atom, a nitrogen atom and / or When the number of oxygen atoms is an organic group of 1 to 20 and W is not present, W is directly bonded to the naphthyl group.)
Item 14. Item 13. The polymerizable unsaturated monomer having a naphthyl group or a derivative (A-2) thereof is a naphthyl (meth) acrylate represented by the following formula (3) or a derivative (A-3) thereof: The method described in 1.
(式中、Rは水素原子又はメチル基を示し、X及びYは同一であっても異なっていてもよく、水素原子、アルキル基、アルコキシ基、水酸基、スルホン酸基、カルボキシル基、アルコキシカルボニルオキシ基、ホスホリルオキシ基、アミノ基、ニトロ基、ハロゲン原子、アリールオキシ基、アルキルチオ基又はアリールチオ基のいずれかを示す。)
項15.ナフチル(メタ)アクリレート又はその誘導体(A−3)が、下記式(4)で表わされる4−置換−1−ナフチル(メタ)アクリレート(A−4)であることを特徴とする前記項14に記載の方法。(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, alkyl group, alkoxy group, hydroxyl group, sulfonic acid group, carboxyl group, alkoxycarbonyloxy group) Group, phosphoryloxy group, amino group, nitro group, halogen atom, aryloxy group, alkylthio group or arylthio group.)
Item 15. Item 14 is characterized in that the naphthyl (meth) acrylate or derivative (A-3) thereof is 4-substituted-1-naphthyl (meth) acrylate (A-4) represented by the following formula (4). The method described.
(式中、Rは水素原子又はメチル基を示し、Zは水酸基、炭素数1〜8のアルキル基、炭素数1〜8のアルコキシ基、又は炭素数1〜8のアルコキシカルボニルオキシ基、ホスホリルオキシ基を示す。)
項16.重合性不飽和モノマー成分の総量を基準として、スチレンを5〜65質量%含有することを特徴とする前記項12〜15のいずれか1項に記載の方法。(In the formula, R represents a hydrogen atom or a methyl group, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, or phosphoryloxy. Group.)
Item 16. Item 16. The method according to any one of Items 12 to 15, which contains 5 to 65% by mass of styrene based on the total amount of the polymerizable unsaturated monomer component.
項17.重合性不飽和モノマー成分の総量を基準として、さらに、ポリアルキレングリコールマクロモノマーを1〜30質量%含有することを特徴とする前記項12〜16のいずれか1項に記載の方法。 Item 17. Item 17. The method according to any one of Items 12 to 16, further comprising 1 to 30% by mass of a polyalkylene glycol macromonomer based on the total amount of the polymerizable unsaturated monomer component.
項18.さらに、少なくとも1種の(メタ)アクリルアミド化合物を含有することを特徴とする前記項12〜17のいずれか1項に記載の方法。 Item 18. Item 18. The method according to any one of Items 12 to 17, further comprising at least one (meth) acrylamide compound.
項19.前記項11〜18のいずれか1項に記載の方法により顔料分散樹脂を得る工程、及び
当該工程で得られた顔料分散樹脂と顔料とを混合する工程
を含む、顔料分散ペーストの製造方法。Item 19. The manufacturing method of a pigment dispersion paste including the process of obtaining the pigment dispersion resin by the method of any one of said claim | items 11-18, and the process of mixing the pigment dispersion resin and pigment obtained at the said process.
項20.前記項11〜18のいずれか1項に記載の方法により顔料分散樹脂を得る工程、及び
当該工程で得られた顔料分散樹脂と導電性顔料とを混合する工程
を含む、導電性顔料分散ペーストの製造方法。Item 20. A conductive pigment dispersion paste comprising the steps of obtaining a pigment dispersion resin by the method according to any one of items 11 to 18 and a step of mixing the pigment dispersion resin and the conductive pigment obtained in the step. Production method.
本発明の顔料分散樹脂により、高顔料濃度においても、顔料の分散性、安定性などに優れた顔料分散ペーストを得ることができる。 With the pigment dispersion resin of the present invention, a pigment dispersion paste excellent in pigment dispersibility and stability can be obtained even at a high pigment concentration.
顔料分散樹脂
本発明の顔料分散樹脂は、固形分の総量を基準として、多環芳香族炭化水素を有するモノマー(A)を1〜70質量%、好ましくは5〜60質量%、より好ましくは10〜50質量%含有することを特徴とする。本明細書において、樹脂がその原料となるモノマーXを含有する、とは、相反する内容を別途明記しない限り、上記樹脂が、上記モノマーXを含む原料モノマーの(共)重合体であることを意味する。本明細書において、(共)重合体とは重合体又は共重合体を意味する。本発明の顔料分散樹脂は、多環芳香族炭化水素を有するモノマー(A)を1〜70質量%、好ましくは5〜60質量%、より好ましくは10〜50質量%含む原料モノマーの共重合体であることを特徴とする。 Pigment-dispersed resin The pigment-dispersed resin of the present invention contains 1 to 70% by mass, preferably 5 to 60% by mass, more preferably 10% of the monomer (A) having polycyclic aromatic hydrocarbons based on the total amount of solids. It is characterized by containing ˜50 mass%. In the present specification, “the resin contains the monomer X as a raw material” means that the resin is a (co) polymer of the raw material monomer containing the monomer X, unless otherwise specified. means. In the present specification, the (co) polymer means a polymer or a copolymer. The pigment dispersion resin of the present invention is a copolymer of raw material monomers containing 1 to 70% by mass, preferably 5 to 60% by mass, more preferably 10 to 50% by mass of the monomer (A) having a polycyclic aromatic hydrocarbon. It is characterized by being.
上記顔料分散樹脂の種類としては、例えば、アクリル樹脂、ポリエステル樹脂、エポキシ樹脂、ポリエーテル樹脂、アルキド樹脂、ウレタン樹脂、シリコーン樹脂、ポリカーボネート樹脂、シリケート樹脂、塩素系樹脂、フッ素系樹脂、及びこれらの複合樹脂などが挙げられるが、特にアクリル樹脂が好ましい。 Examples of the pigment dispersion resin include acrylic resin, polyester resin, epoxy resin, polyether resin, alkyd resin, urethane resin, silicone resin, polycarbonate resin, silicate resin, chlorine resin, fluorine resin, and these. Examples include composite resins, and acrylic resin is particularly preferable.
尚、本明細書において、「(メタ)アクリレート」は、アクリレート及び/又はメタクリレートを意味し、「(メタ)アクリル酸」は、アクリル酸及び/又はメタクリル酸を意味する。また、「(メタ)アクリロイル」は、アクリロイル及び/又はメタクリロイルを意味する。また、「(メタ)アクリルアミド」は、アクリルアミド及び/又はメタクリルアミドを意味する。また、本明細書において、「誘導体」とは、ある化合物に対し、官能基の導入、原子の置換、又はその他の化学反応により分子内の小部分(複数の部分でもよい)を変化させて得られる化合物を意味する。例えば、ナフタレンに、アルキル基、アルコキシ基、水酸基、スルホン酸基、カルボキシル基、アミノ基、ニトロ基、ハロゲン原子、アリールオキシ基、アルキルチオ基、アリールチオ基などの官能基を、1種又は2種以上(例えば、1種又は2種)導入した化合物はナフタレン誘導体である。かかる誘導体において導入する官能基の数は限定されず、1個又は2個以上の官能基を導入することができ、好ましくは1〜3個、より好ましくは1〜2個である。 In the present specification, “(meth) acrylate” means acrylate and / or methacrylate, and “(meth) acrylic acid” means acrylic acid and / or methacrylic acid. “(Meth) acryloyl” means acryloyl and / or methacryloyl. “(Meth) acrylamide” means acrylamide and / or methacrylamide. In this specification, a “derivative” is obtained by changing a small part (or a plurality of parts) in a molecule by introducing a functional group, substituting an atom, or other chemical reaction with respect to a compound. Means a compound. For example, naphthalene has one or more functional groups such as an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, a nitro group, a halogen atom, an aryloxy group, an alkylthio group, and an arylthio group. The introduced compound is a naphthalene derivative (for example, one or two). The number of functional groups introduced in such a derivative is not limited, and one or more functional groups can be introduced, preferably 1 to 3, more preferably 1 to 2.
多環芳香族炭化水素を有するモノマー(A)
本発明の顔料分散樹脂で用いることができる多環芳香族炭化水素を有するモノマー(A)の多環芳香族炭化水素としては、例えば、ナフタレン環、アントラセン環、トリフェニレン環、テトラフェン環、テトラセン環、クリセン環、ピレン環、ペンタセン環、ヘキサセン環、ヘプタセン環、コロネン環、ケクレン環等を有する炭化水素基及びその誘導体が挙げられる。 Monomer having polycyclic aromatic hydrocarbon (A)
Examples of the polycyclic aromatic hydrocarbon of the monomer (A) having a polycyclic aromatic hydrocarbon that can be used in the pigment dispersion resin of the present invention include a naphthalene ring, an anthracene ring, a triphenylene ring, a tetraphen ring, and a tetracene ring. , A hydrocarbon group having a chrysene ring, a pyrene ring, a pentacene ring, a hexacene ring, a heptacene ring, a coronene ring, a ketrene ring, and the like, and derivatives thereof.
なかでも、上記多環芳香族炭化水素を有するモノマー(A)としては、下記式(1)で表わされる多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)であることが好ましい。 Among these, the monomer (A) having a polycyclic aromatic hydrocarbon is preferably a polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon represented by the following formula (1). .
(式中、Rは水素原子又はメチル基を示し、Aは多環芳香族炭化水素基を示し、Wは存在しても存在しなくても良い。Wが存在する場合、Wは炭素原子、窒素原子及び/又は酸素原子の数が1〜20の有機基であり、Wが存在しない場合、WはAに直接結合する。)
Wが存在しない場合とは、Wが単結合である場合と言い換えることもできる。従って、式(1)において、「Wは存在しても存在しなくても良い。Wが存在する場合、Wは炭素原子、窒素原子及び/又は酸素原子の数が1〜20の有機基であり、Wが存在しない場合、WはAに直接結合する。」とは、「Wは単結合であるか、又は炭素原子、窒素原子及び/もしくは酸素原子の数が1〜20の有機基である」と言い換えることができる。(Wherein R represents a hydrogen atom or a methyl group, A represents a polycyclic aromatic hydrocarbon group, W may or may not be present. When W is present, W is a carbon atom, When the number of nitrogen atoms and / or oxygen atoms is 1-20, and W is not present, W is directly bonded to A.)
The case where W does not exist can be paraphrased as the case where W is a single bond. Therefore, in the formula (1), “W may or may not be present. When W is present, W is an organic group having 1 to 20 carbon atoms, nitrogen atoms and / or oxygen atoms. Yes, when W is not present, W is directly bonded to A ”means“ W is a single bond or an organic group having 1 to 20 carbon atoms, nitrogen atoms and / or oxygen atoms. In other words.
尚、「重合性不飽和モノマー」は、ラジカル重合しうる重合性不飽和基を有するモノマーを意味し、該重合性不飽和基としては、例えば、(メタ)アクリロイル基、アクリルアミド基、ビニル基、アリル基、(メタ)アクリロイルオキシ基、ビニルエーテル基などが挙げられる。 The “polymerizable unsaturated monomer” means a monomer having a polymerizable unsaturated group capable of radical polymerization, and examples of the polymerizable unsaturated group include (meth) acryloyl group, acrylamide group, vinyl group, Examples include an allyl group, a (meth) acryloyloxy group, and a vinyl ether group.
上記多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)としては、具体的には、例えば、ビニルナフタレン、ナフチル(メタ)アクリレート、ナフチルアルキル(メタ)アクリレート、ビニルアントラセン、アントラセニル(メタ)アクリレート、アントラセニルアルキル(メタ)アクリレート、ビニルピレン、ピレニル(メタ)アクリレート、ピレニルアルキル(メタ)アクリレート、ビニルクリセン、ビニルナフタセン、ビニルペンタセン、及びこれらの誘導体などが挙げられる。また、グリシジル基やイソシアネート基などの反応性官能基を有する重合性不飽和基モノマーと、該反応性官能基と反応する官能基を有する多環芳香族炭化水素とを反応せしめたものも含まれる。互いに反応する官能基の組み合わせであればいずれも好適に使用できるが、カルボキシル基とグリシジル基、アミノ基とグリシジル基、水酸基とイソシアネート基の組み合わせがより好ましい。具体的には、例えば、グリシジル(メタ)アクリレートと1−ナフチル酢酸、2−(メタ)アクリロイルオキシエチルイソシアネートと1−ナフトール、2−(メタ)アクリロイルオキシエチルイソシアネートと1−(2−ナフチル)エタノールの組み合わせなどが挙げられる。
これらは1種を単独で又は2種以上を併用して用いることができる。Specific examples of the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon include, for example, vinyl naphthalene, naphthyl (meth) acrylate, naphthylalkyl (meth) acrylate, vinylanthracene, anthracenyl ( Examples include meth) acrylate, anthracenylalkyl (meth) acrylate, vinylpyrene, pyrenyl (meth) acrylate, pyrenylalkyl (meth) acrylate, vinyl chrysene, vinyl naphthacene, vinyl pentacene, and derivatives thereof. Also included are those obtained by reacting a polymerizable unsaturated group monomer having a reactive functional group such as a glycidyl group or an isocyanate group with a polycyclic aromatic hydrocarbon having a functional group that reacts with the reactive functional group. . Any combination of functional groups that react with each other can be suitably used, but a combination of a carboxyl group and a glycidyl group, an amino group and a glycidyl group, or a hydroxyl group and an isocyanate group is more preferable. Specifically, for example, glycidyl (meth) acrylate and 1-naphthyl acetic acid, 2- (meth) acryloyloxyethyl isocyanate and 1-naphthol, 2- (meth) acryloyloxyethyl isocyanate and 1- (2-naphthyl) ethanol The combination etc. are mentioned.
These can be used alone or in combination of two or more.
多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)及び当該モノマーが有する多環芳香族炭化水素において、誘導体とは、例えば、多環芳香族部分に水酸基、炭素数1〜8のアルキル基、炭素数1〜8のアルコキシ基、又は炭素数1〜8のアルコキシカルボニルオキシ基、ホスホリルオキシ基等の置換基が1〜3個(例えば、1個、2個、3個等)置換したものを意味する。 In the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon and the polycyclic aromatic hydrocarbon of the monomer, the derivative is, for example, a hydroxyl group, a carbon number of 1 to 8 in the polycyclic aromatic moiety. 1 to 3 substituents such as an alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, and a phosphoryloxy group (for example, 1, 2, 3, etc.) Means a replacement.
なかでも、多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)としては、下記式(2)で表わされるナフチル基を有する重合性不飽和モノマー又はその誘導体(A−2)であることが好ましい。 Among them, the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer having a naphthyl group represented by the following formula (2) or a derivative (A-2) thereof. Preferably there is.
(式中、Rは水素原子又はメチル基を示し、X及びYは同一であっても異なっていてもよく、水素原子、アルキル基、アルコキシ基、水酸基、スルホン酸基、カルボキシル基、アミノ基、ニトロ基、ハロゲン原子、アリールオキシ基、アルキルチオ基又はアリールチオ基のいずれかを示し、Wは存在しても存在しなくても良い。Wが存在する場合、Wは炭素原子、窒素原子及び/又は酸素原子の数が1〜20の有機基であり、Wが存在しない場合、Wはナフチル基に直接結合する。)
上記ナフチル基を有する重合性不飽和モノマー又はその誘導体(A−2)としては、例えば、ビニルナフタレン、ナフチル(メタ)アクリレート、ナフチルアルキル(メタ)アクリレート、及びこれらの誘導体などが挙げられる。これらは1種を単独で又は2種以上を併用して用いることができる。(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, Represents a nitro group, a halogen atom, an aryloxy group, an alkylthio group or an arylthio group, and W may or may not be present, and when W is present, W is a carbon atom, a nitrogen atom and / or When the number of oxygen atoms is an organic group of 1 to 20 and W is not present, W is directly bonded to the naphthyl group.)
Examples of the polymerizable unsaturated monomer having a naphthyl group or a derivative (A-2) thereof include vinyl naphthalene, naphthyl (meth) acrylate, naphthylalkyl (meth) acrylate, and derivatives thereof. These can be used alone or in combination of two or more.
なかでも、ナフチル(メタ)アクリレート又はその誘導体(A−2)が、下記式(3)で表わされるナフチル(メタ)アクリレート又はその誘導体(A−3)であることが好ましい。 Especially, it is preferable that a naphthyl (meth) acrylate or its derivative (A-2) is a naphthyl (meth) acrylate or its derivative (A-3) represented by following formula (3).
(式中、Rは水素原子又はメチル基を示し、X及びYは同一であっても異なっていてもよく、水素原子、アルキル基、アルコキシ基、水酸基、スルホン酸基、カルボキシル基、アルコキシカルボニルオキシ基、ホスホリルオキシ基、アミノ基、ニトロ基、ハロゲン原子、アリールオキシ基、アルキルチオ基又はアリールチオ基のいずれかを示す。)
上記ナフチル(メタ)アクリレート又はその誘導体(A−3)としては、例えば、1−ナフチル(メタ)アクリレート、2−ナフチル(メタ)アクリレート、及びこれらの誘導体などが挙げられ、これらは1種を単独で又は2種以上を併用して用いることができる。(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, alkyl group, alkoxy group, hydroxyl group, sulfonic acid group, carboxyl group, alkoxycarbonyloxy group) Group, phosphoryloxy group, amino group, nitro group, halogen atom, aryloxy group, alkylthio group or arylthio group.)
As said naphthyl (meth) acrylate or its derivative (A-3), 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, these derivatives, etc. are mentioned, for example, These are individual 1 type. Or in combination of two or more.
なかでも、ナフチル(メタ)アクリレート又はその誘導体(A−3)が、下記式(4)で表わされる4−置換−1−ナフチル(メタ)アクリレート(A−4)又はその誘導体であることが好ましい。 Especially, it is preferable that a naphthyl (meth) acrylate or its derivative (A-3) is 4-substituted-1-naphthyl (meth) acrylate (A-4) or its derivative represented by following formula (4). .
(式中、Rは水素原子又はメチル基を示し、Zは水酸基、炭素数1〜8のアルキル基、炭素数1〜8のアルコキシ基、又は炭素数1〜8のアルコキシカルボニルオキシ基、ホスホリルオキシ基を示す。)
上記4−置換−1−ナフチル(メタ)アクリレート(A−4)又はその誘導体としては、例えば、下記式(5)で表される4−置換−1−ナフチル(メタ)アクリレート(A−5)が挙げられる。(In the formula, R represents a hydrogen atom or a methyl group, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, or phosphoryloxy. Group.)
Examples of the 4-substituted-1-naphthyl (meth) acrylate (A-4) or a derivative thereof include 4-substituted-1-naphthyl (meth) acrylate (A-5) represented by the following formula (5). Is mentioned.
(式中、Rは水素原子又はメチル基を示し、X’は水酸基又は炭素数1〜8のアルコキシ基を示し、Zは水酸基、炭素数1〜8のアルキル基、炭素数1〜8のアルコキシ基、又は炭素数1〜8のアルコキシカルボニルオキシ基、ホスホリルオキシ基を示す。)。4−置換−1−ナフチル(メタ)アクリレート(A−5)においては、X’はナフチル基の2位に置換していることが好ましい。 (In the formula, R represents a hydrogen atom or a methyl group, X ′ represents a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Group, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, or a phosphoryloxy group.). In 4-substituted-1-naphthyl (meth) acrylate (A-5), X ′ is preferably substituted at the 2-position of the naphthyl group.
また、より具体的には、多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)としては、例えば、4−メチル−1−ナフチル(メタ)アクリレート、4−エチル−1−ナフチル(メタ)アクリレート、4−メトキシ−1−ナフチル(メタ)アクリレート、4−エトキシ−1−ナフチル(メタ)アクリレート、4−ヒドロキシ−1−ナフチル(メタ)アクリレート、2−メトキシ−4−ヒドロキシ−1−ナフチル(メタ)アクリレート、2−エトキシ−4−ヒドロキシ−1−ナフチル(メタ)アクリレート、2−ヒドロキシ−4−メトキシ−1−ナフチル(メタ)アクリレート、2−ヒドロキシ−4−エトキシ−1−ナフチル(メタ)アクリレート、4−メトキシカルボニルオキシ−1−ナフチル(メタ)アクリレート、4−フェノキシカルボニルオキシ−1−ナフチル(メタ)アクリレート、及び4−ホスホリルオキシ−1−ナフチル(メタ)アクリレート、若しくはその誘導体などが挙げられる。これらは1種を単独で又は2種以上を併用して用いることができる。 More specifically, examples of the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon include 4-methyl-1-naphthyl (meth) acrylate and 4-ethyl-1-naphthyl. (Meth) acrylate, 4-methoxy-1-naphthyl (meth) acrylate, 4-ethoxy-1-naphthyl (meth) acrylate, 4-hydroxy-1-naphthyl (meth) acrylate, 2-methoxy-4-hydroxy-1 -Naphtyl (meth) acrylate, 2-ethoxy-4-hydroxy-1-naphthyl (meth) acrylate, 2-hydroxy-4-methoxy-1-naphthyl (meth) acrylate, 2-hydroxy-4-ethoxy-1-naphthyl (Meth) acrylate, 4-methoxycarbonyloxy-1-naphthyl (meth) acrylate, 4-phenoxy Carbonyloxy-1-naphthyl (meth) acrylate, and 4-phosphoryloxy-1-naphthyl (meth) acrylate, or a derivative thereof, and the like. These can be used alone or in combination of two or more.
本発明の多環芳香族炭化水素を有する分散樹脂が、顔料の分散性及び安定性に効果がある理由としては、詳しい事は解っていないが、例えば、顔料が芳香環を有している場合、顔料と分散樹脂間のπ−π相互作用により安定化するためだと考えられる。尚、π−π相互作用とは、芳香環の間に働く分散力であり、2つの芳香環がコインを積み重ねたような配置で安定化する傾向があるため、スタッキング相互作用とも呼ばれる。 The reason why the dispersion resin having the polycyclic aromatic hydrocarbon of the present invention is effective in the dispersibility and stability of the pigment is not known in detail, but for example, when the pigment has an aromatic ring This is thought to be due to the stabilization by the π-π interaction between the pigment and the dispersion resin. The π-π interaction is a dispersion force acting between the aromatic rings and is also called a stacking interaction because it tends to be stabilized in an arrangement in which two aromatic rings are stacked with coins.
また、上記4−置換−1−ナフチル(メタ)アクリレート(A−4)の置換基が、顔料の分散性及び安定性に効果がある理由としては、詳しい事は解っていないが、例えば、置換基を有することによって芳香環の静電ポテンシャルが上昇し顔料との親和性を高めるためだと推測している。 Further, the reason why the substituent of the 4-substituted-1-naphthyl (meth) acrylate (A-4) is effective in the dispersibility and stability of the pigment is not known in detail. It is speculated that this is because the electrostatic potential of the aromatic ring is increased and the affinity with the pigment is increased.
多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)以外の重合性不飽和モノマー
本発明の顔料分散樹脂は、多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)と該(A−1)以外の重合性不飽和モノマーを共重合して得ることができる。多環芳香族炭化水素を有する重合性不飽和モノマー(A−1)以外の重合性不飽和モノマーとしては、通常、アクリル樹脂の合成で使用される重合性不飽和モノマーであれば特に制限なく用いることができ、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート等の炭素数3以下のアルキル(メタ)アクリレート、n−ブチル(メタ)アクリレート、i−ブチル(メタ)アクリレート、t−ブチル(メタ)アクリレート、n−ヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、トリデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、メチルシクロヘキシル(メタ)アクリレート、t−ブチルシクロヘキシル(メタ)アクリレート、シクロドデシル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート等のアルキル又はシクロアルキル(メタ)アクリレート;イソボルニル(メタ)アクリレートなどのイソボルニル基を有する重合性不飽和化合物;アダマンチル(メタ)アクリレートなどのアダマンチル基を有する重合性不飽和化合物;ベンジル(メタ)アクリレート、スチレン、α−メチルスチレン、ビニルトルエン等の単環芳香環含有重合性不飽和モノマー;2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレートなどの(メタ)アクリル酸と炭素数2〜8の2価アルコールとのモノエステル化物、該(メタ)アクリル酸と炭素数2〜8の2価アルコールとのモノエステル化物のε−カプロラクトン変性体、N−ヒドロキシメチル(メタ)アクリルアミド、アリルアルコ−ル、分子末端が水酸基であるポリオキシアルキレン鎖を有する(メタ)アクリレート等の水酸基含有重合性不飽和モノマー;(メタ)アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレート等のカルボキシル基含有重合性不飽和モノマー;(メタ)アクリロニトリル、(メタ)アクリルアミド、N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、グリシジル(メタ)アクリレートとアミン類との付加物等のウレタン結合を含まない含窒素重合性不飽和モノマー;イソシアネート基含有重合性不飽和モノマーと水酸基含有化合物との反応生成物又は水酸基含有重合性不飽和モノマーとイソシアネート基含有化合物との反応生成物等のウレタン結合を有する重合性不飽和モノマー;グリシジル(メタ)アクリレート、β−メチルグリシジル(メタ)アクリレート、3,4−エポキシシクロヘキシルメチル(メタ)アクリレート、3,4−エポキシシクロヘキシルエチル(メタ)アクリレート、3,4−エポキシシクロヘキシルプロピル(メタ)アクリレート、アリルグリシジルエーテル等のエポキシ基含有重合性不飽和モノマー;分子末端がアルコキシ基であるポリオキシエチレン鎖を有する(メタ)アクリレート;2−アクリルアミド−2−メチルプロパンスルホン酸、2−スルホエチル(メタ)アクリレート、アリルスルホン酸、4−スチレンスルホン酸等、これらスルホン酸のナトリウム塩及びアンモニウム塩等のスルホン酸基を有する重合性不飽和モノマー;2−アクリロイルオキシエチルアシッドホスフェート、2−メタクリロイルオキシエチルアシッドホスフェート、2−アクリロイルオキシプロピルアシッドホスフェート、2−メタクリロイルオキシプロピルアシッドホスフェート等のリン酸基を有する重合性不飽和モノマー;ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2−メトキシエトキシ)シラン、γ−(メタ)アクリロイルオキシプロピルトリメトキシシラン、γ−(メタ)アクリロイルオキシプロピルトリエトキシシランなどのアルコキシシリル基を有する重合性不飽和モノマー;パーフルオロブチルエチル(メタ)アクリレート、パーフルオロオクチルエチル(メタ)アクリレート等のパーフルオロアルキル(メタ)アクリレート;フルオロオレフィン等のフッ素化アルキル基を有する重合性不飽和モノマー;マレイミド基等の光重合性官能基を有する重合性不飽和モノマー;分子末端がアルコキシ基であるポリオキシエチレン鎖を有する(メタ)アクリレート;アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、1,3−ブチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、グリセロールジ(メタ)アクリレート、1,1,1−トリスヒドロキシメチルエタンジ(メタ)アクリレート、1,1,1−トリスヒドロキシメチルエタントリ(メタ)アクリレート、1,1,1−トリスヒドロキシメチルプロパントリ(メタ)アクリレート、トリアリルイソシアヌレート、ジアリルテレフタレート、ジビニルベンゼン等の重合性不飽和基を1分子中に2個以上有する重合性不飽和モノマーなどが挙げられる。これらは1種を単独で又は2種以上を併用して用いることができる。 Polymerizable unsaturated monomer other than polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon The pigment dispersion resin of the present invention is a polymerizable unsaturated monomer having a polycyclic aromatic hydrocarbon (A-1). ) And a polymerizable unsaturated monomer other than (A-1). As the polymerizable unsaturated monomer other than the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon, any polymerizable unsaturated monomer usually used in the synthesis of an acrylic resin can be used without any particular limitation. For example, alkyl (meth) acrylates having 3 or less carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) Acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) Acrylate, lauryl (meth) acrylate, stearyl ( ) Acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate, etc. Alkyl or cycloalkyl (meth) acrylate; polymerizable unsaturated compound having an isobornyl group such as isobornyl (meth) acrylate; polymerizable unsaturated compound having an adamantyl group such as adamantyl (meth) acrylate; benzyl (meth) acrylate, styrene Monocyclic aromatic ring-containing polymerizable unsaturated monomers such as α-methylstyrene and vinyltoluene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Monoesterified product of (meth) acrylic acid such as hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms, the (meth) acrylic acid and 2 to 2 carbon atoms Hydroxyl-containing compounds such as ε-caprolactone modified product of monoesterified product with dihydric alcohol of 8, N-hydroxymethyl (meth) acrylamide, allyl alcohol, (meth) acrylate having a polyoxyalkylene chain whose molecular terminal is a hydroxyl group Polymerizable unsaturated monomers; carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate; (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylamino Ethyl (meth) acrylate, N, N-diethylamino Nitrogen-containing polymerizable unsaturated monomers not containing urethane bonds such as ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, adducts of glycidyl (meth) acrylate and amines; Polymerizable unsaturated monomer having a urethane bond such as a reaction product of an unsaturated monomer and a hydroxyl group-containing compound or a reaction product of a hydroxyl group-containing polymerizable unsaturated monomer and an isocyanate group-containing compound; glycidyl (meth) acrylate, β- Epoxy such as methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether Containing polymerizable unsaturated monomer; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is an alkoxy group; 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4- Polymerizable unsaturated monomers having a sulfonic acid group such as sodium salt and ammonium salt of these sulfonic acids such as styrene sulfonic acid; 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate Polymerizable unsaturated monomers having a phosphate group such as 2-methacryloyloxypropyl acid phosphate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) Polymerizable unsaturated monomers having an alkoxysilyl group such as silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, perfluorooctyl Perfluoroalkyl (meth) acrylate such as ethyl (meth) acrylate; polymerizable unsaturated monomer having a fluorinated alkyl group such as fluoroolefin; polymerizable unsaturated monomer having a photopolymerizable functional group such as maleimide group; (Meth) acrylate having a polyoxyethylene chain in which is an alkoxy group; allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (me Acrylate), 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate, 1,1 , 1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene, etc. Such polymerizable unsaturated monomer having two or more in one molecule thereof. These can be used alone or in combination of two or more.
なかでも、少なくとも1種のスチレンを含有していることが好ましく、重合性不飽和モノマー成分の総量を基準として、スチレンを5〜65質量%含有することがより好ましい。 Especially, it is preferable to contain at least 1 sort (s) of styrene, and it is more preferable to contain 5-65 mass% of styrene on the basis of the total amount of a polymerizable unsaturated monomer component.
さらに、樹脂の立体反発層を形成し顔料分散ペーストの安定性を確保する観点から、少なくとも1種のポリアルキレングリコールマクロモノマーを含有していることが好ましく、重合性不飽和モノマー成分の総量を基準として、ポリアルキレングリコールマクロモノマーを1〜30質量%含有することがより好ましい。 Furthermore, from the viewpoint of forming a resin steric repulsion layer and ensuring the stability of the pigment dispersion paste, it preferably contains at least one polyalkylene glycol macromonomer, based on the total amount of polymerizable unsaturated monomer components. It is more preferable to contain 1-30 mass% of polyalkylene glycol macromonomer.
また、ポリアルキレングリコールマクロモノマーは、下記式(5)で示される非イオン性の重合性不飽和モノマーであり、そのようなモノマーの具体例としては、例えば、ポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、エトキシポリエチレングリコール(メタ)アクリレートなどを挙げることができる。これらのうち、特に、ポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコール(メタ)アクリレートが好適である。
CH2=C(R1)COO(CnH2nO)m−R2 ・・・式(5)
〔式中、R1は水素原子またはCH3を表し、R2は水素原子又は炭素数1〜4のアルキル基を表し、mは4〜60、特に4〜55の整数であり、nは2〜3の整数であり、ここで、m個のオキシアルキレン単位(CnH2nO)は同じであっても又は互いに異なっていてもよい。〕Further, the polyalkylene glycol macromonomer is a nonionic polymerizable unsaturated monomer represented by the following formula (5). Specific examples of such a monomer include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate and the like can be mentioned. Of these, polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate are particularly preferable.
CH 2 = C (R 1) COO (C n H 2n O) m -R 2 ··· Equation (5)
[Wherein, R 1 represents a hydrogen atom or CH 3 , R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 4 to 60, particularly 4 to 55, and n is 2 an -3 integer, where, m oxyalkylene units (C n H 2n O) may be or different from one another the same. ]
また、少なくとも1種の(メタ)アクリルアミド化合物を含有することが好ましい。上記(メタ)アクリルアミド化合物としては、それ自体既知のものを特に制限なく用いることができ、具体的には、例えば、アクリルアミド、メタクリルアミド、2−アクリルアミド−2−メチルプロパンスルホン酸、N−メチルアクリルアミド、N−メチルメタクリルアミド、N−メチロールアクリルアミドブチルエーテル、N−メチロールメタクリルアミドブチルエーテル、N−エチルアクリルアミド、N−エチルメタクリルアミド、N−n−プロピルアクリルアミド、N−n−プロピルメタクリルアミド、N−イソプロピルアクリルアミド、N−イソプロピルメタクリルアミド、N−シクロプロピルアクリルアミド、N−シクロプロピルメタクリルアミド、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、N−ヒドロキシメチルアクリルアミド、N−ヒドロキシメチルメタクリルアミド、N−ヒドロキシエチルアクリルアミド、N−ヒドロキシプロピルアクリルアミド、N−ヒドロキシブチルアクリルアミド、N−ヒドロキシペンチルアクリルアミド、N−ヒドロキシメチル−N−エチルアクリルアミド、N−メチル−N−ヒドロキシエチルアクリルアミド、N,N−ジヒドロキシメチルアクリルアミド、N,N−ジヒドロキシエチルアクリルアミド、N,N−ジヒドロキシプロピルアクリルアミド、N,N−ジヒドロキシブチルアクリルアミド、N,N−ジヒドロキシペンチルアクリルアミド、N−ヒドロキシメチルメタクリルアミド、N−ヒドロキシエチルメタクリルアミド、N−ヒドロキシプロピルメタクリルアミド、N−ヒドロキシブチルメタクリルアミド、N−ヒドロキシペンチルメタクリルアミド、N−ヒドロキシメチル−N−エチルメタクリルアミド、N−メチル−N−ヒドロキシエチルメタクリルアミド、N,N−ジヒドロキシメチルメタクリルアミド、N,N−ジヒドロキシエチルメタクリルアミド、N,N−ジヒドロキシプロピルメタクリルアミド、N,N−ジヒドロキシブチルメタクリルアミド、N,N−ジヒドロキシペンチルメタクリルアミド、N,N−ジヒドロキシブチル(メタ)アクリルアミド、及びN−[トリス(ヒドロキシメチル)メチル)アクリルアミド、N,N−ジメチルアクリルアミド、N,N−ジメチルメタクリルアミド、N,N−ジエチルアクリルアミド、N,N−ジエチルメタクリルアミド、N−メチル,N−エチルアクリルアミド、N−メチル,N−エチルメタクリルアミド、N−メチロールアクリルアミドメチルエーテル、N−メチロールメタクリルアミドメチルエーテル、N−メチロールアクリルアミドエチルエーテル、N−メチロールメタクリルアミドエチルエーテル、N−メチロールアクリルアミドプロピルエーテル、N−メチロールメタクリルアミドプロピルエーテル、N−メチロールアクリルアミドブチルエーテル、N−メチロールメタクリルアミドブチルエーテル、N,N−ジメチルアミノエチル(メタ)アクリルアミド、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、N,N−ジエチルアミノエチル(メタ)アクリルアミド、N,N−ジプロピルアミノエチル(メタ)アクリルアミドなどのアミノ基含有(メタ)アクリルアミド化合物、メタクリロイルオキシエチルトリメチルアンモニウムクロライド(アクリエステルDMC、商品名、三菱レイヨン社製)などの第4級アンモニウム塩基含有アクリルアミド化合物、アクリロイルモルホリンなどを挙げることができる。これらは1種を単独で又は2種以上を併用して用いることができる。 Further, it preferably contains at least one (meth) acrylamide compound. As the (meth) acrylamide compound, those known per se can be used without particular limitation. Specific examples include acrylamide, methacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, N-methylacrylamide. N-methylmethacrylamide, N-methylolacrylamide butyl ether, N-methylol methacrylamide butyl ether, N-ethylacrylamide, N-ethylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-isopropylacrylamide N-isopropylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide, diacetone acrylamide, diacetone methacrylamide, N-hydroxy Methylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxypropylacrylamide, N-hydroxybutylacrylamide, N-hydroxypentylacrylamide, N-hydroxymethyl-N-ethylacrylamide, N-methyl-N- Hydroxyethyl acrylamide, N, N-dihydroxymethyl acrylamide, N, N-dihydroxyethyl acrylamide, N, N-dihydroxypropyl acrylamide, N, N-dihydroxybutyl acrylamide, N, N-dihydroxypentyl acrylamide, N-hydroxymethyl methacrylamide N-hydroxyethyl methacrylamide, N-hydroxypropyl methacrylamide, N-hydroxybutyl methacryl N-hydroxypentyl methacrylamide, N-hydroxymethyl-N-ethyl methacrylamide, N-methyl-N-hydroxyethyl methacrylamide, N, N-dihydroxymethyl methacrylamide, N, N-dihydroxyethyl methacrylamide, N , N-dihydroxypropyl methacrylamide, N, N-dihydroxybutyl methacrylamide, N, N-dihydroxypentyl methacrylamide, N, N-dihydroxybutyl (meth) acrylamide, and N- [tris (hydroxymethyl) methyl) acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-methyl, N-ethylacrylamide, N-methyl, N- Ethyl methacrylamide, N-methylol acrylamide methyl ether, N-methylol methacrylamide methyl ether, N-methylol acrylamide ethyl ether, N-methylol methacrylamide ethyl ether, N-methylol acrylamide propyl ether, N-methylol methacrylamide propyl ether, N -Methylolacrylamide butyl ether, N-methylol methacrylamide butyl ether, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N -Amino group-containing (meth) acrylamide compounds such as dipropylaminoethyl (meth) acrylamide, methacryloyloxy Tilt trimethyl ammonium chloride (ACRYESTER DMC, tradename, manufactured by Mitsubishi Rayon Co., Ltd.) Quaternary ammonium salt group-containing acrylamide compounds such as, and the like acryloyl morpholine. These can be used alone or in combination of two or more.
なかでも、下記式(6)で表わされる(メタ)アクリルアミド化合物であることが好ましい。
CH2=C(−R1)−C(=O)−N(−R2)−R3 ・・・式(6)
上記式(6)中のR1は水素原子またはメチル基であり、R2及びR3は異なっていても同じでも良く、水素原子、水酸基を有する有機基及びアルキル基から選ばれる少なくとも1種であることが好ましい。さらにR2及びR3の両方又は片方が水酸基を有する有機基であることがより好ましく、具体的には、例えば、N−ヒドロキシメチル(メタ)アクリルアミド、N−ヒドロキシエチル(メタ)アクリルアミド、N−ヒドロキシプロピル(メタ)アクリルアミド、N−ヒドロキシブチル(メタ)アクリルアミド、N−ヒドロキシメチル−N−エチル(メタ)アクリルアミド、N−メチル−N−ヒドロキシエチル(メタ)アクリルアミド、N−エチル−N−ヒドロキシエチル(メタ)アクリルアミド、N−ヒドロキシエチル−N−ブチル(メタ)アクリルアミド、N−ヒドロキシブチル−N−ブチル(メタ)アクリルアミド、N,N−ジヒドロキシメチル(メタ)アクリルアミド、N,N−ジヒドロキシエチル(メタ)アクリルアミド、N,N−ジヒドロキシプロピル(メタ)アクリルアミド、N,N−ジヒドロキシブチル(メタ)アクリルアミド、及びN−[トリス(ヒドロキシメチル)メチル)アクリルアミドから選ばれる少なくとも1種であることが特に好ましい。Especially, it is preferable that it is a (meth) acrylamide compound represented by following formula (6).
CH 2 = C (—R 1 ) —C (═O) —N (—R 2 ) —R 3 (6)
R 1 in the above formula (6) is a hydrogen atom or a methyl group, and R 2 and R 3 may be different or the same, and are at least one selected from a hydrogen atom, an organic group having a hydroxyl group, and an alkyl group. Preferably there is. Furthermore, it is more preferable that both or one of R 2 and R 3 is an organic group having a hydroxyl group. Specifically, for example, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- Hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxymethyl-N-ethyl (meth) acrylamide, N-methyl-N-hydroxyethyl (meth) acrylamide, N-ethyl-N-hydroxyethyl (Meth) acrylamide, N-hydroxyethyl-N-butyl (meth) acrylamide, N-hydroxybutyl-N-butyl (meth) acrylamide, N, N-dihydroxymethyl (meth) acrylamide, N, N-dihydroxyethyl (meta) ) Acrylamide, N, N-di Particularly preferred is at least one selected from hydroxypropyl (meth) acrylamide, N, N-dihydroxybutyl (meth) acrylamide, and N- [tris (hydroxymethyl) methyl) acrylamide.
上記(メタ)アクリルアミド化合物の含有量としては、重合性不飽和モノマー成分の総量を基準として、1〜30質量%含有することが好ましい。 As content of the said (meth) acrylamide compound, it is preferable to contain 1-30 mass% on the basis of the total amount of a polymerizable unsaturated monomer component.
顔料分散樹脂の合成
本発明の顔料分散樹脂は、ラジカル重合開始剤の存在下に、有機溶剤中で溶液重合する方法、または水性媒体中でエマルション重合する方法などの、それ自体既知のラジカル重合法によって得ることができる。 Synthesis of Pigment Dispersion Resin The pigment dispersion resin of the present invention is a radical polymerization method known per se, such as a solution polymerization method in an organic solvent or an emulsion polymerization method in an aqueous medium in the presence of a radical polymerization initiator. Can be obtained by:
重合に用いられるラジカル重合開始剤としては、例えば、シクロヘキサノンパーオキサイド、3,3,5−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、1,1−ビス(tert−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、1,1−ビス(tert−ブチルパーオキシ)シクロヘキサン、n−ブチル−4,4−ビス(tert−ブチルパーオキシ)バレレート、クメンハイドロパーオキサイド、2,5−ジメチルヘキサン−2,5−ジハイドロパーオキサイド、1,3−ビス(tert−ブチルパーオキシ−m−イソプロピル)ベンゼン、2,5−ジメチル−2,5−ジ(tert−ブチルパーオキシ)ヘキサン、ジイソプロピルベンゼンパーオキサイド、tert−ブチルクミルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、2,4−ジクロロベンゾイルパーオキサイド、ジ−tert−アミルパーオキサイド、ビス(tert−ブチルシクロヘキシル)パーオキシジカーボネート、tert−ブチルパーオキシベンゾエート、2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサン、tert−ブチルパーオキシ−2−エチルヘキサノエート等の過酸化物系重合開始剤;2,2´−アゾビス(イソブチロニトリル)、1,1−アゾビス(シクロヘキサン−1−カルボニトリル)、アゾクメン、2,2´−アゾビス(2−メチルブチロニトリル)、2,2´−アゾビスジメチルバレロニトリル、4,4´−アゾビス(4−シアノ吉草酸)、2−(t−ブチルアゾ)−2−シアノプロパン、2,2´−アゾビス(2,4,4−トリメチルペンタン)、2,2´−アゾビス(2−メチルプロパン)、ジメチル2,2´−アゾビス(2−メチルプロピオネート)等のアゾ系重合開始剤を挙げることができる。これらは1種を単独で又は2種以上を併用して用いることができる。 Examples of the radical polymerization initiator used for polymerization include cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2 , 5-Dihydroperoxide, 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide , Tert-butyl cumyl peroxide, decanoyl Oxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-amyl peroxide, bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, 2,5- Peroxide-based polymerization initiators such as dimethyl-2,5-di (benzoylperoxy) hexane and tert-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1 , 1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisdimethylvaleronitrile, 4,4′-azobis (4- Cyanovaleric acid), 2- (t-butylazo) -2-cyanopropane, 2,2′-azobis ( 2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2,2'-azobis (2-methylpropionate), and the like. . These can be used alone or in combination of two or more.
上記の重合又は希釈に使用される溶媒としては、特に制限はなく、水や有機溶剤、またはその混合物などを挙げることができる。有機溶剤としては、例えば、n−ブタン、n−ヘキサン、n−ヘプタン、n−オクタン、シクロペンタン、シクロヘキサン、シクロブタンなどの炭化水素溶剤;トルエン、キシレン等の芳香族系溶剤;メチルイソブチルケトン等のケトン系溶剤;n−ブチルエーテル、ジオキサン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールなどのエーテル系溶剤;酢酸エチル、酢酸n−ブチル、酢酸イソブチル、エチレングリコールモノメチルエーテルアセテート、ブチルカルビトールアセテート等のエステル系溶剤;メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン等のケトン系溶剤;エタノール、イソプロパノール、n−ブタノール、sec−ブタノール、イソブタノール等の等のアルコール系溶剤;エクアミド(商品名、出光興産株式会社製、アミド系溶剤)、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチルホルムアミド、N−メチルアセトアミド、N−メチルプロピオアミド、N−メチル−2−ピロリドンなどのアミド系溶剤など、従来公知の溶剤を挙げることができる。これらは1種を単独で又は2種以上を併用して用いることができる。 There is no restriction | limiting in particular as a solvent used for said superposition | polymerization or dilution, Water, an organic solvent, or its mixture etc. can be mentioned. Examples of the organic solvent include hydrocarbon solvents such as n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and cyclobutane; aromatic solvents such as toluene and xylene; methyl isobutyl ketone and the like Ketone solvents; ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol; ethyl acetate, n-butyl acetate, isobutyl acetate, Ester solvents such as ethylene glycol monomethyl ether acetate and butyl carbitol acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone; Alcohol solvents such as tanol, isopropanol, n-butanol, sec-butanol, isobutanol, etc .; Examide (trade name, manufactured by Idemitsu Kosan Co., Ltd., amide solvent), N, N-dimethylformamide, N, N-dimethyl Conventionally known solvents such as amide solvents such as acetamide, N-methylformamide, N-methylacetamide, N-methylpropioamide and N-methyl-2-pyrrolidone can be listed. These can be used alone or in combination of two or more.
有機溶剤中での溶液重合において重合開始剤、重合性不飽和モノマー成分、及び有機溶剤を混合し、攪拌しながら加熱する方法、反応熱による系の温度上昇を抑えるために有機溶剤を反応槽に仕込み、60℃〜200℃の温度で攪拌しながら必要に応じて窒素やアルゴンなどの不活性ガスを吹き込みながら、重合性不飽和モノマー成分と重合開始剤を所定の時間かけて混合滴下又は分離滴下する方法などが用いられる。 In solution polymerization in an organic solvent, a polymerization initiator, a polymerizable unsaturated monomer component, and an organic solvent are mixed and heated while stirring. While being stirred at a temperature of 60 ° C. to 200 ° C. while introducing an inert gas such as nitrogen or argon as necessary, the polymerizable unsaturated monomer component and the polymerization initiator are mixed or dropped over a predetermined time. The method to do is used.
重合は、一般に1〜10時間程度行うことができる。各段階の重合の後に必要に応じて重合開始剤を滴下しながら反応槽を加熱する追加触媒工程を設けてもよい。 The polymerization can be generally performed for about 1 to 10 hours. You may provide the additional catalyst process which heats a reaction tank, dripping a polymerization initiator as needed after superposition | polymerization of each step.
上記の通り得られる本発明の顔料分散樹脂は、重量平均分子量が好ましくは1,000〜100,000、より好ましくは3,000〜50,000の範囲内であることが好適である。 The pigment-dispersed resin of the present invention obtained as described above preferably has a weight average molecular weight in the range of 1,000 to 100,000, more preferably 3,000 to 50,000.
尚、本明細書において、数平均分子量及び重量平均分子量は、ゲルパーミエーションクロマトグラフ(GPC)を用いて測定した保持時間(保持容量)を、同一条件で測定した分子量既知の標準ポリスチレンの保持時間(保持容量)によりポリスチレンの分子量に換算して求めた値である。具体的には、ゲルパーミュエーションクロマトグラフとして、「HLC8120GPC」(商品名、東ソー社製)を使用し、カラムとして、「TSKgel G−4000HXL」、「TSKgel G−3000HXL」、「TSKgel G−2500HXL」及び「TSKgel G−2000HXL」(商品名、いずれも東ソー社製)の4本を使用し、移動相テトラヒドロフラン、測定温度40℃、流速1mL/min及び検出器RIの条件下で測定することができる。 In the present specification, the number average molecular weight and the weight average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC) and the retention time of a standard polystyrene having a known molecular weight measured under the same conditions. (Retention capacity) is a value obtained by converting to the molecular weight of polystyrene. Specifically, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” are used as columns. ”And“ TSKgel G-2000HXL ”(trade names, all manufactured by Tosoh Corporation), and can be measured under the conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow rate 1 mL / min, and detector RI. it can.
顔料分散ペースト
本発明の顔料分散ペーストは、上記顔料分散樹脂、顔料、顔料誘導体、溶媒、及び必要に応じて、その他の添加剤などを含有するものである。 Pigment Dispersion Paste The pigment dispersion paste of the present invention contains the above pigment dispersion resin, pigment, pigment derivative, solvent, and, if necessary, other additives.
本発明において、上記顔料分散樹脂によって分散される顔料としては、従来公知のものを制限なく使用することができ、例えば、チタン白、亜鉛華などの白色顔料;シアニンブルー、インダスレンブルーなどの青色顔料;シアニングリーン、緑青などの緑色顔料;アゾ系やキナクリドン系などの有機赤色顔料、ベンガラなどの赤色顔料;ベンツイミダゾロン系、イソインドリノン系、イソインドリン系及びキノフタロン系などの有機黄色顔料、チタンイエロー、黄鉛などの黄色顔料;カーボン、松煙などの黒色顔料;アルミニウム粉、銅粉、ニッケル粉、酸化チタン被覆マイカ粉、酸化鉄被覆マイカ粉及び光輝性グラファイトなどの光輝性顔料などが挙げられる。なかでも、芳香族炭化水素を有する顔料が好ましい。 In the present invention, as the pigment dispersed by the pigment dispersion resin, conventionally known pigments can be used without limitation. For example, white pigments such as titanium white and zinc white; blue colors such as cyanine blue and induslen blue Pigments; Green pigments such as cyanine green and patina; Organic red pigments such as azo and quinacridone; Red pigments such as Bengala; Organic yellow pigments such as benzimidazolone, isoindolinone, isoindoline, and quinophthalone Yellow pigments such as titanium yellow and yellow lead; black pigments such as carbon and pine smoke; bright pigments such as aluminum powder, copper powder, nickel powder, titanium oxide-coated mica powder, iron oxide-coated mica powder, and glitter graphite Can be mentioned. Among these, a pigment having an aromatic hydrocarbon is preferable.
また、本発明の顔料分散樹脂は、顔料を微細かつ均一に分散し、顔料分散ペーストを長期に渡って安定化できるため、特に厳しい性能が要求される導電性顔料の分散に好適である。 In addition, the pigment dispersion resin of the present invention is suitable for dispersing conductive pigments that require particularly strict performance because the pigment can be finely and uniformly dispersed and the pigment dispersion paste can be stabilized over a long period of time.
芳香族炭化水素を有する導電性顔料としては、例えば、アセチレンブラック、ファーネスブラック、サーマルブラック、チャネルブラック、ケッチェンブラック、バルカン、カーボンナノチューブ、グラフェン、気相成長カーボンファイバー(VGCF)、黒鉛などが挙げられる。 Examples of the conductive pigment having an aromatic hydrocarbon include acetylene black, furnace black, thermal black, channel black, ketjen black, vulcan, carbon nanotube, graphene, vapor grown carbon fiber (VGCF), and graphite. It is done.
溶媒に関しては、前述した顔料分散樹脂の重合又は希釈に使用される溶媒を好適に用いることができる。 Regarding the solvent, the solvent used for the polymerization or dilution of the pigment-dispersed resin described above can be suitably used.
その他の添加剤としては、中和剤、顔料分散剤、結着剤、消泡剤、防腐剤、防錆剤、可塑剤などを挙げることができる。顔料分散剤及び/又は結着剤としては、例えば、上記顔料分散樹脂以外のアクリル樹脂、ポリエステル樹脂、エポキシ樹脂、ポリエーテル樹脂、アルキド樹脂、ウレタン樹脂、シリコーン樹脂、ポリカーボネート樹脂、シリケート樹脂、塩素系樹脂、フッ素系樹脂、ポリビニルピロリドン樹脂、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、及びこれらの複合樹脂などが挙げられる。これらの樹脂は1種を単独で又は2種以上を併用して用いることができる。 Examples of other additives include neutralizers, pigment dispersants, binders, antifoaming agents, antiseptics, rust inhibitors, and plasticizers. Examples of the pigment dispersant and / or binder include acrylic resins other than the above-described pigment dispersion resins, polyester resins, epoxy resins, polyether resins, alkyd resins, urethane resins, silicone resins, polycarbonate resins, silicate resins, and chlorine-based resins. Examples thereof include resins, fluorine resins, polyvinyl pyrrolidone resins, polyvinyl alcohol resins, polyvinyl acetal resins, and composite resins thereof. These resins can be used alone or in combination of two or more.
顔料分散ペースト中の顔料分散樹脂固形分の含有量は、通常30重量%以下、好ましくは20重量%以下であることが、顔料分散時の粘度、顔料分散性、分散安定性及び生産効率などの面から好適である。特に導電性顔料分散ペーストの場合は、塗膜の導電性の観点から、導電性顔料分散ペースト固形分中の顔料分散樹脂固形分の含有量は、通常、20質量%以下、好ましくは0.1〜15質量%、より好ましくは1.0〜10質量%であることが好適である。 The content of the pigment-dispersed resin solid content in the pigment-dispersed paste is usually 30% by weight or less, preferably 20% by weight or less, such as viscosity during pigment dispersion, pigment dispersibility, dispersion stability, and production efficiency. From the aspect, it is preferable. In particular, in the case of a conductive pigment dispersion paste, from the viewpoint of the conductivity of the coating film, the content of the pigment dispersion resin solid content in the conductive pigment dispersion paste solid content is usually 20% by mass or less, preferably 0.1%. It is suitable that it is -15 mass%, More preferably, it is 1.0-10 mass%.
顔料分散ペーストは、以上に述べた各成分を、例えば、ペイントシェーカー、サンドミル、ボールミル、ペブルミル、LMZミル、DCPパールミル、遊星ボールミル、ホモジナイザー、二軸混練機、薄膜旋回型高速ミキサーなどの従来公知の分散機を用いて均一に混合、分散させることにより調製することができる。 In the pigment dispersion paste, each of the above-described components is conventionally known, such as a paint shaker, a sand mill, a ball mill, a pebble mill, an LMZ mill, a DCP pearl mill, a planetary ball mill, a homogenizer, a twin-screw kneader, and a thin film swirl type high-speed mixer. It can be prepared by uniformly mixing and dispersing using a disperser.
以下、製造例、実施例及び比較例により、本発明をさらに詳細に説明するが、本発明はこれに限定されるものではない。各例中の「部」は質量部、「%」は質量%を示す。 Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. In each example, “parts” indicates mass parts, and “%” indicates mass%.
ナフチル基含有モノマーの製造
製造例1 ナフチル基含有モノマーの製造
攪拌加熱装置と冷却管を備えた反応容器に、酢酸ブチル373部、1−ナフチル酢酸202部、ヒドロキノンモノメチルエーテル0.1部、及びテトラブチルアンモニウムブロマイド0.3部を仕込んだ後、撹拌しながら120℃に昇温した。次いで乾燥空気を溶液中に吹き込みながら、グリシジルメタクリレート154部を1時間かけて滴下し、120℃で2時間反応を進め、ナフチル基含有モノマー溶液1を得た。 Production and Production Example 1 of Naphthyl Group-Containing Monomer Production of Naphthyl Group-Containing Monomer In a reaction vessel equipped with a stirring and heating device and a cooling tube, 373 parts of butyl acetate, 202 parts of 1-naphthylacetic acid, 0.1 part of hydroquinone monomethyl ether, and tetra After charging 0.3 part of butylammonium bromide, the temperature was raised to 120 ° C. with stirring. Next, 154 parts of glycidyl methacrylate was dropped over 1 hour while blowing dry air into the solution, and the reaction was allowed to proceed at 120 ° C. for 2 hours to obtain a naphthyl group-containing monomer solution 1.
製造例2 ナフチル基含有モノマーの製造
攪拌加熱装置と冷却管を備えた反応容器に、酢酸ブチル208部、1−ナフトール100部、ヒドロキノンモノメチルエーテル0.1部を仕込んだ後、撹拌しながら60℃に昇温した。次いで乾燥空気を溶液中に吹き込みながら、2−メタクリロイルオキシエチルイソシアネート107.6部を1時間かけて滴下し、60℃で2時間反応を進め、ナフチル基含有モノマー溶液2を得た。Production Example 2 Production of naphthyl group-containing monomer Into a reaction vessel equipped with a stirring heating apparatus and a cooling tube, 208 parts of butyl acetate, 100 parts of 1-naphthol and 0.1 part of hydroquinone monomethyl ether were charged, and then stirred at 60 ° C. The temperature was raised to. Next, while blowing dry air into the solution, 107.6 parts of 2-methacryloyloxyethyl isocyanate was added dropwise over 1 hour, and the reaction was allowed to proceed at 60 ° C. for 2 hours to obtain a naphthyl group-containing monomer solution 2.
顔料分散樹脂の製造
実施例1 顔料分散樹脂の製造
攪拌加熱装置と冷却管を備えた反応容器に、プロピレングリコールモノメチルエーテル300部を仕込み、窒素置換後、110℃に保った。この中に、以下に示すモノマー混合物を3時間かけて滴下した。
9−アントラセニルメチルメタクリレート 300部
スチレン 200部
n−ブチルメタクリレート 300部
2−エチルヘキシルアクリレート 100部
2−ヒドロキシエチルメタクリレート 100部
2,2’−アゾビス(2−メチルブチロニトリル) 40部
滴下終了後から1時間経過後、この中に2,2´−アゾビス(2−メチルブチロニトリル)5部をプロピレングリコールモノメチルエーテル100部に溶かした溶液を1時間かけて滴下した。滴下終了後、これをさらに1時間110℃に保持したのち、メチルイソブチルケトンで調整し、固形分70%の顔料分散樹脂X−1溶液を得た。顔料分散樹脂X−1は、重量平均分子量10,000であった。 Production Example 1 of Pigment Dispersing Resin Manufacture of Pigment Dispersing Resin 300 parts of propylene glycol monomethyl ether was charged into a reaction vessel equipped with a stirring heating device and a cooling tube, and maintained at 110 ° C. after nitrogen substitution. Into this, the monomer mixture shown below was dripped over 3 hours.
9-anthracenylmethyl methacrylate 300 parts styrene 200 parts n-butyl methacrylate 300 parts 2-ethylhexyl acrylate 100 parts 2-hydroxyethyl methacrylate 100 parts 2,2'-azobis (2-methylbutyronitrile) 40 parts 1 hour later, a solution prepared by dissolving 5 parts of 2,2′-azobis (2-methylbutyronitrile) in 100 parts of propylene glycol monomethyl ether was added dropwise thereto over 1 hour. After completion of dropping, this was further maintained at 110 ° C. for 1 hour, and then adjusted with methyl isobutyl ketone to obtain a pigment dispersion resin X-1 solution having a solid content of 70%. Pigment dispersion resin X-1 had a weight average molecular weight of 10,000.
実施例2〜33及び比較例1〜6 顔料分散樹脂の製造
実施例1のモノマー組成を下記表1の種類及び配合量とする以外は、実施例1と同じ組成及び製造方法で顔料分散樹脂X−2〜X−39溶液を製造した。
尚、表中のMPEG2000に関しては他のモノマーと混ざらないため、モノマー混合物とは別に並行して滴下した。Examples 2-33 and Comparative Examples 1-6 Production of Pigment Dispersion Resin Pigment Dispersion Resin X with the same composition and production method as Example 1 except that the monomer composition of Example 1 is the type and blending amount shown in Table 1 below. A −2 to X-39 solution was prepared.
In addition, since MPEG2000 in the table is not mixed with other monomers, it was dropped in parallel separately from the monomer mixture.
(注1)MPEG2000:商品名、日本油脂株式会社製、ポリオキシエチレングリコールモノメチルエーテル、数平均分子量約2000。
尚、表中の配合量は有効成分の値である。従って、表中の成分として、溶剤等の添加剤を含む製品等を用いた場合、表中の配合量は、それらの添加剤を除いた、表中の成分の配合量を意味する。(Note 1) MPEG2000: trade name, manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, number average molecular weight of about 2000.
In addition, the compounding quantity in a table | surface is a value of an active ingredient. Therefore, when the product etc. which contain additives, such as a solvent, are used as a component in a table | surface, the compounding quantity in a table | surface means the compounding quantity of the component in a table | surface except those additives.
顔料分散ペーストの製造
実施例34 導電性顔料分散ペーストの製造
実施例1で得た顔料分散用樹脂X−1溶液を8.6部(固形分6部)、デンカブラックHS−100(商品名、電気化学工業社製、カーボンブラック)99部、ケッチェンブラックECP300(商品名、ライオン株式会社製、ケッチェンブラック)1部及びプロピレングリコールモノメチルエーテルを580部加え、ボールミルにて5時間分散し、導電性顔料分散ペーストY−1を得た。 Production Example 34 of Pigment Dispersion Paste Production of Conductive Pigment Dispersion Paste 8.6 parts of pigment dispersion resin X-1 solution obtained in Example 1 (solid content 6 parts), Denka Black HS-100 (trade name, 99 parts of carbon black manufactured by Denki Kagaku Kogyo Co., Ltd., 1 part of ketjen black ECP300 (trade name, manufactured by Lion Co., Ltd., ketjen black) and 580 parts of propylene glycol monomethyl ether are added and dispersed in a ball mill for 5 hours. Pigment dispersion paste Y-1 was obtained.
実施例35〜59及び比較例7〜9 導電性顔料分散ペーストの製造
下記表2で示される以外は実施例34と同様にして、導電性顔料分散ペーストY−2〜Y−26及びY−35〜37、を得た。Examples 35 to 59 and Comparative Examples 7 to 9 Production of conductive pigment dispersion pastes Conductive pigment dispersion pastes Y-2 to Y-26 and Y-35 in the same manner as in Example 34 except that they are shown in Table 2 below. ~ 37 was obtained.
実施例60 導電性顔料分散ペーストの製造
実施例26で得た顔料分散用樹脂X−26溶液を8.6部(固形分6部)、デンカブラックHS−100(商品名、電気化学工業社製、カーボンブラック)99部、ケッチェンブラックECP300(商品名、ライオン株式会社製、ケッチェンブラック)1部及び脱イオン水を580部加え、ボールミルにて5時間分散し、導電性顔料分散ペーストY−27を得た。Example 60 Production of Conductive Pigment Dispersion Paste 8.6 parts (solid content 6 parts) of the resin X-26 for pigment dispersion obtained in Example 26, Denka Black HS-100 (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) 99 parts of carbon black), 1 part of Ketjen Black ECP300 (trade name, manufactured by Lion Corporation, Ketjen Black) and 580 parts of deionized water were added and dispersed in a ball mill for 5 hours. 27 was obtained.
実施例61〜67及び比較例10〜12 導電性顔料分散ペーストの製造
下記表2で示される以外は実施例60と同様にして、導電性顔料分散ペーストY−28〜Y−34及びY−38〜40を得た。Examples 61 to 67 and Comparative Examples 10 to 12 Production of conductive pigment dispersion pastes Conductive pigment dispersion pastes Y-28 to Y-34 and Y-38 were carried out in the same manner as in Example 60 except that they were shown in Table 2 below. ~ 40 was obtained.
また、下記表2に、後述する評価試験の結果(分散性、導電性)を記載する。
本発明においては、分散性及び導電性の両方の性能に優れていることが重要であり、どちらか片方に「D(非常に劣る)」の評価がある場合、その顔料分散ペーストは不合格である。Table 2 below shows the results (dispersibility, conductivity) of the evaluation test described later.
In the present invention, it is important that both the dispersibility and the electroconductivity are excellent, and when either one has an evaluation of “D (very inferior)”, the pigment dispersion paste is rejected. is there.
(注2)黒鉛:粒子径が50〜600μmの天然黒鉛粒子
尚、表中の配合量は固形分の値である。(Note 2) Graphite: Natural graphite particles having a particle size of 50 to 600 μm. The blending amount in the table is a solid content value.
実施例68 着色顔料分散ペーストの製造
攪拌混合容器に、実施例31で得た顔料分散樹脂X−31溶液143部(固形分100部)、「Raven5000UIII」(商品名、コロンビアンカーボン社製、カーボンブラック顔料)60部及び脱イオン水800部を入れ、均一に混合した。次いで、得られた混合液を容量225ccの広口ガラス瓶中に入れ、分散メジアとして直径約0.5mmφのジルコニアビーズを加えて密閉し、ペイントシェーカーにて5時間分散して着色顔料分散ペーストY−41を得た。Example 68 Production of Colored Pigment Dispersion Paste In a stirring and mixing container, 143 parts of pigment dispersion resin X-31 solution obtained in Example 31 (solid content: 100 parts), “Raven5000UIII” (trade name, manufactured by Columbian Carbon Co., Ltd., carbon Black pigment) 60 parts and deionized water 800 parts were added and mixed uniformly. Next, the obtained mixed liquid was put in a wide-mouth glass bottle having a capacity of 225 cc, and zirconia beads having a diameter of about 0.5 mmφ were added as a dispersion medium and sealed, and dispersed for 5 hours with a paint shaker to disperse the colored pigment dispersion paste Y-41. Got.
実施例69〜72、比較例13〜17 着色顔料分散ペーストの製造
下記表3で示される以外は実施例68と同様にして、着色顔料分散ペーストY−42〜Y−50を得た。あわせて後述する評価試験の結果(発色性)も記載する。Examples 69 to 72, Comparative Examples 13 to 17 Production of Colored Pigment Dispersion Pastes Colored pigment dispersion pastes Y-42 to Y-50 were obtained in the same manner as in Example 68 except that they are shown in Table 3 below. In addition, the result (coloring property) of the evaluation test described later is also described.
(注3)シアニンブルー5206:商品名、大日精化工業社製、有機系青色顔料。
(注4)RT355D:商品名、BASF社製、有機系赤色顔料。
尚、表中の配合量は固形分の値である。(Note 3) Cyanine Blue 5206: Trade name, manufactured by Dainichi Seika Kogyo Co., Ltd., organic blue pigment.
(Note 4) RT355D: trade name, manufactured by BASF, organic red pigment.
In addition, the compounding quantity in a table | surface is a value of solid content.
評価試験
<分散性>
得られた顔料分散ペーストをJISK−5600−2−5の分散度試験に準じ、ツブゲージを用いて下記基準により分散性を評価した。
A:顔料が10μm未満で分散されている。分散性は非常に良好である。
B:顔料が10μm以上、かつ15μm未満で分散されている。分散性は良好である。
C:顔料が15μm以上で分散されているが、目視で凝集物は確認できない。分散性はやや劣る。
D:目視で凝集物が確認される。分散性は非常に劣る。 Evaluation test <dispersibility>
Dispersibility of the obtained pigment dispersion paste was evaluated according to the following criteria using a tube gauge in accordance with the dispersity test of JISK-5600-2-5.
A: The pigment is dispersed below 10 μm. Dispersibility is very good.
B: The pigment is dispersed at 10 μm or more and less than 15 μm. Dispersibility is good.
C: Although the pigment is dispersed at 15 μm or more, no aggregate can be visually confirmed. Dispersibility is slightly inferior.
D: Aggregates are confirmed visually. Dispersibility is very poor.
<導電性>
ポリプロピレン板(10cm×15cm×3mm)の上にアルミ箔テープ(住友3M社製、No.425)を3cm間隔で平行に2本貼り付けた。次いで、得られた導電性顔料分散ペーストをアルミ箔テープの間に長さ5cm、乾燥膜厚15μmになるようにアプリケーターで塗装し、室温で2分間放置してから、80℃で10分間加熱乾燥した。(幅3cm×長さ5cm×膜厚15μmの乾燥塗膜を作成した。)
アルミ箔テープ間に塗装した乾燥塗膜の抵抗率を「ディジタルマルチメーター MODEL73401」(商品名、横河メータ&インスツルメンツ社製)を用いて20℃の雰囲気で測定し、下記基準により導電性を評価した。
S:抵抗率が、0.005Ωm未満であり、導電性は最も良好である。
A:抵抗率が、0.005Ωm以上、かつ0.0065Ωm未満であり、導電性は非常に良好である。
B:抵抗率が、0.0065Ωm以上、かつ0.008Ωm未満であり、導電性は良好である。
C:抵抗率が、0.008Ωm以上、かつ0.01Ωm未満であり、導電性はやや劣る。
D:抵抗率が、0.01Ωm以上であり、導電性は非常に劣る。<Conductivity>
Two aluminum foil tapes (manufactured by Sumitomo 3M, No. 425) were attached in parallel at intervals of 3 cm on a polypropylene plate (10 cm × 15 cm × 3 mm). Next, the obtained conductive pigment dispersion paste was coated with an applicator so as to have a length of 5 cm and a dry film thickness of 15 μm between aluminum foil tapes, allowed to stand at room temperature for 2 minutes, and then heat-dried at 80 ° C. for 10 minutes. did. (A dry coating film having a width of 3 cm, a length of 5 cm, and a film thickness of 15 μm was prepared.)
The resistivity of the dried coating film applied between the aluminum foil tapes was measured in a 20 ° C. atmosphere using “Digital Multimeter Model 7401” (trade name, manufactured by Yokogawa Meter & Instruments), and the conductivity was evaluated according to the following criteria. did.
S: The resistivity is less than 0.005 Ωm, and the conductivity is the best.
A: The resistivity is 0.005 Ωm or more and less than 0.0065 Ωm, and the conductivity is very good.
B: The resistivity is 0.0065 Ωm or more and less than 0.008 Ωm, and the conductivity is good.
C: The resistivity is 0.008 Ωm or more and less than 0.01 Ωm, and the conductivity is slightly inferior.
D: The resistivity is 0.01 Ωm or more, and the conductivity is very poor.
<発色性>
得られた着色顔料分散ペーストを透明なPETフィルム上に乾燥膜厚25μmとなるよう塗布し、140℃で30分間焼付けることによって得た塗膜を「MA−68II」(商品名、X−Rite社製、多角度分光測色計)を使用し、塗膜について、測定対象面に垂直な軸に対し45°の角度から標準の光D65を照射し、反射した光のうち測定対象面に垂直な方向の光(正反射光に対して45°の角度で受光した光)についてL*値(L*45)を測定した。黒色以外の顔料ではL*45の値で発色性を評価した。
黒色顔料ではL*45値に加えて、25°、75°の角度から標準の光D65を照射したときのL*値(それぞれL*25、L*75)を測定し、3つの値の和で評価した。
値が低いほど発色性が良好であり、本発明においては、黒色顔料の場合は0.3以下、青色顔料の場合は1.5以下、赤色顔料の場合は7以下が合格である。<Color development>
The obtained colored pigment dispersion paste was applied onto a transparent PET film so as to have a dry film thickness of 25 μm, and baked at 140 ° C. for 30 minutes to obtain a coating film obtained by “MA-68II” (trade name, X-Rite). A multi-angle spectrocolorimeter (manufactured by Kogyo Co., Ltd.) was used, and the coating film was irradiated with standard light D65 from an angle of 45 ° with respect to an axis perpendicular to the measurement object surface, and the reflected light was perpendicular to the measurement object surface. L * values (L * 45) were measured for light in various directions (light received at an angle of 45 ° with respect to specularly reflected light). For pigments other than black, the color developability was evaluated with a value of L * 45.
For black pigment, in addition to the L * 45 value, the L * value (L * 25 and L * 75, respectively) when standard light D65 is irradiated from 25 ° and 75 ° angles is measured, and the sum of the three values It was evaluated with.
The lower the value, the better the color developability. In the present invention, a black pigment is 0.3 or less, a blue pigment is 1.5 or less, and a red pigment is 7 or less.
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WO2020043462A1 (en) | 2018-08-27 | 2020-03-05 | Basf Coatings Gmbh | Pigment dispersant for coating |
JP2020132749A (en) * | 2019-02-19 | 2020-08-31 | メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングMerck Patent GmbH | Polymer, semiconductor composition comprising polymer, and method for producing film using semiconductor composition |
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JPH09122472A (en) * | 1995-10-27 | 1997-05-13 | Dainichiseika Color & Chem Mfg Co Ltd | Dispersant and colorant |
JPH11158321A (en) * | 1997-11-27 | 1999-06-15 | Mikuni Shikiso Kk | Electroconductive highly concentrated carbon black dispersion, its production and composition comprising the dispersion |
JP2004209937A (en) * | 2003-01-08 | 2004-07-29 | Pentel Corp | Ball-point pen |
JP2009299005A (en) * | 2007-11-09 | 2009-12-24 | Fujifilm Corp | Pigment composition, water-based pigment dispersion, method of producing water-based pigment dispersion, water-based ink for inkjet recording, and polymer compound |
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JPH09122472A (en) * | 1995-10-27 | 1997-05-13 | Dainichiseika Color & Chem Mfg Co Ltd | Dispersant and colorant |
JPH11158321A (en) * | 1997-11-27 | 1999-06-15 | Mikuni Shikiso Kk | Electroconductive highly concentrated carbon black dispersion, its production and composition comprising the dispersion |
JP2004209937A (en) * | 2003-01-08 | 2004-07-29 | Pentel Corp | Ball-point pen |
JP2009299005A (en) * | 2007-11-09 | 2009-12-24 | Fujifilm Corp | Pigment composition, water-based pigment dispersion, method of producing water-based pigment dispersion, water-based ink for inkjet recording, and polymer compound |
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