EP1347342B1 - Toner for electrophotography - Google Patents
Toner for electrophotography Download PDFInfo
- Publication number
- EP1347342B1 EP1347342B1 EP03006072A EP03006072A EP1347342B1 EP 1347342 B1 EP1347342 B1 EP 1347342B1 EP 03006072 A EP03006072 A EP 03006072A EP 03006072 A EP03006072 A EP 03006072A EP 1347342 B1 EP1347342 B1 EP 1347342B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- toner
- bisphenol
- weight
- resin
- image
- 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.)
- Expired - Lifetime
Links
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 137
- 229920005989 resin Polymers 0.000 claims abstract description 101
- 239000011347 resin Substances 0.000 claims abstract description 101
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 47
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- 229920005862 polyol Polymers 0.000 claims abstract description 45
- 150000003077 polyols Chemical class 0.000 claims abstract description 44
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000003086 colorant Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 45
- 229930185605 Bisphenol Natural products 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 2
- 239000000598 endocrine disruptor Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 31
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 239000008096 xylene Substances 0.000 description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 bisphenol A Chemical class 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 7
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229910002012 AerosilĀ® Inorganic materials 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 206010040880 Skin irritation Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000036556 skin irritation Effects 0.000 description 3
- 231100000475 skin irritation Toxicity 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 235000010187 litholrubine BK Nutrition 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- QBZIEGUIYWGBMY-FUZXWUMZSA-N (5Z)-5-hydroxyimino-6-oxonaphthalene-2-sulfonic acid iron Chemical compound [Fe].O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O.O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O.O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O QBZIEGUIYWGBMY-FUZXWUMZSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- AWZLXVAPLHUDSY-UHFFFAOYSA-N 2-ethyl-1-methylpiperazine Chemical compound CCC1CNCCN1C AWZLXVAPLHUDSY-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- WZSFTHVIIGGDOI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3-[2-methyl-3-[(4,5,6,7-tetrachloro-3-oxoisoindol-1-yl)amino]anilino]isoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(NC1=CC=CC(NC=3C4=C(C(=C(Cl)C(Cl)=C4Cl)Cl)C(=O)N=3)=C1C)=NC2=O WZSFTHVIIGGDOI-UHFFFAOYSA-N 0.000 description 1
- DWDURZSYQTXVIN-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]aniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 DWDURZSYQTXVIN-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- LVOJOIBIVGEQBP-UHFFFAOYSA-N 4-[[2-chloro-4-[3-chloro-4-[(5-hydroxy-3-methyl-1-phenylpyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-methyl-2-phenylpyrazol-3-ol Chemical compound CC1=NN(C(O)=C1N=NC1=CC=C(C=C1Cl)C1=CC(Cl)=C(C=C1)N=NC1=C(O)N(N=C1C)C1=CC=CC=C1)C1=CC=CC=C1 LVOJOIBIVGEQBP-UHFFFAOYSA-N 0.000 description 1
- DSBIJCMXAIKKKI-UHFFFAOYSA-N 5-nitro-o-toluidine Chemical compound CC1=CC=C([N+]([O-])=O)C=C1N DSBIJCMXAIKKKI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VVAVKBBTPWYADW-UHFFFAOYSA-L Biebrich scarlet Chemical compound [Na+].[Na+].OC1=CC=C2C=CC=CC2=C1N=NC(C(=C1)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 VVAVKBBTPWYADW-UHFFFAOYSA-L 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
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- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702Ā -Ā G03G9/08775
- G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702Ā -Ā G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08753—Epoxyresins
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08759—Polyethers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702Ā -Ā G03G9/08775
- G03G9/08786—Graft polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702Ā -Ā G03G9/08775
- G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702Ā -Ā G03G9/08775 characterised by the presence of specified groups or side chains
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702Ā -Ā G03G9/08775
- G03G9/08793—Crosslinked polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702Ā -Ā G03G9/08775
- G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702Ā -Ā G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
Definitions
- the present invention relates to a toner for electrophotography.
- a latent electrostatic image is formed on a photoconductor by a conventional method, and developed with a dry toner. Thereafter, the resulting toner image is transferred onto a sheet of copy paper, and is fixed onto the sheet by thermal fixing (generally, using a heat roller) so as to obtain a copy image.
- the dry toner for this method contains a binder resin and a coloring agent as the main components. If required, the dry toner may further contain additives, such as a charge control agent and an offset-preventing agent.
- binder resins are polystyrenes, styrene-acrylic copolymers, polyester resins, epoxy resins, in terms of the properties required for the toner, for instance, transparency, insulating properties, water-resistance, flowability (as a powder), mechanical strength, glossiness, thermoplasticity, grindability.
- styrene resins are widely used because of the excellent grindability, water-resistance, and flowability.
- a plasticizer contained in the resin sheet, which is formed of the vinyl chloride resin is transferred to the fixed toner image, and plasticizes the fixed toner image.
- the plasticizer is then fused onto a side of the resin sheet.
- JP-A Japanese Patent Application Laid-Open
- 07-77832 discloses the use of a polyol resin synthesized by using an epoxy resin as a raw material.
- Such a polyol resin uses an epoxy resin and bisphenol A as raw materials.
- the epoxy groups in the epoxy resin and the active hydrogen moiety of bisphenol A are allowed to react with each other to perform synthesis.
- Epoxy groups in the epoxy resin are chemically very active, and, biochemically, considered to have a toxicity such as skin irritation. For this reason, for the synthesis of a polyol resin, the number of moles of the active hydrogen atoms is set to be larger than the number of moles of the epoxy groups.
- US-A-5998073 relates to a dry toner for electrophotography comprising a colorant, a releasing agent, and a polyol resin as a binder resin, wherein the polyol resin is obtained by reacting an epoxy resin, a dihydric phenol, and an alkylene oxide adduct of a dihydric phenol or a glycidyl ether thereof.
- a polyol resin used in the examples has an epoxy equivalent of 20,000 or more.
- the present invention provides, in a first aspect, a toner for electrophotography which is characterized by containing a coloring agent and a binder resin.
- the binder resin is a polyol resin which is prepared by reacting a) a bisphenol-A-type epoxy resin, b) a compound having one or more active hydrogen atoms which react with an epoxy group in molecules of the compound having one or more active hydrogen atoms, and c) a compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms, wherein the compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms comprises bisphenol A, in which a weight concentration of non-reacted bisphenol A in the toner is 1000 ā g/g or less, and the toner has an epoxy equivalent of 20000 or more, measured in accordance with an indicator-titration method defined in paragraph 4.2 of JIS K7236.
- the present invention also provides, in a second aspect, an image-forming process in which a latent electrostatic image on a latent electrostatic image support is developed by the toner of the present invention.
- the present invention further provides, in a third aspect, an image-forming apparatus which includes an image developer where the toner of the present invention is utilized as a developer.
- the present invention still further provides, in a fourth aspect, an image-forming process cartridge.
- the image-forming process cartridge of the present invention includes an image developer configured to supply a developer onto a latent electrostatic image so as to visualize and develop the latent electrostatic image.
- the image-forming process cartridge of the present invention is formed in one-piece construction, and is attachable to and detachable from an image-forming apparatus.
- the developer in the image-forming process cartridge of the present invention contains the toner of the present invention.
- FIGURE is a diagram showing one example of the image-forming process cartridge of the present invention.
- the toner for electrophotography of the present invention contains a coloring agent and a binder resin, and if required, other materials may be added thereto.
- a polyol resin according to present claim 1 is used as the binder resin.
- the polyol resin to be used in the present invention is synthesized in the following manner.
- a compound having active hydrogen atoms which react with epoxy groups is used as a raw material.
- This compound and an epoxy resin are allowed to react with each other so that the resulting reaction product has a linear chain or network molecular structure.
- a compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms is used as a raw material to enlarge the molecule.
- a compound having one or more active hydrogen atoms which react with an epoxy group in molecules of the compound having one or more active hydrogen atoms is used to cap the end of the resin molecule, thereby preventing the resin molecule from increasing in size.
- any bisphenol-A-type epoxy resin may be used in the present invention so long as it has two or more epoxy bonds.
- the bisphenol A-type epoxy resins expressed by the following Formula (2) are typical ones. These are low priced and readily available also on a chemical industrial scale, and also chemically stable. '
- such an epoxy resin obtained by bonding the bisphenol such as bisphenol A with epichlorohydrin is used in part, because it favorably results in a low cost. wherein "n" expresses 0 or more.
- the epoxy resin to be used in the present invention is preferably obtained by bonding bisphenol A with epichlorohydrin.
- the epoxy resin includes at least two or more kinds of bisphenol A-type epoxy resin components having different number-average molecular weights.
- the number-average molecular weight of the low molecule weight is 360 to 2000
- the number-average molecular weight of the high molecule weight is 3000 to 10,000.
- the content of the low molecule weight is 20 % by weight to 50 % by weight relative to the amount of the polyol resin
- the content of the high molecule weight is 5 % by weight to 40 % by weight, relative to the amount of the polyol resin.
- Examples of the compound having one active hydrogen atom which reacts with an epoxy group in the molecule to be used in the present invention may include monovalent phenols, secondary amines, carboxylic acid, and the like.
- Examples of the monovalent phenols include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol.
- Examples of the secondary amines include diethylamine, dipropylamine, dibutylamine, N-methyl(ethyl)piperazine, piperazine.
- Examples of the carboxylic acids include propionic acid, caproic acid, benzoic acid, stearic acid.
- bisphenol A is excellent in terms of cost, and enables improving the chemical resistance of the toner resin. Furthermore, the use of bisphenol A also perfectly prevents toners from being transferred onto a vinyl chloride resin sheet.
- the amount of residual bisphenol A in the toner which has been suspected of an endocrine disrupting chemical in recent years, is set to be 1000 ā g/g or less from the viewpoint of the safety of the toner.
- a description will be given to a process for reducing the amount of residual bisphenol A.
- the one containing bisphenol A as the skeleton is used, when considering the chemical resistance.
- the amount of residual bisphenol A is also possible to set the amount of residual bisphenol A at 1000 ā g/g or less, by using bisphenol A. This can be achieved by making the number of epoxy groups in the epoxy resin equal to the number of active hydrogen atoms which react with epoxy groups with high accuracy.
- the number of epoxy groups is set to be larger than the number of active hydrogen atoms which react with epoxy groups, bisphenol A having active hydrogen atoms will not remain alone, but epoxy groups will remain in the resin.
- the epoxy groups are chemically active, and considered to have a toxicity such as skin irritation.
- the number of active hydrogen atoms which react with epoxy groups has been set to be larger than the number of epoxy groups, so that no epoxy groups remain.
- the compounds such as bisphenol A having active hydrogen atoms will remain in a slight amount.
- the present invention by making the number of epoxy groups in the epoxy resin equal to the number of active hydrogen atoms which react with epoxy groups with high accuracy, it is possible to eliminate epoxy groups in the polyol resin, and to control the amount of residual bisphenol A to 1000 ā g/g or less.
- the raw materials are weighed with high accuracy, and that sufficient stirring is performed and sufficient time is taken for the reaction so as to leave no reaction residue.
- the weight concentration of the polar solvent soluble component of the present invention can be determined by, for example, the high performance liquid chromatography (HPLC) as shown below. There is also another method for determining the concentration by a gas chromatography. However, HPLC is preferred in terms of accuracy.
- a sample is dissolved in a toner-soluble or resin-soluble solvent (for example, tetrahydrofuran (THF), toluene, methylethylketone, dichloromethane, chloroform).
- a polar solvent such as methanol, or the like (for example, methanol, ethanol, n-propanol, acetonitrile, water, or a mixed solution thereof), is added, thereby forming a precipitate.
- a polar solvent such as methanol, or the like (for example, methanol, ethanol, n-propanol, acetonitrile, water, or a mixed solution thereof)
- any of the techniques are not limited to the following apparatus and conditions, so long as it is capable of analyzing the polar solvent soluble matter with high accuracy.
- the polyol resin to be used in the present invention employs an epoxy resin as a raw material.
- the polyol resin has no epoxy group because the epoxy group is chemically very active, and biochemically considered to have a toxicity such as skin irritation.
- the polyol resin of the present invention refers to a polyol resin which has an epoxy skeleton, but has no terminal epoxy substantially.
- the epoxy equivalent is used for expressing the number of epoxy groups.
- the term, "epoxy equivalent,ā refers to the equivalent weight per epoxy group (g/equiv.). The value obtained by dividing the average molecular weight by the number of epoxy groups per molecule.
- the epoxy equivalent is determined in accordance with an indicator titration method defined in paragraph 4.2 of JIS K 7236. However, the epoxy equivalent has an identification limit of about 20,000. Thus, if it is 20,000 or more, it is considered that there are almost no epoxy groups.
- the toner of the present invention shows excellent image-fixing properties, and prevents curling on a fixed image.
- methods for introducing the material obtained by adding an alkylene oxide to bisphenol include the following two methods.
- the first method is a method using a product of epoxidation reactive between the bisphenol-alkylene oxide adduct and epichlorohydrin.
- the reaction product is used as an epoxy resin for synthesizing a polyol resin.
- dihydric phenol-alkylene oxide adduct examples include reaction products of ethylene oxide, propylene oxide, butylene oxide, or mixture thereof, and bisphenol such as bisphenol A, bisphenol B. Further, the adduct thus obtained may also be glycidylated with epichlorohydrin or ā -methylepichlorohydrin.
- the dihydric phenol-alkylene oxide adduct or a diglycidyl ether thereof is preferably contained in an amount of 10 to 40 % by weight relative to the amount of the polyol resin. If the content of the dihydric phenol-alkylene oxide adduct is low, the toner resin itself has no flexibility, and, unfavorably, a printed copy paper tends to curl increasingly, the toners are insufficiently fixed onto a copy paper, or other deficiencies occur. If "n + m" is equal to 9 or more, or the content is too high, the image transferred from the copy fixed image side to the vinyl chloride resin sheet may become more likely to occur, too much glossiness may occur, and further the storageability may deteriorate.
- the second method is a method using a compound prepared by ester-bonding a polyvalent carboxylic acid to the dihydric phenol-alkylene oxide adduct such as bisphenol A as a compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms.
- polyvalent carboxylic acids may include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride.
- the compound prepared by allowing the dihydric phenol-alkylene oxide adduct and a polyvalent carboxylic acid to react is preferably contained in an amount of 10 % by weight to 40 % by weight relative to the amount of the polyol resin. If the content thereof is low, the toner resin itself has no flexibility, a printed copy paper is more likely to curl, and, unfavorably, the toners are insufficiently fixed onto paper, or other deficiencies occur. If "n + m" is equal to 7 or more, or the content is too high, the image is transferred from a side on which the image is fixed, to the vinyl chloride resin sheet may become more likely to occur, too much glossiness may occur, and further the storageability may deteriorate.
- the Tg of the resulting resin is preferably from 50Ā°C to 70 Ā°C, and more preferably from 55Ā°C to 70 Ā°C. If the Tg is low, agglomerate tends to occur in a toner bottle or a development unit. As a result, the agglomerate is also developed. The developed agglomerate remains on the photoconductor, and leaves one or more white spots on an image, when the toners are transferred. On the other hand, if the Tg is high, unfavorably, image glossiness tends to be insufficient.
- any known dyes and pigments can be used as the coloring agents.
- the coloring agent include carbon black, nigrosine dyes, black oxide of iron, Naphthol Yellow S, Hansa Yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, yellow ochre, chrome yellow, titanic yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, benzidine yellow (G, GR), permanent yellow (NCG), vulcan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthragen yellow BGL, isoindolinone yellow, red oxide, red lead oxide, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, Fire Red, para-chloro-ortho-nitroaniline red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD
- the coloring agent is preferably used in an amount of 0.1 part by weight to 50 parts by weight relative to 100 parts by weight of the binder resin.
- a so-called release agent for imparting the releasability to the toner may also be used.
- the softening point of the release agent to be used is preferably 70Ā°C to 100 Ā°C.
- the softening point of lower than 70 Ā°C results in deficient storage stability.
- the softening point is higher than 100 Ā°C, not only the image-fixing properties tend to deteriorate, but also the resulting color image tends to be poor in quality because of its lower glossiness.
- the release agent may include synthesized waxes such as low-molecular weight polyethylene, low-molecular weight polypropylene, copolymers thereof, vegetable waxes such as candelilla wax, carnauba wax, rice wax, Japan tallow, jojoba wax, or the like; animal waxes such as bees wax, lanolin, spermaceti, or the like; mineral waxes such as montan wax, ozocerite and grease waxes such as hardened castor oil, hydroxystearic acid, aliphatic acid amide, phenol aliphatic aid ester. From the viewpoint of chemical structures of the waxes, hydrocarbon waxes, ester waxes, amide waxes are known. However, in the present invention, ester waxes are preferable from the viewpoint of evaluating the storageability, image quality, the range of the fixing temperature.
- vegetable waxes such as candelilla wax, carnauba wax, rice wax, Japan tallow, jojoba wax,
- the amount of the release agent is preferably 1 part by weight to 6 parts by weight relative to the total amount of the toner.
- the toner If the amount is larger than 6 parts by weight, the toner shows deficient storage stability, rough surface of an image, and lower glossiness. Further, even if the amount is less than 1 part by weight, the surface of an image tends to be rough, and the resulting color image tends to be poor in quality because of the lower glossiness.
- the toner of the present invention may contain a charge control agent, if required.
- a charge control agent Any known charge control agents can be used in the present invention.
- the charge control agent include a nigrosine dye, a triphenylmethane dye, a chromium-containing metal complex dye, a molybdic acid chelate pigment, a rhodamine dye, an alkoxyamine, a quaternary ammonium salt (including a fluorine-modified quaternary ammonium salt), alkylamide, a simplex or a compound of phosphorus, a simplex or a compound of tungsten, a fluorine-containing activator, a metallic salt of salicylic acid, a metallic salt of a salicylic acid derivative.
- the toner of the present invention may further contain other additives, for example; silica fine particles, aliphatic metallic salts (such as zinc stearate, aluminum stearate. metallic oxides (such as titanium oxide, aluminum oxide, tin oxide, antimony oxide), fluoropolymers.
- silica fine particles such as zinc stearate, aluminum stearate.
- metallic oxides such as titanium oxide, aluminum oxide, tin oxide, antimony oxide
- fluoropolymers such as hydrophobilized silica, titania, and alumina fine particles are preferred.
- silica fine particles may include HDK H 2000, HDK H 2000/4, HDK H 2050EP, and HDK H 1303VP (all of which are manufactured by Clariant Ltd.), and R972, R974, RX200, RY200, R202, R805, and R812 (all of which are manufactured by Nippon Aerosil K.K.).
- examples of the titania fine particles may include P-25 (manufactured by Nippon Aerosil K.K.), STT-30, and STT-65C-S (all of which are manufactured by Titan Kogyo K.K.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), and MT-150W, MT-500B, MT-600B (all of which are manufactured by Tayca Corp.).
- hydrophobically treated titanium oxide fine particles there can be used the anatase type or rutile type crystalline ones, or amorphous ones.
- examples thereof may include T-805 (manufactured by Nippon Aerosil K.
- MT-100S, MT-100T, MT150A, MT150AFM, and MT-150AI all of which are manufactured by Tayca Corp.
- STT-30A, STT-65S-S all of which are manufactured by Titan Kogyo K.K.
- TAF-500T and TAF-1500T all of which are manufactured by Fuji Titanium Industry Co., Ltd.
- MT-100S and MT-100T all of which are manufactured by Tayca Corp.
- IT-S manufactured by Ishihara Sangyo Kaisha, Ltd.
- the hydrophobically treated silica fine particles, titania fine particles, or alumina fine particles can be obtained by treating hydrophilic fine particles with a silane coupling agent such as methyl trimethoxy silane, methyl triethoxy silane, octyl trimethoxy silane.
- a silane coupling agent such as methyl trimethoxy silane, methyl triethoxy silane, octyl trimethoxy silane.
- an alphilic acid metal salt such as zinc stearate or aluminum stearate
- a metal oxide such as alumina, tin oxide, or antimony oxide
- fluoropolymers such as alumina, tin oxide, or antimony oxide
- the toner made of the materials as described above of the present invention may be used as a double-component developer in combination with a carrier shown below. Alternatively, the toner may be used alone as a single-component developer.
- developer herein refers to any kinds of agent used for developing a latent electrostatic image.
- the carrier when the toner is used as a double-component developer, as the carrier, the same materials as those employed in the related art such as iron powders, ferrite particles, glass beads, or the like can be employed. It is noted that these carrier may be coated with a resin. Known resins may also be used in this case. Examples of the resin may include acrylic resin, polyfluorocarbon, polyvinyl chloride, polyvinylidene chloride, phenolic resin, polyvinyl acetal, silicone resin.
- the mixing ratio of the toner to the carrier in general, it is proper that the toner is mixed in an amount of 2.5 parts by weight to 8.0 parts by weight relative to 100 parts by weight of the carrier.
- the softening point and the Tg of the resin for use in the present invention are determined in the following manner.
- the measurement is carried out using a full-automatic dropping point measurement apparatus "FP5/FP53" manufactured by Mettler Co., Ltd., as an apparatus for determining the softening point in accordance with the following procedure:
- the measurement is carried out, using DSC-200 made by Seiko Instruments Inc., as an apparatus for determining the Tg in accordance with the following procedure:
- the sample is heated from room temperature up to 150 Ā°C with a temperature increasing rate of 20 Ā°C/min, and is then allowed to stand at 150 Ā°C for 10 minutes.
- the sample is then cooled to 0 Ā°C at a temperature decreasing rate of 50 Ā°C/min, and is then allowed to stand for 10 minutes.
- the sample is again heated up to 150 Ā°C with a temperature increasing rate of 20 Ā°C/min, and subjected to the DSC measurement.
- the Tg is measured by reading a peak rise-up temperature, using an analysis software "Tg Job.ā
- the epoxy equivalent is measured in accordance with an indicator titration method defined in paragraph 4.2 of JIS K7236.
- An image-forming process of the present invention has no particular restriction, except that the toner for electrophotography of the present invention is used for developing a latent electrostatic image, and can be appropriately selected according to the intended purpose.
- the image-forming apparatus of the present invention has no particular restriction, except that the image-forming apparatus accommodates an image developer in which the toner for electrophotography of the present invention is provided as a developing unit.
- image developer herein refers to a developing device that enables developing a latent electrostatic image with a developer.
- the image-forming process cartridge of the present invention is characterized by including a latent electrostatic image support; a charger configured to charge a surface of the latent electrostatic image support; a light-irradiator configured to irradiate a light to the latent electrostatic image; a cleaner configured to clean the surface of the latent electrostatic support; and an image developer configured to supply a developer onto a latent electrostatic image so as to develop the latent electrostatic image and to form a visible image.
- the image-forming process cartridge is formed in one-piece construction, and is attachable to and detachable from an image-forming apparatus.
- the image developer in the image-forming process cartridge of the present invention includes the developer which contains the toner for electrophotography including a color toner for forming an image according to the present invention.
- the image-forming process cartridge When installed in an image-forming apparatus, the image-forming process cartridge provides sufficient offset-resistance even in a fixing step where no lubricant oil is coated on a fixing roller, or a very small amount of lubricant oil is coated on a fixing roller.
- FIGURE shows an example of a structure of an image-forming process unit (process cartridge) (106), which includes all of a photoconductive drum (101) as the latent electrostatic image support, a charging roller (103) as the charger, a cleaning unit (105) as the cleaner, and a developing unit (102) as the image developer.
- the image-forming process cartridge is attachable to and detachable from a printer.
- the developing unit includes a developing sleeve (104).
- the mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin having a softening point of 108 Ā°C and a Tg of 61 Ā°C (which may be referred to as "resin 1,ā hereinafter).
- the amount of residual bisphenol A was found to be 0 ā g/g, and the epoxy equivalent was found to be 20,000 or more.
- the resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure.
- the mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 107 Ā°C and a Tg of 58 Ā°C (which may be referred to as "resin 2,ā hereinafter).
- the amount of the residual bisphenol A was found to be 830 ā g/g, and the epoxy equivalent was found to be 20,000 or more.
- reaction 3 a polyol resin with a softening point of 109 Ā°C and a Tg of 58 Ā°C (hereinafter, may be referred to as "resin 3").
- the amount of residual bisphenol A was found to be 280 ā g/g, and the epoxy equivalent was found to be 20,000 or more.
- the resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N 2 atmosphere, and 0.183 g of lithium chloride was added thereto.
- the resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure.
- the mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 109 Ā°C and a Tg of 58 Ā°C (hereinafter, may be referred to as "resin 4").
- the amount of residual bisphenol A was found to be 950 ā g/g, and the epoxy equivalent was found to be 20,000 or more.
- the resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N 2 atmosphere, and 0.183 g of lithium chloride was added thereto.
- the resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure.
- the mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 112 Ā°C and a Tg of 59 Ā°C (hereinafter, may be referred to as "resin 6").
- the amount of residual bisphenol A was found to be 620 ā g/g, and the epoxy equivalent was found to be 20,000 or more.
- reaction 7 a polyol resin with a softening point of 118 Ā°C and a Tg of 62 Ā°C (hereinafter, may be referred to as "resin 7").
- the amount of residual bisphenol A was found to be 0 ā g/g, and the epoxy equivalent was found to be 20,000 or more.
- reaction 8 a polyol resin with a softening point of 108 Ā°C and a Tg of 61 Ā°C (hereinafter, may be referred to as "resin 8").
- the amount of residual bisphenol A was found to be 0 ā g/g, and the epoxy equivalent was found to be 9380.
- the resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N 2 atmosphere, and 0.183 g of lithium chloride was added thereto.
- the resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under reduced pressure.
- the mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 112 Ā°C and a Tg of 59 Ā°C (hereinafter, may be referred to as "resin 9").
- the amount of residual bisphenol A was found to be 8850 ā g/g, and the epoxy equivalent was found to be 20,000 or more.
- the resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N 2 atmosphere, and 0.183 g of lithium chloride was added thereto.
- the resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure.
- the mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 112 Ā°C and a Tg of 59 Ā°C (hereinafter, may be referred to as "resin 10").
- the amount of residual bisphenol A was found to be 120 ā g/g, and the epoxy equivalent was found to be 9800.
- a mixture of the materials above was melt-kneaded by a hot roll mill. After cooling the mixture, the resulting mixture was roughly ground in a hammer mill, and then finely pulverized in an air-jet grinder. The resulting fine powder was classified to form a matrix toner having an average particle diameter of about 7 ā m.
- Each of the toners of Examples 1 to 4 was obtained in the same manner as in the Reference Example, except that the resin was altered to each of the resins of Synthetic Examples 2 to 5 in the Reference Example.
- a toner of Comparative Example 4 was obtained with in the same manner as in the Reference Example, except that the resin of the Reference Example was altered to a polyester resin.
- the polyester resin is a resin obtained from the condensation polymerization of a bisphenol A ethylene oxide adduct, a bisphenol A propylene oxide adduct, a terephthalic acid, and a fumaric acid in a molar ratio of 60 : 40 : 25 : 75.
- the polyester resin has a softening point of 107 Ā°C and a Tg of 59Ā°C.
- Each of the toners of the Reference Example, Examples 1 to 4, and the toners of Comparative Examples 1 to 4 was installed into a color copier Imagio Color 2800 manufactured by Ricoh Company Ltd., to produce image-bearing copy sheets.
- Each of the image-bearing copy sheets was brought in intimate contact with a vinyl chloride sheet, and then stored at 50 Ā°C for 1 week to evaluate the adhesion of the toner to the vinyl chloride sheet.
- Curl of the paper was also evaluated as to the toners of the Reference Example, Examples 1 to 4 and the toners of Comaprative Examples 1 to 4.
- the curl of the paper was measured based upon how the paper became curled up, when an image with 1mg/cm of the toners was transferred, and was then fixed onto paper.
- the evaluation was ranked as follows:
- each of the toners of Examples of the present invention is characterized in that the amount of the residual bisphenol A is smaller, the epoxy equivalent is larger, and less toners adheres to the vinyl chloride sheet, compared with the toners of Comparative Examples.
- the toner for electrophotography of the present invention enables obtaining a toner which contains less the residual bisphenol A and less residual epoxy groups. Hence the toner for electrophotography of the present invention enables obtaining a safer toner. Further, the toner for electrophotography of the present invention enables obtaining a toner which is less likely to adhere a vinyl chloride mat when used in a copied image.
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Abstract
Description
- The present invention relates to a toner for electrophotography.
- With an electrophotographic method, a latent electrostatic image is formed on a photoconductor by a conventional method, and developed with a dry toner. Thereafter, the resulting toner image is transferred onto a sheet of copy paper, and is fixed onto the sheet by thermal fixing (generally, using a heat roller) so as to obtain a copy image. As generally known, the dry toner for this method contains a binder resin and a coloring agent as the main components. If required, the dry toner may further contain additives, such as a charge control agent and an offset-preventing agent.
- Here, examples of the binder resins are polystyrenes, styrene-acrylic copolymers, polyester resins, epoxy resins, in terms of the properties required for the toner, for instance, transparency, insulating properties, water-resistance, flowability (as a powder), mechanical strength, glossiness, thermoplasticity, grindability. Of these, styrene resins are widely used because of the excellent grindability, water-resistance, and flowability.
- However, when a sheet of paper bearing a copy image formed by a toner containing a styrene resin is held in a document folder made of a vinyl chloride resin sheet for storage, the side on which an image is formed is left in intimate contact with the resin sheet.
- Accordingly, a plasticizer contained in the resin sheet, which is formed of the vinyl chloride resin, is transferred to the fixed toner image, and plasticizes the fixed toner image. The plasticizer is then fused onto a side of the resin sheet. As a result, if the side on which an image is formed is separated from the resin sheet, unfavorably, the toner image is partially or entirely peeled from the image, and the resin sheet is also contaminated. Such a deficiency can also be observed for a polyester resin-containing toner.
- As a countermeasure for preventing the transfer onto the vinyl chloride resin sheet, Japanese Patent Application Laid-Open (JP-A) No. 07-77832 discloses the use of a polyol resin synthesized by using an epoxy resin as a raw material.
- Such a polyol resin uses an epoxy resin and bisphenol A as raw materials. The epoxy groups in the epoxy resin and the active hydrogen moiety of bisphenol A are allowed to react with each other to perform synthesis. Epoxy groups in the epoxy resin are chemically very active, and, biochemically, considered to have a toxicity such as skin irritation. For this reason, for the synthesis of a polyol resin, the number of moles of the active hydrogen atoms is set to be larger than the number of moles of the epoxy groups.
- Accordingly, all of the epoxy groups are allowed to react, so that no epoxy group is left, resulting in a polyol resin.
- However, some active hydrogen atoms remain, and hence bisphenol A used as a raw maternal also partially remains unreacted in the resulting polyol resin.
- In recent years, bisphenol A has been suspected of being an endocrine disrupting chemical, and hence it is considered to possibly cause a problem in terms of the safety of the toner.
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US-A-5998073 relates to a dry toner for electrophotography comprising a colorant, a releasing agent, and a polyol resin as a binder resin, wherein the polyol resin is obtained by reacting an epoxy resin, a dihydric phenol, and an alkylene oxide adduct of a dihydric phenol or a glycidyl ether thereof. A polyol resin used in the examples has an epoxy equivalent of 20,000 or more. - It is an object of the present invention to provide a safer toner by controlling the amount of the residual bisphenol A, which is suspected of being an endocrine disrupting chemical, in the toner to 1000 Āµg/g or less in weight concentration.
- Further, it is another object of the present invention to provide a toner for electrophotography which, even if the fixed image side of the copy image-bearing paper sheet is brought in intimate contact with a vinyl chloride resign sheet, the toner image is not transferred to the vinyl chloride resin sheet.
- Still further, it is a still another object of the present invention to provide a toner for electrophotography whereby the resulting image is excellent in color reproducibility and has stable glossiness not causing non-uniformity.
- The present invention provides, in a first aspect, a toner for electrophotography which is characterized by containing a coloring agent and a binder resin. In the toner of the present invention, the binder resin is a polyol resin which is prepared by reacting a) a bisphenol-A-type epoxy resin, b) a compound having one or more active hydrogen atoms which react with an epoxy group in molecules of the compound having one or more active hydrogen atoms, and c) a compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms, wherein the compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms comprises bisphenol A, in which a weight concentration of non-reacted bisphenol A in the toner is 1000 Āµg/g or less, and the toner has an epoxy equivalent of 20000 or more, measured in accordance with an indicator-titration method defined in paragraph 4.2 of JIS K7236.
- The present invention also provides, in a second aspect, an image-forming process in which a latent electrostatic image on a latent electrostatic image support is developed by the toner of the present invention.
- The present invention further provides, in a third aspect, an image-forming apparatus which includes an image developer where the toner of the present invention is utilized as a developer.
- The present invention still further provides, in a fourth aspect, an image-forming process cartridge. The image-forming process cartridge of the present invention includes an image developer configured to supply a developer onto a latent electrostatic image so as to visualize and develop the latent electrostatic image. The image-forming process cartridge of the present invention is formed in one-piece construction, and is attachable to and detachable from an image-forming apparatus. The developer in the image-forming process cartridge of the present invention contains the toner of the present invention.
- A single FIGURE is a diagram showing one example of the image-forming process cartridge of the present invention.
- The toner for electrophotography of the present invention contains a coloring agent and a binder resin, and if required, other materials may be added thereto.
- As the binder resin, a polyol resin according to present claim 1 is used.
- The polyol resin to be used in the present invention is synthesized in the following manner. A compound having active hydrogen atoms which react with epoxy groups is used as a raw material. This compound and an epoxy resin are allowed to react with each other so that the resulting reaction product has a linear chain or network molecular structure. Namely, in order that the resulting polyol resin may have a linear chain or network molecular structure, a compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms is used as a raw material to enlarge the molecule. Further, for achieving a proper molecular weight in synthesizing the polyol resin, a compound having one or more active hydrogen atoms which react with an epoxy group in molecules of the compound having one or more active hydrogen atoms is used to cap the end of the resin molecule, thereby preventing the resin molecule from increasing in size.
- Any bisphenol-A-type epoxy resin may be used in the present invention so long as it has two or more epoxy bonds. In general, the bisphenol A-type epoxy resins expressed by the following Formula (2) are typical ones. These are low priced and readily available also on a chemical industrial scale, and also chemically stable. ' In the present invention, such an epoxy resin obtained by bonding the bisphenol such as bisphenol A with epichlorohydrin is used in part, because it favorably results in a low cost.
- The epoxy resin to be used in the present invention is preferably obtained by bonding bisphenol A with epichlorohydrin. In order to obtain stable image-fixing properties and glossiness, the epoxy resin includes at least two or more kinds of bisphenol A-type epoxy resin components having different number-average molecular weights. The number-average molecular weight of the low molecule weight is 360 to 2000, and the number-average molecular weight of the high molecule weight is 3000 to 10,000. Further, the content of the low molecule weight is 20 % by weight to 50 % by weight relative to the amount of the polyol resin, and the content of the high molecule weight is 5 % by weight to 40 % by weight, relative to the amount of the polyol resin.
- When the low molecule weight is present in too large amounts, or has a molecular weight of still lower than 360, too much glossiness may occur, and further the storageability may deteriorate. Moreover, when the high molecule weight is present in too large amounts, or has a molecular weight of still higher than 10,000, the glossiness of the resulting image may be insufficient, and further the image-fixing properties may deteriorate.
- Examples of the compound having one active hydrogen atom which reacts with an epoxy group in the molecule to be used in the present invention may include monovalent phenols, secondary amines, carboxylic acid, and the like. Examples of the monovalent phenols include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol. Examples of the secondary amines include diethylamine, dipropylamine, dibutylamine, N-methyl(ethyl)piperazine, piperazine. Examples of the carboxylic acids include propionic acid, caproic acid, benzoic acid, stearic acid.
- The use of bisphenol A is excellent in terms of cost, and enables improving the chemical resistance of the toner resin. Furthermore, the use of bisphenol A also perfectly prevents toners from being transferred onto a vinyl chloride resin sheet.
- In the present invention, the amount of residual bisphenol A in the toner, which has been suspected of an endocrine disrupting chemical in recent years, is set to be 1000 Āµg/g or less from the viewpoint of the safety of the toner. Hereinafter, a description will be given to a process for reducing the amount of residual bisphenol A.
- As a polyol resin, the one containing bisphenol A as the skeleton, is used, when considering the chemical resistance.
- Thus, as a process for forming a polyol resin comprising bisphenol A as the skeleton, and free of residual bisphenol A, the following process is preferably used. Namely, as the compound having two or more active hydrogen atoms which react with epoxy groups, the compound expressed by the following Formula (3) is used:
- It is possible to obtain the above-described compound as the one free of residual bisphenol A, by allowing epichlorohydrin and bisphenol A to react with each other in an appropriate ratio. Conventionally, this process for reacting epichloryhydrin and bisphenol A has not been employed, because the viscosity of the resin increases with this method, the amount of a solvent becomes larger than in a case that the bisphenol A is used alone. Accordingly, the cost increases. However, the use of the process is most preferred, considering the safety of the toner and the acquisition of chemical resistance.
- Further, it is also possible to set the amount of residual bisphenol A at 1000 Āµg/g or less, by using bisphenol A. This can be achieved by making the number of epoxy groups in the epoxy resin equal to the number of active hydrogen atoms which react with epoxy groups with high accuracy.
- If the number of epoxy groups is set to be larger than the number of active hydrogen atoms which react with epoxy groups, bisphenol A having active hydrogen atoms will not remain alone, but epoxy groups will remain in the resin. The epoxy groups are chemically active, and considered to have a toxicity such as skin irritation. For this reason, in the related art, the number of active hydrogen atoms which react with epoxy groups has been set to be larger than the number of epoxy groups, so that no epoxy groups remain. However, with this method, the compounds such as bisphenol A having active hydrogen atoms will remain in a slight amount.
- In the present invention, by making the number of epoxy groups in the epoxy resin equal to the number of active hydrogen atoms which react with epoxy groups with high accuracy, it is possible to eliminate epoxy groups in the polyol resin, and to control the amount of residual bisphenol A to 1000 Āµg/g or less. In addition, it should also be noted that the raw materials are weighed with high accuracy, and that sufficient stirring is performed and sufficient time is taken for the reaction so as to leave no reaction residue.
- Further, it is necessary to take into consideration the case where the number of epoxy groups becomes slightly larger than the number of active hydrogen atoms due to a variation in number of raw material epoxy groups, the purity of the raw material, weighing error. Specifically, by applying a sufficient reaction time and a sufficient temperature for the reaction, the alcoholic OH groups formed from the reaction of the epoxy groups and active hydrogen atoms, react with epoxy groups. For this reason, by applying a sufficient reaction time and temperature thereto, no epoxy groups will remain in the polyol resin.
- Hereinafter, a method for determining the concentration of unreacted bisphenol A which solely remains in a toner will be described. The weight concentration of the polar solvent soluble component of the present invention can be determined by, for example, the high performance liquid chromatography (HPLC) as shown below. There is also another method for determining the concentration by a gas chromatography. However, HPLC is preferred in terms of accuracy.
- A sample is dissolved in a toner-soluble or resin-soluble solvent (for example, tetrahydrofuran (THF), toluene, methylethylketone, dichloromethane, chloroform). Thereafter, to the resulting solution, a polar solvent such as methanol, or the like (for example, methanol, ethanol, n-propanol, acetonitrile, water, or a mixed solution thereof), is added, thereby forming a precipitate. Thus, an insoluble portion of the polar solvent is removed, and a soluble portion of the polar solvent is extracted. The extracted component is separated and subjected to the qualitative analysis by HPLC, followed by the quantitative analysis by using a standard sample.
- Although detailed exampled are shown below, any of the techniques are not limited to the following apparatus and conditions, so long as it is capable of analyzing the polar solvent soluble matter with high accuracy.
- 1) Method: high performance liquid chromatography (HPLC)
- 2) Apparatus: Alliance 2690, UV 2487 detector, manufactured by Waters Corporation
- 3) Conditions: column Develosil ODS-Hg-3 (manufactured by Nomura Chemical Co., Ltd.)
- Ļ 4.6mm Ć 150 mm
- Moving phase: water / acetonitrile = 65/35
- Flow rateāāā 1.0 ml/min
- Detectionāāā 228 nm
- Injection amountāāā 15 Āµl
- 4) Procedure for preparing a sample
- 1. One gram of a sample is accurately weighed, and is added into a 100ml Erlenmeyer flask;
- 2. 30ml of THF is added to the flask, and is dissolved therein;
- 3. Upon completing dissolving, 50 ml of methanol is added thereto, so as to form a precipitate;
- 4. After filtration with a 5A filter paper, the solvent is removed;
- 5. A constant volume is maintained with 5 ml of acetonitrile and 5 ml of distilled water;
- 6. The solution is filtrated through a filter, resulting in a HPLC sample; and
- 7. A standard sample is also prepared in the same manner.
- The polyol resin to be used in the present invention employs an epoxy resin as a raw material. However, the polyol resin has no epoxy group because the epoxy group is chemically very active, and biochemically considered to have a toxicity such as skin irritation. Namely, the polyol resin of the present invention refers to a polyol resin which has an epoxy skeleton, but has no terminal epoxy substantially.
- The epoxy equivalent is used for expressing the number of epoxy groups. The term, "epoxy equivalent," refers to the equivalent weight per epoxy group (g/equiv.). The value obtained by dividing the average molecular weight by the number of epoxy groups per molecule. The epoxy equivalent is determined in accordance with an indicator titration method defined in paragraph 4.2 of JIS K 7236. However, the epoxy equivalent has an identification limit of about 20,000. Thus, if it is 20,000 or more, it is considered that there are almost no epoxy groups.
- Using materials in which alkylene oxide is added to the polyol resin, preferably to bisphenols such as bisphenol A, gives a suitable flexibility to resins for the toner of the present invention. Accordingly, the toner of the present invention shows excellent image-fixing properties, and prevents curling on a fixed image.
- In the present invention, methods for introducing the material obtained by adding an alkylene oxide to bisphenol include the following two methods.
- The first method is a method using a product of epoxidation reactive between the bisphenol-alkylene oxide adduct and epichlorohydrin. The reaction product is used as an epoxy resin for synthesizing a polyol resin.
- Specific examples of the dihydric phenol-alkylene oxide adduct include reaction products of ethylene oxide, propylene oxide, butylene oxide, or mixture thereof, and bisphenol such as bisphenol A, bisphenol B. Further, the adduct thus obtained may also be glycidylated with epichlorohydrin or Ī²-methylepichlorohydrin. In particular, a preferable example of the dihydric phenol-alkylene oxide adduct includes a diglycidyl ether of the bisphenol A-alkylene oxide adduct expressed by the following Formula (1).
- Further, the dihydric phenol-alkylene oxide adduct or a diglycidyl ether thereof is preferably contained in an amount of 10 to 40 % by weight relative to the amount of the polyol resin. If the content of the dihydric phenol-alkylene oxide adduct is low, the toner resin itself has no flexibility, and, unfavorably, a printed copy paper tends to curl increasingly, the toners are insufficiently fixed onto a copy paper, or other deficiencies occur. If "n + m" is equal to 9 or more, or the content is too high, the image transferred from the copy fixed image side to the vinyl chloride resin sheet may become more likely to occur, too much glossiness may occur, and further the storageability may deteriorate.
- The second method is a method using a compound prepared by ester-bonding a polyvalent carboxylic acid to the dihydric phenol-alkylene oxide adduct such as bisphenol A as a compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms. In particular, the compound expressed by the following Formula (4) is preferred.
- Examples of the polyvalent carboxylic acids may include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride.
- Further, the compound prepared by allowing the dihydric phenol-alkylene oxide adduct and a polyvalent carboxylic acid to react is preferably contained in an amount of 10 % by weight to 40 % by weight relative to the amount of the polyol resin. If the content thereof is low, the toner resin itself has no flexibility, a printed copy paper is more likely to curl, and, unfavorably, the toners are insufficiently fixed onto paper, or other deficiencies occur. If "n + m" is equal to 7 or more, or the content is too high, the image is transferred from a side on which the image is fixed, to the vinyl chloride resin sheet may become more likely to occur, too much glossiness may occur, and further the storageability may deteriorate.
- The Tg of the resulting resin is preferably from 50Ā°C to 70 Ā°C, and more preferably from 55Ā°C to 70 Ā°C. If the Tg is low, agglomerate tends to occur in a toner bottle or a development unit. As a result, the agglomerate is also developed. The developed agglomerate remains on the photoconductor, and leaves one or more white spots on an image, when the toners are transferred. On the other hand, if the Tg is high, unfavorably, image glossiness tends to be insufficient.
- Any known dyes and pigments can be used as the coloring agents. Examples of the coloring agent include carbon black, nigrosine dyes, black oxide of iron, Naphthol Yellow S, Hansa Yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, yellow ochre, chrome yellow, titanic yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, benzidine yellow (G, GR), permanent yellow (NCG), vulcan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthragen yellow BGL, isoindolinone yellow, red oxide, red lead oxide, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, Fire Red, para-chloro-ortho-nitroaniline red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Vulcan Fast Rubine B, Brilliant Scarlet G, Lithol Rubine GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, bordeaux 5B, toluidine maroon, permanent bordeaux F2K, helio bordeaux BL, bordeaux 10B, BON maroon light, BON maroon medium, eosine lake, rhodamine lake B, rhodamine lake Y, alizarine lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perynone orange, oil orange, cobalt blue, cerulean blue, alkali blue lake, peacock blue lake, victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine, Prussian blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese violet, dioxan violet, anthraquinone violet, chrome green, zinc green, chrome oxide, Persian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone, and mixtures thereof.
- In general, the coloring agent is preferably used in an amount of 0.1 part by weight to 50 parts by weight relative to 100 parts by weight of the binder resin.
- Then, a description will be given to other materials to be used for the toner of the present invention.
- For the toner of the present invention, a so-called release agent for imparting the releasability to the toner may also be used. The softening point of the release agent to be used is preferably 70Ā°C to 100 Ā°C. The softening point of lower than 70 Ā°C results in deficient storage stability. On the other hand, if the softening point is higher than 100 Ā°C, not only the image-fixing properties tend to deteriorate, but also the resulting color image tends to be poor in quality because of its lower glossiness.
- Specific examples of the release agent may include synthesized waxes such as low-molecular weight polyethylene, low-molecular weight polypropylene, copolymers thereof, vegetable waxes such as candelilla wax, carnauba wax, rice wax, Japan tallow, jojoba wax, or the like; animal waxes such as bees wax, lanolin, spermaceti, or the like; mineral waxes such as montan wax, ozocerite and grease waxes such as hardened castor oil, hydroxystearic acid, aliphatic acid amide, phenol aliphatic aid ester. From the viewpoint of chemical structures of the waxes, hydrocarbon waxes, ester waxes, amide waxes are known. However, in the present invention, ester waxes are preferable from the viewpoint of evaluating the storageability, image quality, the range of the fixing temperature.
- The amount of the release agent is preferably 1 part by weight to 6 parts by weight relative to the total amount of the toner.
- If the amount is larger than 6 parts by weight, the toner shows deficient storage stability, rough surface of an image, and lower glossiness. Further, even if the amount is less than 1 part by weight, the surface of an image tends to be rough, and the resulting color image tends to be poor in quality because of the lower glossiness.
- The toner of the present invention may contain a charge control agent, if required. Any known charge control agents can be used in the present invention. Examples of the charge control agent include a nigrosine dye, a triphenylmethane dye, a chromium-containing metal complex dye, a molybdic acid chelate pigment, a rhodamine dye, an alkoxyamine, a quaternary ammonium salt (including a fluorine-modified quaternary ammonium salt), alkylamide, a simplex or a compound of phosphorus, a simplex or a compound of tungsten, a fluorine-containing activator, a metallic salt of salicylic acid, a metallic salt of a salicylic acid derivative.
- In addition, the toner of the present invention may further contain other additives, for example; silica fine particles, aliphatic metallic salts (such as zinc stearate, aluminum stearate. metallic oxides (such as titanium oxide, aluminum oxide, tin oxide, antimony oxide), fluoropolymers. In particular, hydrophobilized silica, titania, and alumina fine particles are preferred.
- Examples of the silica fine particles may include HDK H 2000, HDK H 2000/4, HDK H 2050EP, and HDK H 1303VP (all of which are manufactured by Clariant Ltd.), and R972, R974, RX200, RY200, R202, R805, and R812 (all of which are manufactured by Nippon Aerosil K.K.).
- Further, examples of the titania fine particles may include P-25 (manufactured by Nippon Aerosil K.K.), STT-30, and STT-65C-S (all of which are manufactured by Titan Kogyo K.K.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), and MT-150W, MT-500B, MT-600B (all of which are manufactured by Tayca Corp.).
- In particular, as the hydrophobically treated titanium oxide fine particles, there can be used the anatase type or rutile type crystalline ones, or amorphous ones. Examples thereof may include T-805 (manufactured by Nippon Aerosil K. K.), and as the rutile type, MT-100S, MT-100T, MT150A, MT150AFM, and MT-150AI (all of which are manufactured by Tayca Corp.), STT-30A, STT-65S-S (all of which are manufactured by Titan Kogyo K.K.), TAF-500T and TAF-1500T (all of which are manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S and MT-100T (all of which are manufactured by Tayca Corp.), IT-S (manufactured by Ishihara Sangyo Kaisha, Ltd.).
- The hydrophobically treated silica fine particles, titania fine particles, or alumina fine particles can be obtained by treating hydrophilic fine particles with a silane coupling agent such as methyl trimethoxy silane, methyl triethoxy silane, octyl trimethoxy silane. Further, as additives, an alphilic acid metal salt (such as zinc stearate or aluminum stearate), a metal oxide (such as alumina, tin oxide, or antimony oxide), and fluoropolymers.
- The toner made of the materials as described above of the present inventionmay be used as a double-component developer in combination with a carrier shown below. Alternatively, the toner may be used alone as a single-component developer. The term, "developer," herein refers to any kinds of agent used for developing a latent electrostatic image.
- When the toner is used as a double-component developer, as the carrier, the same materials as those employed in the related art such as iron powders, ferrite particles, glass beads, or the like can be employed. It is noted that these carrier may be coated with a resin. Known resins may also be used in this case. Examples of the resin may include acrylic resin, polyfluorocarbon, polyvinyl chloride, polyvinylidene chloride, phenolic resin, polyvinyl acetal, silicone resin.
- In any case, as the mixing ratio of the toner to the carrier, in general, it is proper that the toner is mixed in an amount of 2.5 parts by weight to 8.0 parts by weight relative to 100 parts by weight of the carrier.
- The softening point and the Tg of the resin for use in the present invention are determined in the following manner.
- First, the measurement is carried out using a full-automatic dropping point measurement apparatus "FP5/FP53" manufactured by Mettler Co., Ltd., as an apparatus for determining the softening point in accordance with the following procedure:
- (1) A pulverized sample is placed in a fusing jar, and is allowed to stand for 20 minutes. The fused sample is then poured into a sample cup (with a dropping hole diameter of 6.35 mm) up to a brim of the sample cup, cooled to ordinary temperature, and then set in a cartridge;
- (2) In the FP-5 control unit, a prescribed temperature elevation rate (1 Ā°C/min) and measurement initiation temperature (set to be lower by 15 Ā°C than the expected softening point, or less) are set;
- (3) The cartridge is then set in a heating furnace of FP-53, and allowed to stand for 30 seconds. Thereafter, a start lever is pushed down, whereby the measurement is started (the subsequent measurement is automatically carried out);
- (4) Upon completion of the measurement, the cartridge is detached; and
- (5) The softening point (Ā°C) is calculated in the following manner.
- Value indicated in a result display panel A of FP-5 + Correction value
- Note) The value obtained by adding the correction value to the result obtained corresponds to the result by Duran's mercury method.
- Note) When the difference between the value displayed in the result display panel A and the measurement initiation temperature (the value displayed in the panel B or C) is not 15 Ā°C or more, the above test is once again carried out.
- The measurement is carried out, using DSC-200 made by Seiko Instruments Inc., as an apparatus for determining the Tg in accordance with the following procedure:
- (1) A sample is pulverized, and 10Ā±1 mg of the pulverized sample is weighed out in a sample container made of aluminum, and an aluminum lid is put thereon for crimping; and
- (2) The glass transition temperature (Tg) is determined in an atmosphere of nitrogen by the DSC method.
- The sample is heated from room temperature up to 150 Ā°C with a temperature increasing rate of 20 Ā°C/min, and is then allowed to stand at 150 Ā°C for 10 minutes. The sample is then cooled to 0 Ā°C at a temperature decreasing rate of 50 Ā°C/min, and is then allowed to stand for 10 minutes. In a stream of an atmosphere of nitrogen (20 cc/min), the sample is again heated up to 150 Ā°C with a temperature increasing rate of 20 Ā°C/min, and subjected to the DSC measurement. The Tg is measured by reading a peak rise-up temperature, using an analysis software "Tg Job."
- The epoxy equivalent is measured in accordance with an indicator titration method defined in paragraph 4.2 of JIS K7236.
- An image-forming process of the present invention has no particular restriction, except that the toner for electrophotography of the present invention is used for developing a latent electrostatic image, and can be appropriately selected according to the intended purpose.
- The image-forming apparatus of the present invention has no particular restriction, except that the image-forming apparatus accommodates an image developer in which the toner for electrophotography of the present invention is provided as a developing unit. The term, "image developer," herein refers to a developing device that enables developing a latent electrostatic image with a developer.
- Aspects of the image developer, aspects of other configurations can be appropriately selected according to the intended purpose.
- Further, the image-forming process cartridge of the present invention is characterized by including a latent electrostatic image support; a charger configured to charge a surface of the latent electrostatic image support; a light-irradiator configured to irradiate a light to the latent electrostatic image; a cleaner configured to clean the surface of the latent electrostatic support; and an image developer configured to supply a developer onto a latent electrostatic image so as to develop the latent electrostatic image and to form a visible image. The image-forming process cartridge is formed in one-piece construction, and is attachable to and detachable from an image-forming apparatus. The image developer in the image-forming process cartridge of the present invention includes the developer which contains the toner for electrophotography including a color toner for forming an image according to the present invention.
- When installed in an image-forming apparatus, the image-forming process cartridge provides sufficient offset-resistance even in a fixing step where no lubricant oil is coated on a fixing roller, or a very small amount of lubricant oil is coated on a fixing roller.
- FIGURE shows an example of a structure of an image-forming process unit (process cartridge) (106), which includes all of a photoconductive drum (101) as the latent electrostatic image support, a charging roller (103) as the charger, a cleaning unit (105) as the cleaner, and a developing unit (102) as the image developer. The image-forming process cartridge is attachable to and detachable from a printer. The developing unit includes a developing sleeve (104).
- Hereinafter, the present invention will be described by way of examples. It should be noted that "part(s)" expresses "part(s) by weight" in all of the cases.
- Synthesis examples of a polyol resin which is used in the examples, will be firstly given.
- 1000 g of a low-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 1000), 50 g of terephthalic acid, 10 g of benzoic acid, and 300 g of xylene were added into a separable flask equipped with a propeller stirrer, a thermometer, a N2 inlet, and a condenser tube. The resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N2 atmosphere, and 0.183 g of lithium chloride was added thereto. The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin having a softening point of 108 Ā°C and a Tg of 61 Ā°C (which may be referred to as "resin 1," hereinafter).
- The amount of residual bisphenol A was found to be 0 Āµg/g, and the epoxy equivalent was found to be 20,000 or more.
- 562 g of a low-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 360), 104 g of a high-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 2,700), 325 g of bisphenol A, 80 g of p-cumylphenol, and 300 g of xylene were added into a separable flask equipped with a propeller stirrer, a thermometer, a N2 inlet, and a condenser tube. The resulting mixture was heated to 70 Ā°C to 100Ā°C under a N2 atmosphere, and 0.183 g of lithium chloride was added thereto. The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 107 Ā°C and a Tg of 58 Ā°C (which may be referred to as "resin 2," hereinafter).
- The amount of the residual bisphenol A was found to be 830 Āµg/g, and the epoxy equivalent was found to be 20,000 or more.
- Using the separable flask of Synthesis Example 1, 500 g of a low-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 1000), 404 g of a high-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 5000), 103 g of bisphenol A, 59 g of p-cumylphenol, and 300 g of xylene were prepared in a separable flask. The resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N2 atmosphere, and 0.183 g of lithium chloride was added thereto. The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1000 g of a polyol resin with a softening point of 109 Ā°C and a Tg of 58 Ā°C (hereinafter, may be referred to as "resin 3").
- The amount of residual bisphenol A was found to be 280 Āµg/g, and the epoxy equivalent was found to be 20,000 or more.
- Using the separable flask of Synthesis Example 1, 302 g of a low-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 360), 100 g of a high-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 3000), 336.0 g of a diglycidylated product of a bisphenol A type ethylene oxide adduct ["n+m" is about 5.9 in the aforementioned Formula (3)], 210 g of bisphenol A, 100 g of p-cumylphenol, and 300 g of xylene were prepared in a separable flask. The resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N2 atmosphere, and 0.183 g of lithium chloride was added thereto. The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 109 Ā°C and a Tg of 58 Ā°C (hereinafter, may be referred to as "resin 4").
- The amount of residual bisphenol A was found to be 950 Āµg/g, and the epoxy equivalent was found to be 20,000 or more.
- Using the separable flask of Synthesis Example 1, 398 g of a low-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 680), 403 g of a high-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 6,500), 199 g of a bivalent acid of a bisphenol A-propylene oxide adduct and phthalic anhydride condensation, 50 g of bisphenol A, 51 g of p-cumylphenol, and 300 g of xylene were prepared in a separable flask. The resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N2 atmosphere, and 0.183 g of lithium chloride was added thereto. The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 112 Ā°C and a Tg of 59 Ā°C (hereinafter, may be referred to as "resin 6").
- The amount of residual bisphenol A was found to be 620 Āµg/g, and the epoxy equivalent was found to be 20,000 or more.
- The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 118 Ā°C and a Tg of 62 Ā°C (hereinafter, may be referred to as "resin 7").
- The amount of residual bisphenol A was found to be 0 Āµg/g, and the epoxy equivalent was found to be 20,000 or more.
- Using the separable flask of Synthesis Example 1, 1000 g of a low-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 1000), 40 g of terephthalic acid, 10 g of benzoic acid, and 300 g of xylene were prepared in a separable flask. The resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N2 atmosphere, and 0.183 g of lithium chloride was added thereto. The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 108 Ā°C and a Tg of 61 Ā°C (hereinafter, may be referred to as "resin 8").
- The amount of residual bisphenol A was found to be 0 Āµg/g, and the epoxy equivalent was found to be 9380.
- Using the separable flask of Synthesis Example 1, 390 g of a low-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 680), 403 g of a high-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 6,500), 199 g of a bivalent acid of a bisphenol A-propylene oxide adduct and phthalic anhydride condensation, 50 g of bisphenol A, 51 g of p-cumylphenol, and 300 g of xylene were prepared in a separable flask. The resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N2 atmosphere, and 0.183 g of lithium chloride was added thereto. The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 112 Ā°C and a Tg of 59 Ā°C (hereinafter, may be referred to as "resin 9").
- The amount of residual bisphenol A was found to be 8850 Āµg/g, and the epoxy equivalent was found to be 20,000 or more.
- Using the separable flask of Synthesis Example 1, 435 g of a low-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 680), 403 g of a high-molecular weight bisphenol A-type epoxy resin (number-average molecular weight: about 6,500), 199 g of a bivalent acid of a bisphenol A-propylene oxide adduct and phthalic anhydride condensation, 50 g of bisphenol A, 51 g of p-cumylphenol, and 300 g of xylene were prepared in a separable flask. The resulting mixture was heated to 70 Ā°C to 100 Ā°C under a N2 atmosphere, and 0.183 g of lithium chloride was added thereto. The resulting mixture was further heated to 160 Ā°C, and xylene was distilled off under a reduced pressure. The mixture was polymerized at a reaction temperature of 180 Ā°C for 6 to 9 hours, resulting in about 1 kg of a polyol resin with a softening point of 112 Ā°C and a Tg of 59 Ā°C (hereinafter, may be referred to as "resin 10").
- The amount of residual bisphenol A was found to be 120 Āµg/g, and the epoxy equivalent was found to be 9800.
-
Manufacturing a toner Resin 1 100 parts Cyan pigment (copper phthalocyanine) 4 parts E-84 manufactured by Orient Chemical Industries Ltd. (a zinc complex used as a charge controlling agent) 2 parts - A mixture of the materials above was melt-kneaded by a hot roll mill. After cooling the mixture, the resulting mixture was roughly ground in a hammer mill, and then finely pulverized in an air-jet grinder. The resulting fine powder was classified to form a matrix toner having an average particle diameter of about 7 Āµm.
- Thereafter, 0.8 part of a hydrophobic silica HDK2000H (manufactured by Clariant Japan K.K.) was mixed to 100 parts of the resulting matrix toner, so as to obtain a toner.
- Each of the toners of Examples 1 to 4 was obtained in the same manner as in the Reference Example, except that the resin was altered to each of the resins of Synthetic Examples 2 to 5 in the Reference Example.
- Each of the toners of Comparative Examples 1 to 3 was obtained with in the same manner as in the Reference Example, except that the resin was altered to each of the resins of Synthetic Examples 6 to 8 in the Reference Example.
- A toner of Comparative Example 4 was obtained with in the same manner as in the Reference Example, except that the resin of the Reference Example was altered to a polyester resin. The polyester resin is a resin obtained from the condensation polymerization of a bisphenol A ethylene oxide adduct, a bisphenol A propylene oxide adduct, a terephthalic acid, and a fumaric acid in a molar ratio of 60 : 40 : 25 : 75. The polyester resin has a softening point of 107 Ā°C and a Tg of 59Ā°C.
- The amount of residual bisphenol A and the epoxy equivalent were measured with respect to each of the toners of Reference Example, Examples 1 to 4, and the toners of Comparative Examples 1 to 4.
- Each of the toners of the Reference Example, Examples 1 to 4, and the toners of Comparative Examples 1 to 4 was installed into a color copier Imagio Color 2800 manufactured by Ricoh Company Ltd., to produce image-bearing copy sheets. Each of the image-bearing copy sheets was brought in intimate contact with a vinyl chloride sheet, and then stored at 50 Ā°C for 1 week to evaluate the adhesion of the toner to the vinyl chloride sheet.
- Curl of the paper was also evaluated as to the toners of the Reference Example, Examples 1 to 4 and the toners of Comaprative Examples 1 to 4. The curl of the paper was measured based upon how the paper became curled up, when an image with 1mg/cm of the toners was transferred, and was then fixed onto paper.
- The results of the evaluation are shown in Table 1.
- The evaluation was ranked as follows:
- ā:
- No problem at all
- ā:
- No problem
- Ī:
- Slightly troublesome but at an acceptable level
- Ć:
- Problem occurred
- As shown in Table 1, each of the toners of Examples of the present invention is characterized in that the amount of the residual bisphenol A is smaller, the epoxy equivalent is larger, and less toners adheres to the vinyl chloride sheet, compared with the toners of Comparative Examples.
- The toner for electrophotography of the present invention enables obtaining a toner which contains less the residual bisphenol A and less residual epoxy groups. Hence the toner for electrophotography of the present invention enables obtaining a safer toner. Further, the toner for electrophotography of the present invention enables obtaining a toner which is less likely to adhere a vinyl chloride mat when used in a copied image.
Amount of residual bisphenol A [Āµg/g] | Epoxy equivalent | Toner adhesion to vinyl chloride sheet | Curl of paper | |
Reference Example | 0 | 20000 or more | ā | ā |
Example 1 | 780 | 20000 or more | ā | ā |
Example 2 | 260 | 20000 or more | ā | ā |
Example 3 | 890 | 20000 or more | ā | ā |
Example 4 | 580 | 20000 or more | ā | ā |
Comparative Example 1 | 0 | 9980 | Ī | ā |
Comparative Example 2 | 8320 | 20000 or more | ā | Ī |
Comparative Example 3 | 110 | 10400 | ā | Ī |
Comparative Example 4 | 0 | 20000 or more | Ć | Ć |
Claims (19)
- A toner for electrophotography comprising:a coloring agent; anda binder resin, wherein the binder resin is a polyol resin which is prepared by reacting:wherein the weight concentration of non-reacted bisphenol A in the toner is 1000 Āµg/g or less, and the toner has an epoxy equivalent of 20000 or more, wherein the epoxy equivalent is measured in accordance with an indicator titration method defined in paragraph 4.2 of JIS K7236.a) a bisphenol-A-type epoxy resin;b) a compound having one or more active hydrogen atoms which react with an epoxy group in molecules of the compound having one or more active hydrogen atoms; andc) a compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms, wherein the compound having two or more active hydrogen atoms which react with an epoxy group in molecules of the compound having two or more active hydrogen atoms comprises bisphenol A;
- A toner for electrophotography according to Claim 1, wherein the epoxy resin has two or more epoxy bonds.
- A toner for electrophotography according to one of Claims 1 and 2, wherein the epoxy resin comprises two or more types of bisphenol A-type epoxy resins having different number average molecular weights.
- A toner for electrophotography according to Claim 3, wherein the two or more types of bisphenol A-type epoxy resins having different number average molecular weights have:360 to 2000 in number weight average molecular weight for low molecular weight bisphenol A-type epoxy resins; and3000 to 10000 in number weight average molecular weight for high molecular weight bisphenol A-type epoxy resins.
- A toner for electrophotography according to Claim 3, wherein the two or more types of bisphenol A-type epoxy resins having different number average molecular weights comprise:20% by weight to 50% by weight of low molecular weight bisphenol A-type epoxy resins relative to the polyol resin; and5% by weight to 40% by weight of high molecular weight bisphenol A-type epoxy resins relative to the polyol resin.
- A toner for electrophotography according to Claim 1, wherein the polyol resin comprises a monomer unit of diglycidylether of a bisphenol A-alkyl oxide adduct expressed by the following Formula (1), as the epoxy resin:
- A toner for electrophotography according to Claim 1, wherein the toner contains 10 % by weight to 40 % by weight of the epoxy resin as a monomer unit relative to the amount of the polyol resin, and the epoxy resin is one of a dihydric phenol-alkylene oxide adduct, and a glycidyl ether of the dihydric phenol-alkylene oxide adduct.
- A toner for electrophotography according to Claim 1, wherein the compound having two or more active hydrogen atoms which reacts with an epoxy group in molecules of the compound having two or more hydrogen atoms comprises a compound prepared by reacting a dihydric phenol-alkylene oxide adduct and a polyvalent carboxylic acid..
- A toner for electrophotography according to Claim 8, wherein the polyvalent carboxylic acid is selected from at least one of malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, trimellitic acid, and trimellitic acid anhydride.
- A toner for electrophotography according to Claim 8, wherein the toner contains 10% by weight to 40% by weight of the compound having two or more active hydrogen atoms which react with an epoxy group, and the compound is a compound prepared by reacting a dihydric phenol-alkylene oxide and a polyvalent carboxylic acid.
- A toner for electrophotography according to any one of Claims 1 to 10, wherein the glass transition temperature of the polyol resin is 50Ā°C to 75 Ā°C.
- A toner for electrophotography according to any one of Claims 1 to 11, further containing a release agent..
- A toner for electrophotography according to Claim 12, wherein the softening point of the release agent is 70 Ā°C to 100 Ā°C.
- A toner for electrophotography according to one of Claims 12 and 13, wherein the content of the release agent is 1 part by weight to 6 parts by weight, relative to the total amount of toner.
- A toner for electrophotography according to any one of Claims 1 to 14, wherein the content of the coloring agent is 0.1 part by weight to 50 parts by weight relative to 100 parts by weight of the binder resin.
- A two-component developer for electrophotography comprising a toner according to any one of Claims 1 to 15.
- An image-forming process including the step of developing a latent electrostatic image utilizing a toner for electrophotography according to any one of Claims 1 to 15 or a developer according to claim 16.
- An image-forming apparatus which comprises an image developer, wherein the image developer has a developer, and the developer contains a toner according to any one of Claims 1 to 15.
- An image-forming process cartridge comprising:an image developer supplying a developer to a latent electrostatic image so as to visualize and develop the latent electrostatic image, wherein the image-forming process cartridge is formed in one-piece construction, and is attachable to and detachable from an image-forming apparatus, and the developer contains a tone according to any one of Claims 1 to 15.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2002077856A JP3867900B2 (en) | 2002-03-20 | 2002-03-20 | Toner for electrophotography |
JP2002077856 | 2002-03-20 |
Publications (2)
Publication Number | Publication Date |
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EP1347342A1 EP1347342A1 (en) | 2003-09-24 |
EP1347342B1 true EP1347342B1 (en) | 2011-08-03 |
Family
ID=27785292
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03006072A Expired - Lifetime EP1347342B1 (en) | 2002-03-20 | 2003-03-19 | Toner for electrophotography |
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EP (1) | EP1347342B1 (en) |
JP (1) | JP3867900B2 (en) |
AT (1) | ATE519143T1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE60320973D1 (en) | 2002-03-25 | 2008-06-26 | Sanyo Chemical Ind Ltd | TONER BINDER FOR ELECTROPHOTOGRAPHY AND TONER FOR ELECTROPHOTOGRAPHY |
JP2007156168A (en) * | 2005-12-06 | 2007-06-21 | Kao Corp | Yellow toner |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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NL7605372A (en) * | 1976-05-20 | 1977-11-22 | Oce Van Der Grinten Nv | TONER POWDER FOR DEVELOPING ELECTROSTATIC IMAGES. |
JP3313895B2 (en) * | 1993-07-12 | 2002-08-12 | ę Ŗå¼ä¼ē¤¾ćŖć³ć¼ | Dry type electrophotographic toner |
US5998073A (en) | 1997-03-10 | 1999-12-07 | Ricoh Company, Ltd. | Dry toner for electrophotography |
JPH1184719A (en) * | 1997-07-10 | 1999-03-30 | Ricoh Co Ltd | Dry electrophotographic toner |
DE60025408T2 (en) * | 1999-04-08 | 2006-08-31 | Ricoh Co., Ltd. | Toners, toner production processes, imaging processes and toner containers |
-
2002
- 2002-03-20 JP JP2002077856A patent/JP3867900B2/en not_active Expired - Fee Related
-
2003
- 2003-03-19 EP EP03006072A patent/EP1347342B1/en not_active Expired - Lifetime
- 2003-03-19 AT AT03006072T patent/ATE519143T1/en not_active IP Right Cessation
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JP3867900B2 (en) | 2007-01-17 |
ATE519143T1 (en) | 2011-08-15 |
JP2003280262A (en) | 2003-10-02 |
EP1347342A1 (en) | 2003-09-24 |
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