JP4390643B2 - Polyester for toner - Google Patents
Polyester for toner Download PDFInfo
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- JP4390643B2 JP4390643B2 JP2004195890A JP2004195890A JP4390643B2 JP 4390643 B2 JP4390643 B2 JP 4390643B2 JP 2004195890 A JP2004195890 A JP 2004195890A JP 2004195890 A JP2004195890 A JP 2004195890A JP 4390643 B2 JP4390643 B2 JP 4390643B2
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- Prior art keywords
- wax
- toner
- polyester
- acid
- group
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- 229920000728 polyester Polymers 0.000 title claims description 45
- 239000001993 wax Substances 0.000 claims description 71
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 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 description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 11
- -1 polyoxyethylene Polymers 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000012643 polycondensation polymerization Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 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 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- DMCJFWXGXUEHFD-UHFFFAOYSA-N pentatriacontan-18-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)CCCCCCCCCCCCCCCCC DMCJFWXGXUEHFD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- ZNLXEDDUXFMEML-UHFFFAOYSA-N 2-[5-(2-chloroacetyl)thiophen-2-yl]acetic acid Chemical compound OC(=O)CC1=CC=C(C(=O)CCl)S1 ZNLXEDDUXFMEML-UHFFFAOYSA-N 0.000 description 1
- FPOGSOBFOIGXPR-UHFFFAOYSA-N 2-octylbutanedioic acid Chemical compound CCCCCCCCC(C(O)=O)CC(O)=O FPOGSOBFOIGXPR-UHFFFAOYSA-N 0.000 description 1
- CVRPSWGFUCJAFC-UHFFFAOYSA-N 4-[(2,5-dichlorophenyl)diazenyl]-N-(2,5-dimethoxyphenyl)-3-hydroxynaphthalene-2-carboxamide Chemical compound ClC1=C(C=C(C=C1)Cl)N=NC1=C(C(=CC2=CC=CC=C12)C(=O)NC1=C(C=CC(=C1)OC)OC)O CVRPSWGFUCJAFC-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 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 1
- 238000011161 development Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- LATKICLYWYUXCN-UHFFFAOYSA-N naphthalene-1,3,6-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 LATKICLYWYUXCN-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Developing Agents For Electrophotography (AREA)
Description
本発明は、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられるトナーの結着樹脂として好適なトナー用ポリエステル及び該ポリエステルを含有したトナーに関する。 The present invention relates to a polyester for toner suitable as a binder resin for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and a toner containing the polyester.
従来、ホットオフセット改善のためにトナーにワックスを添加する技術が知られている。しかし、結着樹脂としてポリエステルを含有したトナーの場合、ポリエステルとワックスとの相溶性が低いために、樹脂中にワックスが分散しにくい。さらに、樹脂とワックスの粘度差が大きいと、溶融粘度の低いワックス部分にカーボンブラック等の添加剤が凝集しやすく、それに伴う帯電量の低下を生じることがある。そこで、ポリエステルと親和性の高い水酸基変性ワックスを使用することが知られているが(特許文献1参照)、効果は不十分である。 2. Description of the Related Art Conventionally, a technique for adding wax to toner for improving hot offset is known. However, in the case of a toner containing polyester as a binder resin, since the compatibility between the polyester and the wax is low, the wax is difficult to disperse in the resin. Furthermore, when the difference in viscosity between the resin and the wax is large, additives such as carbon black tend to aggregate on the wax portion having a low melt viscosity, which may cause a decrease in charge amount. Thus, it is known to use a hydroxyl group-modified wax having a high affinity for polyester (see Patent Document 1), but the effect is insufficient.
一方、結着樹脂とワックスの物性値の差を調整したトナーバインダー組成物(特許文献2参照)やバインダー樹脂としてワックスが内添されたポリエステルを用い、さらにトナーの流出開始温度と流出終了温度を特定範囲に調整したトナー(特許文献3参照)も報告されているが、ワックスの分散性の観点からは、やはりさらなる性能の向上が望まれている。
本発明の目的は、耐ホットオフセット性及び帯電性のいずれにも優れたトナー用ポリエステル及び該ポリエステルを含有したトナーを提供することにある。 An object of the present invention is to provide a polyester for toner excellent in both hot offset resistance and chargeability and a toner containing the polyester.
本発明は、アルコール成分とカルボン酸成分との縮重合反応の少なくとも一部を極性基を有するワックスの存在下で行って得られるトナー用ポリエステルであって、前記ワックスを0.5〜20重量%含有してなるトナー用ポリエステル、並びに該トナー用ポリエステルを含有したトナーに関する。 The present invention relates to a polyester for toner obtained by performing at least a part of the condensation polymerization reaction between an alcohol component and a carboxylic acid component in the presence of a wax having a polar group, and the wax is added in an amount of 0.5 to 20% by weight. The present invention relates to a polyester for toner and a toner containing the polyester for toner.
本発明のトナー用ポリエステルは、耐ホットオフセット性及び帯電性のいずれにも優れているため、トナーの結着樹脂として好適に用いることができる。 Since the polyester for toner of the present invention is excellent in both hot offset resistance and chargeability, it can be suitably used as a binder resin for toner.
本発明者らは、ポリエステル中のワックスの分散性を向上させる手段について検討したところ、ワックスとしてポリエステルとの相溶性が良好な極性基を有するワックスを用い、さらに、アルコール成分とカルボン酸成分との縮重合反応の少なくとも一部をかかるワックスの存在下で行うことによりワックスの分散性に優れたポリエステルが得られることを見出した。かかるポリエステルは、トナー製造時にカーボンブラック等の添加剤と混合した際にも、添加剤がワックス部に凝集することなく樹脂中に均一に分散されるため、トナーの帯電性を低下させることなく、耐ホットオフセット性を向上させることができる。 The present inventors examined a means for improving the dispersibility of the wax in the polyester. As the wax, a wax having a polar group having a good compatibility with the polyester was used, and further, an alcohol component and a carboxylic acid component were used. It has been found that a polyester having excellent wax dispersibility can be obtained by performing at least a part of the condensation polymerization reaction in the presence of such a wax. Even when such a polyester is mixed with an additive such as carbon black at the time of toner production, the additive is uniformly dispersed in the resin without agglomerating in the wax part. Hot offset resistance can be improved.
本発明において、ワックスが有する極性基としては、水酸基(−OH)、カルボキシル基(−COOH)、エステル結合(−COO−)、ウレタン基(−NHCOO−)、カルボニル基(>CO)、エーテル結合(−O−)、アミド基(−CONH2 )等が挙げられ、本発明に用いられるワックスとしては、ポリエステルとの相溶性の観点から、少なくとも水酸基を有するものが好ましい。 In the present invention, the polar group possessed by the wax includes a hydroxyl group (—OH), a carboxyl group (—COOH), an ester bond (—COO—), a urethane group (—NHCOO—), a carbonyl group (> CO), and an ether bond. (—O—), amide group (—CONH 2 ) and the like can be mentioned, and the wax used in the present invention preferably has at least a hydroxyl group from the viewpoint of compatibility with polyester.
水酸基を有するワックスにおいて、水酸基価と酸価の合計値は、ワックスの分散性の観点から、5〜150mgKOH/gが好ましく、10〜100mgKOH/gがより好ましく、10〜60mgKOH/gがさらに好ましい。水酸基を有するワックスが複数種含有されている場合には、それらの加重平均値が上記範囲内となることが好ましい。 In the wax having a hydroxyl group, the total value of the hydroxyl value and the acid value is preferably 5 to 150 mgKOH / g, more preferably 10 to 100 mgKOH / g, and still more preferably 10 to 60 mgKOH / g, from the viewpoint of dispersibility of the wax. When a plurality of types of wax having a hydroxyl group are contained, it is preferable that the weighted average value thereof falls within the above range.
水酸基を有するワックスとしては、パラフィンワックス「FT−100」(日本精蝋社製)をベースにアルコールで変性されたワックス、例えば、「PARACOHOL−5300」(水酸基価:17mgKOH/g、酸価:1mgKOH/g)、「PARACOHOL−6110」(水酸基価:50mgKOH/g、酸価:4mgKOH/g)、「PARACOHOL−5003A」(水酸基価:32mgKOH/g、酸価:5mgKOH/g)(以上、日本精蝋社製)等が挙げられる。 As the wax having a hydroxyl group, a wax modified with alcohol based on paraffin wax “FT-100” (manufactured by Nippon Seiwa Co., Ltd.), for example, “PARACOHOL-5300” (hydroxyl value: 17 mgKOH / g, acid value: 1 mgKOH) / PAR), "PARACOHOL-6110" (hydroxyl value: 50 mgKOH / g, acid value: 4 mgKOH / g), "PARACOHOL-5003A" (hydroxyl value: 32 mgKOH / g, acid value: 5 mgKOH / g) Wax Co.).
カルボキシル基を有するワックスとしては、「FT−100」をベースに酸で変性されたワックス、例えば「OX−0420」(日本精蝋社製、水酸基価:6mgKOH/g、酸価:3mgKOH/g)等が挙げられる。 As the wax having a carboxyl group, a wax modified with an acid based on “FT-100”, for example, “OX-0420” (manufactured by Nippon Seiwa Co., Ltd., hydroxyl value: 6 mgKOH / g, acid value: 3 mgKOH / g) Etc.
エステル結合を有するワックスとしては、カルナバワックス等が挙げられる。 Examples of the wax having an ester bond include carnauba wax.
ウレタン基を有するワックスとしては、「NPS−6010」、「HAD−5150」(以上、日本精蝋社製)等が挙げられる。 Examples of the wax having a urethane group include “NPS-6010” and “HAD-5150” (manufactured by Nippon Seiwa Co., Ltd.).
カルボニル基を有するワックスとしては、ジヘプタデシルケトン等が挙げられる。 Examples of the wax having a carbonyl group include diheptadecyl ketone.
エーテル結合を有するワックスとしては、n−ヘキサデシルエーテル等が挙げられる。 Examples of the wax having an ether bond include n-hexadecyl ether.
以上、具体的に例示した極性基を有するワックスの中では、「PARACOHOL−5300」、「PARACOHOL−6110」、「PARACOHOL−5003A」等のアルコールで変性されたワックスが好ましい。 As described above, among the waxes having polar groups specifically exemplified, waxes modified with alcohols such as “PARACOHOL-5300”, “PARACOHOL-6110”, “PARACOHOL-5003A” and the like are preferable.
極性基を有するワックスの融点は、トナーの定着性、耐ホットオフセット性及び帯電性の観点から、70〜150℃が好ましく、70〜100℃がより好ましい。 The melting point of the wax having a polar group is preferably from 70 to 150 ° C., more preferably from 70 to 100 ° C., from the viewpoints of toner fixing property, hot offset resistance and chargeability.
極性基を有するワックスの含有量は、ポリエステル中、トナーの定着性及び耐ホットオフセット性の観点から、0.5〜20重量%であり、好ましくは1〜15重量%、より好ましくは3〜15重量%である。 The content of the wax having a polar group is 0.5 to 20% by weight, preferably 1 to 15% by weight, more preferably 3 to 15%, from the viewpoint of toner fixing property and hot offset resistance in the polyester. % By weight.
本発明のトナー用ポリエステルは、原料モノマーとして用いられるアルコール成分とカルボン酸成分との縮重合反応の少なくとも一部を、前記極性基を有するワックスの存在下で行って得られる。 The polyester for toner of the present invention is obtained by performing at least a part of the condensation polymerization reaction of an alcohol component and a carboxylic acid component used as raw material monomers in the presence of the wax having the polar group.
2価のアルコール成分としては、ポリオキシエチレン(2.0)−2,2−ビス (4−ヒドロキシフェニル) プロパン、ポリオキシエチレン(2.2)−2,2−ビス (4−ヒドロキシフェニル) プロパン、ポリオキシプロピレン(2.2)−2,2−ビス (4−ヒドロキシフェニル) プロパン等の、式(I): Examples of the divalent alcohol component include polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) Formula (I) such as propane, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, etc .:
(式中、Rは炭素数2又は3のアルキレン基、x及びyは正の数を示し、xとyの和は1〜16、好ましくは1.5〜5.0である)
で表されるビスフェノールAのアルキレンオキサイド付加物、エチレングリコール、1,2 −プロピレングリコール、1,4 −ブタンジオール、ネオペンチルグリコール、ポリエチレングリコール、ポリプロピレングリコール、水素添加ビスフェノールA等が挙げられる。
(Wherein R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers, and the sum of x and y is 1 to 16, preferably 1.5 to 5.0)
And an alkylene oxide adduct of bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, and the like.
これらの中では、トナーの耐久性及び帯電性の観点から、式(I)で表されるビスフェノールAのアルキレンオキサイド付加物が好ましい。ビスフェノールAのアルキレンオキサイド付加物の含有量は、アルコール成分中、70モル%以上が好ましく、80モル%以上がより好ましい。 Among these, from the viewpoint of toner durability and chargeability, an alkylene oxide adduct of bisphenol A represented by the formula (I) is preferable. 70 mol% or more is preferable in an alcohol component, and, as for content of the alkylene oxide adduct of bisphenol A, 80 mol% or more is more preferable.
3価以上の多価アルコール成分としては、ソルビトール、ペンタエリスリトール、グリセリン、トリメチロールプロパン等が挙げられる。 Examples of the trihydric or higher polyhydric alcohol component include sorbitol, pentaerythritol, glycerin, trimethylolpropane and the like.
また、2価のカルボン酸成分としては、フタル酸、イソフタル酸、テレフタル酸等の芳香族ジカルボン酸;シュウ酸、マロン酸、マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸、コハク酸、アジピン酸、ドデセニルコハク酸、オクチルコハク酸等の炭素数1〜20のアルキル基又は炭素数2〜20のアルケニル基で置換されたコハク酸等の脂肪族ジカルボン酸;それらの酸の無水物及びそれらの酸のアルキル(炭素数1〜3)エステル等が挙げられる。 Divalent carboxylic acid components include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, Aliphatic dicarboxylic acids such as succinic acid substituted with alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms such as adipic acid, dodecenyl succinic acid, octyl succinic acid; anhydrides of these acids and their Alkyl (C1-C3) ester of an acid etc. are mentioned.
3価以上の多価カルボン酸成分としては、1,2,4−ベンゼントリカルボン酸(トリメリット酸)、2,5,7−ナフタレントリカルボン酸、ピロメリット酸及びこれらの酸無水物、低級アルキル(炭素数1〜3)エステル等が挙げられる。 Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides thereof, lower alkyl ( Examples thereof include esters having 1 to 3 carbon atoms.
本発明のポリエステルには、原料モノマーの1種として、3価以上の単量体が用いられているのが好ましい。3価以上の単量体、即ち3価以上の多価アルコール及び多価カルボン酸化合物、好ましくは3価以上の多価カルボン酸化合物の含有量は、耐久性の観点から、各成分中、10〜40モル%が好ましく、10〜30モル%がより好ましい。 In the polyester of the present invention, a trivalent or higher monomer is preferably used as one kind of raw material monomer. From the viewpoint of durability, the content of the trivalent or higher monomer, that is, the trivalent or higher polyhydric alcohol and the polyvalent carboxylic acid compound, preferably the trivalent or higher polyvalent carboxylic acid compound is 10 -40 mol% is preferable and 10-30 mol% is more preferable.
さらに、分子量調整等の観点から、1価のアルコールや1価のカルボン酸化合物が、本発明の効果を損なわない範囲で各成分中に適宜含有されていてもよい。 Furthermore, from the viewpoint of molecular weight adjustment and the like, a monovalent alcohol or a monovalent carboxylic acid compound may be appropriately contained in each component as long as the effects of the present invention are not impaired.
アルコール成分とカルボン酸成分との縮重合反応は、その少なくとも一部をワックスの存在下で行う以外は通常のポリエステルを製造する場合と同様に行うことができ、本発明のポリエステルは、例えば、アルコール成分とカルボン酸成分からなる原料モノマーを、ワックスの存在下、不活性ガス雰囲気中、要すればエステル化触媒、重合禁止剤等の存在下で、150〜280℃で縮重合させて得られる。ワックスの添加時期は特に限定されず、縮重合反応当初からワックスを存在させていても、反応途中で添加してもよいが、トナーの生産性の観点から、反応途中で添加することが好ましい。 The polycondensation reaction between the alcohol component and the carboxylic acid component can be carried out in the same manner as in the case of producing a normal polyester except that at least a part thereof is carried out in the presence of wax. It is obtained by subjecting a raw material monomer comprising a component and a carboxylic acid component to condensation polymerization at 150 to 280 ° C. in the presence of a wax and in an inert gas atmosphere, if necessary, in the presence of an esterification catalyst, a polymerization inhibitor and the like. The addition timing of the wax is not particularly limited, and the wax may be added from the beginning of the condensation polymerization reaction or may be added during the reaction, but it is preferably added during the reaction from the viewpoint of toner productivity.
本発明のポリエステルの軟化点は、トナーの定着性、耐久性及び耐ホットオフセット性の観点から、90〜160℃が好ましく、100〜150℃がより好ましい。また、ガラス転移点は、トナーの定着性及び保存性の観点から、50〜80℃が好ましく、55〜75℃がより好ましい。 The softening point of the polyester of the present invention is preferably from 90 to 160 ° C., more preferably from 100 to 150 ° C., from the viewpoint of toner fixability, durability and hot offset resistance. The glass transition point is preferably from 50 to 80 ° C., more preferably from 55 to 75 ° C., from the viewpoint of toner fixability and storage stability.
本発明のポリエステルの酸価は、トナーの帯電性の観点から、3〜40mgKOH/gが好ましく、5〜30mgKOH/gがより好ましい。 The acid value of the polyester of the present invention is preferably from 3 to 40 mgKOH / g, more preferably from 5 to 30 mgKOH / g, from the viewpoint of chargeability of the toner.
ポリエステル中の極性基を有するワックスの体積平均分散径は、トナーの定着性、耐久性及び耐ホットオフセット性の観点から、1〜20μmが好ましく、1〜15μmがより好ましい。ワックスの分散径は、ワックスの添加時期、原料モノマーの種類、原料モノマーを重合させる際の攪拌強度や重合後の冷却速度等によって調整することができる。例えば、ワックスを重合の早期で添加する程、ワックスの分散径は小さくなる傾向がある。 The volume average dispersion diameter of the wax having a polar group in the polyester is preferably 1 to 20 μm, and more preferably 1 to 15 μm, from the viewpoints of toner fixability, durability, and hot offset resistance. The dispersion diameter of the wax can be adjusted by the addition timing of the wax, the kind of raw material monomer, the stirring strength when polymerizing the raw material monomer, the cooling rate after polymerization, and the like. For example, as the wax is added at an earlier stage of polymerization, the dispersion diameter of the wax tends to be smaller.
ワックスが適度な粒径で分散した本発明のポリエステルを結着樹脂として含有した本発明のトナーは、優れた帯電性及び耐ホットオフセット性を有する。従って、本発明のトナーは、高い耐久性が要求される非磁性一成分現像用トナー及び非磁性二成分現像用トナーとして好適に用いることができる。 The toner of the present invention containing, as a binder resin, the polyester of the present invention in which a wax is dispersed with an appropriate particle size has excellent chargeability and hot offset resistance. Therefore, the toner of the present invention can be suitably used as a non-magnetic one-component developing toner and a non-magnetic two-component developing toner that require high durability.
本発明のトナーには、さらに、着色剤、荷電制御剤、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、老化防止剤、流動性向上剤、クリーニング性向上剤等の添加剤が、適宜含有されていてもよい。 The toner of the present invention further includes a colorant, a charge control agent, a conductivity regulator, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, a fluidity improver, and a cleaning property improver. Such additives may be appropriately contained.
着色剤としては、トナー用着色剤として用いられている染料、顔料等のすべてを使用することができ、カーボンブラック、フタロシアニンブルー、パーマネントブラウンFG、ブリリアントファーストスカーレット、ピグメントグリーンB、ローダミン−Bベース、ソルベントレッド49、ソルベントレッド146 、ソルベントブルー35、キナクリドン、カーミン6B、ジスアゾエロー等が挙げられ、これらは単独で又は2種以上を混合して用いることができ、本発明のトナーは、黒トナー、カラートナー、フルカラートナーのいずれであってもよい。着色剤の含有量は、結着樹脂100重量部に対して、1〜40重量部が好ましく、3〜10重量部がより好ましい。 As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used alone or in combination of two or more. The toner of the present invention is a black toner, color Either toner or full color toner may be used. The content of the colorant is preferably 1 to 40 parts by weight and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
荷電制御剤としては、ニグロシン染料、3級アミンを側鎖として含有するトリフェニルメタン系染料、4級アンモニウム塩化合物、ポリアミン樹脂、イミダゾール誘導体等の正帯電性荷電制御剤及び含金属アゾ染料、銅フタロシアニン染料、サリチル酸のアルキル誘導体の金属錯体、ベンジル酸のホウ素錯体等の負帯電性荷電制御剤が挙げられる。 Charge control agents include nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, polyamine resins, imidazole derivatives and other positively chargeable charge control agents and metal-containing azo dyes, copper Examples include negatively chargeable charge control agents such as phthalocyanine dyes, metal complexes of alkyl derivatives of salicylic acid, and boron complexes of benzylic acid.
トナーの製造方法は、混練粉砕法、転相乳化法、重合法等の従来より公知のいずれの方法であってもよいが、例えば、混練粉砕法による粉砕トナーの場合、本発明のポリエステルを含む結着樹脂、着色剤、荷電制御剤等をヘンシェルミキサー等の混合機で均一に混合した後、密閉式ニーダー又は1軸もしくは2軸の押出機、オープンロール型混練機等で溶融混練し、冷却、粉砕、分級して製造することができる。さらに得られたトナー表面に疎水性シリカ等の無機微粒子や樹脂微粒子を外添してもよい。トナーの重量平均粒径(D4 )は3〜15μmが好ましく、4〜8μmがより好ましい。 The toner production method may be any conventionally known method such as a kneading and pulverizing method, a phase inversion emulsification method, and a polymerization method. For example, in the case of a pulverized toner by a kneading and pulverizing method, the polyester of the present invention is included. Binder resin, colorant, charge control agent, etc. are uniformly mixed with a mixer such as a Henschel mixer, then melt-kneaded with a closed kneader, a single or twin screw extruder, an open roll kneader, etc., and cooled. , Pulverized and classified. Further, inorganic fine particles such as hydrophobic silica or resin fine particles may be externally added to the obtained toner surface. The weight average particle diameter (D 4 ) of the toner is preferably 3 to 15 μm, and more preferably 4 to 8 μm.
〔樹脂の軟化点〕
高化式フローテスター((株)島津製作所製、CFT−500)を用い、1gの試料を昇温速度6℃/分で加熱しながら、プランジャーにより1.96MPaの荷重を与え、直径1mm、長さ1mmのノズルを押し出すようにし、これによりフローテスターのプランジャー降下量(流れ値)―温度曲線を描き、そのS字曲線の高さをhとするときh/2に対応する温度(試料の半分が流出した温度)を軟化点とする。
[Softening point of resin]
Using a Koka type flow tester (manufactured by Shimadzu Corporation, CFT-500), a 1 g sample was heated at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, a diameter of 1 mm, A nozzle with a length of 1 mm is pushed out, and this draws a plunger drop amount (flow value) -temperature curve of the flow tester. When the height of the S-shaped curve is h, the temperature corresponding to h / 2 (sample) The temperature at which half of the effluent flowed out) is taken as the softening point.
〔樹脂のガラス転移点及びワックスの融点〕
示差走査熱量計(セイコー電子工業社製、DSC210)を用いて200℃まで昇温し、その温度から降温速度10℃/分で0℃まで冷却した試料を昇温速度10℃/分で測定し、試料としてワックスを使用した場合は、最大ピーク温度を融点とする。また、試料として樹脂を使用した場合は、最大ピーク温度以下のベースラインの延長線とピークの立ち上がり部分から、ピークの頂点まで最大傾斜を示す接線との交点の温度をガラス転移点とする。
[Glass transition point of resin and melting point of wax]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the sample was heated to 200 ° C., and the sample cooled to 0 ° C. at a temperature decrease rate of 10 ° C./min was measured at a temperature increase rate of 10 ° C./min. When wax is used as a sample, the maximum peak temperature is taken as the melting point. Further, when a resin is used as a sample, the glass transition point is defined as the temperature at the intersection of the base line extension below the maximum peak temperature and the tangential line showing the maximum slope from the peak rising portion to the peak apex.
〔樹脂及びワックスの酸価及び水酸基価〕
JIS K0070の方法に従って測定する。
[Acid value and hydroxyl value of resin and wax]
Measured according to the method of JIS K0070.
〔ワックスの体積平均分散径〕
50mlサンプル管に樹脂0.5gを量り取り、テトラヒドロフラン20mlを添加して、ボールミル荷台に載せ、1時間攪拌して十分に樹脂を溶解させて、試料溶液を調製する。得られた試料溶液をワックスが測定濃度となるまでテトラヒドロフランで希釈し、島津レーザー回折式粒度分布測定装置「SALD−2000J」((株)島津製作所製)によってワックスの体積平均分散粒径を測定した。
なお、溶液中に樹脂不溶分が確認される場合は、1Nの水酸化カリウム(KOH)水溶液の滴下及び超音波照射を不溶分が無くなるまで繰り返し行い、試料溶液中に不溶分が無いことを確認してから上記測定を行う。
[Volume average dispersion diameter of wax]
A sample solution is prepared by weighing 0.5 g of resin into a 50 ml sample tube, adding 20 ml of tetrahydrofuran, placing it on a ball mill bed and stirring for 1 hour to sufficiently dissolve the resin. The obtained sample solution was diluted with tetrahydrofuran until the wax had a measured concentration, and the volume average dispersed particle size of the wax was measured with a Shimadzu laser diffraction particle size distribution analyzer “SALD-2000J” (manufactured by Shimadzu Corporation). .
In addition, when resin-insoluble matter is confirmed in the solution, the dropping of 1N potassium hydroxide (KOH) aqueous solution and ultrasonic irradiation are repeated until the insoluble matter disappears, and it is confirmed that there is no insoluble matter in the sample solution. Then, the above measurement is performed.
実施例1、7及び比較例2、3
表1に示すアルコール成分、フマル酸及び無水トリメリット酸以外のカルボン酸成分、エステル化触媒及びワックスを窒素導入管、脱水管、攪拌器および熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、230℃で反応率が90%に達するまで反応させた後、8.3kPaにて1時間反応させた。その後、185℃まで冷却し、フマル酸及び重合禁止剤を投入し、210℃まで段階昇温により反応させた後、無水トリメリット酸を投入し、1時間常圧反応を行った後26.7kPaにて所望の軟化点に達するまで反応を行って、ポリエステルを得た。なお、本発明において反応率とは、反応水量(mol)/理論生成水量(mol)×100の値をいう。
Examples 1 and 7 and Comparative Examples 2 and 3
The alcohol component shown in Table 1, carboxylic acid components other than fumaric acid and trimellitic anhydride, esterification catalyst, and wax were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. The reaction was continued in a nitrogen atmosphere at 230 ° C. until the reaction rate reached 90%, and then reacted at 8.3 kPa for 1 hour. Thereafter, the mixture was cooled to 185 ° C., fumaric acid and a polymerization inhibitor were added, reacted to 210 ° C. by stepwise temperature increase, trimellitic anhydride was added, and after 1 hour of atmospheric pressure reaction, 26.7 kPa The reaction was carried out until the desired softening point was reached, to obtain a polyester. In the present invention, the reaction rate means a value of reaction water amount (mol) / theoretical water generation amount (mol) × 100.
実施例2
ワックスを、重合開始時ではなく無水トリメリット酸とともに添加した以外は、実施例1と同様にして、ポリエステルを得た。
Example 2
A polyester was obtained in the same manner as in Example 1 except that the wax was added together with trimellitic anhydride instead of at the start of polymerization.
実施例3
表1に示すアルコール成分、無水トリメリット酸以外のカルボン酸成分及びエステル化触媒を窒素導入管、脱水管、攪拌器および熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、230℃で反応率が90%に達するまで反応させた後、8.3kPaにて1時間反応させた。その後、210℃まで冷却し、ワックス及び無水トリメリット酸を添加し、常圧にて1時間反応させた後、8.3kPaにて1時間反応させた後、200kPaにて所望の軟化点に達するまで反応を行って、ポリエステルを得た。
Example 3
The alcohol component shown in Table 1, a carboxylic acid component other than trimellitic anhydride, and an esterification catalyst were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and under a nitrogen atmosphere The reaction was allowed to proceed at 230 ° C. until the reaction rate reached 90%, and then reacted at 8.3 kPa for 1 hour. Thereafter, it is cooled to 210 ° C., wax and trimellitic anhydride are added, reacted at normal pressure for 1 hour, reacted at 8.3 kPa for 1 hour, and then reaches a desired softening point at 200 kPa. The reaction was performed until polyester was obtained.
実施例4
表1に示すアルコール成分、カルボン酸成分、エステル化触媒及びワックスを窒素導入管、脱水管、攪拌器および熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、230℃で反応率が90%に達するまで反応させた後、8.3kPaにて所望の軟化点に達するまで反応を行って、ポリエステルを得た。
Example 4
The alcohol component, carboxylic acid component, esterification catalyst and wax shown in Table 1 were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and at 230 ° C. under a nitrogen atmosphere. After reacting until the reaction rate reached 90%, the reaction was performed at 8.3 kPa until a desired softening point was reached, thereby obtaining a polyester.
実施例5、6
表1に示すアルコール成分、無水トリメリット酸以外のカルボン酸成分、エステル化触媒及びワックスを窒素導入管、精留塔のついた脱水管、攪拌器および熱電対を装備した5リットル容の四つ口フラスコに入れ、180℃まで昇温した後、8時間かけて230℃まで昇温し、2時間反応させた後に200℃まで冷却し、無水トリメリット酸を投入し、所望の軟化点に達するまで反応を行って、ポリエステルを得た。
Examples 5 and 6
Four 5-liter capacity equipped with alcohol components, carboxylic acid components other than trimellitic anhydride, esterification catalyst and wax shown in Table 1, equipped with nitrogen introduction tube, dehydration tube with rectifying column, stirrer and thermocouple Put in a neck flask, raise the temperature to 180 ° C., raise the temperature to 230 ° C. over 8 hours, react for 2 hours, cool to 200 ° C., add trimellitic anhydride, and reach the desired softening point The reaction was performed until polyester was obtained.
比較例1
ワックスを使用しなかった以外は、実施例と同様にしてポリエステルを得た。
Comparative Example 1
A polyester was obtained in the same manner as in Example except that no wax was used.
実施例及び比較例で得られたポリエステルの軟化点、ガラス転移点、酸価及びワックスの体積平均分散径を表1に示す。 Table 1 shows the softening point, glass transition point, acid value, and volume average dispersion diameter of the waxes obtained in the examples and comparative examples.
なお、表1中のワックスA〜Cには、以下の市販品を用いた。
ワックスA:「PARACOHOL−5300」(日本精蝋社製)
水酸基価:17mgKOH/g 、酸価:1mgKOH/g、融点:87.0℃
ワックスB:「PARACOHOL−6110」(日本精蝋社製)
水酸基価:50mgKOH/g 、酸価:4mgKOH/g、融点:85.8℃
ワックスC:「PARACOHOL−5003A」(日本精蝋社製)
水酸基価:32mgKOH/g 、酸価:5mgKOH/g、融点:74.6℃
ポリエチレンワックス:「FT−100」(日本精蝋社製)
融点:98.0℃
The following commercially available products were used for waxes A to C in Table 1.
Wax A: “PARACOHOL-5300” (manufactured by Nippon Seiwa Co., Ltd.)
Hydroxyl value: 17 mg KOH / g, acid value: 1 mg KOH / g, melting point: 87.0 ° C
Wax B: “PARACOHOL-6110” (manufactured by Nippon Seiwa Co., Ltd.)
Hydroxyl value: 50 mgKOH / g, acid value: 4 mgKOH / g, melting point: 85.8 ° C
Wax C: “PARACOHOL-5003A” (manufactured by Nippon Seiwa Co., Ltd.)
Hydroxyl value: 32 mgKOH / g, acid value: 5 mgKOH / g, melting point: 74.6 ° C
Polyethylene wax: “FT-100” (manufactured by Nippon Seiwa Co., Ltd.)
Melting point: 98.0 ℃
トナー製造例
(1)実施例1〜7及び比較例2、3
ポリエステル100重量部、カーボンブラック「MOGUL−L」(キャボット社製)4重量部及び負帯電性電荷制御剤「ボントロン S−34」(オリエント化学工業社製)1重量部からなる原料をヘンシェルミキサーで十分混合した後、ロール内加熱温度100℃の同方向回転二軸押出し機を用い溶融混練を行い、得られた混合物を冷却、粗粉砕した後、ジェットミルにて粉砕し、分級して、体積平均粒径8.0μmの粉体を得た。
得られた粉体100重量部に、外添剤として疎水性シリカ「TS−530」(キャボット社製、平均粒子径:8nm)0.1重量部を添加し、ヘンシェルミキサーで混合してトナーを得た。
Toner Production Example (1) Examples 1 to 7 and Comparative Examples 2 and 3
A raw material consisting of 100 parts by weight of polyester, 4 parts by weight of carbon black “MOGUL-L” (Cabot) and 1 part by weight of negatively chargeable charge control agent “Bontron S-34” (Orient Chemical Co., Ltd.) After thorough mixing, melt kneading is performed using a co-rotating twin-screw extruder with a heating temperature in the roll of 100 ° C., and the resulting mixture is cooled, coarsely pulverized, pulverized with a jet mill, classified, and volume A powder having an average particle size of 8.0 μm was obtained.
To 100 parts by weight of the obtained powder, 0.1 part by weight of hydrophobic silica “TS-530” (manufactured by Cabot, average particle size: 8 nm) is added as an external additive, and mixed with a Henschel mixer to prepare a toner. Obtained.
(2)比較例1
原料として、さらに実施例1と同じワックスA 5重量部を使用した以外は、実施例1と同様にして、トナーを得た。
(2) Comparative Example 1
A toner was obtained in the same manner as in Example 1 except that 5 parts by weight of the same wax A as in Example 1 was used as a raw material.
試験例
(1)耐ホットオフセット性
市販の非磁性一成分現像方式のフルカラー電子写真記録装置において、定着速度を100mm/secに設定し、オイル塗布装置を除去した装置にトナーを実装した。定着装置中のヒートローラ温度を可変にし、ヒートローラ温度を100℃から240℃に昇温しながら、10℃昇温する毎に画像出しを行い、各温度でトナーのヒートローラ表面上への付着を肉眼により観察した。ヒートローラ表面上にトナーが付着した温度をホットオフセット発生温度とし、以下の評価基準に従って、耐ホットオフセット性を評価した。結果を表2に示す。
Test Example (1) Hot-offset resistance In a commercially available full-color electrophotographic recording apparatus of a non-magnetic one-component development system, the fixing speed was set to 100 mm / sec, and the toner was mounted on the apparatus from which the oil coating apparatus was removed. The temperature of the heat roller in the fixing device is made variable, and the temperature is raised from 100 ° C. to 240 ° C., an image is printed every time the temperature is raised by 10 ° C., and the toner adheres to the surface of the heat roller at each temperature. Was observed with the naked eye. The temperature at which the toner adhered to the surface of the heat roller was defined as the hot offset occurrence temperature, and the hot offset resistance was evaluated according to the following evaluation criteria. The results are shown in Table 2.
〔評価基準〕
ホットオフセット発生温度が
◎:210℃以上
○:180℃以上210℃未満
×:180℃未満
〔Evaluation criteria〕
Hot offset generation temperature is ◎: 210 ° C or higher ○: 180 ° C or higher and lower than 210 ° C ×: Less than 180 ° C
(2)帯電性
トナー0.6gとシリコーンフェライトキャリア(関東電化工業社製、平均粒子径:90μm)19.4gとをボールミルを用い、250r/minの回転速度で混合した。混合開始から、60秒後、300秒後、600秒後、1200秒後、3000秒後に、「q/mメーター」(EPPING社製)を用いてトナーの帯電量を測定し、以下の評価基準に従って帯電性を評価した。結果を表2に示す。
(2) Chargeability 0.6 g of toner and 19.4 g of a silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 90 μm) were mixed at a rotational speed of 250 r / min using a ball mill. The toner charge amount was measured using a “q / m meter” (manufactured by EPPING) after 60 seconds, 300 seconds, 600 seconds, 1200 seconds, and 3000 seconds from the start of mixing, and the following evaluation criteria The chargeability was evaluated according to The results are shown in Table 2.
〔評価基準〕
最大帯電量が
◎:20μC/g以上
○:10μC/g以上、20μC/g未満
×:10μC/g未満
〔Evaluation criteria〕
Maximum charge amount: ◎: 20 μC / g or more ○: 10 μC / g or more, less than 20 μC / g ×: Less than 10 μC / g
以上の結果から、実施例のポリエステルを含有したトナーは、耐ホットオフセット性及び帯電性のいずれにも優れていることが明らかである。
これに対し、比較例の結果より、以下のことが分かる。
(1) 比較例1
極性基を有するワックスを使用していても、ポリエステル製造後にワックスと混合しているために、耐ホットオフセット性は良好であるものの、帯電性が低下している。これは、ワックスの分散が悪いことによるものと推定される。
(2) 比較例2
極性基を有するワックスを使用していないために、帯電性が低下している。これは、ポリエチレンワックスとポリエステルとの相溶性が低いために、トナーを製造する際に、カーボンブラック等の添加剤がワックス部に凝集しているためと推定される。
(3) 比較例3
ポリエステル中のワックスの含有量が多すぎるために、帯電性が低下している。これは、ワックスの分散が悪いことによるものと推定される。
From the above results, it is clear that the toner containing the polyester of the example is excellent in both hot offset resistance and chargeability.
On the other hand, the following can be seen from the results of the comparative example.
(1) Comparative Example 1
Even when a wax having a polar group is used, although it is mixed with the wax after the production of the polyester, the hot offset resistance is good, but the chargeability is lowered. This is presumably due to poor wax dispersion.
(2) Comparative Example 2
Since the wax having a polar group is not used, the chargeability is lowered. This is presumably because additives such as carbon black are aggregated in the wax part when the toner is produced because the compatibility between the polyethylene wax and the polyester is low.
(3) Comparative Example 3
Since the content of the wax in the polyester is too large, the chargeability is lowered. This is presumably due to poor wax dispersion.
本発明のトナー用ポリエステルは、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられるトナーの結着樹脂等として用いられる。 The polyester for toner of the present invention is used as a binder resin for a toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.
Claims (5)
で表されるビスフェノールAのアルキレンオキサイド付加物を70モル%以上含有してなるアルコール成分と、カルボン酸成分との縮重合反応の少なくとも一部を、水酸基を有するパラフィンワックスの存在下で行って得られるトナー用ポリエステルであって、前記ワックスを0.5〜20重量%含有してなるトナー用ポリエステル。 Formula (I):
An alcohol component an alkylene oxide adduct of bisphenol A comprising more than 70 mole% represented in at least a portion of the polycondensation reaction of a carboxylic acid component, carried out in the presence of a paraffin wax having a hydroxyl group A polyester for toner obtained by containing 0.5 to 20% by weight of the wax.
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JP4770611B2 (en) * | 2006-07-07 | 2011-09-14 | 富士ゼロックス株式会社 | Method for producing toner for developing electrostatic image |
JP4671363B2 (en) * | 2006-11-08 | 2011-04-13 | 三菱レイヨン株式会社 | Binder resin composition for toner, method for producing the same, and toner |
JP4953880B2 (en) * | 2007-03-29 | 2012-06-13 | 花王株式会社 | Toner for electrostatic image development |
US7829255B2 (en) * | 2007-12-03 | 2010-11-09 | Xerox Corporation | Polyester-wax based emulsion aggregation toner compositions |
JP5412965B2 (en) * | 2009-06-08 | 2014-02-12 | 富士ゼロックス株式会社 | Electrostatic image developing toner, electrostatic image developer, toner cartridge, process cartridge, and image forming apparatus |
JP6223109B2 (en) * | 2013-10-10 | 2017-11-01 | 花王株式会社 | Binder resin composition for toner |
JP6184023B2 (en) * | 2014-03-14 | 2017-08-23 | 花王株式会社 | Binder resin composition for toner |
JP6249890B2 (en) * | 2014-06-24 | 2017-12-20 | 花王株式会社 | Binder resin composition for toner |
JP6274990B2 (en) * | 2014-06-30 | 2018-02-07 | 花王株式会社 | Toner for electrophotography |
JP6318063B2 (en) * | 2014-09-24 | 2018-04-25 | 花王株式会社 | Image forming method |
JP6405173B2 (en) * | 2014-09-24 | 2018-10-17 | 花王株式会社 | Binder resin composition for electrostatic image developing toner |
JP6392635B2 (en) * | 2014-11-06 | 2018-09-19 | 花王株式会社 | Method for producing binder resin composition for toner |
JP6368632B2 (en) * | 2014-12-08 | 2018-08-01 | 花王株式会社 | Binder resin composition for electrostatic image developing toner |
JP2016196571A (en) * | 2015-04-03 | 2016-11-24 | 三菱レイヨン株式会社 | Polyester resin for toner and method for producing the same, and toner |
JP6593757B2 (en) * | 2015-12-25 | 2019-10-23 | 花王株式会社 | Toner for electrophotography |
EP3553110B1 (en) * | 2016-12-07 | 2024-06-12 | Mitsubishi Chemical Corporation | Polyester resin for toner, method for producing same, and toner |
JP2020008816A (en) * | 2018-07-12 | 2020-01-16 | 花王株式会社 | Toner binder resin composition |
JP7286467B2 (en) * | 2019-04-12 | 2023-06-05 | 花王株式会社 | Toner for electrostatic charge image development |
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