JPH03188468A - Developer for electrostatic charge image - Google Patents
Developer for electrostatic charge imageInfo
- Publication number
- JPH03188468A JPH03188468A JP1328979A JP32897989A JPH03188468A JP H03188468 A JPH03188468 A JP H03188468A JP 1328979 A JP1328979 A JP 1328979A JP 32897989 A JP32897989 A JP 32897989A JP H03188468 A JPH03188468 A JP H03188468A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- acid
- toner
- peak
- polyester resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004645 polyester resin Substances 0.000 claims abstract description 36
- 229920001225 polyester resin Polymers 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000009826 distribution Methods 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 238000005227 gel permeation chromatography Methods 0.000 claims description 12
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 239000000523 sample Substances 0.000 description 9
- 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 description 7
- 230000000903 blocking effect Effects 0.000 description 7
- -1 polytetramethylene Polymers 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 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 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 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
- 238000011088 calibration curve Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000001771 impaired effect Effects 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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-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
- 229920001155 polypropylene Polymers 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
- 238000010008 shearing Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- URMOYRZATJTSJV-UHFFFAOYSA-N 2-(10-methylundec-1-enyl)butanedioic acid Chemical compound CC(C)CCCCCCCC=CC(C(O)=O)CC(O)=O URMOYRZATJTSJV-UHFFFAOYSA-N 0.000 description 1
- LIDLDSRSPKIEQI-UHFFFAOYSA-N 2-(10-methylundecyl)butanedioic acid Chemical compound CC(C)CCCCCCCCCC(C(O)=O)CC(O)=O LIDLDSRSPKIEQI-UHFFFAOYSA-N 0.000 description 1
- KHWCPXGTAVKMNS-UHFFFAOYSA-N 2-(2-methylprop-1-enyl)butanedioic acid Chemical compound CC(C)=CC(C(O)=O)CC(O)=O KHWCPXGTAVKMNS-UHFFFAOYSA-N 0.000 description 1
- PIYZBBVETVKTQT-UHFFFAOYSA-N 2-(2-methylpropyl)butanedioic acid Chemical compound CC(C)CC(C(O)=O)CC(O)=O PIYZBBVETVKTQT-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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- FGDWASZPMIGAFI-UHFFFAOYSA-N 2-but-1-enylbutanedioic acid Chemical compound CCC=CC(C(O)=O)CC(O)=O FGDWASZPMIGAFI-UHFFFAOYSA-N 0.000 description 1
- WOPLHDNLGYOSPG-UHFFFAOYSA-N 2-butylbutanedioic acid Chemical compound CCCCC(C(O)=O)CC(O)=O WOPLHDNLGYOSPG-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-UHFFFAOYSA-N 2-dodec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCC=CC(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
- SZJXEIBPJWMWQR-UHFFFAOYSA-N 2-methylpropane-1,1,1-triol Chemical compound CC(C)C(O)(O)O SZJXEIBPJWMWQR-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
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000788 chromium alloy Substances 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
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- KCYQMQGPYWZZNJ-UHFFFAOYSA-N hydron;2-oct-1-enylbutanedioate Chemical compound CCCCCCC=CC(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000000696 magnetic material Substances 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
- 239000000463 material Substances 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WDAISVDZHKFVQP-UHFFFAOYSA-N octane-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)CCCCC(C(O)=O)CC(O)=O WDAISVDZHKFVQP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
産 土の
本発明は、電子写真法、静電記録法、静電印刷法等の現
像プロセスにおいて用いられる静電荷像用現像剤（トナ
ー）に関し、特にトナーの定着性能の改善に関する。[Detailed Description of the Invention] The present invention relates to a developer (toner) for electrostatic images used in development processes such as electrophotography, electrostatic recording, and electrostatic printing, and particularly relates to toner fixing performance. Regarding improvements.
丈米立抜権
電子写真法においては、一般に、光導電体からなる感光
体表面に静電潜像を形成し、この潜像をトナー粒子によ
り現像して可視像とし、これを直接、あるいは紙等に転
写した後、熱や圧力などで定着している。In general, in the electrophotographic method, an electrostatic latent image is formed on the surface of a photoreceptor made of a photoconductor, and this latent image is developed with toner particles to become a visible image, which is then directly or After being transferred to paper, etc., it is fixed using heat, pressure, etc.
トナーの定着法としては、バインダー樹脂を含むトナー
を加熱・軟化させて定着する加熱定着法や、圧力により
塑性変形させて定着する圧力定着法が知られているが、
ヒートローラ定着方式が広く採用されている。ヒートロ
ーラ定着方式は、加熱、加圧下に定着ローラと画像を形
成したトナー粒子とを接触させ、トナーを軟化させて紙
等に定着する方法であり、高速機対応の観点から、低温
・低圧定着が要望されている。Known toner fixing methods include a heat fixing method in which toner containing a binder resin is heated and softened to fix it, and a pressure fixing method in which the toner is plastically deformed by pressure and fixed.
A heat roller fixing method is widely used. The heat roller fixing method is a method that brings the fixing roller into contact with toner particles on which an image has been formed under heat and pressure, softening the toner and fixing it on paper, etc. From the viewpoint of compatibility with high-speed machines, low temperature and low pressure fixing is used. is requested.
また、定着ローラにトナーの一部が付着し、この付着ト
ナーが後に送られてくる紙を汚す、いわゆるオフセット
の発生が問題となることから、その十分な防止対策も必
要となる。Furthermore, since a part of the toner adheres to the fixing roller and this adhered toner stains the paper that is subsequently fed, so-called offset occurs, which requires sufficient preventive measures.
そこで、トナーには、良好な熱応答性を示し。Therefore, the toner exhibits good thermal responsiveness.
広い温度範囲でオフセットを起こすことなく定着ローラ
から離型する非オフセット性と１紙等にしっかりと密着
する定着性の、相反する特性を満たすことが要求される
。It is required to satisfy the contradictory characteristics of non-offset property, which allows the film to be released from the fixing roller without causing offset in a wide temperature range, and fixing property, which allows it to firmly adhere to a piece of paper or the like.
特開昭６３−６８８４８号公報、同６３−６８８４９号
公報、同６３−６８８５０号公報、同６３−６８８５１
号公報には、ＯＨｖ（水酸基価）／ＡＶ（酸価）が１．
２以上（ＡＶｌｏＨＶが０．８３以下）のポリエステル
樹脂を用いた電子写真現像剤を使用することにより、オ
フセットを防止して低温度で定着でき、しかも、トナー
の流動性を改良してブロッキング特性を改善しうろこと
が報告されている。また、上記各公報には、酸価を低下
し過ぎるとポリエステル樹脂の摩擦帯電量が低下し、一
方、酸価が大きくなり過ぎるとトナーの環境安定性を損
なうことから、酸価が５〜６０のポリエステル樹脂が従
来から用いられていることが記載されている。JP 63-68848, JP 63-68849, JP 63-68850, JP 63-68851
In the publication, OHv (hydroxyl value)/AV (acid value) is 1.
By using an electrophotographic developer using a polyester resin with an AVloHV of 2 or more (AVloHV of 0.83 or less), offset can be prevented and fixing can be performed at low temperatures, and the toner fluidity can be improved to improve blocking properties. It has been reported that it is likely to improve. In addition, each of the above-mentioned publications states that if the acid value is too low, the amount of triboelectricity of the polyester resin will be reduced, and on the other hand, if the acid value is too high, the environmental stability of the toner will be impaired. It is stated that polyester resins have been conventionally used.
しかし、これらのトナーは定着性が未だ十分でなく、ま
た定着とオフセットとのバランスもされていない。However, these toners still do not have sufficient fixing properties, and the fixing and offset are not well balanced.
さらに、トナーにおけるバインダー樹脂の分子量分布を
制御することについては、特開昭６３−２２３６６２号
公報に、以下の条件を満たすバインダーを用いトナーの
オフセット性等を改善することが報告されている。Furthermore, regarding controlling the molecular weight distribution of the binder resin in the toner, Japanese Patent Laid-Open No. 63-223662 reports that a binder satisfying the following conditions is used to improve the offset properties of the toner.
■ バインダー樹脂のＴＨＦ（テトラヒドロフラン）不
溶分が１０〜６０重量％（バインダー樹脂基準）含有さ
九ていること６
■ バインダー樹脂のＴＨＦ可溶分のＧＰＣによる分子
量分布において、重量平均分子量／数平均分子量（Ｍｗ
／Ｍｎ）≧５であり、分子量２ 、０００〜１０，００
０の領域にピークを少なくとも１つ有し、かつ分子量１
５，０００〜１００．０００の領域にピークまたは肩を
少なくとも１つ有し、分子量１０，０００以下の成分が
バインダー樹脂に１０〜５０重量％含有されていること
。■ The binder resin must contain 10 to 60% by weight (based on the binder resin) of THF (tetrahydrofuran) insoluble matter. 6. In the molecular weight distribution of the THF-soluble component of the binder resin by GPC, the weight average molecular weight / number average molecular weight (Mw
/Mn)≧5, and the molecular weight is 2,000 to 10,00.
has at least one peak in the region of 0, and has a molecular weight of 1
The binder resin contains 10 to 50% by weight of a component having a molecular weight of 10,000 or less and having at least one peak or shoulder in the region of 5,000 to 100,000.
しかしこのトナーも、定着性が未だ十分でなく、定着と
オフセットとのバランスが取れていない。However, this toner still does not have sufficient fixing properties, and the balance between fixing and offset is not maintained.
が しようとする
本発明は、定着性に優れ、定着とオフセットとのバラン
スも取れた静電荷像用現像剤を提供するものである。The object of the present invention is to provide a developer for electrostatic images that has excellent fixing properties and a good balance between fixing and offset.
見豆立豊双
本発明の静電荷像用現像剤は、現像剤粒子中におけるバ
インダーとしてのポリエステル樹脂が、以下の（Ａ）〜
（Ｃ）の条件を満たすことを特徴とする。In the developer for electrostatic images of the present invention, the polyester resin as a binder in the developer particles is one of the following (A)-
It is characterized by satisfying the condition (C).
（Ａ）ポリエステル樹脂の酸価をＡＶ、水酸基価をＯＨ
ｖとしたとき、Ａｖが２０〜３５（Ｋ ＯＨｕｇ／ｇ）
、Ａｖ／ ＯＨｖ＝１．０〜１．５の範囲にあること。(A) The acid value of the polyester resin is AV, the hydroxyl value is OH
When v, Av is 20 to 35 (K OHug/g)
, Av/OHv should be in the range of 1.0 to 1.5.
（Ｂ）テトラヒドロフラン不溶分が１０％以下であるこ
と。(B) The content of tetrahydrofuran insoluble matter is 10% or less.
（Ｃ）テトラヒドロフラン可溶分のゲル・パーミテーシ
ョン・クロマトグラフィー
（Ｇ Ｐ Ｃ）による分子量分布において、重量平均分
子量Ｍ、と数平均分子量Ｍｎとの比率がＭ ｇ ／ Ｍ
ｎ≧１０であり、数平均分子量３．０００〜８，００
０の領域にピーク（低分子側ピーク）を少なくとも１つ
有し、また、数平均分子量１００，０００〜６００，０
００の領域にピークまたは肩（高分子側ピーク）を１つ
有し、かつ高分子側ピーク領域が５〜１５％存在するこ
と。(C) In the molecular weight distribution of the tetrahydrofuran soluble portion determined by gel permeation chromatography (GPC), the ratio between the weight average molecular weight M and the number average molecular weight Mn is M g / M
n≧10, number average molecular weight 3.000 to 8,00
has at least one peak (low molecular side peak) in the region of 0, and has a number average molecular weight of 100,000 to 600,0
It must have one peak or shoulder (polymer-side peak) in the 00 region, and the polymer-side peak area should be 5 to 15%.
以下、本発明についてさらに詳細に説明する。The present invention will be explained in more detail below.
ポリエステル樹脂のＡＶ値を上げ極性を高めることによ
り紙への化学的な密着力を向上させることができる。し
かしながら、ＡＶ値を上げると温度・湿度に対して影響
を受けやすくなり、画質を安定させることが困難となる
。そこで本発明では、ポリエステル樹脂の酸価ＡＶを２
０〜３５（Ｋ ＯＨｍｇ／ｇ）、好ましくは２０〜３０
とし、かつ５酸価ＡＶと水酸基価ＯＨｖとの比率Ａｖ１
０Ｈｖを１．０〜１．５、好ましくは１．２〜１．５の
範囲に設定することにより、バランスの取れたトナー物
性を実現した。すなわち、カブリ、トナー飛散等に対す
る汚れに対し、各環境において安定で良好な画像を得る
ことを可能とし、しかも、紙への密着性が高まり、ブロ
ッキング等に対しても安定である。By increasing the AV value and polarity of the polyester resin, chemical adhesion to paper can be improved. However, increasing the AV value makes it more susceptible to temperature and humidity, making it difficult to stabilize the image quality. Therefore, in the present invention, the acid value AV of the polyester resin is set to 2.
0-35 (K OHmg/g), preferably 20-30
and the ratio Av1 of the 5 acid value AV and the hydroxyl value OHv
By setting 0Hv in the range of 1.0 to 1.5, preferably 1.2 to 1.5, well-balanced toner physical properties were achieved. In other words, it is possible to obtain stable and good images in various environments against stains caused by fogging, toner scattering, etc. Furthermore, the adhesiveness to paper is improved and it is stable against blocking and the like.
ポリエステル樹脂の酸価、水酸基価は、ＪＩＳＫ ００
７０に規定される方法に準じて測定される。The acid value and hydroxyl value of polyester resin are JISK 00
It is measured according to the method specified in 70.
ポリエステル樹脂におけるＡＶ値、
Ａ ｖ ／ ＯＨｖ比の調整は、大きくは、■二価以上
の酸とアルコールとのモノマーの種類、比率、■反応温
度、時間等の縮重合の条件、■架橋剤としてのトリメリ
ット酸無水物等の配合量によってｍｖ；ｘできる。ポリ
エステル樹脂は、前述の公開特許公報に記載されている
ような、公知の共縮重合反応によって製造される。Adjustment of the AV value and A v / OHv ratio in polyester resins is mainly done by: ■ type and ratio of monomers of divalent or higher acid and alcohol, ■ condensation polymerization conditions such as reaction temperature and time, and ■ crosslinking agent. mv;x can be determined by the amount of trimellitic anhydride etc. added. Polyester resins are produced by known cocondensation polymerization reactions, such as those described in the above-mentioned published patent publications.
本発明の現像剤（トナー）では、さらに、バインダーと
してのポリエステル樹脂の架橋の程度と分子量分布を最
適の範囲に設定することにより、いっそう定着とオフセ
ットのバランスを取り、定着性能を改善した。ここで注
意すべきことは、ポリエステル樹脂の上記特性は、トナ
ー化された後の樹脂特性として評価されるべきであり、
原料としての樹脂特性ではないことである。トナーは一
般に原料樹脂１着色剤などを溶融混線、粉砕して製造さ
れるが、混線時に架橋ポイントが切断されることがある
。特に酸架橋タイプのポリエステル樹脂バインダーはこ
の傾向が強く、原料樹脂の際にはＴＨＦに不溶であった
ものが、混線時の熱と剪断力によって架橋部が切れ、一
部あるいは大部分がＴＨＦ可溶になることがある。トナ
ーとしての特性を見る場合は、加工前の原料樹脂として
の物性よりも、トナー化された状態での樹脂物性が重要
である。In the developer (toner) of the present invention, the degree of crosslinking and molecular weight distribution of the polyester resin as a binder are set to an optimal range, thereby achieving a better balance between fixing and offset and improving fixing performance. It should be noted here that the above properties of polyester resin should be evaluated as the resin properties after being made into a toner.
This is not due to the characteristics of the resin as a raw material. Toner is generally manufactured by melting and pulverizing raw material resins, colorants, etc., but crosslinking points may be cut during cross-mixing. This tendency is particularly strong with acid-crosslinked polyester resin binders, and although the raw resin was insoluble in THF, the crosslinks are broken by the heat and shearing force during cross-connection, and some or most of it becomes THF-soluble. May melt. When looking at the properties of a toner, the physical properties of the resin in the toner state are more important than the physical properties of the raw material resin before processing.
よって、本発明では、トナー用バインダーの原料樹脂と
しての物性は規定しない。Therefore, the present invention does not specify the physical properties of the raw material resin of the toner binder.
架橋密度は、ＴＨＦ（テトラヒドロフラン）溶剤に対す
る不溶分として測定できる。本発明では、トナー粒子中
のポリエステル樹脂のＴＨＦ不溶分を１０％以下、好ま
しくは２〜１０％、さらに好ましくは５％以下とする。The crosslinking density can be measured as the insoluble content in THF (tetrahydrofuran) solvent. In the present invention, the THF-insoluble content of the polyester resin in the toner particles is set to 10% or less, preferably 2 to 10%, and more preferably 5% or less.
ＴＨＦ不溶分は、試料をＴＨＦに溶解したときのＰ紙不
透過分を言い、次のように求めることができる。すなわ
ち、試料をコーヒーミルで適度に粉砕し、この２．ＯＯ
ｇと濾過助剤としてのラジオライト（＃７００）５．０
０ｇとを、１００ｇのＴＨＦと共に１５０ｍρの容器に
入れ、３時間ボールミルで混合、溶解させた後、洗浄、
乾燥、秤量、計算する。The THF-insoluble content refers to the P paper-unpermeable content when a sample is dissolved in THF, and can be determined as follows. That is, the sample is appropriately ground with a coffee mill, and then the sample is ground in a coffee grinder. OO
g and Radiolite (#700) as a filter aid 5.0
0g and 100g of THF in a 150mρ container, mixed and dissolved in a ball mill for 3 hours, then washed,
Dry, weigh and calculate.
トナー粒子中のポリエステル樹脂の架橋密度は、大きく
は、■二価以上の酸とアルコールとのモノマーの種類、
比率、■反応温度、時間の縮重合の条件、■架橋剤とし
ての無水トリメリット酸等の配合量、■トナー製造時の
混線条件によって調整できる。The crosslinking density of the polyester resin in the toner particles largely depends on: ■ the type of monomer containing divalent or higher acid and alcohol;
It can be adjusted by adjusting the ratio, (1) condensation polymerization conditions such as reaction temperature and time, (2) blending amount of trimellitic anhydride as a crosslinking agent, and (2) crosstalk conditions during toner production.
ポリエステル樹脂の分子量分布は、ＴＨＦ可溶分のＧＰ
Ｃによる分子量分布で規定される。The molecular weight distribution of polyester resin is GP of THF soluble content.
It is defined by the molecular weight distribution according to C.
第１図は、ＧＰＣによる分子量分布を示し、横軸に検出
時間、即ち分子量の大きさを対数で取ってあり、右側が
低分子側、左側が高分子側である。本発明では、この分
子量分布において、トナー中のポリエステル樹脂が次の
４つの条件を満たすことが必要である。FIG. 1 shows the molecular weight distribution by GPC, and the horizontal axis shows the detection time, that is, the size of the molecular weight in logarithm, and the right side is the low molecular side and the left side is the high molecular side. In the present invention, it is necessary for the polyester resin in the toner to satisfy the following four conditions in this molecular weight distribution.
（Ｃ−１）Ｍｙ／Ｍｎ≧ｌＯ１好ましくはＭｙ／Ｍｎ＝
１０〜３０゜
（Ｃ−２）分子量３，０００〜８，０００の領域にピー
クｐｇ（低分子側ピーク）を少なくとも１つ有する。(C-1) My/Mn≧lO1 Preferably My/Mn=
It has at least one peak pg (low molecular side peak) in the region of 10 to 30 degrees (C-2) and a molecular weight of 3,000 to 8,000.
（Ｃ−３）分子量１００，０００〜６００，０００の領
域にピークまたは肩Ｐ□（高分子側ピーク）を少なくと
も１つ有する。(C-3) It has at least one peak or shoulder P□ (polymer side peak) in the molecular weight region of 100,000 to 600,000.
（Ｃ−４）高分子側ピーク領域（第１図中に示した斜線
部Ａ）が５〜１５％存在する。なお、この値は、全ピー
ク面積に対する高分子側ピーク面積の比率として求めら
れる。(C-4) 5 to 15% of the peak region on the polymer side (hatched area A shown in FIG. 1) is present. Note that this value is determined as the ratio of the polymer side peak area to the total peak area.
上記範囲を逸脱すると、オフセット性と定着性の双方を
満足することができない。より具体的に説明すると、Ｐ
ｌの分子量、高分子側ピーク領域の大きさ、Ｍ ｙ ／
Ｍ ６およびＴＨＦ不溶分が主としてオフセット性に
影響を与える。また。If it deviates from the above range, it will not be possible to satisfy both offset properties and fixing properties. To explain more specifically, P
The molecular weight of l, the size of the polymer side peak area, M y /
M6 and THF-insoluble components mainly affect offset properties. Also.
Ｍｎの大きさ、ポリエステルの酸価、ＴＨＦ可溶分が主
として定着性に影響を与える。The size of Mn, the acid value of polyester, and the THF soluble content mainly affect fixing properties.
ＧＰＣによる分子量分布の測定は、次のようにして行な
うことができる。すなわち、４０℃のヒートチャンバー
中でカラムを安定させ、この温度におけるカラムに、溶
媒としてＴＨＦを毎分ＩＩＩＱの流速で流し、試料濃度
を３．Ｏｔｍｇ／ｒａ Ｑに調整したＴＨＦ試料溶液を
５０〜２００μＩＩＱ注入して測定する。Measurement of molecular weight distribution by GPC can be performed as follows. That is, the column was stabilized in a heat chamber at 40°C, THF was flowed as a solvent through the column at this temperature at a flow rate of IIIQ per minute, and the sample concentration was adjusted to 3. Measurement is performed by injecting 50 to 200 μIIQ of a THF sample solution adjusted to Otmg/raQ.
試料の分子量測定にあっては、試料の有する分子量分布
を、数種の単分散ポリスチレン標準試料により作製され
た検量線の対数値とカウント数との関係から算出した。In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm value and the count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples.
検量線作成用の標準ポリスチレン試料としては１例えば
、以下のような東ソー■製のＴＳＫ標準ポリスチレンを
用いることができ、このうち少なくとも４点程度の標準
ポリスチレン試料を用いることが適当である。As a standard polystyrene sample for preparing a calibration curve, for example, the following TSK standard polystyrene manufactured by Tosoh Corporation can be used, and it is appropriate to use at least four standard polystyrene samples among these.
タイプ −ｙテＧＰＣニー
Ａ−１０００９，５ＸＩＯ”
Ａ−２５００２，８ＸＩＯ”
Ｆ−１１，０１Ｘ１０’
Ｆ−１０９，８９Ｘ １０’
Ｆ−４０４，２７Ｘ１０’
Ｆ −１２８１，３０Ｘ１０＠
カラムとしては、１０′〜２Ｘ１０＠の分子量領域を適
確に測定するために市販のポリスチレンゲルカラムを複
数組み合わせるのが良く、ＴＳＫｇｅｌＧＭＨ（東ソー
社製）等の組合わせが好ましい。酸価の高いポリエステ
ル樹脂の測定にあたっては、極性タイプのカラムが好適
である。Type -yte GPC knee A-10009,5XIO"A-25002,8XIO"F-11,01X10' F-109,89X 10'F-404,27X10' F-1281,30X10@ Column: 10'~ In order to accurately measure the molecular weight range of 2×10@, it is recommended to combine a plurality of commercially available polystyrene gel columns, and combinations such as TSKgelGMH (manufactured by Tosoh Corporation) are preferred. A polar type column is suitable for measuring polyester resins with high acid values.
ポリエステル樹脂は、アルコール成分とカルボン酸成分
との縮重合ないしは共縮重合によって得られ、用いられ
る各成分の具体例としては。The polyester resin is obtained by condensation polymerization or cocondensation polymerization of an alcohol component and a carboxylic acid component, and specific examples of each component used are as follows.
以下のものが挙げられる。These include:
２価または３価以上のアルコール成分とじては、以下の
ものが例示される。Examples of divalent or trivalent or higher alcohol components include the following.
１） ジオール類；エチレングリコール、ジエチレング
リコール、トリエチレングリコール、１，２−プロピレ
ングリコール、１゜３−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、１゜４−
ブチンジオール、１，５−ベンタンジオール、１，６−
ヘキサンジオール、１゜４−シクロヘキサンジメタツー
ル、ジプロピレングリコール、ポリエチレングリコール
、ポリプロピレングリコール、ポリテトラメチレングリ
コールなど。1) Diols; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1°3-propylene glycol, 1,4
-Butanediol, neopentyl glycol, 1゜4-
Butynediol, 1,5-bentanediol, 1,6-
Hexanediol, 1°4-cyclohexane dimetatool, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.
２） ビスフェノール類：ビスフェノールＡ、水素添加
ビスフェノールＡ、ポリオキシエチレン化ビスフェノー
ルＡ、ポリオキシプロピレン化ビスフェノールＡ等のエ
ーテル化ビスフェノール類など。2) Bisphenols: etherified bisphenols such as bisphenol A, hydrogenated bisphenol A, polyoxyethylated bisphenol A, and polyoxypropylenated bisphenol A.
３）３価以上のアルコール類；ソルビトール。3) Trihydric or higher alcohols; sorbitol.
１．２，３．６−ヘキサンテトロール、１゜４−ソルビ
タン、ペンタエリスリトール、ジペンタエリスリトール
、トリペンタエリスリトール、１，２．４−ブタントリ
オール、１，２，５−ペンタントリオール、グリセロー
ル、ジグリセロール、２−メチルプロパントリオール、
２−メチル−１，２゜４−ブタントリオール、トリメチ
ロールエタン、トリメチロールプロパン、１，３゜５−
トリヒドロキシメチルベンゼンなど。1.2,3.6-hexanetetrol, 1゜4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, di glycerol, 2-methylpropanetriol,
2-methyl-1,2゜4-butanetriol, trimethylolethane, trimethylolpropane, 1,3゜5-
trihydroxymethylbenzene etc.
２価または３価以上のカルボン酸類としては、２価また
は３価カルボン酸、この酸無水物またはこの低級アルキ
ルエステルが用いられ、カルボン酸として以下のものが
例示される。As the divalent or trivalent or higher carboxylic acids, divalent or trivalent carboxylic acids, their acid anhydrides, or their lower alkyl esters are used, and the following are exemplified as the carboxylic acids.
４）２価カルボン酸；マレイン酸、フマール酸、シトラ
コン酸、イタコン酸、グルタコン酸、フタル酸、イソフ
タル酸、テレフタル酸、シクロヘキサンジカルボン酸、
コハク酸、アジピン酸、セパチン酸、アゼライン酸、マ
ロン酸、あるいはｎ−ブチルコハク酸、ｎ−ブテニルコ
ハク酸、イソブチルコハク酸、イソブテニルコハク酸、
ｎ−オクチルコハク酸、ｎ−オクテニルコハク酸、ｎ−
ドデシルコハク酸、ｎ−ドデセニルコハク酸、イソドデ
シルコハク酸、イソドデセニルコハク酸等のアルキルま
たはアルケニルコハク酸など。4) Divalent carboxylic acids; maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid,
Succinic acid, adipic acid, sepacic acid, azelaic acid, malonic acid, or n-butylsuccinic acid, n-butenylsuccinic acid, isobutylsuccinic acid, isobutenylsuccinic acid,
n-octylsuccinic acid, n-octenylsuccinic acid, n-
Alkyl or alkenyl succinic acids such as dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, etc.
５）３価以上のカルボン酸；１，２．４−ベンゼントリ
カルボン酸（トリメリット酸）、１．２．５−ベンゼン
トリカルボン酸、２゜５．７−ナフタレントリカルボン
酸、１゜２．４−ナフタレントリカルボン酸、１゜２．
４−ブタントリカルボン酸、１，２゜５−ヘキサントリ
カルボン酸、１，３−ジカルボキシル−２−メチル−２
−メチレンカルボキシプロパン、１，２．４−シクロヘ
キサントリカルボン酸、テトラ（メチレンカルボキシル
）メタン、１，２，７．８−オクタンテトラカルボン酸
、ピロメリット酸、エンポール三量体酸など。5) Trivalent or higher carboxylic acids; 1,2.4-benzenetricarboxylic acid (trimellitic acid), 1.2.5-benzenetricarboxylic acid, 2°5.7-naphthalenetricarboxylic acid, 1°2.4- Naphthalene tricarboxylic acid, 1°2.
4-butanetricarboxylic acid, 1,2゜5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2
-methylenecarboxypropane, 1,2.4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7.8-octanetetracarboxylic acid, pyromellitic acid, Empol trimer acid, etc.
これらカルボン酸の酸無水物または低級アルキルエステ
ルも使用できる。Acid anhydrides or lower alkyl esters of these carboxylic acids can also be used.
ポリエステル樹脂の中でも、下記（ａ）、 （ｂ）およ
び（ｃ）を共縮重合したポリエステル樹脂をバインダー
として用いることが好ましい、このようなポリエステル
樹脂を用いることにより、オフセット性、ブロッキング
性を損なうことなく。Among polyester resins, it is preferable to use a polyester resin obtained by cocondensation polymerization of the following (a), (b), and (c) as a binder. By using such a polyester resin, offset property and blocking property are not impaired. Without.
本発明の定着性能をいかんなく発揮させることができる
。The fixing performance of the present invention can be fully exhibited.
（ａ）−能代（１）で示されるジオール成分。(a) - Diol component represented by Noshiro (1).
（式中の記号は以下のものを示す
ＯＲ１，ＯＲ”ニオキシエチレン基またはオキシプロピ
レン基
ｘ、ｙ：１以上の整数、但しｘ＋ｙの平均値は２〜７）
（ｂ）二価のカルボン酸、その酸無水物またはその低級
アルキルエステルの少なくとも１種。(The symbols in the formula indicate the following: OR1, OR" nioxyethylene group or oxypropylene group , an acid anhydride thereof, or a lower alkyl ester thereof.
（Ｃ）三価以上の多価カルボン酸、その酸無水物または
その低級アルキルエステルの少なくとも１種、または／
および三価以上の多価アルコール。(C) at least one of trivalent or higher polycarboxylic acids, acid anhydrides thereof, or lower alkyl esters thereof, or/
and trivalent or higher polyhydric alcohols.
本発明のトナー中には、上記ポリエステル樹脂に加え、
着色剤、電荷制御剤、流動性改良剤、定着向上助剤、磁
性体、外添剤などを含むことができる。In addition to the above polyester resin, the toner of the present invention contains:
It may contain a colorant, a charge control agent, a fluidity improver, a fixing aid, a magnetic substance, an external additive, and the like.
着色剤としてはカーボンブラックをはじめ各種の顔料、
染料が；磁性体としてはマグネタイト、フェライト等が
；電荷制御剤としては第４級アンモニウム化合物、ニグ
ロシン、ニグロシン塩基、クリスタルバイオレット、１
，２型クロム合金錯塩染料等が；オフセット防止剤、定
着向上助剤としては低分子量ポリプロピレン。As colorants, various pigments including carbon black,
Dyes; magnetic substances include magnetite, ferrite, etc.; charge control agents include quaternary ammonium compounds, nigrosine, nigrosine base, crystal violet, 1
, type 2 chromium alloy complex dye, etc.; low molecular weight polypropylene as an anti-offset agent and fixing aid.
低分子ポリエチレンあるいはその変性物等のオレフィン
ワックスなどが使用できる。Olefin wax such as low molecular weight polyethylene or its modified product can be used.
本発明のトナーは、常法により１例えば２軸押出機、ニ
ーダ等で各成分を溶融混線後、ジェットミル等で粉砕し
、分級することにより得られる。The toner of the present invention can be obtained by melting and blending each component in a conventional method such as a twin-screw extruder or kneader, followed by pulverization and classification using a jet mill or the like.
本発明のトナーは、キャリアと混合して二成分現像剤と
して、磁性体を含有せしめて一成分現像剤として、ある
いは、光導電材料を含有せしめて光導電性トナーとして
等、種々の使用形態を取ることができる。The toner of the present invention can be used in various forms, such as mixed with a carrier as a two-component developer, containing a magnetic material as a single-component developer, or containing a photoconductive material as a photoconductive toner. You can take it.
見豆ム羞米
本発明によれば、特定の酸価、および酸価／水酸基価を
有する極性の高いポリエステル樹脂を用い、かつ、トナ
ーにおけるポリエステル樹脂の架橋密度、分子量分布を
制御することにより、オフセット性と定着性のバランス
が取れ、カブリ、トナー飛散による汚れ等に対して各環
境下において安定で良好な画像が得られ、しかも紙への
密着性が高く、ブロッキングに対しても安定なバランス
の取れた特性を有するトナーが得られる。このトナーは
、低速機から高速機までの種々のタイプの静電記録に要
求される条件をカバーし、低エネルギーでの紙への定着
を可能にし、しかも、ブロッキング、オフセット等に対
しても良好な特性を示す。According to the present invention, by using a highly polar polyester resin having a specific acid value and acid value/hydroxyl value, and controlling the crosslinking density and molecular weight distribution of the polyester resin in the toner, It has a good balance between offset and fixing properties, and provides stable and good images in various environments against fogging and stains caused by toner scattering.In addition, it has high adhesion to paper, and has a stable balance against blocking. A toner with excellent characteristics can be obtained. This toner covers the conditions required for various types of electrostatic recording from low-speed machines to high-speed machines, enables fixing to paper with low energy, and is also resistant to blocking, offset, etc. It shows certain characteristics.
スー」Ｌ二匠
一般式（１）のビスフェノールＡポリオキシエチレン付
加物（平均付加モル数２．２）１０重量部、テレフタル
酸５重量部、アルケニルコハク酸３重量部、無水トリメ
リット酸２重量部を共縮重合させて以下の性状のポリエ
ステル樹脂を製造した。10 parts by weight of bisphenol A polyoxyethylene adduct of general formula (1) (average number of added moles: 2.2), 5 parts by weight of terephthalic acid, 3 parts by weight of alkenylsuccinic acid, 2 parts by weight of trimellitic anhydride. A polyester resin having the following properties was produced by cocondensation polymerization of the following parts.
酸価Ａｖ＝３０．０（Ｋ ＯＨａｇ７ｇ）水酸基価ＯＨ
ｖ＝２０．０（Ｋ ＯＨｕｇ／ｇ）Ａ ｖ ／ ＯＨｖ
＝１ 、５
軟化点：１２８℃
ガラス転移点Ｔｇ：６０℃
ＴＨＦ不溶分：２５％
ここで、酸価および水酸基価は、ＪＩＳ Ｋ ００７０
に準拠して測定した。但し、酸価は溶媒としてジオキサ
ンを用い、水酸基価は、アセチル化時間を２時間とした
。Acid value Av=30.0 (K OHag7g) Hydroxyl value OH
v=20.0(KOHug/g)Av/OHv
= 1, 5 Softening point: 128°C Glass transition point Tg: 60°C THF insoluble content: 25% Here, the acid value and hydroxyl value are JIS K 0070
Measured according to. However, for the acid value, dioxane was used as the solvent, and for the hydroxyl value, the acetylation time was 2 hours.
また、軟化点はフローテスタで半分流出する温度とした
。In addition, the softening point was determined as the temperature at which half of the sample flowed out using a flow tester.
このポリエステル樹脂を用いて以下の組成で計量、混合
した。Using this polyester resin, the following composition was measured and mixed.
ポリエステル樹脂 ８５重量％ポリプ
ロピレンワックス５５０Ｐ ５重量％カーボン
ブラック（リーガル４００Ｒ） ９重量％電荷制御
剤（ボンドロンＳ−３４） １重量％この混合
物を混線後、ジェットミルで５〜２５μ麗に粉砕し、ト
ナーを得た（実施例１）。Polyester resin 85% by weight Polypropylene wax 550P 5% by weight Carbon black (Regal 400R) 9% by weight Charge control agent (Bondron S-34) 1% by weight After cross-mixing, this mixture is ground to a fine particle size of 5 to 25 μm using a jet mill to form a toner. was obtained (Example 1).
ジオール成分と二価カルボン酸および多価カルボン酸成
分との使用比率を変える以外は上記と同様の操作を繰り
返し、後記表−２に示した種々の性状のポリエステル樹
脂をバインダーとするトナーを製造した。The same operation as above was repeated except for changing the ratio of the diol component and the dicarboxylic acid and polycarboxylic acid components to produce toners using polyester resins of various properties as shown in Table 2 below as a binder. .
さらに、実施例１のトナーで用いたポリエステル樹脂に
ついては、樹脂の合成後およびトナー製造後の両方につ
いて、ＴＨＦ不溶分およびＧＰＣによる分子量分布測定
を行ない、その結果を以下の表−１に示した。トナー製
造時に掛かる熱と剪断力により、架橋部が切断され、Ｔ
ＨＦ不溶分のかなり部分がＴＨＦ可溶分となっているこ
とが判る。Furthermore, regarding the polyester resin used in the toner of Example 1, THF-insoluble content and molecular weight distribution measurements were performed by GPC both after resin synthesis and after toner production, and the results are shown in Table 1 below. . Due to the heat and shearing force applied during toner production, the crosslinked portion is cut and the T
It can be seen that a considerable portion of the HF-insoluble matter is THF-soluble.
ユニで、ＴＨＦ不溶分については前述の方法に依って測
定した。また、ＧＰＣによる分子量分布測定は以下の方
法に依った。The THF-insoluble content was measured using the method described above. Moreover, the molecular weight distribution measurement by GPC was carried out by the following method.
且旦旦分五ｌｌ主
４０℃のヒートチャンバーに組み込まれたカラムに、Ｔ
ＨＦを流速１ ｍ ｍ ／ｗｉｎで流し。In addition, T
HF was flowed at a flow rate of 1 mm/win.
３０ｍｇ／ｍ Ｑの濃度で一昼夜放置した後０．４μの
テフロンフィルターでｒ過した溶液（ＴＨＦ可溶分）を
１００μΩ注入し、以下の条件で分子量分布を測定した
。After standing overnight at a concentration of 30 mg/m Q, a solution (THF soluble content) filtered through a 0.4 μ Teflon filter was injected at 100 μΩ, and the molecular weight distribution was measured under the following conditions.
ＧＰＣ測定装置： ＨＬＣ−８０２０，東ソー社製検出
器：Ｒ工
標準ポリスチレン： ２．８ Ｘ １０” 、 １．０
１ Ｘ １０’ 。GPC measuring device: HLC-8020, Tosoh Corporation Detector: R engineering standard polystyrene: 2.8 x 10”, 1.0
1 x 10'.
９．８９ Ｘ １０’ 、 ４．２７ Ｘ １０’ 、
１．３０ Ｘ １０’カラム：極性ＴＳＫｇｅｌＧＭ
Ｈ、直列２個（以下余白）
表−１：ポリエステル樹脂の性状
後記表−２に示した各性状のポリエステル樹脂を含むト
ナーについて、その性状を評価し、その結果を表−３に
示した。9.89 x 10', 4.27 x 10',
1.30 x 10' column: polar TSKgelGM
H, 2 in series (blank below) Table 1: Properties of polyester resin Postscript The properties of toners containing polyester resins having the respective properties shown in Table 2 were evaluated, and the results are shown in Table 3.
（以下余白）
〔性能評価法〕
（１）オフセット性
クリーナーバットを付けずに定着ローラを、トナー画像
を有する転写紙に圧接触させ、トナーを融着させて定着
する０次に。(The following is a blank space) [Performance evaluation method] (1) Zero-order, in which a fixing roller is brought into pressure contact with a transfer paper having a toner image without an offset cleaner bat, and the toner is fused and fixed.
トナー画像を有しない転写紙を同様に定着ローラに圧接
触させ、転写紙上にオフセット汚れが発生するか否かを
観察する。定着ローラの温度を変化させて上記操作を繰
り返しオフセットが発生することなく定着可能な温度範
囲を決定し、以下の基準で判断した。A transfer paper without a toner image is similarly brought into pressure contact with a fixing roller, and it is observed whether offset stains occur on the transfer paper. The above operation was repeated by changing the temperature of the fixing roller to determine the temperature range in which fixing was possible without causing offset, and judgment was made based on the following criteria.
０：全くオフセット汚れが発生しない
Δ：オフセット汚れが一部発生する
×：オフセット汚れがひどい
（２）定着性
定着温度を１８０℃±２℃に設定し、スイッチＯＦＦの
状態で１０分間ファンで冷却した後、電源ＯＮＬ、定着
パターンを連続５枚通紙し、測定用画像を得る。0: No offset stains occur Δ: Some offset stains occur ×: Severe offset stains (2) Fixability Set the fixing temperature to 180°C ± 2°C and cool with a fan for 10 minutes with the switch OFF. After that, the power is turned on and five sheets of fixed patterns are passed in succession to obtain images for measurement.
この画像を、綿布で包んだ黄銅製の１ｋｇの荷重をかけ
て、１０往復擦る。この操作の前後の画像濃度をマクベ
ス反射計で測定し、その濃度の比率を求めて定着性とす
るが、ここでは、２５％ハーフ濃度画像の定着率の最低
の値をもって定着性を判断する。また、試験環境は、温
度２３℃、相対温度５５％の常温−常湿条件とした。This image is rubbed back and forth 10 times with a 1 kg load made of brass wrapped in cotton cloth. The image density before and after this operation is measured with a Macbeth reflectometer, and the ratio of the densities is determined to determine the fixability. Here, the fixability is determined based on the lowest value of the fixation rate of the 25% half-density image. Moreover, the test environment was set to normal temperature and normal humidity conditions of a temperature of 23° C. and a relative temperature of 55%.
紙は、いわゆるボンド紙を用いた。The paper used was so-called bond paper.
０：９０〜１００％
Δ：８０〜９０％
×：８０％以下
（３）ブロッキング性
１００■Ωのガラスビンに１０ｇのトナーを入れ、５０
℃のオーブン中で２００時間放置し、以下の基準で評価
した。0: 90-100% Δ: 80-90% ×: 80% or less (3) Blocking property Put 10g of toner in a 100Ω glass bottle,
It was left in an oven at ℃ for 200 hours and evaluated based on the following criteria.
０：全くブロッキングが見られない Δ：ソフトケーキング状態 ×ニハードケーキングしている （４）画像 限度見本にて、カブリを判定した。0: No blocking observed at all Δ: Soft caking state × Nihard caking (4) Image Fog was determined using a limit sample.
回定蓋！
０：カブリが見られない
Δ：肉眼でカブリが確認できる
×：ハツキリとカブリが確認される
（５）トナー飛散
同様のレーザープリンタを用い、ｌＯ万枚プリント後に
目視で観察し、以下の基準で機内飛散を評価した。Rotating lid! 0: No fogging Δ: Fogging can be seen with the naked eye ×: Chipping and fogging can be seen. In-flight scattering was evaluated.
立定基！ ０：飛散がない Δ：少し飛散有り Ｘ：飛散大 （以下余白） ４、Standing base! 0: No scattering Δ: Slight scattering X: Large scattering (Margin below) 4,
第１図は、 ＧＰＣによる分子量分布を示すグ ラフである。 第 図 検出時間 Figure 1 shows Group showing molecular weight distribution by GPC It's rough. No. figure Detection time
Claims (1)
テル樹脂が、以下の（Ａ）〜（Ｃ）の条件を満たすこと
を特徴とする静電荷像用現像剤。 （Ａ）ポリエステル樹脂の酸価をＡ＿ｖ、水酸基価をＯ
Ｈ＿ｖとしたとき、Ａ＿ｖが２０〜３５（ＫＯＨｍｇ／
ｇ）、Ａ＿ｖ／ＯＨ＿ｖ＝１．０〜１．５の範囲にある
こと、 （Ｂ）テトラヒドロフラン不溶分が１０％以下であるこ
と、 （Ｃ）テトラヒドロフラン可溶分のゲル・パーミテーシ
ョン・クロマトグラフィー （ＧＰＣ）による分子量分布において、重 量平均分子量Ｍ＿ｗと数平均分子量Ｍ＿ｎとの比率がＭ
＿ｗ／Ｍ＿ｎ≧１０であり、数平均分子量３，０００〜
８，０００の領域にピーク（低分子側ピーク）を少なく
とも１つ有し、また、 数平均分子量１００，０００〜６００，０００の領域に
ピークまたは肩（高分子側ピーク）を１つ有し、かつ、
高分子側ピーク領域が５〜１５％存在すること。[Scope of Claims] 1. A developer for electrostatic images, characterized in that a polyester resin as a binder in the developer particles satisfies the following conditions (A) to (C). (A) The acid value of the polyester resin is A_v, the hydroxyl value is O
When H_v, A_v is 20 to 35 (KOHmg/
g), A_v/OH_v is in the range of 1.0 to 1.5; (B) the tetrahydrofuran-insoluble content is 10% or less; (C) the tetrahydrofuran-soluble content is subjected to gel permeation chromatography ( In the molecular weight distribution by GPC), the ratio between the weight average molecular weight M_w and the number average molecular weight M_n is M
_w/M_n≧10, number average molecular weight 3,000~
It has at least one peak (peak on the low molecular weight side) in the region of 8,000, and one peak or shoulder (peak on the high molecular weight side) in the region of number average molecular weight 100,000 to 600,000, and,
The peak area on the polymer side should be 5 to 15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1328979A JP2904520B2 (en) | 1989-12-18 | 1989-12-18 | Developer for electrostatic image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1328979A JP2904520B2 (en) | 1989-12-18 | 1989-12-18 | Developer for electrostatic image |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03188468A true JPH03188468A (en) | 1991-08-16 |
| JP2904520B2 JP2904520B2 (en) | 1999-06-14 |
Family
ID=18216250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1328979A Expired - Lifetime JP2904520B2 (en) | 1989-12-18 | 1989-12-18 | Developer for electrostatic image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2904520B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996002869A1 (en) * | 1994-07-18 | 1996-02-01 | Unitika Ltd. | Polyester resin for toner binder, process for producing the resin, and toner prepared therefrom |
| US5578408A (en) * | 1993-12-29 | 1996-11-26 | Canon Kabushiki Kaisha | Toner for developing electrostatic image |
| EP0774695A1 (en) | 1995-11-20 | 1997-05-21 | Canon Kabushiki Kaisha | Toner for developing electrostatic images |
| JPH10239981A (en) * | 1997-03-03 | 1998-09-11 | Canon Inc | Image forming device |
| EP0961175A2 (en) * | 1998-05-26 | 1999-12-01 | Canon Kabushiki Kaisha | Toner having negative triboelectric chargeability and image forming method |
| FR2795190A1 (en) * | 1999-06-17 | 2000-12-22 | Ricoh Kk | Electrophotographic developer has colorant, separating agent and resin binder including components soluble in tetrahydrofuran and having specified molecular weight distribution |
| US6300024B1 (en) | 1999-06-30 | 2001-10-09 | Canon Kabushiki Kaisha | Toner, two-component type developer, heat fixing method, image forming method and apparatus unit |
| JP2008097042A (en) * | 2007-12-25 | 2008-04-24 | Ricoh Co Ltd | Dry toner, method for manufacturing toner concerned and image forming apparatus using toner concerned |
| US7374848B2 (en) | 2003-06-24 | 2008-05-20 | Ricoh Company, Limited | Toner and method or preparing the toner |
| WO2008149740A1 (en) * | 2007-05-31 | 2008-12-11 | Sanyo Chemical Industries, Ltd. | Resin for toner and toner composition |
-
1989
- 1989-12-18 JP JP1328979A patent/JP2904520B2/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578408A (en) * | 1993-12-29 | 1996-11-26 | Canon Kabushiki Kaisha | Toner for developing electrostatic image |
| WO1996002869A1 (en) * | 1994-07-18 | 1996-02-01 | Unitika Ltd. | Polyester resin for toner binder, process for producing the resin, and toner prepared therefrom |
| US5789527A (en) * | 1994-07-18 | 1998-08-04 | Tomoegawa Paper Co., Ltd. | Polyester resin for use in toner binder and process for producing the same |
| EP0774695A1 (en) | 1995-11-20 | 1997-05-21 | Canon Kabushiki Kaisha | Toner for developing electrostatic images |
| US5773183A (en) * | 1995-11-20 | 1998-06-30 | Canon Kabushiki Kaisha | Toner for developing electrostatic images |
| JPH10239981A (en) * | 1997-03-03 | 1998-09-11 | Canon Inc | Image forming device |
| EP0961175A2 (en) * | 1998-05-26 | 1999-12-01 | Canon Kabushiki Kaisha | Toner having negative triboelectric chargeability and image forming method |
| EP0961175A3 (en) * | 1998-05-26 | 2000-04-19 | Canon Kabushiki Kaisha | Toner having negative triboelectric chargeability and image forming method |
| FR2795190A1 (en) * | 1999-06-17 | 2000-12-22 | Ricoh Kk | Electrophotographic developer has colorant, separating agent and resin binder including components soluble in tetrahydrofuran and having specified molecular weight distribution |
| US6335137B1 (en) | 1999-06-17 | 2002-01-01 | Ricoh Company Limited | Electrophotographic toner and electrophotographic image forming method and apparatus using the toner |
| US6300024B1 (en) | 1999-06-30 | 2001-10-09 | Canon Kabushiki Kaisha | Toner, two-component type developer, heat fixing method, image forming method and apparatus unit |
| US7374848B2 (en) | 2003-06-24 | 2008-05-20 | Ricoh Company, Limited | Toner and method or preparing the toner |
| WO2008149740A1 (en) * | 2007-05-31 | 2008-12-11 | Sanyo Chemical Industries, Ltd. | Resin for toner and toner composition |
| US8592120B2 (en) | 2007-05-31 | 2013-11-26 | Sanyo Chemical Industries, Ltd. | Resin for toner and toner composition |
| JP2008097042A (en) * | 2007-12-25 | 2008-04-24 | Ricoh Co Ltd | Dry toner, method for manufacturing toner concerned and image forming apparatus using toner concerned |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2904520B2 (en) | 1999-06-14 |
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