JPH04239021A - Crystalline polyester resin for toner - Google Patents
Crystalline polyester resin for tonerInfo
- Publication number
- JPH04239021A JPH04239021A JP3001453A JP145391A JPH04239021A JP H04239021 A JPH04239021 A JP H04239021A JP 3001453 A JP3001453 A JP 3001453A JP 145391 A JP145391 A JP 145391A JP H04239021 A JPH04239021 A JP H04239021A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- toner
- resin
- melting point
- diol
- 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
- 229920001225 polyester resin Polymers 0.000 title claims description 8
- 239000004645 polyester resin Substances 0.000 title claims description 8
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000728 polyester Polymers 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229920005989 resin Polymers 0.000 abstract description 34
- 239000011347 resin Substances 0.000 abstract description 34
- 230000000903 blocking effect Effects 0.000 abstract description 15
- 150000002009 diols Chemical class 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 108091008695 photoreceptors Proteins 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
- 239000000843 powder Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 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
- 230000009257 reactivity Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 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
- 238000012546 transfer Methods 0.000 description 2
- 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 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 229940084778 1,4-sorbitan Drugs 0.000 description 1
- LIBOYZGDGVDKKH-UHFFFAOYSA-N 2-(8-methylnonyl)butanedioic acid Chemical compound CC(C)CCCCCCCC(C(O)=O)CC(O)=O LIBOYZGDGVDKKH-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
- XYHGSPUTABMVOC-UHFFFAOYSA-N 2-methylbutane-1,2,4-triol Chemical compound OCC(O)(C)CCO XYHGSPUTABMVOC-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
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- NNYOSLMHXUVJJH-UHFFFAOYSA-N heptane-1,5-diol Chemical compound CCC(O)CCCCO NNYOSLMHXUVJJH-UHFFFAOYSA-N 0.000 description 1
- GWCHPNKHMFKKIQ-UHFFFAOYSA-N hexane-1,2,5-tricarboxylic acid Chemical compound OC(=O)C(C)CCC(C(O)=O)CC(O)=O GWCHPNKHMFKKIQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 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
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WRYWBRATLBWSSG-UHFFFAOYSA-N naphthalene-1,2,4-tricarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 WRYWBRATLBWSSG-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
- 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
- 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、電子写真法、静電記録
法や静電印刷法などにおいて静電荷像または磁気潜像の
現像に用いる乾式トナーとして有用なポリエステル樹脂
に関する。さらに詳しくは、耐ブロッキング性、溶融流
動性、定着性に優れ、特に高流動性を要するフルカラー
用トナー、および低温定着性を要する高速複写機、高速
プリンター用トナーまたは粉体塗料用として有用なポリ
エステル樹脂に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin useful as a dry toner used for developing electrostatic images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like. More specifically, the polyester has excellent blocking resistance, melt fluidity, and fixing properties, and is useful for full-color toners that require particularly high fluidity, as well as toners for high-speed copiers and printers that require low-temperature fixing properties, and for powder coatings. Regarding resin.
【０００２】0002
【従来の技術】静電荷像よりも恒久的な顕像を得る方法
においては、光導電性感光体または静電記録体上に形成
された静電荷像をあらかじめ摩擦により帯電させたトナ
ーによって現像したのち定着される。磁気潜像の場合は
磁気ドラム上の潜像を磁性体を含むトナーによって現像
した後、定着される。定着は、光導電性感光体または静
電記録体上に現像によって得られたトナー像を直接融着
させるか、紙やフィルム上にトナー像を転写した後、こ
れを転写シート上に融着させることによって行われる。
トナー像の融着は溶剤蒸気との接触、加圧及び加熱によ
って行われ、加熱方式には電気オーブンによる無接触加
熱方式と加圧ローラーによる圧着加熱方式があるが、定
着工程の高速化が要請される最近では主として後者が用
いられている。[Prior Art] In a method for obtaining a more permanent developed image than an electrostatic charge image, an electrostatic charge image formed on a photoconductive photoreceptor or an electrostatic recording medium is developed with toner that has been previously charged by friction. It will be established later. In the case of a magnetic latent image, the latent image on the magnetic drum is developed with toner containing a magnetic material and then fixed. Fixing involves directly fusing the toner image obtained by development onto a photoconductive photoreceptor or electrostatic recording medium, or by transferring the toner image onto paper or film and then fusing it onto a transfer sheet. It is done by Fusing of toner images is performed by contact with solvent vapor, pressure, and heating.Heating methods include non-contact heating using an electric oven and pressure heating using a pressure roller, but there is a need for faster fixing processes. Recently, the latter has been mainly used.
【０００３】さらに、カラー画像を得るためには、上述
の現像工程において、３〜４色のトナーを転写紙に付着
させ、次いで定着工程において、各種トナーを溶融混合
しながら発色し、定着させなければならない。フルカラ
ートナー用バインダーには上述のごとく定着工程での混
合性の良い樹脂、換言すれば、溶融流動性の良い樹脂が
強く望まれている。溶融流動性の良好なバインダーを用
いた場合、定着工程でのオフセット現象が生じるという
問題がある。Furthermore, in order to obtain a color image, three to four color toners must be attached to the transfer paper in the above-mentioned developing process, and then in the fixing process, the various toners must be melted and mixed to develop and fix the color. Must be. As described above, a resin with good mixability in the fixing process, in other words, a resin with good melt flowability is strongly desired as a binder for full color toner. When a binder with good melt flowability is used, there is a problem in that an offset phenomenon occurs during the fixing process.
【０００４】しかしながら、オフセット現象を防止する
ため、バインダーを架橋化させたり高分子化させると、
溶融流動性が低下し、フルカラーコピーには適さない。
従って、コピーマシーンの定着ローラー表面にシリコー
ンを塗布し、オフセットを防止する手法が用いられてい
る。However, in order to prevent the offset phenomenon, if the binder is crosslinked or polymerized,
Melt fluidity decreases, making it unsuitable for full-color copying. Therefore, a technique is used to prevent offset by coating the surface of the fixing roller of a copy machine with silicone.
【０００５】また、溶融流動性を高めるためバインダー
樹脂を低分子化させるとガラス転移温度Ｔｇ が低下し
、耐ブロッキング性が低下する。[0005] Furthermore, if the binder resin is made to have a lower molecular weight in order to improve melt fluidity, the glass transition temperature Tg will be lowered and the blocking resistance will be lowered.
【０００６】従来より、この低分子ポリエステル樹脂と
して、２価の不飽和カルボン酸と芳香族ジオール成分と
からなる樹脂が提案されている。しかし、酸との反応性
の悪い芳香族ジオールのみを使用しているため、目的の
物性を得ようとすると、高い温度での反応が必要であり
、そのため、芳香族ジオールが分解し、悪臭、画質劣化
等の問題が生じる。[0006] Conventionally, a resin comprising a divalent unsaturated carboxylic acid and an aromatic diol component has been proposed as this low-molecular polyester resin. However, since only aromatic diols are used, which have poor reactivity with acids, reactions at high temperatures are required to obtain the desired physical properties. Problems such as image quality deterioration occur.
【０００７】さらに、芳香族ジオールは一般に高価であ
り、それを多量に用いた高価なトナーは複写機が一般大
衆化されている現在では、産業上好ましくない。さらに
、２価カルボン酸として不飽和カルボン酸を用いている
ため、ラジカル反応防止剤に用いられているハイドロキ
ノン等が原因での公害問題が懸念されている。Furthermore, aromatic diols are generally expensive, and expensive toners using large amounts of aromatic diols are not preferred industrially now that copying machines have become popular. Furthermore, since an unsaturated carboxylic acid is used as the divalent carboxylic acid, there are concerns about pollution problems caused by hydroquinone, etc. used as a radical reaction inhibitor.
【０００８】以上述べてきたように、フルカラー及び高
速複写機用低分子バインダーには、溶融流動性が良好で
、なおかつ耐ブロッキング性および熱安定性が良好な樹
脂が強く熱望されている。As described above, resins with good melt flowability, blocking resistance and thermal stability are strongly desired as low-molecular binders for full-color and high-speed copying machines.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、従来
技術において溶融流動性が良好で、耐ブロッキング性に
優れ、なおかつ、安価で公害問題等の心配のない、一般
大衆化されつつある複写機にふさわしいバインダー樹脂
を与えることにある。SUMMARY OF THE INVENTION The object of the present invention is to provide a copying machine which is becoming popular among the general public, has good melt flowability, excellent anti-blocking properties, is inexpensive and free from pollution problems, etc. in the prior art. The purpose is to provide a suitable binder resin for the machine.
【００１０】更に詳しくは、ポリエステル樹脂に部分的
な結晶構造を持たせることで、溶融流動性に優れ、なお
かつ樹脂の持つ結晶構造により耐オフセット性を付与す
ることにある。More specifically, by imparting a partial crystalline structure to the polyester resin, it is possible to have excellent melt flowability, and also to provide offset resistance due to the crystalline structure of the resin.
【００１１】[0011]
【課題を解決するための手段、その作用】本発明者らは
、上記の問題を解決するために鋭意検討したところ、樹
脂の結晶構造が耐ブロッキング性を付与し、低粘度でな
おかつ耐ブロッキング性が良好である樹脂が得られるこ
とを見だし本発明を完成した。[Means for Solving the Problems and Their Effects] In order to solve the above problems, the present inventors have made extensive studies and found that the crystal structure of the resin provides anti-blocking properties and has low viscosity and anti-blocking properties. The present invention was completed by discovering that a resin with good properties can be obtained.
【００１２】本発明は、テレフタル酸及び／またはその
低級アルキルエステルと炭素数２〜６の直鎖型アルキレ
ングリコールが全使用モノマー中５０モル％以上を占め
るモノマーから得られるポリエステル重合体からなり、
２００℃以下の融点を有し、軟化温度Ｔｉ が １５
０℃以下であり、酸価が２０ｍｇ ＫＯＨ／ｇ以下であ
ることを特徴とする結晶性トナー用ポリエステル樹脂を
提供する。The present invention comprises a polyester polymer obtained from monomers in which terephthalic acid and/or its lower alkyl ester and linear alkylene glycol having 2 to 6 carbon atoms account for 50 mol% or more of the total monomers used,
It has a melting point of 200℃ or less, and a softening temperature Ti of 15
Provided is a polyester resin for crystalline toner, which is characterized by having a temperature of 0° C. or lower and an acid value of 20 mg KOH/g or lower.
【００１３】本発明でいうテレフタル酸の低級アルキル
エステルとはテレフタル酸ジメチル、テレフタル酸ジエ
チルなどの炭素数１〜３のアルキル基を有するテレフタ
ル酸エステルを言い、Ｔｇ を上げる効果とコストとい
う点からテレフタル酸ジメチルが好ましい。The lower alkyl ester of terephthalic acid as used in the present invention refers to a terephthalic acid ester having an alkyl group having 1 to 3 carbon atoms, such as dimethyl terephthalate and diethyl terephthalate. Dimethyl acid is preferred.
【００１４】本発明で言う炭素数２〜６の直鎖型アルキ
レンジオールとは、エチレングリコール、１，３−プロ
ピレングリコール、１，４−ブタンジオール、１，５−
ヘプタンジオール、１，６−ヘキサンジオールをいい、
その中でもエチレングリコール、１，４−ブタンジオー
ル、１，６−ヘキサンジオールは結晶性に寄与し、結晶
化のコントロールをするのに効果がある。[0014] In the present invention, the linear alkylene diol having 2 to 6 carbon atoms includes ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-
Heptanediol, 1,6-hexanediol,
Among them, ethylene glycol, 1,4-butanediol, and 1,6-hexanediol contribute to crystallinity and are effective in controlling crystallization.
【００１５】本発明で重要な点は、重合したポリエステ
ルが ２００℃以下の融点および １５０℃以下の軟化
温度を有し、酸価が２０ｍｇ ＫＯＨ／ｇ以下で有るこ
とである。融点が ２００℃を超えると、耐ブロッキン
グ性は良好であるが、溶融温度が高過ぎて、フルカラー
での一般の溶融混練工程で、溶融混練するのは困難であ
る。従って、樹脂の融点は、 ２００℃以下でなければ
ならない。次に、樹脂の軟化温度が １５０℃を超える
とトナーとして用いる場合溶融させるのに非常に大きな
エネルギーを要し、しかも、溶融混合しにくくなる。従
って、軟化温度Ｔｉ は １５０℃以下の必要があり、
好ましくは １４０℃以下である。酸価が２０ｍｇ Ｋ
ＯＨ／ｇ以上になると、トナーにした場合、湿度の帯電
量への影響が大きくなり、複写機の環境の変化によって
、溶融混合の比率が変わり、色むらの原因になる。
また、一般の高速複写時においても、同じ理由で環境湿
度の変化によって濃度が変わってしまう。[0015] What is important in the present invention is that the polymerized polyester has a melting point of less than 200°C, a softening temperature of less than 150°C, and an acid value of less than 20 mg KOH/g. When the melting point exceeds 200°C, blocking resistance is good, but the melting temperature is too high and it is difficult to melt-knead in a general full-color melt-kneading process. Therefore, the melting point of the resin must be 200°C or less. Next, if the softening temperature of the resin exceeds 150°C, it will take a very large amount of energy to melt it when used as a toner, and it will be difficult to melt and mix it. Therefore, the softening temperature Ti needs to be 150℃ or less,
Preferably it is 140°C or lower. Acid value is 20mg K
When the amount exceeds OH/g, the influence of humidity on the amount of charge becomes large when it is made into toner, and changes in the environment of the copying machine change the ratio of melting and mixing, causing color unevenness. Furthermore, even during general high-speed copying, the density changes due to changes in environmental humidity for the same reason.
【００１６】本発明において、テレフタル酸及び／また
はその低級アルキルエステルと炭素数２〜６の直鎖型ア
ルキレングリコール以外のモノマーは、その必要性能に
応じて請求範囲を越えない範囲で、使用することができ
る。一般に、ポリエステルの原料として公知のモノマー
は、本発明の効果が奏される範囲で、使用してさしつか
えない。例えば、イソフタル酸、フタル酸、セバシン酸
、イソデシル琥珀酸、マレイン酸、フマル酸、アジピン
酸などのジカルボン酸及びこれらのモノメチル、モノエ
チル、ジメチル、ジエチルエステルなどが挙げられ、特
にイソフタル酸及びそのジメチルエステルが耐ブロッキ
ング性及びコストの点で好ましい。これらのジカルボン
酸およびその低級エステルはトナーの定着性及び耐ブロ
ッキング性に影響を与える。イソフタル酸のような芳香
族ジカルボン酸を用いると耐ブロッキング性は向上する
が、定着性は低下する。逆に、セバシン酸やアジピン酸
のような脂肪族ジカルボン酸を用いると定着性は向上す
るが、ガラス転移温度Ｔｇ の低下をもたらすため耐ブ
ロッキング性の低下につながる。脂肪族ジカルボン酸の
場合、長鎖のモノマー程この傾向は強い。In the present invention, monomers other than terephthalic acid and/or its lower alkyl ester and linear alkylene glycol having 2 to 6 carbon atoms may be used within the scope of the claims according to the required performance. I can do it. In general, monomers known as raw materials for polyester may be used as long as the effects of the present invention are achieved. Examples include dicarboxylic acids such as isophthalic acid, phthalic acid, sebacic acid, isodecyl succinic acid, maleic acid, fumaric acid, and adipic acid, and their monomethyl, monoethyl, dimethyl, and diethyl esters, particularly isophthalic acid and its dimethyl ester. is preferable in terms of blocking resistance and cost. These dicarboxylic acids and their lower esters affect the fixing properties and blocking resistance of the toner. When an aromatic dicarboxylic acid such as isophthalic acid is used, blocking resistance is improved, but fixing performance is reduced. On the other hand, when an aliphatic dicarboxylic acid such as sebacic acid or adipic acid is used, fixing properties are improved, but the glass transition temperature Tg is lowered, leading to a decrease in blocking resistance. In the case of aliphatic dicarboxylic acids, this tendency is stronger as the monomer has a longer chain.
【００１７】炭素数２〜６の直鎖型アルキレングリコー
ル以外のジオールとしては、脂肪族及び芳香族ジオール
が用いられる。脂肪族ジオールの例として、ネオペンチ
ルグリコール、ポリエチレングリコール、シクロヘキサ
ンジメタノール、水添ビスフェノールＡなどが挙げられ
、定着性の面からネオペンチルグリコールが好ましい。
芳香族ジオールの例として、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−（２．３）−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−（２．０）−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）−
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、ポリオキシプロピレン
（６）−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（２．３）−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（２．４）−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（３．３）−２
，２−ビス（４−ヒドロキシフェニル）プロパンなどが
挙げられる。これらのジオール成分は単独または混合で
使用される。芳香族ジオールはガラス転移温度Ｔｇ を
上げる効果があるため、耐ブロッキング性が良好と成る
。また、ジオール成分のなかでも、芳香族ジオールとシ
クロヘキサンジメタノールや水添ビスフェノールＡとい
った脂環式ジオールなどは、反応性を調節可能とすると
ともに、樹脂の耐摩耗性を向上することもすでに知られ
ている。As diols other than linear alkylene glycols having 2 to 6 carbon atoms, aliphatic and aromatic diols are used. Examples of aliphatic diols include neopentyl glycol, polyethylene glycol, cyclohexanedimethanol, and hydrogenated bisphenol A, with neopentyl glycol being preferred from the viewpoint of fixability. Examples of aromatic diols include polyoxyethylene-(2
．． 0)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-(2.3)-2,2-bis(4-hydroxyphenylpropane), polyoxypropylene-(2.0)-2 , 2-bis(4-hydroxyphenyl)propane, polyoxypropylene (2.2)-
Polyoxyethylene-(2.0)-2,2-bis(4-
hydroxyphenyl)propane, polyoxypropylene (6)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (2.4)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (3.3)-2
, 2-bis(4-hydroxyphenyl)propane, and the like. These diol components may be used alone or in combination. Since aromatic diols have the effect of raising the glass transition temperature Tg, they provide good blocking resistance. Furthermore, among diol components, aromatic diols and alicyclic diols such as cyclohexanedimethanol and hydrogenated bisphenol A are already known to be able to control reactivity and improve the wear resistance of resins. ing.
【００１８】本発明において、多官能モノマーを用いて
、ポリマーに架橋構造を持たせることができる。多官能
モノマーとしては多価カルボン酸および多価アルコール
が用いられる。多価カルボン酸の例として、トリメリッ
ト酸、ピロメリット酸、１，２，４−シクロヘキサント
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、１，２，５
−ヘキサントリカルボン酸、１，２，７，８−オクタン
テトラカルボン酸及びこれらの酸無水物及び低級アルキ
ルエステルがある。多価アルコールの例としては、ソル
ビトール、１，２，３，６−ヘキサンテトラロール、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、庶糖、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、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が挙げられる、多
官能モノマーは単独または混合で用いられる。このよう
な多官能モノマーは樹脂のガラス転移温度Ｔｇ を高め
る効果があると共に、生じた架橋構造が結晶部分ととも
に耐オフセット性を高める効果があるので、必要に応じ
て自由に用いればよい。In the present invention, a polyfunctional monomer can be used to impart a crosslinked structure to the polymer. Polyhydric carboxylic acids and polyhydric alcohols are used as the polyfunctional monomer. Examples of polyvalent carboxylic acids include trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2, 5
-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, and their acid anhydrides and lower alkyl esters. Examples of polyhydric alcohols include sorbitol, 1,2,3,6-hexanetetralol, 1
, 4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,
2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5
Polyfunctional monomers such as -trihydroxymethylbenzene can be used alone or in combination. Such a polyfunctional monomer has the effect of increasing the glass transition temperature Tg of the resin, and the resulting crosslinked structure has the effect of increasing the offset resistance together with the crystalline portion, so it may be used freely as necessary.
【００１９】本発明のポリエステル樹脂を製造するには
、前記モノマーを反応釜に仕込、加熱昇温することによ
り、エステル化反応またはエステル交換反応を行う。
この時必要に応じて硫酸、チタンブトキサイド、ジブチ
ルスズオキシド、酢酸マグネシウム、酢酸マンガン等の
通常のエステル化反応またはエステル交換反応で使用さ
れるエステル化触媒またはエステル交換触媒を使用する
ことができる。次いで、常法に従って該反応で生じた水
またはアルコールを除去する。In order to produce the polyester resin of the present invention, the above-mentioned monomers are charged into a reaction vessel and heated to an elevated temperature to carry out an esterification reaction or transesterification reaction. At this time, an esterification catalyst or a transesterification catalyst used in a normal esterification reaction or transesterification reaction, such as sulfuric acid, titanium butoxide, dibutyltin oxide, magnesium acetate, manganese acetate, etc., can be used if necessary. Next, water or alcohol produced in the reaction is removed according to a conventional method.
【００２０】本発明においては、引き続き重合反応を実
施するが、このとき １５０ｍｍＨｇ以下の真空下でジ
オール成分を留出除去させながら重合を行う。重合に際
しては通常公知の重合触媒、例としてチタンブトキサイ
ド、ジブチルスズオキシド、酢酸スズ、酢酸亜鉛、２硫
化スズ、３酸化アンチモン、２酸化ゲルマニウム、等を
用いることができる。重合温度、触媒量については特に
限定されるものではなく、必要に応じて任意に設定すれ
ば良い。In the present invention, a polymerization reaction is subsequently carried out, and at this time, the polymerization is carried out while distilling and removing the diol component under a vacuum of 150 mmHg or less. In the polymerization, commonly known polymerization catalysts such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, etc. can be used. The polymerization temperature and the amount of catalyst are not particularly limited, and may be set arbitrarily as necessary.
【００２１】本発明において、融点は示差走査熱量計Ｄ
ＳＣを用いて、昇温速度５℃／分で測定した時の吸熱カ
ーブのピークの温度とした。また、本発明で言う軟化温
度Ｔｉ とは、フローテスター（島津製作所Ｔ−５００
）を用いて、ノズル１．０ｍｍφ×１０ｍｍ、荷重３０
ｋｇｆ 、昇温速度３℃／ｍｉｎ で測定した時の樹脂
が流出し始める温度を言う。In the present invention, the melting point is measured using a differential scanning calorimeter D.
The temperature was defined as the peak temperature of the endothermic curve when measured using SC at a heating rate of 5° C./min. In addition, the softening temperature Ti referred to in the present invention is a flow tester (Shimadzu T-500
), nozzle 1.0mmφ x 10mm, load 30
kgf is the temperature at which the resin begins to flow out when measured at a temperature increase rate of 3°C/min.
【００２２】本発明中の実施例での組成分析においては
、樹脂をヒドラジンで加水分解し、液体クロマトグラフ
ィーを用いて定量した。[0022] In the compositional analysis in the Examples of the present invention, the resin was hydrolyzed with hydrazine and quantified using liquid chromatography.
【００２３】[0023]
【実施例】次に、実施例について、本発明を説明するが
、本発明の実施態様はこれによって限定されるものでは
ない。EXAMPLES Next, the present invention will be explained with reference to Examples, but the embodiments of the present invention are not limited thereto.
【００２４】実施例−１
第１表の組成に従い、テレフタル酸 １００モル％、エ
チレングリコール１００モル％、ポリオキシプロピレン
（２．３）−２，２−ビス（４−ヒドロキシフェニル）
プロパンジオールＡを３０モル％を蒸留塔を有する反応
容器に投入した。さらに反応容器にジブチルスズオキシ
ドを全酸成分に対して０．０３重量％添加し、内温を２
６０ ℃、攪拌回転数２００ｒｐｍに保ち、常圧下で５
時間エステル化反応させたのち、反応系内を３０分かけ
て１．０ｍｍＨｇまで減圧し、内温 ２６０℃に保ち、
エチレングリコールを留出せしめながら縮合反応を２時
間行い、淡黄色透明の樹脂Ｒ−１を得た。得られた樹脂
Ｒ−１は、融点が １７５℃で酸価が６．０ｍｇ ＫＯ
Ｈ／ｇであった。得られた樹脂Ｒ−１の補正分析結果を
第１−２表に示す。Example-1 According to the composition shown in Table 1, terephthalic acid 100 mol%, ethylene glycol 100 mol%, polyoxypropylene (2.3)-2,2-bis(4-hydroxyphenyl)
30 mol% of propanediol A was charged into a reaction vessel having a distillation column. Furthermore, dibutyltin oxide was added in an amount of 0.03% by weight based on the total acid components, and the internal temperature was lowered to 2.
Maintain the stirring speed at 60 °C and 200 rpm, and heat at 5 ℃ under normal pressure.
After carrying out the esterification reaction for a period of time, the pressure inside the reaction system was reduced to 1.0 mmHg over 30 minutes, and the internal temperature was maintained at 260°C.
The condensation reaction was carried out for 2 hours while distilling off ethylene glycol to obtain a pale yellow transparent resin R-1. The obtained resin R-1 had a melting point of 175°C and an acid value of 6.0 mg KO.
It was H/g. The corrected analysis results of the obtained resin R-1 are shown in Table 1-2.
【００２５】[0025]
【表１】[Table 1]
【００２６】第１−１表
＊ジオールＡ：ポリオキシプロピレン（２．３）−２，
２−ビス（４−ヒドドロキシフェニル）プロパンTable 1-1 *Diol A: Polyoxypropylene (2.3)-2,
2-bis(4-hydroxyphenyl)propane
【００
２７】00
27]
【表２】[Table 2]
【００２８】第１−２表Table 1-2
【００２９】耐ブロッキング性の評価は、５０ｍｌのガ
ラス製サンプル瓶中に５〜２０μｍに微粉砕した樹脂５
ｇを入れ、５０℃の高温槽中に５０時間放置した後、そ
の凝集度を観察した。その凝集度は次の基準に準拠して
評価した。For evaluation of blocking resistance, resin 5 finely pulverized to 5 to 20 μm was placed in a 50 ml glass sample bottle.
g was placed in a high temperature bath at 50° C. for 50 hours, and the degree of aggregation was observed. The degree of cohesion was evaluated based on the following criteria.
【００３０】
５０℃に５０時間放置したサンプル瓶を室温まで冷却し
、Ａ：サンプル瓶を逆さにしただけでトナーが落ちる。
Ｂ：サンプル瓶を逆さにし、軽く振っただけでトナーが
落ちる。
Ｃ：サンプル瓶を逆さにし、軽くたたくとトナーが落ち
る。
Ｄ：サンプル瓶を逆さにし、強い振動を与えてやるとト
ナーが落ちる。A sample bottle that had been left at 50° C. for 50 hours was cooled to room temperature. A: The toner fell out just by turning the sample bottle upside down. B: Turn the sample bottle upside down and shake it lightly to remove the toner. C: Turn the sample bottle upside down and tap it lightly to remove the toner. D: If you turn the sample bottle upside down and give it strong vibration, the toner will fall out.
【００３１】Ｅ：サンプル瓶を逆さにし、強い振動を与
えてもトナーは落ちない。（凝集度Ａ，Ｂ，Ｃは使用可
能と判断した。）E: Even when the sample bottle is turned upside down and subjected to strong vibrations, the toner does not fall off. (Cohesion degrees A, B, and C were judged to be usable.)
【００３２】第１−２表より樹脂Ｒ−１は、耐ブロッキ
ング性が良好であり、フルカラーに用いた場合溶融混合
性の良好な樹脂であることがわかる。さらに酸価も低い
ことより、帯電特性も良好なことがわかる。From Table 1-2, it can be seen that resin R-1 has good anti-blocking properties and good melt-mixability when used in full color. Furthermore, the low acid value indicates good charging characteristics.
【００３３】実施例−２〜４
モノマー仕込組成を第２−１表のようにする以外は、実
施例−１と同様の操作を行い、樹脂Ｒ−２／Ｒ−４を得
た。樹脂Ｒ−２〜Ｒ−４の組成分析結果及び樹脂物性値
を第２−２表に示す。Examples 2 to 4 Resins R-2/R-4 were obtained in the same manner as in Example 1, except that the monomer charge composition was changed as shown in Table 2-1. The compositional analysis results and resin physical property values of Resins R-2 to R-4 are shown in Table 2-2.
【００３４】[0034]
【表３】[Table 3]
【００３５】第２−１表
＊ジオールＡ：ポリオキシプロピレン（２．３）−２，
２−ビス（４−ヒドロキシフェニル）プロパン＊＊ジオ
ールＢ：ポリオキシエチレン（２．３）−２，２−ビス
（４−ヒドロキシフェニル）プロパンTable 2-1 *Diol A: Polyoxypropylene (2.3)-2,
2-bis(4-hydroxyphenyl)propane** Diol B: Polyoxyethylene (2.3)-2,2-bis(4-hydroxyphenyl)propane
【００３６】[0036]
【表４】[Table 4]
【００３７】第２−２表
＊ジオールＡ：ポリオキシプロピレン（２．３）−２，
２−ビス（４−ヒドロキシフェニル）プロパン＊ジオー
ルＢ：ポリオキシエチレン（２．３）−２，２−ビス（
４−ヒドロキシフェニル）プロパンTable 2-2 *Diol A: Polyoxypropylene (2.3)-2,
2-bis(4-hydroxyphenyl)propane*diol B: polyoxyethylene (2.3)-2,2-bis(
4-hydroxyphenyl)propane
【００３８】第２−
２表より、トナーＴ−２〜Ｔ−４は、耐ブロッキング性
が非常に良好であり、また酸価が低いことより、帯電性
の耐環境依存度が低い良好な樹脂であることがわかる。2nd -
From Table 2, it can be seen that toners T-2 to T-4 have very good blocking resistance and are good resins with low dependence on environmental resistance of chargeability due to their low acid values.
【００３９】比較例１〜４
モノマー仕込組成を第３−１表のようにする以外は、実
施例−１と同様の操作を行い、樹脂Ｒ−５〜Ｒ−９を得
た。樹脂Ｒ−５〜Ｒ−９の組成分析結果及び樹脂物性値
を第３−２表に示す。Comparative Examples 1 to 4 Resins R-5 to R-9 were obtained in the same manner as in Example 1, except that the monomer charge composition was changed as shown in Table 3-1. The compositional analysis results and resin physical property values of Resins R-5 to R-9 are shown in Table 3-2.
【００４０】[0040]
【表５】[Table 5]
【００４１】第３−１表
＊ジオールＢ：ポリオキシエチレン（２．３）−２，２
−ビス（４−ヒドロキシフェニル）プロパンTable 3-1 *Diol B: Polyoxyethylene (2.3)-2,2
-bis(4-hydroxyphenyl)propane
【００４２
】0042
]
【表６】[Table 6]
【００４３】第３−２表Table 3-2
【００４４】樹脂Ｒ−５はＤＳＣで融点が確認されなか
ったため結晶化度が少なく耐ブロッキング性が悪い。樹
脂Ｒ−６は低酸価ではあるが、融点が ２６０℃と高い
ためトナーとして用いる場合定着性が悪くなり、フルカ
ラー用トナーとして用いる場合、溶融混合するには高い
温度が必要となるため、トナー用樹脂には適さない。Resin R-5 had a low degree of crystallinity and poor blocking resistance because no melting point was confirmed by DSC. Resin R-6 has a low acid value, but its melting point is as high as 260°C, so it has poor fixing properties when used as a toner, and when used as a full-color toner, high temperatures are required for melting and mixing. Not suitable for commercial resins.
【００４５】樹脂Ｒ−７は融点も １６９℃と低く、耐
ブロッキング性も良好であるが、酸価が２７ｍｇ ＫＯ
Ｈ／ｇと高いためトナーにした場合、帯電量が、湿度の
影響を受け易い。従って、トナーに用いる樹脂には適さ
ない。Resin R-7 has a low melting point of 169°C and good blocking resistance, but its acid value is 27 mg KO.
Since it has a high H/g, when made into toner, the amount of charge is easily affected by humidity. Therefore, it is not suitable for resins used in toners.
【００４６】樹脂Ｒ−８は樹脂の組成的に配向しにくく
、耐ブロッキング性が極めて低下する。樹脂Ｒ−９は軟
化温度Ｔｉ が １９８℃と高いため、溶融するのに高
いエネルギーを要し、トナー用樹脂には適さない。Resin R-8 is difficult to orient due to its composition, and its anti-blocking properties are extremely low. Since resin R-9 has a high softening temperature Ti of 198° C., it requires high energy to melt and is not suitable as a toner resin.
【００４７】[0047]
【発明の効果】本発明のポリエステル樹脂は、部分的な
結晶構造を有するため、良好な耐ブロッキング性を有し
、耐オフセット性に優れており、かつ低粘度で良好な溶
融流動性を示す。従って、高流動性を要するフルカラー
用トナーおよび低温定着性を要する高速複写機、高速プ
リンター用トナーおよび粉体塗料用として有用である。[Effects of the Invention] Since the polyester resin of the present invention has a partial crystal structure, it has good blocking resistance, excellent offset resistance, and exhibits low viscosity and good melt flowability. Therefore, it is useful as a full-color toner that requires high fluidity, a toner for high-speed copying machines and high-speed printers that requires low-temperature fixability, and a toner for powder coatings.
Claims (1)
ルキルエステルと炭素数２〜６の直鎖型アルキレングリ
コールが５０モル％以上を占めるモノマーから得られる
ポリエステル重合体からなり、 ２００℃以下の融点を
有し、軟化温度Ｔｉ が１５０℃であり、酸価が２０ｍ
ｇ ＫＯＨ／ｇ以下であることを特徴とする結晶性トナ
ー用ポリエステル樹脂。Claim 1: A polyester polymer obtained from monomers in which terephthalic acid and/or its lower alkyl ester and linear alkylene glycol having 2 to 6 carbon atoms account for 50 mol% or more, and has a melting point of 200°C or less. The softening temperature Ti is 150℃, and the acid value is 20m
A polyester resin for crystalline toner, characterized in that it has a KOH/g or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00145391A JP3354577B2 (en) | 1991-01-10 | 1991-01-10 | Polyester resin for crystalline toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00145391A JP3354577B2 (en) | 1991-01-10 | 1991-01-10 | Polyester resin for crystalline toner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04239021A true JPH04239021A (en) | 1992-08-26 |
| JP3354577B2 JP3354577B2 (en) | 2002-12-09 |
Family
ID=11501869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00145391A Expired - Lifetime JP3354577B2 (en) | 1991-01-10 | 1991-01-10 | Polyester resin for crystalline toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3354577B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996002870A1 (en) * | 1994-07-13 | 1996-02-01 | Mitsubishi Rayon Co., Ltd. | Polyester resin for toner, process for producing the resin, and toner |
| WO2001063366A1 (en) * | 2000-02-24 | 2001-08-30 | Oce Printing Systems Gmbh | Toner mixture and process for preparing the same |
| US6500594B2 (en) | 2000-12-12 | 2002-12-31 | Fuji Xerox Co., Ltd. | Electrophotographic developer and process for forming image |
| US6582869B2 (en) | 2000-06-28 | 2003-06-24 | Fuji Xerox Co., Ltd. | Electrophotographic toner, method of manufacturing the same, electrophotographic developer, and image forming method |
| JP2005025144A (en) * | 2002-07-30 | 2005-01-27 | Sekisui Chem Co Ltd | Resin composition for toner, and toner |
| US6864029B2 (en) | 2001-12-04 | 2005-03-08 | Fuji Xerox Co., Ltd. | Electrophotographic toner, manufacture of the same, electrostatic latent image developer, and image forming method |
| US7410741B2 (en) | 2005-02-28 | 2008-08-12 | Fuji Xerox Co., Ltd | Toner for electrophotography and developer for electrophotography, as well as image forming method |
| US7745085B2 (en) | 2006-07-28 | 2010-06-29 | Fuji Xerox Co., Ltd. | Toner for developing electrostatic latent image and method of manufacturing same, electrostatic latent image developer, cartridge, and image forming apparatus |
| US7867683B2 (en) | 2006-10-04 | 2011-01-11 | Fuji Xerox Co., Ltd. | Toner, method of producing the same, developer, and image forming apparatus |
| WO2014168252A1 (en) * | 2013-04-09 | 2014-10-16 | Canon Kabushiki Kaisha | Resin for toner and toner |
| WO2014168251A1 (en) * | 2013-04-09 | 2014-10-16 | Canon Kabushiki Kaisha | Resin for toner and toner |
| CN105102502A (en) * | 2013-04-09 | 2015-11-25 | 佳能株式会社 | Toner resin and toner |
-
1991
- 1991-01-10 JP JP00145391A patent/JP3354577B2/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6103438A (en) * | 1994-03-14 | 2000-08-15 | Mitsubishi Rayon Company Ltd. | Polyester resin for toner, process for its production and toner |
| WO1996002870A1 (en) * | 1994-07-13 | 1996-02-01 | Mitsubishi Rayon Co., Ltd. | Polyester resin for toner, process for producing the resin, and toner |
| WO2001063366A1 (en) * | 2000-02-24 | 2001-08-30 | Oce Printing Systems Gmbh | Toner mixture and process for preparing the same |
| US6582869B2 (en) | 2000-06-28 | 2003-06-24 | Fuji Xerox Co., Ltd. | Electrophotographic toner, method of manufacturing the same, electrophotographic developer, and image forming method |
| US6500594B2 (en) | 2000-12-12 | 2002-12-31 | Fuji Xerox Co., Ltd. | Electrophotographic developer and process for forming image |
| US6864029B2 (en) | 2001-12-04 | 2005-03-08 | Fuji Xerox Co., Ltd. | Electrophotographic toner, manufacture of the same, electrostatic latent image developer, and image forming method |
| JP2005025144A (en) * | 2002-07-30 | 2005-01-27 | Sekisui Chem Co Ltd | Resin composition for toner, and toner |
| US7410741B2 (en) | 2005-02-28 | 2008-08-12 | Fuji Xerox Co., Ltd | Toner for electrophotography and developer for electrophotography, as well as image forming method |
| US7745085B2 (en) | 2006-07-28 | 2010-06-29 | Fuji Xerox Co., Ltd. | Toner for developing electrostatic latent image and method of manufacturing same, electrostatic latent image developer, cartridge, and image forming apparatus |
| US7867683B2 (en) | 2006-10-04 | 2011-01-11 | Fuji Xerox Co., Ltd. | Toner, method of producing the same, developer, and image forming apparatus |
| WO2014168252A1 (en) * | 2013-04-09 | 2014-10-16 | Canon Kabushiki Kaisha | Resin for toner and toner |
| WO2014168251A1 (en) * | 2013-04-09 | 2014-10-16 | Canon Kabushiki Kaisha | Resin for toner and toner |
| CN105102502A (en) * | 2013-04-09 | 2015-11-25 | 佳能株式会社 | Toner resin and toner |
| CN105121502A (en) * | 2013-04-09 | 2015-12-02 | 佳能株式会社 | Resin for toner and toner |
| US20150362853A1 (en) * | 2013-04-09 | 2015-12-17 | Canon Kabushiki Kaisha | Resin for toner and toner |
| US9540483B2 (en) | 2013-04-09 | 2017-01-10 | Canon Kabushiki Kaisha | Resin for toner and toner |
| US9696644B2 (en) | 2013-04-09 | 2017-07-04 | Canon Kabushiki Kaisha | Resin for toner and toner |
| CN105121501B (en) * | 2013-04-09 | 2018-01-26 | 佳能株式会社 | Resin for toner and toner |
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|---|---|
| JP3354577B2 (en) | 2002-12-09 |
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