JP4557897B2 - Binder resin for toner - Google Patents
Binder resin for toner Download PDFInfo
- Publication number
- JP4557897B2 JP4557897B2 JP2006007617A JP2006007617A JP4557897B2 JP 4557897 B2 JP4557897 B2 JP 4557897B2 JP 2006007617 A JP2006007617 A JP 2006007617A JP 2006007617 A JP2006007617 A JP 2006007617A JP 4557897 B2 JP4557897 B2 JP 4557897B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- toner
- binder resin
- glass transition
- raw material
- 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.)
- Active
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- 229920005989 resin Polymers 0.000 title claims description 253
- 239000011347 resin Substances 0.000 title claims description 253
- 239000011230 binding agent Substances 0.000 title claims description 72
- 239000000178 monomer Substances 0.000 claims description 73
- 239000002994 raw material Substances 0.000 claims description 53
- 230000009477 glass transition Effects 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 238000012644 addition polymerization Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 238000012643 polycondensation polymerization Methods 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims 1
- -1 carboxylic acid compound Chemical class 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000001993 wax Substances 0.000 description 13
- 238000010298 pulverizing process Methods 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- 230000005291 magnetic effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 239000003054 catalyst Substances 0.000 description 8
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- 125000002947 alkylene group Chemical group 0.000 description 6
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- 125000000217 alkyl group Chemical group 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
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- 238000004898 kneading Methods 0.000 description 4
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- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000006082 mold release agent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012188 paraffin wax Substances 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
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
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- 239000000843 powder Substances 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
- 150000003839 salts Chemical class 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
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- 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 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
- 239000003607 modifier Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- LATKICLYWYUXCN-UHFFFAOYSA-N naphthalene-1,3,6-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 LATKICLYWYUXCN-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられるトナー用結着樹脂及び該結着樹脂を含有した電子写真用トナーに関する。 The present invention relates to a binder resin for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrophotographic toner containing the binder resin.
近年、装置の高速化、小型化等の要求に対し、より低温定着可能なトナー用結着樹脂が望まれている。トナー用結着樹脂としてはビニル系樹脂、ポリエステル系樹脂が汎用されているが、低温定着性の観点からは、ポリエステル系樹脂が好ましいとされている。低温定着性の改善には、樹脂の軟化点やガラス転移点の低下が有効であることが知られているが、反面、耐オフセット性や、耐ブロッキング性等が低下する。そこで、低軟化点の樹脂と高軟化点の樹脂との併用により、これらの性能の両立が図られている。しかし、同一種の樹脂の併用では、樹脂同士が相溶するため前記性能の両立が困難であり、また樹脂のガラス転移点も低くても50℃程度である。 In recent years, there has been a demand for a binder resin for toner that can be fixed at a lower temperature in response to demands for speeding up and downsizing of the apparatus. As the binder resin for toner, vinyl resins and polyester resins are widely used. From the viewpoint of low-temperature fixability, polyester resins are preferred. In order to improve the low-temperature fixability, it is known that lowering of the softening point and glass transition point of the resin is effective, but on the other hand, offset resistance, blocking resistance and the like are lowered. Therefore, the combined use of a low softening point resin and a high softening point resin achieves both of these performances. However, when the same type of resin is used in combination, the resins are compatible with each other, making it difficult to achieve both of the above performances, and the glass transition point of the resin is about 50 ° C. at the lowest.
これを改善し、より低軟化点、低ガラス転移点の樹脂を使いこなすため、非相溶の樹脂をカプセル化する（特許文献１参照）、ドメイン−マトリックス構造を有する樹脂組成物とする（特許文献２参照）、縮重合系樹脂に付加重合系樹脂が微分散している結着樹脂（特許文献３参照）等が検討されている。
しかし、前記の如く、ガラス転移点を低くすると耐ブロッキング性等が低下する傾向がある。また、縮重合系樹脂に付加重合系樹脂が微分散している結着樹脂においては、耐ブロッキング性は改良されるが、粉砕性が悪化し、樹脂やトナーの生産性を低下させる原因となりやすい。 However, as described above, when the glass transition point is lowered, the blocking resistance and the like tend to be lowered. In addition, in the binder resin in which the addition polymerization resin is finely dispersed in the condensation polymerization resin, the anti-blocking property is improved, but the pulverization property is deteriorated and the productivity of the resin and toner is likely to be lowered. .
本発明の課題は、粉砕性を損なうことなく、優れた低温定着性を有するトナー用結着樹脂及び該結着樹脂を含有した電子写真用トナーを提供することにある。 An object of the present invention is to provide a binder resin for toner having excellent low-temperature fixability without impairing grindability, and an electrophotographic toner containing the binder resin.
本発明は、
〔１〕 連続相を形成する縮重合系樹脂(樹脂ａ)と分散相を形成する付加重合系樹脂(樹脂ｂ)とからなるトナー用結着樹脂であって、樹脂ｂのガラス転移点が-30〜35℃であり、45〜65℃に結着樹脂のガラス転移点を有し、35℃以下に結着樹脂のガラス転移点を有していないトナー用結着樹脂、並びに
〔２〕 前記トナー用結着樹脂を含有してなる電子写真用トナー
に関する。
The present invention
[1] A binder resin for toner composed of a condensation polymerization resin (resin a) that forms a continuous phase and an addition polymerization resin (resin b) that forms a dispersed phase, and the glass transition point of the resin b is − A binder resin for toner having a glass transition point of the binder resin at 30 to 35 ° C., having a glass transition point of 45 to 65 ° C., and not having a glass transition point of the binder resin at 35 ° C. or lower, and [2] The present invention relates to an electrophotographic toner containing a binder resin for toner.
本発明のトナー用結着樹脂及び該結着樹脂を含有した電子写真用トナーは、粉砕性及び低温定着性のいずれにも優れているという効果を奏するものである。 The binder resin for toner of the present invention and the electrophotographic toner containing the binder resin exhibit an effect that both the pulverization property and the low-temperature fixability are excellent.
本発明のトナー用結着樹脂は、連続相を形成する縮重合系樹脂（以下、樹脂ａともいう）と分散相を形成する付加重合系樹脂（以下、樹脂ｂともいう）とからなり、樹脂ｂのガラス転移点とかかる樹脂ｂを有する結着樹脂自身が、特定の温度範囲にガラス転移点を有することを特徴とするものである。これにより、粉砕性を損なうことなく優れた低温定着性が発揮される。 The binder resin for toner of the present invention comprises a condensation polymerization resin (hereinafter also referred to as resin a) that forms a continuous phase and an addition polymerization resin (hereinafter also referred to as resin b) that forms a dispersed phase. The glass transition point of b and the binder resin itself having the resin b have a glass transition point in a specific temperature range. Thereby, excellent low-temperature fixability is exhibited without impairing the grindability.
本発明の結着樹脂の粉砕性が改善される理由については、従来の縮重合系樹脂と付加重合系樹脂とからなる結着樹脂は、縮重合系樹脂のガラス転移点及び付加重合系樹脂のガラス転移点にそれぞれ帰属される２つのガラス転移点を有しているのに対して、本発明の結着樹脂は、縮重合系樹脂のガラス転移点と付加重合系樹脂のガラス転移点の平均近傍に少なくとも１つのガラス転移点、即ち45〜65℃、好ましくは47〜60℃、より好ましくは50〜55℃のガラス転移点を有していることから、両樹脂を１種の樹脂と見なしうるほど付加重合系樹脂が縮重合系樹脂に極めて微細に分散していることがその一因と考えられる。従って、付加重合系樹脂の分散性の観点から、本発明の結着樹脂は、付加重合系樹脂に帰属するガラス転移点、すなわち、35℃以下にガラス転移点を有しない結着樹脂であり、結着樹脂は単一のガラス転移点を有し、該ガラス転移点は前記温度範囲に存在することが好ましい。樹脂ａと樹脂ｂのガラス転移点が平均化され、両樹脂を１種の樹脂と見なしうるほど、樹脂ｂの分散性を高める方法としては、後述の両反応性モノマーを多めに使用する方法や、結着樹脂の製造過程において、付加重合反応後、高温で反応させる方法等が挙げられるが、ガラス転移点調整等の観点から、結着樹脂の製造過程において、付加重合反応後、高温で反応させる方法が好ましい。 The reason why the pulverizability of the binder resin of the present invention is improved is that the conventional binder resin composed of the condensation polymerization resin and the addition polymerization resin is the glass transition point of the condensation polymerization resin and the addition polymerization resin. The binder resin of the present invention has an average of the glass transition point of the condensation polymerization resin and the glass transition point of the addition polymerization resin, whereas it has two glass transition points respectively assigned to the glass transition point. Since both have at least one glass transition point in the vicinity, that is, 45 to 65 ° C., preferably 47 to 60 ° C., more preferably 50 to 55 ° C., both resins are regarded as one kind of resin. It is considered that the addition polymerization resin is very finely dispersed in the condensation polymerization resin. Therefore, from the viewpoint of the dispersibility of the addition polymerization resin, the binder resin of the present invention is a glass transition point belonging to the addition polymerization resin, that is, a binder resin having no glass transition point at 35 ° C. or lower. The binder resin has a single glass transition point, and the glass transition point is preferably in the temperature range. As a method of increasing the dispersibility of the resin b so that the glass transition points of the resin a and the resin b are averaged and both resins can be regarded as one kind of resin, a method using a large amount of both reactive monomers described later, In the binder resin production process, there may be mentioned a method of reacting at a high temperature after the addition polymerization reaction. From the viewpoint of adjusting the glass transition point, etc., in the binder resin production process, the reaction is carried out at a high temperature after the addition polymerization reaction. The method of making it preferable is.
また、樹脂ｂのガラス転移点は、-30〜35℃と低く、好ましくは-20〜30℃、より好ましくは-10〜25℃、さらに好ましくは0〜25℃である。本発明の結着樹脂は、ガラス転移点の低い樹脂ｂが微細に分散しているため、樹脂ａ部のガラス転移点が高いにもかかわらず、樹脂全体としては低いガラス転移点を維持することができている。なお、樹脂ｂのガラス転移点は、原料モノマー種とその比率等を考慮し、公知の方法により調整することができる。例えば、「Polymer Handbook」(INTERSCIENCE社出版)を参考に、樹脂のガラス転移点を高くする原料モノマーとして、スチレン、メタクリル酸メチル等を、樹脂のガラス転移点を低くする原料モノマーとしてアクリル酸ブチル、アクリル酸２−エチル等を適宜用いることができる。 The glass transition point of the resin b is as low as -30 to 35 ° C, preferably -20 to 30 ° C, more preferably -10 to 25 ° C, and still more preferably 0 to 25 ° C. In the binder resin of the present invention, since the resin b having a low glass transition point is finely dispersed, the glass transition point of the resin a part is high, but the low glass transition point is maintained as a whole resin. Is done. The glass transition point of the resin b can be adjusted by a known method in consideration of the raw material monomer species and the ratio thereof. For example, referring to `` Polymer Handbook '' (published by INTERSCIENCE), styrene, methyl methacrylate, etc. as raw material monomers that increase the glass transition point of the resin, butyl acrylate as raw material monomers that lower the glass transition point of the resin, 2-ethyl acrylate or the like can be used as appropriate.
本発明のトナー用結着樹脂は、付加重合系樹脂の分散性の観点から、樹脂断面における直径0.5μｍ以下の分散相が、分散相の断面積全体の90％以上が好ましく、95％以上がより好ましく、98％以上がさらに好ましい。ここで、樹脂断面における直径とは、断面において観測される分散相の分散粒径を表し、該粒子の長径と短径との平均値として求められる。ここで、分散相の直径及び分散相の面積比は、直径約0.2mmの樹脂をミクロトームで100〜300nmの厚さにカットし、得られた薄片を透過型走査電子顕微鏡(例えば、JEOL(日本電子(株))製、「JEM-2000」)で観測し、周知の方法で画像解析することにより測定することができる。 In the binder resin for toner of the present invention, from the viewpoint of dispersibility of the addition polymerization resin, the dispersed phase having a diameter of 0.5 μm or less in the resin cross section is preferably 90% or more of the entire cross-sectional area of the dispersed phase, and 95% or more. More preferred is 98% or more. Here, the diameter in the resin cross section represents the dispersed particle diameter of the dispersed phase observed in the cross section, and is obtained as an average value of the major axis and the minor axis of the particle. Here, the diameter of the dispersed phase and the area ratio of the dispersed phase were determined by cutting a resin having a diameter of about 0.2 mm into a thickness of 100 to 300 nm with a microtome, and then obtaining the obtained flakes by a transmission scanning electron microscope (for example, JEOL (Japan It can be measured by “JEM-2000” (manufactured by Electronics Co., Ltd.) and image analysis by a well-known method.
樹脂ａと樹脂ｂとからなる本発明の結着樹脂は、それぞれの樹脂を必要に応じて開始剤等の存在下に溶融混練する、それぞれの樹脂を溶剤に溶解させ混合する、それぞれの樹脂の原料モノマー混合物を重合して得る等の、いずれの方法により製造されたものでもよいが、好ましくは、樹脂ａの原料モノマー及び樹脂ｂの原料モノマーを用いて、縮重合反応と付加重合反応とを行って得られる樹脂（特開平7-98518号公報）である。 The binder resin of the present invention comprising the resin a and the resin b is prepared by melt-kneading each resin in the presence of an initiator or the like, if necessary, dissolving and mixing each resin in a solvent. Although it may be produced by any method such as polymerization of a raw material monomer mixture, preferably, a polycondensation reaction and an addition polymerization reaction are performed using the raw material monomer of resin a and the raw material monomer of resin b. This is a resin obtained by performing the method (Japanese Patent Laid-Open No. 7-98518).
樹脂ａとしては、ポリエステル、ポリエステル−ポリアミド及びポリアミドからなる群より選ばれた少なくとも1種が好ましく、ポリエステルがより好ましい。 The resin a is preferably at least one selected from the group consisting of polyester, polyester-polyamide and polyamide, and more preferably polyester.
ポリエステルの原料モノマーとしては、2価以上のアルコールからなるアルコール成分と、2価以上のカルボン酸化合物からなるカルボン酸成分とが用いられる。 As a raw material monomer for polyester, an alcohol component composed of a divalent or higher alcohol and a carboxylic acid component composed of a divalent or higher carboxylic acid compound are used.
2価のアルコールとしては、ポリオキシプロピレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシエチレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン等の、式(I)： Examples of the dihydric alcohol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, (I):
（式中、ＲＯはアルキレンオキサイドであり、Ｒは炭素数２又は３のアルキレン基、ｘ及びｙはアルキレンオキサイドの平均付加モル数を示す正の数を示し、ｘとｙの和は1〜16、好ましくは1.5〜5.0である）
で表されるビスフェノールＡのアルキレンオキサイド付加物等の芳香族ジオール；エチレングリコール、1,2-プロピレングリコール、1,4-ブタンジオール、ネオペンチルグリコール、ポリエチレングリコール、ポリプロピレングリコール等の脂肪族ジオール；水素添加ビスフェノールＡ等が挙げられる。
(In the formula, RO is an alkylene oxide, R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers indicating the average number of moles of alkylene oxide added, and the sum of x and y is 1-16. (Preferably 1.5 to 5.0)
Aromatic diols such as alkylene oxide adducts of bisphenol A represented by: aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol; hydrogen Additive bisphenol A etc. are mentioned.
アルコール成分としては、式(I)で表されるビスフェノールＡのアルキレンオキサイド付加物が好ましい。ビスフェノールAのアルキレンオキサイド付加物の含有量は、アルコール成分中、50モル％以上が好ましく、80モル％以上がより好ましく、100モル％がさらに好ましい。 As the alcohol component, an alkylene oxide adduct of bisphenol A represented by the formula (I) is preferable. The content of the alkylene oxide adduct of bisphenol A is preferably 50 mol% or more, more preferably 80 mol% or more, and further preferably 100 mol% in the alcohol component.
3価以上の多価アルコールとしては、例えばソルビトール、ペンタエリスリトール、グリセリン、トリメチロールプロパン等が挙げられる。 Examples of the trihydric or higher polyhydric alcohol include sorbitol, pentaerythritol, glycerin, trimethylolpropane and the like.
また、2価のカルボン酸化合物としては、フタル酸、イソフタル酸、テレフタル酸等の芳香族ジカルボン酸；シュウ酸、マロン酸、マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸、コハク酸、アジピン酸、ドデセニルコハク酸、オクチルコハク酸等の炭素数1〜20のアルキル基又は炭素数2〜20、好ましくは炭素数8〜16のアルケニル基で置換されたコハク酸等の脂肪族ジカルボン酸；それらの酸の無水物及びそれらの酸のアルキル(炭素数1〜3)エステル等が挙げられる。 Divalent carboxylic acid compounds include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, Aliphatic dicarboxylic acids such as succinic acid substituted with alkyl groups having 1 to 20 carbon atoms such as adipic acid, dodecenyl succinic acid, octyl succinic acid or the like, or alkenyl groups having 2 to 20 carbon atoms, preferably 8 to 16 carbon atoms; And anhydrides of these acids and alkyl (C1-3) esters of these acids.
これらの中では、テレフタル酸、イソフタル酸、アルケニルコハク酸、アジピン酸、フマル酸及びマレイン酸が好ましい。これらの好適な2価のジカルボン酸化合物の総含有量は、2価のカルボン酸化合物中、50モル％以上が好ましく、80モル％以上がより好ましく、100モル％がさらに好ましい。 Among these, terephthalic acid, isophthalic acid, alkenyl succinic acid, adipic acid, fumaric acid and maleic acid are preferable. The total content of these suitable divalent dicarboxylic acid compounds is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 100 mol% in the divalent carboxylic acid compound.
３価以上の多価カルボン酸化合物としては、例えば1,2,4-ベンゼントリカルボン酸(トリメリット酸)、2,5,7-ナフタレントリカルボン酸、ピロメリット酸及びこれらの酸無水物、低級アルキル(炭素数1〜3)エステル等が挙げられ、これらの中ではトリメリット酸が好ましい。 Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides thereof, and lower alkyls. (C1-C3) ester etc. are mentioned, Among these, trimellitic acid is preferable.
3価以上の多価カルボン酸化合物の含有量は、カルボン酸成分中、5〜50モル％が好ましく、10〜45モル％がより好ましい。 The content of the trivalent or higher polyvalent carboxylic acid compound is preferably 5 to 50 mol%, more preferably 10 to 45 mol% in the carboxylic acid component.
さらに、分子量調整等の観点から、1価のアルコールや1価のカルボン酸化合物が、アルコール成分及び／又はカルボン酸成分に、本発明の効果を損なわない範囲で適宜含有されていてもよい。 Furthermore, from the viewpoint of molecular weight adjustment and the like, a monovalent alcohol and a monovalent carboxylic acid compound may be appropriately contained in the alcohol component and / or carboxylic acid component as long as the effects of the present invention are not impaired.
また、ポリエステル−ポリアミド又はポリアミド中のアミド成分を形成する原料モノマーとしては、例えばエチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、イミノビスプロピルアミン、フェニレンジアミン、キシリレンジアミン、トリエチレンテトラミン等のポリアミン、６−アミノカプロン酸、ε−カプロラクタム等のアミノカルボン酸類、プロパノールアミン等のアミノアルコール等が挙げられ、これらの中ではヘキサメチレンジアミン及びε−カプロラクタムが好ましい。 Examples of the raw material monomer for forming an amide component in polyester-polyamide or polyamide include polyamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, iminobispropylamine, phenylenediamine, xylylenediamine, and triethylenetetramine. , Aminocarboxylic acids such as 6-aminocaproic acid and ε-caprolactam, and aminoalcohols such as propanolamine, among which hexamethylenediamine and ε-caprolactam are preferable.
樹脂ａのガラス転移点は、粉砕性の観点から、50〜80℃が好ましく、55〜75℃がより好ましく、60〜70℃がさらに好ましい。樹脂ａのガラス転移点は、原料モノマー種とその比率、触媒種、反応条件等により、容易に調整することができる。また、樹脂ａのガラス転移点が前記範囲である場合、本発明の結着樹脂のガラス転移点は、低温定着性及び粉砕性の観点から、前記温度範囲であり、かつ樹脂ａのガラス転移点以下であることが好ましい。 The glass transition point of the resin a is preferably 50 to 80 ° C., more preferably 55 to 75 ° C., and further preferably 60 to 70 ° C. from the viewpoint of grindability. The glass transition point of the resin a can be easily adjusted by the raw material monomer species and the ratio thereof, the catalyst species, the reaction conditions, and the like. When the glass transition point of the resin a is in the above range, the glass transition point of the binder resin of the present invention is the above temperature range from the viewpoint of low temperature fixability and grindability, and the glass transition point of the resin a. The following is preferable.
樹脂ｂは、ラジカル重合反応により得られるビニル系樹脂が好ましい。 The resin b is preferably a vinyl resin obtained by radical polymerization reaction.
ビニル系樹脂の原料モノマーとしては、スチレン、α−メチルスチレン等のスチレン化合物；エチレン、プロピレン等のエチレン性不飽和モノオレフィン類；ブタジエン等のジオレフィン類；塩化ビニル等のハロビニル類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；(メタ)アクリル酸のアルキル(炭素数1〜18)エステル、(メタ)アクリル酸ジメチルアミノエチル等のエチレン性モノカルボン酸のエステル；ビニルメチルエーテル等のビニルエーテル類；ビニリデンクロリド等のビニリデンハロゲン化物；Ｎ−ビニルピロリドン等のＮ−ビニル化合物類等が挙げられ、反応性、粉砕性及び帯電安定性の観点から、スチレン、アクリル酸ブチル、アクリル酸２−エチルヘキシル及びメタクリル酸メチルが好ましく、スチレン及び／又は（メタ）アクリル酸のアルキルエステルが、ビニル系樹脂の原料モノマー中、50重量％以上、好ましくは80〜100重量％含有されていることがより好ましい。 Examples of the raw material monomer for the vinyl resin include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate; Vinyl esters such as vinyl propionate; alkyl (1-18) esters of (meth) acrylic acid, esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone, and the like. From the viewpoint of reactivity, grindability and charge stability, styrene, butyl acrylate, 2-ethylhexyl acrylate and Methyl methacrylate is preferred, styrene and / or Meth) alkyl esters of acrylic acid, a raw material monomer in the vinyl resin, 50 wt% or more, and more preferably preferably is contained 80 to 100 wt%.
なお、ビニル系樹脂の原料モノマーを重合させる際には、重合開始剤、架橋剤等を必要に応じて使用してもよい。 In addition, when polymerizing the raw material monomer of the vinyl resin, a polymerization initiator, a crosslinking agent, or the like may be used as necessary.
本発明の結着樹脂における樹脂ａの樹脂ｂに対する重量比（樹脂ａ／樹脂ｂ）は、低温定着性と粉砕性を両立させる観点から、50/50〜95/5が好ましく、60/40〜95/5がより好ましく、70/30〜90/10がさらに好ましい。 The weight ratio of the resin a to the resin b (resin a / resin b) in the binder resin of the present invention is preferably 50/50 to 95/5 from the viewpoint of achieving both low-temperature fixability and pulverizability, and 60/40 to 95/5 is more preferable, and 70/30 to 90/10 is more preferable.
樹脂ａの原料モノマーの樹脂ｂの原料モノマーに対する重量比（樹脂ａの原料モノマー／樹脂ｂの原料モノマー）は、樹脂ａにより連続相を形成する観点から、55/45〜95/5が好ましく、60/40〜95/5がより好ましく、70/30〜90/10がさらに好ましい。 The weight ratio of the raw material monomer of the resin a to the raw material monomer of the resin b (the raw material monomer of the resin a / the raw material monomer of the resin b) is preferably 55/45 to 95/5 from the viewpoint of forming a continuous phase with the resin a. 60/40 to 95/5 is more preferable, and 70/30 to 90/10 is more preferable.
本発明の結着樹脂は、樹脂ａの原料モノマーと樹脂ｂの原料モノマーの両方と反応するモノマー（以下、両反応性モノマーという）を構成単位として有していることが好ましい。従って、本発明において、縮重合反応と付加重合反応は、両反応性モノマーの存在下に行うことが好ましい。これにより、樹脂ａと樹脂ｂとが部分的に両反応性モノマーを介して結合し、樹脂ａ中に樹脂ｂがより微細に、かつ均一に分散した樹脂が得られる。 The binder resin of the present invention preferably has, as a structural unit, a monomer that reacts with both the raw material monomer of resin a and the raw material monomer of resin b (hereinafter referred to as a bireactive monomer). Therefore, in the present invention, the condensation polymerization reaction and the addition polymerization reaction are preferably performed in the presence of both reactive monomers. As a result, the resin a and the resin b are partially bonded via the both reactive monomers, and a resin in which the resin b is more finely and uniformly dispersed in the resin a is obtained.
両反応性モノマーは、分子内に、水酸基、カルボキシル基、エポキシ基、第１級アミノ基及び第２級アミノ基からなる群より選ばれた少なくとも１種の官能基、好ましくは水酸基及び／又はカルボキシル基、より好ましくはカルボキシル基と、エチレン性不飽和結合とを有するモノマーであることが好ましい。両反応性モノマーの具体例としては、例えば、アクリル酸、メタクリル酸、フマル酸、マレイン酸等が挙げられ、さらにこれらのヒドロキシアルキル(炭素数1〜3)エステルであってもよいが、反応性の観点から、アクリル酸、メタクリル酸及びフマル酸が好ましい。 Both reactive monomers have at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule, preferably a hydroxyl group and / or carboxyl. A monomer having a group, more preferably a carboxyl group and an ethylenically unsaturated bond is preferred. Specific examples of the both reactive monomers include, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like, and these hydroxyalkyl (1 to 3 carbon atoms) esters may be used. In view of the above, acrylic acid, methacrylic acid and fumaric acid are preferable.
本発明において、両反応性モノマーのうち、官能基を２個以上有するモノマー(ポリカルボン酸等)及びその誘導体は樹脂ａの原料モノマーとして、官能基を１個有するモノマー(モノカルボン酸等)及びその誘導体は樹脂ｂの原料モノマーとして扱う。両反応性モノマーの使用量は、両反応性モノマーを除く樹脂ａの原料モノマー100モルに対して、1〜30モルが好ましく、より樹脂ｂの分散性をさらに高める観点から、結着樹脂の製造過程において、付加重合反応後、高温で反応させる方法においては、1.5〜20モルがより好ましく、2〜10モルがさらに好ましく、付加重合反応後、温度を一定に保ちつつ両反応性モノマーを多めに使用する方法においては、4〜15モルがより好ましく、5〜10モルがさらに好ましい。 In the present invention, among the two reactive monomers, a monomer having two or more functional groups (polycarboxylic acid or the like) and a derivative thereof are used as a raw material monomer for the resin a, and a monomer having one functional group (monocarboxylic acid or the like) and The derivative is treated as a raw material monomer for the resin b. The amount of the amphoteric monomer used is preferably 1 to 30 mol with respect to 100 mol of the raw material monomer of the resin a excluding the amphoteric monomer. From the viewpoint of further increasing the dispersibility of the resin b, the binder resin is produced. In the process, in the method of reacting at a high temperature after the addition polymerization reaction, 1.5 to 20 mol is more preferable, and 2 to 10 mol is more preferable, and after the addition polymerization reaction, the amount of both reactive monomers is increased while keeping the temperature constant. In the method to be used, 4-15 mol is more preferable, and 5-10 mol is further more preferable.
本発明において、縮重合反応と付加重合反応は、同一反応容器中で行う。また、それぞれの重合反応の進行及び完結が時間的に同時である必要はなく、それぞれの反応機構に応じて反応温度及び時間を適当に選択し、反応を進行、完結させればよい。 In the present invention, the condensation polymerization reaction and the addition polymerization reaction are performed in the same reaction vessel. In addition, the progress and completion of each polymerization reaction do not need to be simultaneous in time, and the reaction temperature and time may be appropriately selected according to each reaction mechanism to advance and complete the reaction.
本発明の結着樹脂の製造方法として、具体的には、樹脂ａの原料モノマーの存在下で付加重合反応を完結させた後、反応温度を上昇させて縮重合反応を行う工程を有する方法等が挙げられ、より具体的には付加重合反応に適した温度条件下で付加重合反応と並行して縮重合反応を行う工程(Ａ)と、反応温度を前記条件下で保持して付加重合反応を完結させる工程(Ｂ)と、次いで反応温度を上昇させて、縮重合反応をさらに行う工程(Ｃ)とを有する方法が好ましい。 As a method for producing the binder resin of the present invention, specifically, a method having a step of performing a condensation polymerization reaction by raising the reaction temperature after completing the addition polymerization reaction in the presence of the raw material monomer of the resin a More specifically, the step (A) of performing a condensation polymerization reaction in parallel with the addition polymerization reaction under a temperature condition suitable for the addition polymerization reaction, and the addition polymerization reaction while maintaining the reaction temperature under the above-mentioned conditions A method comprising a step (B) for completing the step, and then a step (C) for further raising the reaction temperature and further performing a polycondensation reaction is preferred.
工程(Ａ)において、樹脂ａの原料モノマーを含有した混合物中に、樹脂ｂの原料モノマーを含有した混合物を滴下して反応させることが好ましい。 In the step (A), it is preferable that the mixture containing the raw material monomer of the resin a is dropped and reacted in the mixture containing the raw material monomer of the resin a.
ここで、付加重合反応に適した温度条件は、用いられる重合開始剤の種類にもよるが、50〜180℃の温度範囲が好ましい。また、反応温度を上昇させて縮重合反応をさらに行う際の温度範囲は、190〜270℃が好ましく、樹脂ｂの分散性をさらに高める観点から、235〜250℃がより好ましく、さらに235〜240℃がさらに好ましい。このように反応容器中で独立した２つの反応を並行して進行させる方法により２種類の樹脂が効果的に混合分散した結着樹脂を得ることができる。 Here, the temperature condition suitable for the addition polymerization reaction depends on the kind of the polymerization initiator used, but a temperature range of 50 to 180 ° C. is preferable. Further, the temperature range for further conducting the condensation polymerization reaction by raising the reaction temperature is preferably 190 to 270 ° C, more preferably 235 to 250 ° C, and further preferably 235 to 240 ° C, from the viewpoint of further improving the dispersibility of the resin b. More preferably. In this way, a binder resin in which two types of resins are effectively mixed and dispersed can be obtained by a method in which two independent reactions proceed in parallel in a reaction vessel.
本発明の結着樹脂は、離型剤を含有していてもよい。離型剤は、結着樹脂と混合して結着樹脂中に含有されていてもよいが、本発明の結着樹脂を、樹脂ａの原料モノマー及び樹脂ｂの原料モノマーを、同一反応容器中で縮重合反応と付加重合反応とを行って得る場合には、離型剤の存在下で縮重合反応と付加重合反応を行うことにより、離型剤の分散性を高めることができる。離型剤の含有量は、結着樹脂の原料モノマー100重量部に対して、0.5〜50重量部が好ましく、1.0〜40重量部がより好ましく、1.5〜30重量部がさらに好ましい。 The binder resin of the present invention may contain a release agent. The release agent may be mixed with the binder resin and contained in the binder resin, but the binder resin of the present invention is mixed with the raw material monomer of the resin a and the raw material monomer of the resin b in the same reaction vessel. When the polycondensation reaction and the addition polymerization reaction are carried out in (1), the dispersibility of the mold release agent can be enhanced by carrying out the polycondensation reaction and the addition polymerization reaction in the presence of the mold release agent. The content of the release agent is preferably 0.5 to 50 parts by weight, more preferably 1.0 to 40 parts by weight, and even more preferably 1.5 to 30 parts by weight with respect to 100 parts by weight of the raw material monomer of the binder resin.
本発明の結着樹脂に含有する離型剤としては、低分子量ポリプロピレン、低分子量ポリエチレン、低分子量ポリプロピレンポリエチレン共重合体、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックス等の脂肪族炭化水素系ワックス及びそれらの酸化物、脂肪酸アミド類、脂肪酸類、高級アルコール類、脂肪酸金属塩等が挙げられ、これらのなかでは、離型性及び安定性の観点から、脂肪族炭化水素系ワックスが好ましい。 Examples of the release agent contained in the binder resin of the present invention include low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, and These oxides, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like can be mentioned, and among these, aliphatic hydrocarbon waxes are preferable from the viewpoint of releasability and stability.
本発明のトナー用結着樹脂の軟化点は、定着性及び粉砕性の観点から、100〜160℃が好ましく、125〜150℃がより好ましく、130〜145℃がさらに好ましい。結着樹脂の軟化点は、原料モノマー組成、重合開始剤、触媒量等の調整又は反応条件の選択により容易に調整することができる。 The softening point of the binder resin for toner of the present invention is preferably from 100 to 160 ° C, more preferably from 125 to 150 ° C, and even more preferably from 130 to 145 ° C, from the viewpoints of fixability and grindability. The softening point of the binder resin can be easily adjusted by adjusting the raw material monomer composition, the polymerization initiator, the catalyst amount, etc., or selecting the reaction conditions.
さらに、本発明においては、前記トナー用結着樹脂及び着色剤を含有した電子写真用トナーを提供する。 Furthermore, the present invention provides an electrophotographic toner containing the toner binder resin and a colorant.
本発明のトナーには、結着樹脂として、低温定着性の観点から、低軟化点の樹脂と高軟化点の樹脂が併用されていることが好ましい。低軟化点の樹脂の軟化点は、低温定着性の観点から、好ましくは80〜120℃、より好ましくは85〜115℃であり、高軟化点の樹脂の軟化点は、耐オフセット性の観点から、好ましくは120℃を超えて160℃以下、より好ましくは130〜155℃である。低軟化点の樹脂と高軟化点の樹脂の軟化点の差は、20〜60℃が好ましく、30〜50℃がより好ましい。 In the toner of the present invention, a low softening point resin and a high softening point resin are preferably used in combination as a binder resin from the viewpoint of low-temperature fixability. The softening point of the low softening point resin is preferably 80 to 120 ° C., more preferably 85 to 115 ° C. from the viewpoint of low-temperature fixability, and the softening point of the high softening point resin is from the viewpoint of offset resistance. The temperature is preferably higher than 120 ° C and not higher than 160 ° C, more preferably 130 to 155 ° C. The difference in softening point between the low softening point resin and the high softening point resin is preferably 20 to 60 ° C, more preferably 30 to 50 ° C.
従って、本発明のトナー用結着樹脂の軟化点に応じて、高軟化点の樹脂又は低軟化点の樹脂が、さらに結着樹脂として含有されているのが好ましいが、いずれか一方が本発明の結着樹脂であるのが好ましく、高軟化点の樹脂が本発明の結着樹脂であることが好ましい。本発明の樹脂を高軟化点樹脂として低軟化点樹脂と併用する場合の両者の割合（本発明の樹脂／低軟化点樹脂）は95/5〜50/50が好ましく、90/10〜55/45がより好ましい。 Accordingly, it is preferable that a resin having a high softening point or a resin having a low softening point is further contained as a binder resin depending on the softening point of the binder resin for toner of the present invention. Preferably, the resin having a high softening point is the binder resin of the present invention. When the resin of the present invention is used in combination with a low softening point resin as a high softening point resin, the ratio of both (resin of the present invention / low softening point resin) is preferably 95/5 to 50/50, and 90/10 to 55 / 45 is more preferred.
本発明のトナーにおいて、本発明のトナー用結着樹脂と併用される結着樹脂は、ポリエステル、ビニル系樹脂、エポキシ樹脂、ポリカーボネート、ポリウレタン、２種以上の樹脂からなるハイブリッド樹脂等の従来トナー用結着樹脂として知られるいずれの樹脂であってもよいが、本発明のトナーでは、２種以上の樹脂からなるハイブリッド樹脂が好ましい。 In the toner of the present invention, the binder resin used in combination with the toner binder resin of the present invention is for conventional toners such as polyester, vinyl resin, epoxy resin, polycarbonate, polyurethane, and a hybrid resin composed of two or more resins. Any resin known as a binder resin may be used, but in the toner of the present invention, a hybrid resin composed of two or more kinds of resins is preferable.
着色剤としては、トナー用着色剤として用いられている染料、顔料等のすべてを使用することができ、カーボンブラック、フタロシアニンブルー、パーマネントブラウンFG、ブリリアントファーストスカーレット、ピグメントグリーンＢ、ローダミン−Ｂベース、ソルベントレッド49、ソルベントレッド146 、ソルベントブルー35、キナクリドン、カーミン６Ｂ、ジスアゾエロー等が挙げられ、これらは単独で又は２種以上を混合して用いることができ、本発明のトナーは、黒トナー、カラートナー、フルカラートナーのいずれであってもよい。着色剤の含有量は、結着樹脂100重量部に対して、1〜40重量部が好ましく、3〜10重量部がより好ましい。 As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used alone or in combination of two or more. The toner of the present invention is a black toner, color Either toner or full color toner may be used. The content of the colorant is preferably 1 to 40 parts by weight and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
本発明のトナーには、さらに、離型剤、荷電制御剤、磁性粉、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、老化防止剤、流動性向上剤、クリーニング性向上剤等の添加剤が、適宜含有されていてもよい。 The toner of the present invention further includes a release agent, a charge control agent, a magnetic powder, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, a fluidity improver, Additives such as a cleaning property improving agent may be appropriately contained.
離型剤としては、低分子量ポリプロピレン、低分子量ポリエチレン、低分子量ポリプロピレンポリエチレン共重合体、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックス等の脂肪族炭化水素系ワックス及びそれらの酸化物、カルナウバワックス、モンタンワックス、サゾールワックス及びそれらの脱酸ワックス等のエステル系ワックス、脂肪酸アミド類、脂肪酸類、高級アルコール類、脂肪酸金属塩等が挙げられ、これらのなかでは、離型性及び安定性の観点から、脂肪族炭化水素系ワックスが好ましい。 As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and their oxides, carnauba wax, Examples include ester waxes such as montan wax, sazol wax and their deoxidized wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc. Among these, from the viewpoint of releasability and stability Therefore, an aliphatic hydrocarbon wax is preferable.
離型剤の融点は、耐オフセット性及び耐久性の観点から、60〜120℃が好ましく、100〜120℃がより好ましい。 The melting point of the release agent is preferably 60 to 120 ° C, more preferably 100 to 120 ° C, from the viewpoint of offset resistance and durability.
離型剤の含有量は、結着樹脂100重量部に対して、0.5〜10重量部が好ましく、1〜5重量部がより好ましい。 The content of the release agent is preferably 0.5 to 10 parts by weight and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the binder resin.
荷電制御剤としては、ニグロシン染料、３級アミンを側鎖として含有するトリフェニルメタン系染料、４級アンモニウム塩化合物、ポリアミン樹脂、イミダゾール誘導体等の正帯電性荷電制御剤及び含金属アゾ染料、銅フタロシアニン染料、サリチル酸のアルキル誘導体の金属錯体、ベンジル酸のホウ素錯体等の負帯電性荷電制御剤が挙げられる。 Charge control agents include nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, polyamine resins, imidazole derivatives and other positively chargeable charge control agents and metal-containing azo dyes, copper Examples include negatively chargeable charge control agents such as phthalocyanine dyes, metal complexes of alkyl derivatives of salicylic acid, and boron complexes of benzylic acid.
荷電制御剤の含有量は、結着樹脂100重量部に対して、0.1〜5重量部が好ましく、0.5〜2重量部がより好ましい。 The content of the charge control agent is preferably 0.1 to 5 parts by weight and more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the binder resin.
磁性粉としては、コバルト、鉄、ニッケル等の強磁性体、コバルト、鉄、ニッケル、アルミニウム、鉛、マグネシウム、亜鉛、マンガン等の金属の合金、Fe3O4、γ-Fe3O4、コバルト添加酸化鉄等の金属酸化物、Mn-Znフェライト、Ni-Znフェライト等の各種フェライト、マグネタイト、ヘマタイト等が挙げられる。さらに、それらの表面がシランカップリング剤、チタネートシランカップリング剤等の表面処理剤で処理されたもの、又はポリマーコーティングされたものであってもよい。 Magnetic powders include ferromagnetic materials such as cobalt, iron and nickel, alloys of metals such as cobalt, iron, nickel, aluminum, lead, magnesium, zinc and manganese, Fe 3 O 4 , γ-Fe 3 O 4 , cobalt Examples thereof include metal oxides such as added iron oxide, various ferrites such as Mn-Zn ferrite and Ni-Zn ferrite, magnetite and hematite. Furthermore, those surfaces may be treated with a surface treatment agent such as a silane coupling agent or a titanate silane coupling agent, or may be polymer-coated.
磁性粉の一次平均粒子径は、分散性の観点から、0.05〜0.5μｍが好ましく、0.1〜0.3μｍがより好ましい。 The primary average particle size of the magnetic powder is preferably 0.05 to 0.5 μm, more preferably 0.1 to 0.3 μm, from the viewpoint of dispersibility.
磁性トナーの場合、磁性粉の含有量は、トナー中、30重量％以上である好ましく、30〜60重量％がより好ましい。なお、磁性粉は黒色着色剤として含有されていてもよい。 In the case of a magnetic toner, the content of magnetic powder is preferably 30% by weight or more, more preferably 30 to 60% by weight in the toner. The magnetic powder may be contained as a black colorant.
トナーの製造方法は、本発明の結着樹脂を原料の一つとする混練粉砕法、転相乳化法、乳化分散法、懸濁重合法等の従来より公知のいずれの方法であってもよいが、製造が容易なことから、混練粉砕法が好ましい。例えば、混練粉砕法による粉砕トナーの場合、結着樹脂、着色剤等をヘンシェルミキサー等の混合機で均一に混合した後、密閉式ニーダー又は１軸もしくは２軸の押出機等で溶融混練し、冷却、粉砕、分級して製造することができる。トナーの体積中位粒径(Ｄ50)は3〜15μｍが好ましく、4〜8μｍがより好ましい。なお、本明細書において、体積中位粒径（Ｄ50）とは、体積分率で計算した累積体積頻度が粒径の小さい方から計算して50％になる粒径を意味する。 The method for producing the toner may be any conventionally known method such as a kneading and pulverization method using the binder resin of the present invention as one of the raw materials, a phase inversion emulsification method, an emulsion dispersion method, and a suspension polymerization method. The kneading and pulverizing method is preferable because of easy production. For example, in the case of a pulverized toner by a kneading and pulverizing method, a binder resin, a colorant, and the like are uniformly mixed with a mixer such as a Henschel mixer, and then melt-kneaded with a hermetic kneader or a uniaxial or biaxial extruder. It can be produced by cooling, pulverization and classification. The volume median particle size (D 50 ) of the toner is preferably 3 to 15 μm, more preferably 4 to 8 μm. In the present specification, the volume-median particle size (D50) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.
本発明により得られた結着樹脂を含有したトナーは、一成分現像用トナー及び二成分現像用トナーのいずれにも用いることができるが、本発明のトナーは低温定着性に優れることから、低温定着性の達成が困難な磁性一成分現像用トナーであるのが好ましい。 The toner containing the binder resin obtained according to the present invention can be used for both one-component developing toner and two-component developing toner. However, since the toner of the present invention has excellent low-temperature fixability, The toner is preferably a magnetic one-component developing toner that is difficult to achieve the fixing property.
〔樹脂の軟化点〕
フローテスター（島津製作所、CFT-500D）を用い、1gの試料を昇温速度6℃/分で加熱しながら、プランジャーにより1.96MPaの荷重を与え、直径1mm、長さ1mmのノズルから押出した。温度に対し、フローテスターのプランジャー降下量をプロットし、試料の半量が流出した温度を軟化点とする。
[Softening point of resin]
Using a flow tester (Shimadzu Corp., CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C / min, and a 1.96 MPa load was applied by a plunger, and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.
〔樹脂のガラス転移点(Tg)〕
示差走査熱量計(Perkin Elmer社製 Pyris6DSC)を用いて測定を行った。まず、試料温度を-70℃に設定30分間放置後、200℃まで昇温速度10℃／分で測定し、融解熱の最大ピーク温度以下のベースラインの延長線と、ピークの立ち上がり部分からピークの頂点まで最大傾斜を示す接線との交点の温度をガラス転移点とする。ガラス転移点のピークが2つ以上ある場合は、付加重合系樹脂についてその原料モノマーの組成からFox法により算出されるガラス転移点をピークの帰属判断の補助として使用することができる。
(Glass transition point of resin (Tg))
Measurement was performed using a differential scanning calorimeter (Pyris6DSC manufactured by Perkin Elmer). First, set the sample temperature to -70 ° C and let stand for 30 minutes, then measure the temperature up to 200 ° C at a heating rate of 10 ° C / min. Peaks from the baseline extension below the maximum peak temperature of the heat of fusion and from the peak rising part The temperature at the point of intersection with the tangent showing the maximum inclination to the top of the glass transition point is taken as the glass transition point. In the case where there are two or more peaks at the glass transition point, the glass transition point calculated by the Fox method from the composition of the raw material monomers of the addition polymerization resin can be used as an aid in determining the peak assignment.
〔ワックスの融点〕
示差走査熱量計（セイコー電子工業社製、DSC210）を用いて200℃まで昇温し、その温度から降温速度10℃／分で0℃まで冷却したサンプルを昇温速度10℃／分で測定し、融解熱の最大ピーク温度を融点とする。
[Melting point of wax]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the sample was heated to 200 ° C and then cooled to 0 ° C at a temperature decrease rate of 10 ° C / min. The maximum peak temperature of heat of fusion is the melting point.
〔トナーの体積中位粒径（Ｄ50）〕
測定機：コールターマルチサイザーII（ベックマンコールター社製）
アパチャー径：100μｍ
測定粒径範囲：2〜60μｍ
解析ソフト：コールターマルチサイザーアキュコンプ バージョン 1.19（ベックマンコー
ルター社製）
電解液：アイソトンII（ベックマンコールター社製）
分散液：エマルゲン109Ｐ（花王社製、ポリオキシエチレンラウリルエーテル、HLB：13.6）5％電解液
分散条件：分散液5mlに測定試料10mgを添加し、超音波分散機にて1分間分散させ、その後、電解液25mlを添加し、さらに、超音波分散機にて1分間分散させる。
測定条件：ビーカーに電解液100mlと分散液を加え、3万個の粒子の粒径を20秒で測定できる濃度で、3万個の粒子を測定し、その粒度分布から体積中位粒径（Ｄ50）を求める。
[Volume-median particle diameter of toner (D 50 )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Measurement particle size range: 2-60μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of measurement sample is added to 5 ml of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 ml of the electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D 50).
樹脂製造例１
表１に示す樹脂ｂ(ビニル系樹脂)の原料モノマー及び重合開始剤を滴下ロートに入れ、樹脂ａ(ポリエステル)の原料モノマー及びエステル化触媒を窒素導入管、脱水管、攪拌器及び熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、160℃で攪拌しつつ、滴下ロートより樹脂ｂの原料モノマー及び重合開始剤の混合物を1時間かけて滴下した。160℃に保持したまま2時間付加重合反応を熟成させた後、230℃に昇温して所望の軟化点に達するまで縮重合反応させて、連続相を形成する樹脂ａと分散相を形成するｂとからなる樹脂Ａ〜Ｃを得た。
Resin production example 1
The raw material monomer and polymerization initiator of resin b (vinyl resin) shown in Table 1 are put into a dropping funnel, and the raw material monomer and esterification catalyst of resin a (polyester) are connected to a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. The mixture was placed in a 5-liter four-necked flask equipped and stirred at 160 ° C. in a nitrogen atmosphere, and the mixture of the raw material monomer of resin b and the polymerization initiator was added dropwise over 1 hour from the dropping funnel. After aging the addition polymerization reaction for 2 hours while maintaining the temperature at 160 ° C., the temperature is raised to 230 ° C. and the condensation polymerization reaction is performed until the desired softening point is reached, thereby forming a dispersed phase with the resin a that forms a continuous phase. Resins A to C consisting of b were obtained.
なお、表１中、樹脂ａのＴｇとは、樹脂ａの原料モノマーと両反応性モノマーを単独で縮重合させて得られた樹脂、即ち樹脂ａの原料モノマー、両反応性モノマー及びエステル化触媒を混合し、230℃に昇温して、所望の軟化点に達するまで縮重合反応させて得られた樹脂のガラス転移点であり、樹脂ｂのＴｇとは、原料モノマーの組成からFox法により算出されるガラス転移点である。 In Table 1, the Tg of the resin a is a resin obtained by polycondensation of the raw material monomer of the resin a and the bireactive monomer alone, that is, the raw material monomer of the resin a, the bireactive monomer, and the esterification catalyst. Is the glass transition point of the resin obtained by the condensation polymerization reaction until the desired softening point is reached. The Tg of the resin b is determined by the Fox method from the composition of the raw material monomers. This is the calculated glass transition point.
樹脂製造例２
表２に示す樹脂ｂ(ビニル系樹脂)の原料モノマー及び重合開始剤を滴下ロートに入れ、無水トリメリット酸以外の樹脂ａ(ポリエステル)の原料モノマー、ワックス及びエステル化触媒を窒素導入管、脱水管、攪拌器及び熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、160℃で攪拌しつつ、滴下ロートより樹脂ｂの原料モノマー及び重合開始剤の混合物を1時間かけて滴下した。160℃に保持したまま2時間付加重合反応を熟成させた後、235℃に昇温して4時間反応させた後、240℃にて2時間反応させた。その後、無水トリメリット酸を加え230℃にて所望の軟化点に達するまで縮重合反応させて、連続相を形成する樹脂ａと分散相を形成するｂとからなる樹脂Ｄ、Ｅを得た。
Resin production example 2
The raw material monomer of resin b (vinyl resin) and the polymerization initiator shown in Table 2 are put in a dropping funnel, and the raw material monomer of resin a (polyester) other than trimellitic anhydride, wax and esterification catalyst are introduced into a nitrogen inlet tube, dehydrated Place in a 5 liter four-necked flask equipped with a tube, stirrer, and thermocouple, stir at 160 ° C. in a nitrogen atmosphere, and stir the mixture of resin b raw material monomer and polymerization initiator from the dropping funnel over 1 hour. And dripped. After aging the addition polymerization reaction for 2 hours while maintaining the temperature at 160 ° C., the temperature was raised to 235 ° C. for 4 hours, followed by reaction at 240 ° C. for 2 hours. Thereafter, trimellitic anhydride was added and a condensation polymerization reaction was performed at 230 ° C. until a desired softening point was reached, thereby obtaining resins D and E consisting of a resin a forming a continuous phase and b forming a dispersed phase.
なお、表２中、樹脂ａのＴｇとは、樹脂ａの原料モノマーと両反応性モノマーを単独で縮重合させて得られた樹脂、即ち樹脂ａの原料モノマー、両反応性モノマー及びエステル化触媒を混合し、235℃に昇温して4時間反応させた後、240℃にて2時間反応させ、さらに、無水トリメリット酸を加え230℃にて所望の軟化点に達するまで縮重合反応させて得られた樹脂のガラス転移点であり、樹脂ｂのＴｇとは、原料モノマーの組成からFox法により算出されるガラス転移点である。 In Table 2, the Tg of the resin a is a resin obtained by polycondensation of the raw material monomer of the resin a and the bireactive monomer alone, that is, the raw material monomer of the resin a, the bireactive monomer, and the esterification catalyst. The mixture was heated to 235 ° C and allowed to react for 4 hours, then reacted at 240 ° C for 2 hours, and trimellitic anhydride was added, followed by condensation polymerization at 230 ° C until the desired softening point was reached. The Tg of the resin b is the glass transition point calculated by the Fox method from the composition of the raw material monomers.
樹脂製造例３
表２に示す樹脂ｂ(ビニル系樹脂)の原料モノマー及び重合開始剤を滴下ロートに入れ、樹脂ａ(ポリエステル)の原料モノマー、ワックス及びエステル化触媒を窒素導入管、脱水管、攪拌器及び熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、160℃で攪拌しつつ、滴下ロートより樹脂ｂの原料モノマー及び重合開始剤の混合物を1時間かけて滴下した。160℃に保持したまま2時間付加重合反応を熟成させた後、230℃に昇温して所望の軟化点に達するまで縮重合反応させて、連続相を形成する樹脂ａと分散相を形成するｂとからなる樹脂Ｆを得た。
Resin production example 3
The raw material monomer of resin b (vinyl resin) and the polymerization initiator shown in Table 2 are put into a dropping funnel, and the raw material monomer of resin a (polyester), wax and esterification catalyst are introduced into a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermoelectric device. The mixture was placed in a 5-liter four-necked flask equipped with a pair, and the mixture of the raw material monomer of resin b and the polymerization initiator was added dropwise over 1 hour from a dropping funnel while stirring at 160 ° C. in a nitrogen atmosphere. After aging the addition polymerization reaction for 2 hours while maintaining the temperature at 160 ° C., the temperature is raised to 230 ° C. and the condensation polymerization reaction is performed until the desired softening point is reached, thereby forming a dispersed phase with the resin a that forms a continuous phase. Resin F consisting of b was obtained.
なお、表２中、樹脂ａのＴｇとは、樹脂ａのＴｇとは、樹脂ａの原料モノマーと両反応性モノマーを単独で縮重合させて得られた樹脂、即ち樹脂ａの原料モノマー、両反応性モノマー及びエステル化触媒を混合し、230℃に昇温して、所望の軟化点に達するまで縮重合反応させて得られた樹脂のガラス転移点であり、樹脂ｂのＴｇとは、原料モノマーの組成からFox法により算出されるガラス転移点である。 In Table 2, the Tg of the resin a means the Tg of the resin a, a resin obtained by polycondensing the raw material monomer of the resin a and the both reactive monomers alone, that is, the raw material monomer of the resin a, both This is the glass transition point of the resin obtained by mixing the reactive monomer and the esterification catalyst, raising the temperature to 230 ° C., and allowing the condensation polymerization reaction to reach the desired softening point, and the Tg of the resin b is the raw material It is the glass transition point calculated by the Fox method from the monomer composition.
実施例１〜４、比較例１、２
表３に示す結着樹脂100重量部、磁性粉「MTS106HD」(戸田工業社製)54重量部、荷電制御剤「T-77」（保土谷化学工業社製）1.0重量部及び表３に示すワックスをヘンシェルミキサーで十分混合した後、混練部分の全長1560mm、スクリュー径42mm、バレル内径43mmの同方向回転二軸押出機を用いて溶融混練した。ロール内の加熱温度は140℃、ロール回転速度は150r/min、混合物の供給速度は20kg／時、平均滞留時間は約18秒であった。
得られた混練物を冷却ロールで圧延し、機械式粉砕し、分級して、体積中位粒径(Ｄ50)が6μｍの粉体を得た。
Examples 1 to 4, Comparative Examples 1 and 2
100 parts by weight of binder resin shown in Table 3, 54 parts by weight of magnetic powder “MTS106HD” (manufactured by Toda Kogyo Co., Ltd.), 1.0 part by weight of charge control agent “T-77” (manufactured by Hodogaya Chemical Co., Ltd.), and Table 3 After sufficiently mixing the wax with a Henschel mixer, the kneaded portion was melt kneaded using a co-rotating twin screw extruder having a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The heating temperature in the roll was 140 ° C., the roll rotation speed was 150 r / min, the feed rate of the mixture was 20 kg / hour, and the average residence time was about 18 seconds.
The obtained kneaded material was rolled with a cooling roll, mechanically pulverized, and classified to obtain a powder having a volume-median particle size (D 50 ) of 6 μm.
得られた粉体100重量部に、外添剤として疎水性シリカ「R-972」(日本アエロジル社製)1.5重量部及びチタン酸ストロンチウム「TiSr」(富士チタン社製)1重量部を添加し、ヘンシェルミキサーで混合して磁性トナーを得た。 To 100 parts by weight of the obtained powder, 1.5 parts by weight of hydrophobic silica “R-972” (manufactured by Nippon Aerosil Co., Ltd.) and 1 part by weight of strontium titanate “TiSr” (manufactured by Fuji Titanium) are added as external additives. The magnetic toner was obtained by mixing with a Henschel mixer.
実施例５
磁性粉「MTS106HD」の代わりに着色剤「ECB-301」(大日精化社製)4重量部を使用し、チタン酸ストロンチウム「TiSr」を使用しなかった以外は、実施例１と同様にして非磁性トナーを得た。
Example 5
The same procedure as in Example 1 was performed except that 4 parts by weight of the colorant “ECB-301” (manufactured by Dainichi Seika Co., Ltd.) was used instead of the magnetic powder “MTS106HD” and strontium titanate “TiSr” was not used. A non-magnetic toner was obtained.
試験例１〔粉砕性〕
ロートプレックスに3mmメッシュ(目開き：3ｍｍ)のスクリーンを装着して粉砕したトナーを、I-2型粉砕機(日本ニューマチック社)により、目的の体積中位粒径(Ｄ50)を5.5μｍに設定して、0.5Paの粉砕圧で粉砕した。粉砕速度から、以下の評価基準に従って、粉砕性を評価した。結果を表３に示す。
Test Example 1 [Crushability]
Toner pulverized with a 3 mm mesh (mesh opening: 3 mm) screen mounted on a rotochplex using an I-2 type pulverizer (Nippon Pneumatic Co., Ltd.), the target volume-median particle size (D 50 ) is 5.5 μm And was pulverized at a pulverization pressure of 0.5 Pa. From the grinding speed, grindability was evaluated according to the following evaluation criteria. The results are shown in Table 3.
〔評価基準〕
◎：5kg/hr以上の粉砕速度で、目的のトナーが得られる。
○：3kg/hr以上、5Kg/hr未満の粉砕速度で、目的のトナーが得られる。
×：3kg/hr以下の粉砕速度で、目的のトナーが得られる。又は、3kg/hr以下の粉砕速度でも、目的のトナーは得られない。
〔Evaluation criteria〕
A: The target toner can be obtained at a pulverization speed of 5 kg / hr or more.
○: The target toner can be obtained at a pulverization rate of 3 kg / hr or more and less than 5 kg / hr.
X: The target toner is obtained at a pulverization speed of 3 kg / hr or less. Alternatively, the target toner cannot be obtained even at a pulverization rate of 3 kg / hr or less.
試験例２〔低温定着性〕
実施例１〜４及び比較例１、２の磁性トナーには、磁性一成分現像装置「Laser Jet 4200」(ヒューレット・パッカード社製)を、実施例５の非磁性トナーには、非磁性一成分現像装置「AR-505」(シャープ社製)を、それぞれ用い、トナー250gを現像装置に実装して、トナー付着量が0.6mg/cm2の未定着画像(2cm×12cm)を得た。
Test Example 2 [low temperature fixability]
A magnetic one-component developing device “Laser Jet 4200” (manufactured by Hewlett-Packard) is used for the magnetic toners of Examples 1 to 4 and Comparative Examples 1 and 2, and a non-magnetic one-component is used for the non-magnetic toner of Example 5. A developing device “AR-505” (manufactured by Sharp Corporation) was used, and 250 g of toner was mounted on the developing device to obtain an unfixed image (2 cm × 12 cm) with a toner adhesion amount of 0.6 mg / cm 2 .
得られた未定着画像を、非磁性一成分現像装置「AR-505」(シャープ社製)の定着機をオフラインによる定着が可能なように改良した定着機(定着速度：200mm/sec)を用いて、定着ロールの温度を100℃から240℃へと10℃ずつ順次上昇させながら定着試験を行った。定着紙には、「CopyBond SF-70NA」(シャープ社製、75g/m2)を使用した。 Using the fixer (fixing speed: 200 mm / sec), the non-magnetic one-component developing device “AR-505” (manufactured by Sharp Corporation) was improved so that the fixer can be fixed off-line. Then, a fixing test was performed while the temperature of the fixing roll was gradually increased from 100 ° C. to 240 ° C. by 10 ° C. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m 2 ) was used.
各温度で定着させた画像に「ユニセフセロハン」(三菱鉛筆社、幅：18mm、JISZ-1522)を貼り付け、30℃に設定した上記定着機の定着ロールに通過させた後、テープを剥がし、テープ剥離後の画像の光学反射密度を反射濃度計「RD-915」(マクベス社製)を用いて測定した。予めテープを貼る前の画像についても光学反射密度を測定しておき、その値との比(テープ剥離後／テープ貼付前)が最初に80％を超える定着ロールの温度を最低定着温度とし、以下の評価基準に従って、低温定着性を評価した。結果を表３に示す。 “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18mm, JISZ-1522) was pasted on the image fixed at each temperature, passed through the fixing roll of the fixing machine set to 30 ° C., and then the tape was peeled off. The optical reflection density of the image after tape peeling was measured using a reflection densitometer “RD-915” (manufactured by Macbeth). Measure the optical reflection density of the image before applying the tape in advance, and the ratio of that value (after peeling the tape / before applying the tape) first exceeds 80% as the minimum fixing temperature. The low-temperature fixability was evaluated according to the evaluation criteria. The results are shown in Table 3.
〔評価基準〕
◎：最低定着温度が180℃未満である。
○：最低定着温度が180℃以上、200℃未満である。
×：最低定着温度が200℃以上である。
〔Evaluation criteria〕
A: The minimum fixing temperature is less than 180 ° C.
○: The minimum fixing temperature is 180 ° C. or higher and lower than 200 ° C.
X: The minimum fixing temperature is 200 ° C. or higher.
以上の結果より、実施例１〜５のトナーはいずれも、粉砕性と低温定着性の両立が達成されていることが分かる。これに対し、ベンゼン環骨格を有せず軟らかいモノマーであるアジピン酸を使用することにより樹脂ａのガラス転移点を下げている比較例１では粉砕性が欠けており、樹脂ａのガラス転移点が高く、樹脂ｂも分散していない比較例２では低温定着性が欠けている。 From the above results, it can be seen that the toners of Examples 1 to 5 achieve both pulverization and low-temperature fixability. On the other hand, in Comparative Example 1, in which the glass transition point of the resin a is lowered by using a soft acid monomer having no benzene ring skeleton, the grindability is lacking, and the glass transition point of the resin a is low. In Comparative Example 2, which is high and the resin b is not dispersed, the low-temperature fixability is lacking.
本発明のトナー用結着樹脂は、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像等に用いられるトナーの結着樹脂として用いられるものである。 The binder resin for toner of the present invention is used as a binder resin for toner used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.
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| JPH07239572A (en) * | 1994-02-28 | 1995-09-12 | Kao Corp | Electrophotographic binder and electrophotographic toner containing the same |
| JP2004004973A (en) * | 2003-08-22 | 2004-01-08 | Kao Corp | Manufacturing method for toner for electrostatic charge image development |
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