WO1993019101A1 - Process for manufacturing toner resins - Google Patents
Process for manufacturing toner resins Download PDFInfo
- Publication number
- WO1993019101A1 WO1993019101A1 PCT/EP1993/000515 EP9300515W WO9319101A1 WO 1993019101 A1 WO1993019101 A1 WO 1993019101A1 EP 9300515 W EP9300515 W EP 9300515W WO 9319101 A1 WO9319101 A1 WO 9319101A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- molecular weight
- carbon atoms
- toner
- alkylene group
- peroxide
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 title claims abstract description 28
- 239000011347 resin Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 150000001451 organic peroxides Chemical group 0.000 claims abstract description 18
- 150000002978 peroxides Chemical group 0.000 claims abstract description 9
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000002081 peroxide group Chemical group 0.000 claims description 4
- HQUSUVDPDHBQAF-UHFFFAOYSA-N 1-(2-tert-butylperoxypropan-2-yl)-4-prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 HQUSUVDPDHBQAF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001253 acrylic acids Chemical class 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 Cι_8 alkylstyrenes Chemical class 0.000 description 4
- 229920006158 high molecular weight polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- RCSKFKICHQAKEZ-UHFFFAOYSA-N 1-ethenylindole Chemical compound C1=CC=C2N(C=C)C=CC2=C1 RCSKFKICHQAKEZ-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical compound C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers 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
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08706—Polymers of alkenyl-aromatic compounds
- G03G9/08708—Copolymers of styrene
- G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a process for manufacturing toner resins in the presence of peroxides.
- Electrographic methods comprise the use of a heated roller for fixing electrostatic latent images, which are visualized with the use of a dry development toner.
- a low fixing temperature can be obtained by using polymeric material of low molecular weight.
- the use of a low molecular weight polymer alone as the dry development toner material has the disadvantage that it causes blocking.
- high molecular weight polymer is essential to imparting high temperature offset properties to a dry development toner.
- a dry toner must consist of polymers (hereinafter described as toner resins) having both a low molecular weight and a high molecular weight in order to provide fixability at low temperatures, offset properties and anti-blocking properties.
- the present invention relates to a process for manufacturing high molecular weight toner resins by polymerizing at least one polymerizable vinyl monomer in the presence of at least one polyfunctional polymerization initiator having at least one peroxide functionality and at least one unsaturated functionality.
- the polyfunctional polymerization initiator is an organic peroxide represented by the general formula:
- Ri is an alkylene group having from 1 to 22 carbon atoms, a sec-alkylene group having from 2 to 22 carbon atoms, or a tert-a kylene group having from 3 to 22 carbon atoms and n is an integer from 0 to 5, the organic peroxide being present in the process in an amount of 0.001 to 2 wt%.
- the organic peroxides of the present invention have the advantage of not needing to be phlegmatized. Therefore, dry development toners comprising high molecular weight toner resins of the present invention have a good offset resistance. Furthermore, the use of the organic peroxides of the present invention results in nearly complete conversion to polymer.
- Z in the general formula I represents a hydrogen atom.
- the organic peroxide is 4-isopropenylcumyl tert-butyl peroxide.
- the organic peroxides of the present invention may be prepared in a manner as described in M.A. Dikii, V.A. Puchin, S.A. Voronov, V.S. Tokarev, 0.1. Gevus (Lvov. Politekh. Inst., Lvov, USSR), Zh. Org. Khim., 1981, 17 (2), 337-9.
- Suitable polymerizable monomers include aromatic vinyl monomers, such as styrene and styrene homologues or substituted styrenes, including C ⁇ _8 alkylstyrenes, al oxy-substituted styrenes, halogen-substituted styrenes; acrylic or methacrylic monomers, such as C ⁇ _8 alkyl (meth)acrylates, aryl (meth)acrylates, hydroxyl-containing (meth)acrylates, amino-containing ( eth)acrylates, epoxy-containing (meth)acrylates, and ( eth)acrylic acids and derivatives thereof; vinyl esters, such as vinyl acetate and vinyl propionate; aliphatic hydrocarbon monomers, such as butadiene; vinyl ethers, such as vinylmethyl ether, vinylethyl ether, and vinyl-iso-butyl ether; vinyl ketones, such as vinylmethyl ketone, vinylhexyl ketone
- Preferred polymerizable monomers are styrene, alkyl (meth)acrylates (more particularly, methyl, ethyl, butyl, and 2-ethylhexyl (meth)acrylates), (meth)acrylic acids, vinyl esters, aliphatic hydrocarbon monomers, and mixtures thereof.
- copolymers of styrene and alkyl (meth)aerylates are prepared by the process of the present invention.
- the polymerization process It is preferred to carry out the polymerization process at a temperature not lower than 60°C and not higher than 160°C. More preferably, the process is carried out at a temperature of 110 o -140°C.
- the process of the invention may be carried out using any known polymerization technique, such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, and combinations thereof.
- Suitable solvents used in solution polymerization include cycloalkanes, such as cyclohexane; aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, and cu ene; esters, such as ethyl acetate and butyl acetate; ethers, such as methyleellosolve, ethylcellosolve and butylcellosolve; and the like. Preferred among these to obtain high molecular weight polymer are cycloalkanes and aromatic hydrocarbons.
- Suspension polymerization can be carried out in an aqueous medium, as known in the art.
- This invention relates also to dry development toners comprising the high molecular weight toner resin produced by the process of the present invention. Dry development toners of the present invention have a good offset resistance.
- the dry development toner comprising said high molecular weight toner resin may further contain one or more other components. It preferably contains one or more lower molecular weight toner resins.
- toner resins of a molecular weight of 3000 to 50000 are present, such as styrene/acrylic copolymers, polyester resins, ' polyepoxide resins, polyurethane resins, and the like. Among these, styrene/acrylic copolymers and polyester resins are preferred.
- said low molecular weight toner resin can be prepared beforehand, either separately or simultaneously with the preparation of said high molecular weight toner resin.
- dry development toner may be produced by blending, in a solution or in the melted state, the high and low molecular weight toner resins being prepared separately beforehand; or by polymerizing said monomer to a high molecular weight toner resin in the presence of a low molecular weight toner resin and the organic peroxide of the present invention.
- said low molecular weight toner resin may be produced by polymerizing in bulk or in solution at least one precursor monomer for a low molecular weight toner resin in the presence of a high molecular weight polymer.
- a high molecular weight polymer is dissolved in said precursor monomer, which precursor monomer is then polymerized to obtain a low molecular weight polymer.
- the polymerizing of said precursor monomer is by bulk polymerization or solution polymerization rather than suspension polymerization, because when using the former two techniques, one can remarkably reduce the amount of the polymerization initiator to provide the same molecular weight and, therefore, can remedy or reduce objectionable influences (such as excessive charging of toner, environmental instability, and so on) caused by the presence of initiator residues.
- the low and high molecular weight toner resins may be blended or used in bonded form, such as through covalent bonding.
- the content of the high molecular weight toner resin is usually 10-50 wt%, preferably 15-45 wt%, and that of the low molecular weight toner resin 50-90 wt%, preferably 55-85 wt%, based on the total weight of these toner resins.
- the dry development toner may contain one or more known colorants in an amount of 5 to 10 wt%, magnetic powders in an amount of 0 to 50 wt%, and other additives, -such as charge controllers and lubricants in an amount of 0 to 5 wt%.
- Colorants may be inorganic or organic pigments, such as carbon black, iron black, benzidine yellow, quinacridone pigments, rhodamine B, phthalocyanine pigments, and the like.
- Preferred magnetic powders are powders of ferromagnetic metals and compounds such as iron, cobalt, nickel, magnetite, hematite, ferrite, and the like.
- the dry development toner may be prepared by dry blending these components and then melting them under kneading, followed by crushing, finely pulverizing with a grinder, and finally classifying to obtain particles of 5-20 microns diameter.
- the dry development toner may be optionally mixed with one or more carrier particles, such as iron powder, glass beads, nickel powder, ferrite, and the like, and used as a developer for electrical latent images.
- carrier particles such as iron powder, glass beads, nickel powder, ferrite, and the like
- hydrophobic colloidal silica powder may be used to improve flowability of the powders.
- ampoules - 2.5 cm 3 in volume, were 80% filled with a monomer mixture of 80 wt% styrene and 20 wt% butyl acrylate, in which mixture different peroxides in an amount of 0.75 meq active oxygen groups/lOOg were dissolved.
- the ampoules were sealed under nitrogen and immersed in a pre-heated oil bath. Each two hours an ampoule was taken from the oil bath and analysed for monomer conversion and polymer molecular weight. The results obtained after 10 hours of polymerization have been reported in Table I.
- Examples 1-3 are carried out with an organic peroxide according to the invention.
- Examples A-E are comparative examples using organic peroxides disclosed in GB-A-2 232 160. Table I
- Tx 171 4-isopropenylcumyl tert-butyl peroxide
- Px 12 2,2-bis(4,4-di-tert-butylperoxycyclohexyl )propane
- Mw weight-average molecular weight
- Mn number-average molecular weight
- the peroxide of the present invention (Ex. 1-3) is able to convert a styrene/butylacrylate monomer mixture more completely at a higher molecular weight than the other two peroxides (Ex. A-E), under the same reaction conditions. Further, the peroxides of the present invention are able to be applied at higher temperatures than the other mentioned peroxides thus enabling reactor output to be increased.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Developing Agents For Electrophotography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for manufacturing toner resins of high molecular weight by polymerizing at least one polymerizable vinyl monomer in the presence of at least one polyfunctional polymerization initiator having at least one peroxide functionality and at least one unsaturated functionality, characterized in that the polymerization initiator is an organic peroxide present in the process in an amount of 0.001 to 2 wt %.
Description
Process for manufacturing toner resins
The present invention relates to a process for manufacturing toner resins in the presence of peroxides.
Electrographic methods comprise the use of a heated roller for fixing electrostatic latent images, which are visualized with the use of a dry development toner. In these methods it is desired that the minimum temperature for fixing be low and the temperature causing offset to the heated roller be high. A low fixing temperature can be obtained by using polymeric material of low molecular weight. However, the use of a low molecular weight polymer alone as the dry development toner material has the disadvantage that it causes blocking. In addition, high molecular weight polymer is essential to imparting high temperature offset properties to a dry development toner. Thus, a dry toner must consist of polymers (hereinafter described as toner resins) having both a low molecular weight and a high molecular weight in order to provide fixability at low temperatures, offset properties and anti-blocking properties.
The present invention relates to a process for manufacturing high molecular weight toner resins by polymerizing at least one polymerizable vinyl monomer in the presence of at least one polyfunctional polymerization initiator having at least one peroxide functionality and at least one unsaturated functionality.
A similar process is known from GB-A-2 232 160. However, the polyfunctional polymerization initiators disclosed in the British publication need to be phlegmatized and phlegmatizers have undesirable effects on the performance of dry development toner. Furthermore, the initiators disclosed do not give total conversion from monomer to
polymer. Processes comparable to the British process are known from EP-A-0351929 and EP-A-0354466. These processes are attended with the same d sadvantages as mentioned above for the British process.
In the process of the present invention the polyfunctional polymerization initiator is an organic peroxide represented by the general formula:
(I)
or
hydrogen, and Ri is an alkylene group having from 1 to 22 carbon atoms, a sec-alkylene group having from 2 to 22 carbon atoms, or a tert-a kylene group having from 3 to 22 carbon atoms and n is an integer from 0 to 5, the organic peroxide being present in the process in an amount of 0.001 to 2 wt%. The organic peroxides of the present invention have the advantage of not needing to be phlegmatized. Therefore, dry development toners comprising high molecular weight toner resins of the present invention have a good offset resistance. Furthermore, the use of the organic peroxides of the present invention results in nearly complete conversion to polymer. Obtained are polymers having a molecular weight which is as high as or even higher than that of the polymers obtained by the process disclosed in the British publication.
Preferably, Z in the general formula I represents a hydrogen atom. More preferably, the organic peroxide is 4-isopropenylcumyl tert-butyl peroxide.
Of course, two or more of the organic peroxides represented by formula I may be used simultaneously in the process of the present invention.
From JP 5 9204 643 it is known to copolymerize the present organic peroxides together with unsaturated monomers. The organic peroxide therefor reacts with its double bond, resulting in copolymers containing peroxide groups. In the present invention, this is not the case, the organic peroxide being used as an initiator. Accordingly, the peroxide group is decomposed, resulting in polymers with essentially no peroxide groups present in the polymer. SU 887 578, JP 6 0011 349, JP 6 0011 539, and JP 6 0013 828 disclose similar processes as described in JP 5 9204643.
The organic peroxides of the present invention may be prepared in a manner as described in M.A. Dikii, V.A. Puchin, S.A. Voronov, V.S. Tokarev, 0.1. Gevus (Lvov. Politekh. Inst., Lvov, USSR), Zh. Org. Khim., 1981, 17 (2), 337-9.
Suitable polymerizable monomers include aromatic vinyl monomers, such as styrene and styrene homologues or substituted styrenes, including Cι_8 alkylstyrenes, al oxy-substituted styrenes, halogen-substituted styrenes; acrylic or methacrylic monomers, such as Cι_8 alkyl (meth)acrylates, aryl (meth)acrylates, hydroxyl-containing (meth)acrylates, amino-containing ( eth)acrylates, epoxy-containing (meth)acrylates, and ( eth)acrylic acids and derivatives thereof; vinyl esters, such as vinyl acetate and vinyl propionate; aliphatic hydrocarbon monomers, such as butadiene; vinyl ethers, such as vinylmethyl ether, vinylethyl ether, and vinyl-iso-butyl ether; vinyl
ketones, such as vinylmethyl ketone, vinylhexyl ketone, and methyl isopropenyl ketone; N-vinyl compounds, such as N-vinylpyrrole, N- vinylcarbazole, N-vinylindole, and N-vinylpyrrolidine; and mixtures thereof.
Preferred polymerizable monomers are styrene, alkyl (meth)acrylates (more particularly, methyl, ethyl, butyl, and 2-ethylhexyl (meth)acrylates), (meth)acrylic acids, vinyl esters, aliphatic hydrocarbon monomers, and mixtures thereof.
More preferably, copolymers of styrene and alkyl (meth)aerylates are prepared by the process of the present invention.
It is preferred to carry out the polymerization process at a temperature not lower than 60°C and not higher than 160°C. More preferably, the process is carried out at a temperature of 110o-140°C.
The process of the invention may be carried out using any known polymerization technique, such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, and combinations thereof.
Suitable solvents used in solution polymerization include cycloalkanes, such as cyclohexane; aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, and cu ene; esters, such as ethyl acetate and butyl acetate; ethers, such as methyleellosolve, ethylcellosolve and butylcellosolve; and the like. Preferred among these to obtain high molecular weight polymer are cycloalkanes and aromatic hydrocarbons.
Suspension polymerization can be carried out in an aqueous medium, as known in the art.
This invention relates also to dry development toners comprising the high molecular weight toner resin produced by the process of the present invention. Dry development toners of the present invention have a good offset resistance.
The dry development toner comprising said high molecular weight toner resin may further contain one or more other components. It preferably contains one or more lower molecular weight toner resins. Preferably, toner resins of a molecular weight of 3000 to 50000 are present, such as styrene/acrylic copolymers, polyester resins,' polyepoxide resins, polyurethane resins, and the like. Among these, styrene/acrylic copolymers and polyester resins are preferred.
In preferred embodiments said low molecular weight toner resin can be prepared beforehand, either separately or simultaneously with the preparation of said high molecular weight toner resin. In other words, dry development toner may be produced by blending, in a solution or in the melted state, the high and low molecular weight toner resins being prepared separately beforehand; or by polymerizing said monomer to a high molecular weight toner resin in the presence of a low molecular weight toner resin and the organic peroxide of the present invention. In another embodiment, said low molecular weight toner resin may be produced by polymerizing in bulk or in solution at least one precursor monomer for a low molecular weight toner resin in the presence of a high molecular weight polymer. For instance, a high molecular weight polymer is dissolved in said precursor monomer, which precursor monomer is then polymerized to obtain a low molecular weight polymer. The polymerizing of said precursor monomer is by bulk polymerization or solution polymerization rather than suspension polymerization, because when using the former two techniques, one can remarkably reduce the amount of the polymerization initiator to provide the same molecular weight and, therefore, can remedy or reduce objectionable
influences (such as excessive charging of toner, environmental instability, and so on) caused by the presence of initiator residues.
In these dry development toners, the low and high molecular weight toner resins may be blended or used in bonded form, such as through covalent bonding. In these dry development toners, the content of the high molecular weight toner resin is usually 10-50 wt%, preferably 15-45 wt%, and that of the low molecular weight toner resin 50-90 wt%, preferably 55-85 wt%, based on the total weight of these toner resins.
In addition to the high and low molecular weight toner resins generally present in an amount of 50 to 95 wt%, the dry development toner may contain one or more known colorants in an amount of 5 to 10 wt%, magnetic powders in an amount of 0 to 50 wt%, and other additives, -such as charge controllers and lubricants in an amount of 0 to 5 wt%. Colorants may be inorganic or organic pigments, such as carbon black, iron black, benzidine yellow, quinacridone pigments, rhodamine B, phthalocyanine pigments, and the like. Preferred magnetic powders are powders of ferromagnetic metals and compounds such as iron, cobalt, nickel, magnetite, hematite, ferrite, and the like.
The dry development toner may be prepared by dry blending these components and then melting them under kneading, followed by crushing, finely pulverizing with a grinder, and finally classifying to obtain particles of 5-20 microns diameter.
The dry development toner may be optionally mixed with one or more carrier particles, such as iron powder, glass beads, nickel powder, ferrite, and the like, and used as a developer for electrical latent images. Besides, hydrophobic colloidal silica powder may be used to improve flowability of the powders.
The invention will be further illustrated by the following examples which are not to be construed as limiting the invention in any way. The scope of the invention is to be determined from the claims appended hereto.
Examples
Polymerization process
Several ampoules,- 2.5 cm3 in volume, were 80% filled with a monomer mixture of 80 wt% styrene and 20 wt% butyl acrylate, in which mixture different peroxides in an amount of 0.75 meq active oxygen groups/lOOg were dissolved. The ampoules were sealed under nitrogen and immersed in a pre-heated oil bath. Each two hours an ampoule was taken from the oil bath and analysed for monomer conversion and polymer molecular weight. The results obtained after 10 hours of polymerization have been reported in Table I.
Polymer evaluation method
* Conversion into polymer (%) : The amount of residual monomer was determined by gas chromatography to calculate the conversion.
* Molecular weight (Mw, Mn, Mw/Mn) : A calibration curve was prepared by using polystyrene as standard to determine the molecular weight of a polymer according to GPC (Gel Permeation Chromatography).
In table I, Examples 1-3 are carried out with an organic peroxide according to the invention. Examples A-E are comparative examples using organic peroxides disclosed in GB-A-2 232 160.
Table I
Tx 171: 4-isopropenylcumyl tert-butyl peroxide
TBNBF: n-butyl tert-butyl peroxy fumarate
Px 12: 2,2-bis(4,4-di-tert-butylperoxycyclohexyl )propane
Mw: weight-average molecular weight Mn: number-average molecular weight
It can be understood from the results shown in Table I that the peroxide of the present invention (Ex. 1-3) is able to convert a styrene/butylacrylate monomer mixture more completely at a higher molecular weight than the other two peroxides (Ex. A-E), under the same reaction conditions. Further, the peroxides of the present invention are able to be applied at higher temperatures than the other mentioned peroxides thus enabling reactor output to be increased.
Claims
1. Use of organic peroxides of the general formula
(I)
or
2. A process for manufacturing toner resins of high molecular weight by polymerizing at least one polymerizable vinyl monomer in the presence of at least one polyfunctional polymerization initiator having at least one peroxide functionality and at least one unsaturated functionality, characterized in that the polymerization initiator is an organic peroxide represented by the general formula: (I)
3. A process according to claim 2, characterized in that the organic peroxide is 4-isopropenylcumyl tert-butyl peroxide.
4. A process according to any one of claims 2 or 3, characterized in that the polymerizable vinyl monomers are selected from the group of styrene, alkyl ( eth)acrylates, (meth)acrylic acids, vinyl esters, aliphatic hydrocarbon monomers, and mixtures thereof.
5. A process according to any one of claims 2, 3, or 4, characterized in that the process is carried out at a temperature of 110°-140 °C.
6. A process according to any one of claims 2-5, characterized in that the resulting high molecular weight toner resin has essentially no peroxide groups therein. Dry development toner, characterized in that it comprises the toner resin of high molecular weight produced by a process according to any one of claims 2-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5516206A JPH07506199A (en) | 1992-03-25 | 1993-03-05 | Toner resin manufacturing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92200847 | 1992-03-25 | ||
| EP92200847.9 | 1992-03-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993019101A1 true WO1993019101A1 (en) | 1993-09-30 |
Family
ID=8210502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1993/000515 WO1993019101A1 (en) | 1992-03-25 | 1993-03-05 | Process for manufacturing toner resins |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH07506199A (en) |
| WO (1) | WO1993019101A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7582708B2 (en) | 2001-06-13 | 2009-09-01 | Beta Technologie Ag | Bulk polymerization reactor methods |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0208353A1 (en) * | 1985-06-26 | 1987-01-14 | Akzo N.V. | Process for cross-linking or degrading polymers and shaped articles obtained by this process |
| GB2232160A (en) * | 1989-05-24 | 1990-12-05 | Sanyo Chemical Ind Ltd | Resin compositions for electrophotographic toner |
-
1993
- 1993-03-05 WO PCT/EP1993/000515 patent/WO1993019101A1/en active Application Filing
- 1993-03-05 JP JP5516206A patent/JPH07506199A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0208353A1 (en) * | 1985-06-26 | 1987-01-14 | Akzo N.V. | Process for cross-linking or degrading polymers and shaped articles obtained by this process |
| GB2232160A (en) * | 1989-05-24 | 1990-12-05 | Sanyo Chemical Ind Ltd | Resin compositions for electrophotographic toner |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 102, no. 23, 10 June 1985, Columbus, Ohio, US; abstract no. 203721, 'ARYL PEROXIDES HAVING POLYMERIZABLE UNSATURATED GROUPS' page 576 ;column 1 ; * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7582708B2 (en) | 2001-06-13 | 2009-09-01 | Beta Technologie Ag | Bulk polymerization reactor methods |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07506199A (en) | 1995-07-06 |
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