# US 5,700,616 A · Developer for developing an electrostatic image and image forming method > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,700,616 A - Document ID: US5700616A - Status: Granted - Kind: A - Application number: 08/594,795 - Filed: 1996-01-31 - Granted: 1997-12-23 - Earliest claimed: 1995-02-01 - Assignees: Canon Kabushiki Kaisha - Inventors: Takashige Kasuya; Osamu Tamura; Hiroshi Yusa; Takakuni Kobori; Masaichiro Katada - Web page: https://patentgrep.com/patent/US5700616A ## CPC - G03G 9/09716: {treated with organic compounds} - G03G 9/0819: {characterised by the dimensions of the particles} - G03G 9/097: Plasticisers; Charge controlling agents - G03G 9/09725: {Silicon-oxides; Silicates} - G03G: ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY ## Abstract A developer for developing an electrostatic image has a toner which contains a particulate toner, a particulate silica A and a particulate silica B. The toner has a weight-average particle size of not larger than 12.0 .mu.m and a particle-number distribution showing not more than 50% of toner particles not larger than 4.0 .mu.m in particle size and not more than 10% of toner particles not smaller than 10.08 .mu.m in particle size, each of the toner particles having a toner composition containing at least a polymer component and a charge controlling agent. The particulate silica A is composed of silicone oil-treated silica particles and has an average particle size of not larger than 0.1 .mu.m, while the particulate silica B is composed of silicone oil-treated silica particles and has an average particle size of 0.5 to 50 .mu.m. The particulate silica B also has a particle-number distribution showing not more than 50% of silica particles not larger than 1.0 .mu.m in particle size and not more than 10% of silica particles not smaller than 100 .mu.m in particle size. Also disclosed is an image forming method which uses this developer. ## Claims ### Claim 1 A developer for developing an electrostatic image which comprises a toner comprising a particulate toner, a particulate silica A and a particulate silica B, the toner having a weight-average particle size of not larger than 12.0 .mu.m and a particle-number distribution showing not more than 50% of toner particles not larger than 4.0 .mu.m in particle size and not more than 10% of toner particles not smaller than 10.08 .mu.m in particle size, each of the toner particles being formed of a toner composition comprising at least a polymer component and a charge controlling agent, the particulate silica A being composed of silicone oil-treated silica particles and having an average particle size of not larger than 0.1 .mu.m, the particulate silica B being composed of silicone oil-treated silica particles and having an average particle size of 0.5 to 50 .mu.m and a particle-number distribution showing not more than 50% of silica particles not larger than 1.0 .mu.m in particle size and not more than 10% of silica particles not smaller than 100 .mu.m in particle size, the particulate silica A and particulate silica B meeting the following requirements, (a) the average particle size D.sub.B of the particulate silica B is 10 times or more larger than the average particle size D.sub.A of the particulate silica A, (b) the silicone oil amount W.sub.B used to treat the particulate silica B is twice or more larger than the silicone oil amount W.sub.A used to that the particulate silica A, and (c) the particulate silica A is added in an amount 3 times or more larger than the particulate silica B with respect to the toner particles (based on weight). ### Claim 2 (depends on 1) The developer according to claim 1, wherein the silicone oil amount W.sub.A of the particulate silica A is in the range of 1 to 30% by weight based on the weight of the oil-treated silica particles, and the silicone oil amount W.sub.B of the particulate silica B is in the range of 30 to 90% by weight based on the weight of the oil-treated silica particles. ### Claim 3 (depends on 1, 2) The developer according to claim 1 or 2, wherein the amount of the particulate silica A to be added to the toner particles is in the range of 0.3 to 3.0% by weight, and the amount of the particulate silica B to be added to the toner particles is in the range of 0.005 to 0.5% by weight. ### Claim 4 (depends on 1) The developer according to claim 1, wherein the viscosity of silicone oil used to treat the particulate silica B is 10 times or more larger than the viscosity of silicone oil used to treat the particulate silica A. ### Claim 5 (depends on 1) The developer according to claim 1, wherein the particulate silica B meets an atomic ratio of W.sub.s /W.sub.o of 1 to 10 where W.sub.o is the amount of Si atoms induced from the silicone oil, and W.sub.s is the amount of Si atoms present in a matrix particulate silica prior to treatment with the silicone oil. ### Claim 6 (depends on 1) The developer according to claim 1, wherein the polymer component has an acid value of not less than 1 mgKOH/g. ### Claim 7 (depends on 1) The developer according to claim 1, wherein the polymer has a low-molecular weight polymer component and a high-molecular weight polymer component, the low-molecular weight polymer component being in a region of molecular weight less than 50,000, the high-molecular weight polymer component being in a region of molecular weight not less than 50,000, both polymer components meeting the equation A.sub.VL >A.sub.VH where A.sub.VL is the acid value of the low-molecular weight polymer component, and A.sub.VH is the acid value of the high-molecular weight polymer component. ### Claim 8 (depends on 7) The developer according to claim 7, wherein the polymer is substantially free from THF insolubles, the polymer has a main peak in a region of molecular weight from 3.times.10.sup.3 to 3.times.10.sup.4 and a sub peak or shoulder in a region of molecular weight from 1.times.10.sup.5 to 3.times.10.sup.6, both regions being defined on a chromatogram by GPC of THF solubles of the polymer, the low-molecular weight polymer component has an acid value (A.sub.VL) of 21 to 35 mgKOH/g, and the high-molecular weight polymer component has an acid value (A.sub.VH) of 0.5 to 11 mgKOH/g, the difference in acid value being represented by the equation 10.ltoreq.(A.sub.VL -A.sub.VH).ltoreq.27. ### Claim 9 (depends on 7) The developer according to claim 7, wherein the toner composition has a glass transition temperature (Tg) of 50.degree. to 70.degree. C., Tg.sub.L of the low-molecular weight polymer component and Tg.sub.H of the high-molecular weight polymer component meeting the equation, both polymer components being present in the toner composition, Tg.sub.L .gtoreq.Tg.sub.H -5. ### Claim 10 (depends on 7) The developer according to claim 7, wherein the toner composition has a Tg of 55.degree. to 65.degree. C., Tg.sub.L of the low-molecular weight polymer component and Tg.sub.H of the high-molecular weight polymer component meeting the equation, both polymer components being present in the toner composition, Tg.sub.L .gtoreq.Tg.sub.H. ### Claim 11 (depends on 7) The developer according to claim 7, wherein the toner composition meets the equations, W.sub.L :W.sub.H =50:50 to 90:10 A.sub.VL .times.(W.sub.L /(W.sub.L +W.sub.H)).gtoreq.A.sub.VH .times.(W.sub.H /(W.sub.L +W.sub.H)).times.4 11.ltoreq.(1/(W.sub.L +W.sub.H))(A.sub.VL W.sub.L +A.sub.VH W.sub.H).ltoreq.30 where W.sub.L is the amount (% by weight) of the low-molecular weight polymer component, W.sub.H is the amount (% by weight) of the high-molecular weight polymer component, A.sub.VL is the acid value (mgKOH/g) of the low-molecular weight polymer component, and A.sub.VH is the acid value (mgKOH/g) of the high-molecular weight polymer component. ### Claim 12 (depends on 7) The developer according to claim 7, wherein each of the low- and high-molecular weight polymer components has at least one styrene monomer unit of not less than 65% by weight. ### Claim 13 (depends on 7) The developer according to claim 7, wherein the high-molecular weight polymer component is a polymer derived from use of a polyfunctional polymerization initiator. ### Claim 14 (depends on 7) The developer according to claim 7, wherein the high-molecular weight polymer component is a polymer derived from use of a polyfunctional polymerization initiator and a monofunctional polymerization initiator. ### Claim 15 (depends on 1) The developer according to claim 1, wherein the particulate silica A is treated with an organic surface-treating agent before treatment With the silicone oil. ### Claim 16 (depends on 1) The developer according to claim 1, wherein the toner has a weight-average particle size of not larger than 10 .mu.m, and smaller not more than 30% in the number of particles not larger than 4.0 .mu.m and not more than 5% in the number of particles not smaller than 10 .mu.m in the particle-number distribution. ### Claim 17 (depends on 1) The developer according to claim 1, wherein the particulate silica B contains not more than 30% in the number of particles not larger than 1.0 .mu.m and not more than 5% in the number of particles not smaller than 100 .mu.m in the particle-number distribution. ### Claim 18 (depends on 1) The developer according to claim 1, wherein the toner has a weight-average particle size of not larger than 10 .mu.m, and not more than 30% in the number of particles not larger than 4.0 .mu.m and not more than 5% in the number of particles not smaller than 10 .mu.m in the particle-number distribution, and the particulate silica B contains not more than 30% in the number of particles not larger than 1.0 .mu.m and not more than 5% in the number of particles not smaller than 100 .mu.m in the particle-number distribution. ### Claim 19 (depends on 1) The developer according to claim 1, wherein the particulate silicas A and B have the same polarity as the triboelectric property of the toner particles. ### Claim 20 (depends on 19) The developer according to claim 19, wherein the particulate silicas A and B have negative triboelectric characteristics, and the toner particles have negative triboelectrific characteristics. ### Claim 21 (depends on 20) The developer according to claim 20, wherein the toner particles contain as a negative charge controlling agent a compound of the formula, ##STR17## where X.sub.1 and X each are a hydrogen atom, a lower alkyl, lower alkoxy, nitro group, or a halogen atom, m and m' each are an integer of 1 to 3, Y.sub.1 and Y.sub.3 each are a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, sulfonamide, mesyl, sulfonic acid, a carboxyl ester, a hydroxyl group, an alkoxy group of 1 to 18 carbon atoms, an acetylamino group, a benzoyl group, an amino group or a halogen atom, n and n' each are an integer of 1 to 3 Y.sub.2 and Y.sub.4 each are a hydrogen atom or a nitro group, X.sub.1 and X.sub.2, m and m', Y.sub.1 and Y.sub.3, n and n', and Y.sub.2 and Y.sub.4 each are identical or different, and A.sup.+ is H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4.sup.+ or combined ions thereof. ### Claim 22 (depends on 20) The developer according to claim 20, wherein the toner particles contain as a negative charge controlling agent a compound of the formula, ##STR18## where X is ##STR19## which is substituted or unsubstituted, ##STR20## in which Z is a hydrogen, halogen atom, or a nitro group, ##STR21## where R is a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, or an alkenyl group of 2 to 18 carbon atoms, Y is --O--, or ##STR22## A.sup.+ is H.sup.+, Na.sup.+, NH.sub.4.sup.+, aliphatic ammonium or combined ions thereof. ### Claim 23 (depends on 20) The developer according to claim 20, wherein the toner particles contain as a negative charge controlling agent a compound of the formula, ##STR23## where Y.sub.1 and Y.sub.2 each are a phenyl, naphtyl or anthryl group, R.sup.1 and R.sup.2 each are a halogen atom, or a nitro, sulfonate, carboxyl, carboxylate ester, cyano, carbonyl, alkyl, alkoxy or amino group, R.sup.3 and R.sup.4 each are a hydrogen atom, or an alkyl, alkoxy, phenyl which may have a substituent, aralkyl which may have a substituent or amino group, R.sup.5 and R.sup.6 each are a hydrogen atom or an hydrocarbon group of 1 to 8 carbon atoms, k and j each are 0 or an integer of 1 to 3, both parameters being not zero at the same time, m and n each are an integer of 1 or 2, and Y.sup.1 and Y.sup.2, R.sup.1 and R.sup.2, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, k and j, and m and n each are identical or different. ### Claim 24 (depends on 20) The developer according to claim 20, wherein the toner particles contain as a negative charge controlling agent a compound of the formula, ##STR24## where A.sup.+ is H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4.sup.+, or combined ions thereof. ### Claim 25 (depends on 20) The developer according to claim 20, wherein the toner particles contain as a negative charge controlling agent a compound of the formula, ##STR25## where A.sup.+ is H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4.sup.+, or combined ions thereof. ### Claim 26 (depends on 20) The developer according to claim 20, wherein the toner particles contain as a negative charge controlling agent a compound of the formula, ##STR26## where t-Bu is a t-butyl group, and A.sup.+ is H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4.sup.+, or combined ions thereof. ### Claim 27 (depends on 20) The developer according to claim 20, wherein the toner particles contain as a negative charge controlling agent a compound of the formula, ##STR27## where t-Bu is a t-butyl group, and A.sup.+ is H.sup.+, Na.sup.+, K.sup.+ or NH.sub.4.sup.+, or combined thereof. ### Claim 28 An image forming method comprising electrifying an electrostatic image carrying member, exposing the electrified carrying member to light so as to form an elecrostatic image thereon, developing the resulting image with use of a developer so as to form a toner image, transferring the toner image to a transfer material optionally through an intermediate transfer material, and subsequently fixing the image on the transfer material by application of heat and pressure, wherein the developer comprises a toner comprising a particulate toner, a particulate silica A and a particulate silica B, the toner having a weight-average particle size of not larger than 12.0 .mu.m and a particle-number distribution showing not more than 50% of toner particles not larger than 4.0 .mu.m in particle size and not more than 10% of toner particles not smaller than 10.08 .mu.m in particle size, each of the toner particles being formed of a toner composition comprising at least a polymer component and a charge controlling agent, the particulate silica A being composed of silicone oil-treated silica particles and having an average particle size of smaller not larger 0.1 .mu.m, the particulate silica B being composed of silicone oil-treated silica particles and having an average particle size of 0.5 to 50 .mu.m and a particle-number distribution showing not more than 50% of silica particles not larger than 1.0 .mu.m in particle size and not more than 10% of silica particles not smaller than 100 .mu.m in particle size, the particulate silica A and particulate silica B meeting the following requirements, (a) the average particle size D.sub.B of the particulate silica B 10 times or more is larger than the average particle size D.sub.A of the particulate silica A, (b) the silicone oil amount W.sub.B used to treat the particulate silica B is twice or more larger than the silicone oil amount W.sub.A used to that the particulate silica A, and (c) the particulate silica A is added in an amount 3 times or more larger than the particulate silica B with respect to the toner particles (based on weight). ### Claim 29 (depends on 28) The method according to claim 28, wherein said developer employs from 0.3 to 3.0% by weight of the particulate silica A and from 0.005 to 0.5% by weight of the particulate silica B. ### Claim 30 (depends on 28) The method according to claim 28, wherein said electrostatic image carrying member is charged by a contact-type charging means which is biased. ### Claim 31 (depends on 30) The method according to claim 30, wherein said contact-type charging means comprises a charging roller. ### Claim 32 (depends on 30) The method according to claim 30, wherein said contact-type charging means comprises a charging brush. ### Claim 33 (depends on 30) The method according to claim 30, wherein said contact-type charging means comprises a charging blade. ### Claim 34 (depends on 28) The method according to claim 28, wherein said developer is carried by a developer carrying member, said developer carrying member comprising at least a substrate and a coating layer which coats a surface of said substrate, said coating layer being formed of a coating agent which comprises: (i) a mixture of a solid lubricant, a conducting agent or a mixture of a solid lubricant and a conducting agent; and (ii) a binding resin. ### Claim 35 (depends on 28) The method according to claim 28, wherein said toner image is transferred to said transfer material by means of a transfer roller which is biased. ### Claim 36 (depends on 28) The method according to claim 28, wherein said toner image is transferred to said transfer material by means of a transfer roller which is biased. ### Claim 37 (depends on 28) The method according to claim 28, wherein said toner image on said transfer material is fixed thereto by a heat-press-fixing means which comprises a heating roller and a pressing roller. ### Claim 38 (depends on 28) The method according to claim 28, wherein said toner image on said transfer material is fixed by a linear heating member which is fixed and supported through a film.