Toner for developing electrostatically charged image

The present invention relates to a toner for developing an electrostatic charge image used in an electrophotographic method, an electrostatic recording method, or the like.

Generally, an image forming apparatus such as an electrophotographic copying machine or a printer forms a latent image on a photoconductor having photoconductivity, and the latent image is formed with a carrier or a charging member forming a part of a developing apparatus. Insulating toner obtained by frictional charge is electrostatically adhered and developed, and then the formed toner image is transferred to a transfer medium such as plain paper or film, and then heated, pressurized, solvent vapor, etc. The basic principle is to form a copied image or a printed image by fixing the image.

In such an image forming apparatus, a thermal roll fixing method is generally used as a method for fixing toner because of its high thermal efficiency and high-speed fixing. In this method, the toner is fixed by bringing the transfer paper into contact with the heating roll in a fixing machine having a heating roller. However, this method has a problem that a part of the toner adheres to the surface of the heating roll at the time of fixing, and the toner re-transfers to the paper to stain the subsequent image, that is, a so-called offset phenomenon occurs. .. Further, this method has a problem that the transfer paper is wrapped around the surface of the heating roll to cause a paper jam, that is, a so-called winding phenomenon occurs. Such a phenomenon tends to occur when the viscoelasticity of the toner melted by the heating roll is not appropriate and the balance between the viscosity and elasticity of the toner is not appropriate. The viscoelastic property of the toner is determined by the type of the binder resin which is the main component of the toner and the type and content of other contained components.

Styrene-acrylic resin and polyester resin are generally used as the binder resin which is the main component of the toner, but recently, alicyclic olefin resin (cycloolefin resin) has been studied. .. The alicyclic olefin resin is colorless and transparent, has good thermal properties (low temperature fixing and high speed fixing), has a sharp molecular weight distribution, has good grindability (high productivity, sharp particle size distribution), and has low water absorption. Since it has various excellent properties such as non-pollution, it is expected as a binder resin to replace styrene-acrylic resin and polyester resin. However, since the alicyclic olefin resin generally has a narrow molecular weight distribution, there is a problem that an offset phenomenon and a wrapping phenomenon are likely to occur at the time of fixing the toner, and the fixing characteristics are not sufficient.

As a method of preventing the occurrence of the offset phenomenon and the wrapping phenomenon and improving the fixing characteristics, a method of introducing a release agent such as a low molecular weight wax into the toner has been conventionally used. However, in this method, the toner particles are fused to each other, or the toner is easily fused to the charging member constituting the developing device, so that the toner fusion resistance is likely to deteriorate, which hinders uniform image formation. There is a risk of becoming. Further, in this method, it is not easy to uniformly and finely disperse the release agent in the binder resin at the time of toner production. Therefore, if the dispersibility is low, the fusion resistance is deteriorated. It is easy to get worse. Further, since it is not easy to select the molding conditions and the like for improving the dispersibility, the moldability of the toner is not sufficient. The above-mentioned problems are more likely to occur as the amount of the release agent introduced is larger. Therefore, it is difficult to improve the fixing characteristics such as the offset phenomenon and the wrapping phenomenon without deteriorating the characteristics such as the fusion resistance only by introducing the release agent. The moldability means the ease of manufacturing a toner having a good dispersion of raw materials.

<patcit num="1"><text>Japanese Unexamined Patent Publication No. 2003-114546</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 2001-272816</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 10-73959</text></patcit>

Japanese Unexamined Patent Publication No. 2003-114546 contains at least a cycloolefin copolymer resin as a binder resin, and contains 7 to 20% by weight of a total amount of wax added as a mold release agent with respect to the weight of the toner particles. A full-color toner for oilless fixing, characterized in that the glossiness of the printed image surface is 15 or more, is disclosed. However, in this document, since the low molecular weight component (wax) is contained in an amount of 7 to 20% by weight based on the weight of the toner particles, the toner particles are fused to each other, or the toner is attached to the charging member constituting the developing device. Since it is easy to fuse, the fusion resistance of the toner tends to deteriorate. Further, in this method, it is not easy to uniformly and finely disperse a large amount of low molecular weight components in the binder resin at the time of toner production, so that the moldability of the toner is not sufficient, and this method When the dispersibility is low, the fusion resistance tends to deteriorate.

<p> An object of the present invention is that even when the binder resin contains an alicyclic olefin resin, a wide temperature is obtained when the toner image formed by development is fixed to the transfer paper by a normal heating roll fixing machine. In the range, it is an object of the present invention to provide a toner for developing an electrostatic charge image, which does not cause an offset phenomenon and a winding phenomenon, that is, has excellent fixing characteristics. Another object of the present invention is to provide a toner for static charge image development which is excellent in fixing characteristics and also excellent in fusion resistance.</p>

<p> As a result of diligent studies to achieve the above problems, the present inventor melt-kneads at least the alicyclic olefin resin (A), the thermoplastic elastomer (B), and the colorant, and this melt-kneaded product. The toner obtained by crushing and classifying the toner has a wide temperature range in which the offset phenomenon and the winding phenomenon do not occur at the time of fixing the toner, the fusion resistance of the toner is improved, and a good toner image can be formed. The present invention has been completed. That is, the toner for static charge image development of the present invention (hereinafter referred to as toner) is composed of at least a binder resin and a colorant, and the binder resin is an alicyclic olefin resin (A). And a thermoplastic elastomer (B) (claim 1). The alicyclic olefin resin (A) is preferably a copolymer containing a cyclic olefin (A1) and an acyclic unsaturated monomer (A2) as constituent units (claim 2). The acyclic unsaturated monomer (A2) is preferably an olefinic monomer (claim 3). The thermoplastic elastomer (B) is preferably at least one selected from olefin-based elastomers, polyamide-based elastomers, polyester-based elastomers, and styrene-based elastomers (claim 4). The melting point of the thermoplastic elastomer (B) is preferably 60 to 190 ° C (claim 5). The ratio (Ma / Mb) of the melt flow rate (Ma) of the alicyclic olefin resin (A) to the melt flow rate (Mb) of the thermoplastic elastomer (B) is preferably 0.1 to 20 (claimed). Item 6). The ratio [(A) / (B)] of the alicyclic olefin resin (A) to the thermoplastic elastomer (B) is preferably 70/30 to 99.5 / 0.5 by weight (claim 7). .. Further, the toner of the present invention is suitable for a non-magnetic one-component developing method toner (claim 8). Further, the toner of the present invention is suitable for a full-color toner (claim 9).</p>

<p> The toner of the present invention is a toner for static charge image development that solves the above problems, and the binder resin contains an alicyclic olefin resin (A) and a thermoplastic elastomer (B). , The viscoelastic property is appropriate when the toner is melted, and the fixing property is excellent. Further, the toner of the present invention is excellent not only in fixing characteristics but also in fusion resistance.</p>

The toner of the present invention is composed of at least a binder resin containing an alicyclic olefin resin (A) and a thermoplastic elastomer (B), and a colorant. These will be described in detail below.

[Alicyclic olefin resin (A)]

The alicyclic olefin resin (A) contains at least one kind of cyclic olefin (A1), and the following polymers (a), (b), (c) and the like can be exemplified. (a) a homopolymer composed of one type of cyclic olefin (A1), (b) a copolymer composed of two or more types of cyclic olefins (A1), and (c) a cyclic olefin (A1). A copolymer composed of and an acyclic unsaturated monomer (A2). Examples of the cyclic olefin (A1) include monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene, derivatives thereof, cyclic conjugated diene such as cyclopentadiene, cyclohexadiene, cycloheptadiene, and cyclooctadien, or cyclic conjugated diene. These derivatives, polycyclic olefins such as norbornene, dicyclopentadiene, tricyclodecene, tetracyclododecene, hexacycloheptadecene or derivatives thereof, vinylcyclobutane, vinylcyclobutene, vinylcyclopentane, vinylcyclopentene, vinylcyclohexane, Vinyl alicyclic hydrocarbons such as vinylcyclohexene, vinylcycloheptane, vinylcycloheptene, vinylcyclooctane, vinylcyclooctene or derivatives thereof, hydrides of the aromatic ring portion of vinyl aromatic monomers such as styrene, or Cyclic and / or polycyclic olefin compounds having at least one double bond, such as these derivatives, can be exemplified. These cyclic olefins (A1) can be used alone or in combination of two or more. Examples of the derivative include an alkyl-substituted product, an alkylidene-substituted product, an alkoxy-substituted product, an acyl-substituted product, a halogen-substituted product, and a carboxyl-substituted product. The number of carbon atoms constituting the alicyclic structure is usually 4 to 30, preferably 5 to 20, and more preferably about 5 to 15 from the viewpoint of moldability and transparency.

The alicyclic olefin resin (A) is a homopolymer (a) having one kind of cyclic olefin (A1) as a constituent unit and a copolymer (a) having two or more kinds of cyclic olefins (A1) as a constituent unit. Although it may be b), it is a copolymer (c) containing a cyclic olefin (A1) and an acyclic unsaturated monomer (A2) as a constituent unit, which has graffability, processability, and mechanical properties. Etc. are preferable. The acyclic unsaturated monomer (A2) is not particularly limited as long as it is an acyclic unsaturated monomer copolymerizable with the cyclic olefin (A1), and is, for example, an olefin-based monomer; (meth). Acrylic acid-based monomers; for example, (meth) acrylic acid C such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate._1-6(Meta) acrylic acid ester-based monomers such as alkyl esters; for example vinyl acetate monomers such as vinyl acetate and vinyl propionate; eg vinyl cyanide monomers such as (meth) acrylonitrile; eg, Examples thereof include diene-based monomers such as butadiene, 1,4-pentadiene, and isoprene. These acyclic unsaturated monomers (A2) may be used alone or in combination of two or more. As the acyclic unsaturated monomer (A2), it is preferable to use an olefin-based monomer from the viewpoint of imparting flexibility to the toner. Examples of the olefin-based monomer include α-C such as ethylene, propylene, 1-butylene, 1-pentene, 1-hexene, 1-heptene, and 1-octene._2-10Olefin (preferably α-C_2-6Olefin, more preferably α-C_2-4Olefin), branched chain olefins such as isobutene and isoprene, and the like. These olefins may be used alone or in combination of two or more. Of these olefins, ethylene and propylene are particularly preferable. The amount of the acyclic unsaturated monomer (A2) used is in the range of 0 to 100 mol, preferably 0 to 90 mol, and more preferably 0 to 80 mol with respect to 100 mol of the cyclic olefin (A1). You can choose.

As the alicyclic olefin resin (A), specifically, a copolymer of ethylene or propylene and norbornene (ethylene-norbornene copolymer, propylene-norbornene copolymer, etc.) can be preferably used, and it is unsaturated. It is preferable that it has no double bond, is colorless and transparent, and has a high light transmittance.

The alicyclic olefin resin (A) has a molecular weight of 10 to 40 wt% and a molecular weight of 400,000 or more as measured by gel permeation chromatography. It is preferably 5 to 20 wt%. If the content of each molecular weight is out of the above range, the moldability and transparency are not sufficient.

The glass transition temperature of the alicyclic olefin resin (A) is determined by the composition ratio of the cyclic olefin (A1) and the acyclic unsaturated monomer (A2), and is usually about 50 to 200 ° C. It can be appropriately selected according to the application and molding temperature. For toner, it is about 50 to 80 ° C, preferably 50 to 70 ° C, and more preferably about 50 ° C to 65 ° C. If the glass transition temperature of the alicyclic olefin resin (A) exceeds 80 ° C, the fixing characteristics deteriorate and the rigidity and impact resistance increase, so the moldability of the toner is not sufficient, and the temperature is 50 °. If it is less than C, the fixing characteristics are deteriorated and the fusion resistance is lowered.

The alicyclic olefin resin (A) may be introduced with a carboxyl group, a hydroxyl group, an amino group or the like by a known method. Further, a crosslinked structure may be introduced into the alicyclic olefin resin (A) into which a carboxyl group has been introduced by adding a metal such as zinc, copper or calcium. By introducing these substituents or metal crosslinked structures, the fixing characteristics are improved, and at the time of toner production, the mixing property with other resins such as thermoplastic elastomer (B) and colorants is improved. Moldability is also improved.

[Thermoplastic Elastomer (B)]

The thermoplastic elastomer (B) is, for example, an olefin-based elastomer, a styrene-based elastomer, a vinyl chloride-based elastomer, a urethane-based elastomer, a polyamide-based elastomer, a polyester-based elastomer, a fluorine-based elastomer, a silicone-based elastomer, an isoprene-based elastomer, or a butadiene-based elastomer. , Nitrigen-butadiene-based elastomer, chlorinated polyethylene-based elastomer, chloroprene-based elastomer and the like can be used. The thermoplastic elastomer (B) may be used alone or in combination of two or more. Among the above thermoplastic elastomers, olefin-based elastomers, polyamide-based elastomers, polyester-based elastomers, and polystyrene-based elastomers can be preferably used.

The hard component of the olefin-based elastomer is composed of α-olefin-based monomer, and the soft component is ethylene-α-olefin-based copolymer [ethylene-propylene rubber (EPR), ethylene-butylene rubber (EBM), etc.], ethylene. Examples thereof include elastomers composed of olefin-based rubbers such as -α-olefin-diene copolymer [ethylene-propylene-diene rubber (EPDM), etc.]. The olefin rubber may be partially crosslinked. Examples of the α-olefin-based monomer constituting the hard component include α-C such as ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 1-octene, and 1-decene._2-10Olefin, preferably C_2-4Examples thereof include olefins (particularly ethylene and propylene). Examples of the α-olefin-based monomer constituting the soft component include α-C such as ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 1-octene, and 1-decene._2-10Olefin, preferably α-C_3-4Olefin (particularly propylene) can be exemplified. Examples of the diene constituting the soft component include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidene norbornene, 7-methyl-1,6-octadiene and the like. Further, in the ethylene-α-olefin-diene copolymer, a branched structure can be imparted, and examples of preferable diene include 1,9-decaziene and norbornadiene. The olefin elastomer is a polymer elastomer obtained by polymerizing a hard component and a soft component, a blend elastomer obtained by blending a hard component and a soft component, and a blend of a hard component and a crosslinked EPDM. Examples thereof include a cross-linking elastomer obtained by the above.

Examples of the polyamide-based elastomer include elastomers in which the hard component is composed of polyamide units and the soft component is composed of aliphatic polyether or polyester units. Examples of the polyamide unit constituting the hard component include nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, and the like, and nylon-6 and nylon-12 are preferable. Examples of the aliphatic polyether constituting the soft component include poly C such as polyethylene oxide, polypropylene oxide, and polytetramethylene oxide._2-6Aliphatic polyester and the like can be exemplified, and examples of the aliphatic polyester include aliphatic C._2-6Dicarboxylic acids (eg, oxalic acid, succinic acid, adipic acid, etc.) and aliphatic C_2-6Examples thereof include polyesters with diols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, etc.).

Examples of the polyester-based elastomer include elastomers in which the hard component is composed of an alkylene arylate unit and the soft component is composed of an aliphatic polyether or a polyester unit. Examples of the alkylene arylate constituting the hard component include C such as ethylene terephthalate and butylene terephthalate._2-4C such as alkylene terephthalate, ethylene naphthalate and butylene naphthalate_2-4Alkylene naphthalate, preferably C_2-4An example is alkylene terephthalate (particularly butylene terephthalate). Examples of the aliphatic polyether constituting the soft component include poly C such as polyethylene oxide, polypropylene oxide, and polytetramethylene oxide._2-6Aliphatic polyester and the like can be exemplified, and examples of the aliphatic polyester include aliphatic C._2-6Dicarboxylic acids (eg, oxalic acid, succinic acid, adipic acid, etc.) and aliphatic C_2-6Examples thereof include polyesters with diols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, etc.).

The styrene-based elastomer includes an elastomer in which the hard component is composed of styrene-based units and the soft component is composed of diene-based units, for example, a styrene-diene-based block copolymer or a hydrogenated product thereof. Examples of the styrene-diene block copolymer or its hydrogenated product include styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer (SBS), and hydrogenated styrene. -Butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene- Examples thereof include isoprene-styrene block copolymer (SEPS). In the block copolymer, the terminal block may be composed of either a styrene block or a diene block.

From the viewpoint of compatibility and moldability, the olefin-based elastomer and the polyamide-based elastomer may be used alone, but the polyester-based elastomer and the styrene-based elastomer may be used in combination with the olefin-based elastomer or the polyamide-based elastomer. It is preferable to use it. The amount of the polyester-based elastomer and the styrene-based elastomer used is 50% or less, preferably 30% or less, based on the total weight of the thermoplastic elastomer.

In each of the above elastomers, the ratio (weight ratio) of the hard component to the soft component is as follows: hard component / soft component = 95/5 to 30/70, preferably 90/10 to 50/50, and more preferably 90/10 to. It is about 60/40 (especially 90/10 to 70/30). When the ratio of the soft component and the hard component is within the above range, both moldability and mechanical properties can be achieved at the same time.

The melting point of the thermoplastic elastomer (B) can be appropriately selected in the range of 60 to 190 ° C, preferably 80 to 180 ° C, and more preferably 100 to 180 ° C. If the melting point is less than 60 ° C, the elasticity is significantly reduced when the toner is melted, and the fixing characteristics are deteriorated, and the fusion resistance is also deteriorated. If the melting point is higher than 190 ° C, the heat is generated when the toner is melted. In addition to insufficient melting of the plastic elastomer and deterioration of fixing characteristics, the mixture of the alicyclic olefin resin (A) and the thermoplastic elastomer (B) becomes insufficient during the production of the toner, and the moldability of the toner is also improved. descend. The method for measuring the melting point is as follows according to ASTM: D3418-82. Weigh about 5 mg of the sample, put it in an aluminum cell, place it on a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., trade name: SCC-5200), and place 50 ml of N per minute.₂Blow in gas. Then, the temperature is raised between 20 and 220 ° C at a rate of 10 ° C per minute, held at 220 ° C for 10 minutes, and then from 220 ° C to 20 ° C at 10 ° C per minute. The temperature is lowered at a rate, then the temperature is raised a second time under the above conditions, and the temperature at the apex of the endothermic peak that appears on the highest temperature side at that time is defined as the melting point of the present invention.

The toner of the present invention is composed of at least a binder resin containing an alicyclic olefin resin (A) and a thermoplastic elastomer (B), and a colorant. The ratio (weight ratio) of the alicyclic olefin resin (A) to the thermoplastic elastomer (B) can be selected from the range of (A) / (B) = 70/30 to 99.9 / 0.1, preferably 70 /. It is 30 to 99.5 / 0.5, more preferably 80/20 to 99/1 (particularly 90/10 to 99/1). If the proportion of the thermoplastic elastomer is too small, the elasticity of the toner is lowered and the fixing characteristics are deteriorated, and if it is too large, the moldability of the toner is lowered and it is disadvantageous in terms of cost.

The ratio (Ma / Mb) of the melt flow rate (Ma) of the alicyclic olefin resin (A) to the melt flow rate (Mb) of the thermoplastic elastomer (B) is in the range of 0.05 to 20. It can be selected from, preferably 0.1 to 20, and more preferably about 0.1 to 10. When the melt flow rate ratio is out of the above range, the alicyclic olefin resin (A) and the thermoplastic elastomer (B) are difficult to mix, and the moldability of the toner is lowered. The method for measuring the melt flow rate is as follows. It was calculated from the weight of the resin that flowed out in 1 minute under the conditions of a temperature of 200 ° C and a load of 50 N using a flow tester (CF-500, manufactured by Shimadzu Corporation).

As the colorant used for the toner of the present invention, a black pigment can be used for black toner, a magenta pigment, a cyan pigment, a yellow pigment and the like can be used for color toner. As the black pigment, carbon black can usually be used. The carbon black can be used without being limited by the number average particle size, the amount of oil absorbed, PH, etc., but the following are commercially available products. For example, Cabot Corporation, USA Product name: REGAL 400, 660, 330, 300, SRF-S, STERLING SO, V, NS, R, Columbia Carbon Japan, Inc. Product name: RAVEN H20, MT-P, 410, 420, 430, 450, 500, 760, 780, 1000, 1035, 1060, 1080, manufactured by Mitsubishi Chemical Corporation Product names: # 5B, # 10B, # 40, # 2400B, MA-100 Etc. can be used. These carbon blacks can be used alone or in combination of two or more. The proportion of carbon black in the toner of the present invention can be selected from the range of 0.1 to 20% by weight, preferably 1 to 10% by weight, more preferably 1 to 5% by weight (particularly 1 to 3% by weight). .. If the proportion of carbon black is too small, the image density decreases, and if it is too large, the image quality tends to deteriorate and the toner moldability also deteriorates. As the black pigment, in addition to carbon black, black magnetic powder such as iron oxide or ferrite can also be used.

Pigments for magenta include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22 , 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83 , 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209; CI Pigment Violet 19; CI Butlet 1, 2, 10, 13, 15, 23, 29, 35 Etc. can be used. These magenta pigments can be used alone or in combination of two or more. As the cyan pigment, CI Pigment Bull-2, 3, 15, 16, 17; CI Bat Bull-6; CI Acid Bull -45 and the like can be used. These cyan pigments can be used alone or in combination of two or more. As pigments for yellow-CI pigment yellow-1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 94, 97, 155, 180, etc. can be used. These yellow pigments can be used alone or in combination of two or more. From the viewpoint of color mixing and color reproducibility, the magenta pigments are CI pigment red 57 and 122, the cyan pigments are CI pigment blue 15, and the yellow pigments are CI pigment yellow. 17, 93, 155 and 180 can be preferably used. The proportion of the color pigment can be selected from the range of 1 to 20% by weight in the toner of the present invention, preferably 3 to 10% by weight, more preferably 4 to 9% by weight (particularly 4.5 to 8% by weight). Is preferable). If the proportion of these pigments is too small than the above range, the image density is lowered, and if it is too large, the charging stability is deteriorated and the image quality tends to be deteriorated. It is also disadvantageous in terms of cost. Further, as the color pigment, a so-called masterbatch in which a high concentration is dispersed in a resin that can be a binder resin in advance may be used.

If necessary, a charge control agent, a low molecular weight component (waxes), or the like may be added to the toner of the present invention. The charge control agent includes a positive charge control agent and a negative charge control agent. Examples of the positively charged charge control agent include modified products such as niglosin and fatty acid metal salts, and quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammoniumtetrafluoroborate. Diorganosin oxide such as dibutyltin oxide, dioctyltinoxide, dicyclohexylstinoxide, diorganosinbolate such as dibutyltinborate, dioctylstinborate, dicyclohexylstinborate, pyridium salt, azine, triphenylmethane compound and cationic functional group. Examples thereof include low molecular weight polymers having. These positively charged charge control agents may be used alone or in combination of two or more. As these positively charged charge control agents, niglosin-based compounds and quaternary ammonium salts are preferably used. Examples of the negative charge control agent include organometallic compounds such as acetylacetone metal complexes, monoazo metal complexes, naphthoic acid or salicylic acid-based metal complexes or salts, chelate compounds, and low molecular weight polymers having anionic functional groups. Be done. These negatively charged charge control agents can be used alone or in combination of two or more. As these negatively charged charge control agents, salicylic acid-based metal complexes and monoazo metal complexes are preferably used. The amount of the charge control agent added can be usually selected in the range of 0.1 to 5% by weight, preferably 0.5 to 4% by weight, and more preferably 1 to 4% by weight with respect to the toner. Further, the charge control agent is preferably colorless or light-colored for color toner.

The toner of the present invention preferably contains waxes as a release agent. Waxes include polyolefin waxes such as polyethylene wax, polypropylene wax and modified polyethylene wax, synthetic waxes such as Fishertropus wax, petroleum waxes such as paraffin wax and microcrystallin wax, carnauba wax, candelilla wax and rice wax. , Hardened wax oil and the like. These waxes can be used alone or in combination of two or more. The wax content can be selected in the toner in the range of 0.1 to 10% by weight, preferably 0.5 to 7% by weight, and more preferably 1 to 5% by weight. If the amount of wax added is too large, the fusion resistance and toner moldability deteriorate, and if it is too small, the releasability is insufficient and the fixing characteristics deteriorate.

The toner of the present invention further contains magnetic powders such as metals such as cobalt, iron and nickel, aluminum, copper, iron, nickel, magnesium, tin, zinc, gold, silver, selenium, titanium and tungsten, as required. Alloys of zirconium and other metals, metal oxides such as aluminum oxide, iron oxide and nickel oxide, ferrite, magnetite and the like can be used. The amount of the magnetic powder added is usually 1 to 70% by weight, preferably 5 to 50% by weight, and more preferably 10 to 40% by weight with respect to the toner. The average particle size of the magnetic powder is preferably 0.01 to 3 μm.

Further, the toner of the present invention includes various additives such as stabilizers (for example, ultraviolet absorbers, antioxidants, heat stabilizers, etc.), flame retardants, antifogging agents, dispersants, and phosphoric acids, if necessary. , Plasticizers (phthalates, fatty acid plasticizers, phosphoric acid plasticizers, etc.), high molecular weight antistatic agents, low molecular weight antistatic agents, compatibilizers, conductive agents, fillers, fluidity improvers, etc. You may.

The toner of the present invention may further contain other resins, for example, styrene resins, (meth) acrylic resins, styrene- (meth) acrylic copolymer resins, olefin resins (eg, polyethylene, polypropylene), if necessary. Α-Olefin resin such as α-olefin resin), vinyl resin (for example, polyvinyl chloride, polyvinylidene chloride, etc.), polyamide resin, polyether resin, urethane resin, epoxy resin, polyphenylene oxide resin, terpenphenol resin , Polylactic acid resin, hydrogenated rosin, cyclized rubber, thermoplastic polyimide and the like may be added as a part of the binder resin. The amount of these resins added can be appropriately selected from the range of 30% by weight or less with respect to 100% by weight of the binder resin.

Since the binder resin of the toner of the present invention contains an alicyclic olefin resin (A) and a thermoplastic elastomer (B), it is colorless and transparent, and has good thermal characteristics (low temperature fixing and high speed). Has various excellent properties of alicyclic olefin resins such as fixability), sharp molecular weight distribution, good pulverizability (high productivity, sharp particle size distribution), low water absorption, and safety such as pollution-free. At the same time, by containing the thermoplastic elastomer, the balance of viscoelasticity, mechanical properties, and rheological properties are improved, and the fixing properties are also excellent. Further, the toner for developing an electrostatic charge image of the present invention has excellent fusion resistance. Further, the toner for static charge image development of the present invention is also excellent in toner moldability and is advantageous in terms of toner production.

From the viewpoint of imparting fluidity, the toner of the present invention preferably has inorganic fine particles adhered to its surface. Examples of the inorganic fine particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, titanium oxide, carbon black powder, magnetic powder and the like. These inorganic fine particles may be used alone or in combination of two or more. Of these inorganic fine particles, silica can be particularly preferably used. Silica is not particularly limited in terms of average particle size, BET specific surface area, surface treatment, etc., and can be appropriately selected depending on the application, but the BET specific surface area is 50 to 400 m.²It is preferably in the range of / g, preferably surface-treated hydrophobic silica.

In addition to the inorganic fine particles, fine resin powders such as polytetrafluoride ethylene resin powder and polyvinylidene fluoride resin powder may be further attached to the toner of the present invention. The ratio of adding these inorganic fine particles or resin fine powder to the toner can be appropriately selected from the range of 0.01 to 8 parts by weight with respect to 100 parts by weight of the toner, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 5 parts by weight. 4 parts by weight (especially 0.3 to 3 parts by weight). If the addition ratio is out of the above range, the fluidity and charge stability of the toner are lowered, and it is difficult to form a uniform image.

The use of the toner of the present invention is not particularly limited by the developing method, and can be used in a non-magnetic one-component developing method, a magnetic one-component developing method, a two-component developing method, and other developing methods. The magnetic one-component developing method toner is used as a magnetic toner by mixing the magnetic powder described in the above paragraph [0032] with a binder resin, and the two-component developing method toner is used by mixing with a carrier. From the viewpoint of simplicity and cost of the apparatus, it is preferable to use it as a toner for a non-magnetic one-component developing method.

As the carrier in the two-component developing method, for example, nickel, cobalt, iron oxide, ferrite, iron, glass beads and the like can be used. These carriers may be used alone or in combination of two or more. The average particle size of the carriers is preferably 20 to 150 μm. Further, the surface of the carrier may be coated with a coating agent such as a fluorine-based resin, an acrylic resin, or a silicone-based resin.

The toner of the present invention may be a monochrome toner or a full-color toner. In the monochrome toner, the non-magnetic toner is described in the above paragraph [0028] as a colorant, and the magnetic toner is described in the above paragraph [0032] in addition to the carbon black described in the above paragraph [0028]. Among the magnetic powders, black ones can be used. In the full-color toner, the color pigment described in the above paragraph [0029] can be used as the colorant.

[Toner manufacturing method]

The method for producing the toner of the present invention is not particularly limited, but usually, a binder resin, a colorant, and other additives are dry-mixed and heat-melt-kneaded to prepare a melt-kneaded product, and then the melt-kneaded product is used. Toner can be pulverized and classified to obtain a toner having a desired particle size and particle shape. The method for producing the toner may be a method for obtaining toner particles while polymerizing the binder resin. As the dry mixing method, a method using a stirrer such as a Henschel mixer, a super mixer, or a ribbon mixer can be used. As the hot melt kneading method, various methods such as a twin-screw extruder method, a Banbury mixer method, a pressure roller method, and a pressure kneader method can be used. As the hot melt kneading method, a twin-screw extruder method is preferable from the viewpoint of moldability and versatility. The melt-kneaded product is obtained by melt-kneading with a twin-screw extruder and extruding from a die at the tip of the twin-screw extruder. The kneading temperature of the twin-screw extruder is 50 to 220 ° C, preferably 70 to 200 ° C, and more preferably about 80 to 180 ° C. Since the alicyclic olefin resin (A) and the thermoplastic elastomer (B) used in the present invention take into consideration the good dispersibility of each material component during hot melt kneading, they are also excellent in moldability during manufacturing. ing. Examples of the crushing method include a crushing method using a crusher such as a hammer mill, a cutter mill or a jet mill. Further, as the classification method, an air flow classifier such as a dry centrifugal classifier can usually be used. The volume average particle size of the toner thus obtained is usually about 6 to 10 μm, preferably 6 to 9 μm, and more preferably 6 to 8 μm. The volume average particle diameter is a volume 50% diameter measured using a particle size distribution measuring device (Multisizer II, manufactured by Beckman Coulter). Further, even if the inorganic fine particles and the resin fine powder described in the above paragraphs [0036] to [0037] are adhered to the toner surface by stirring with a stirrer such as a turbine type stirrer, a Henschel mixer, or a super mixer. Good.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The material components used in Examples and Comparative Examples, the method for measuring physical properties, and the method for evaluating toner are shown below.

[Material ingredients]

&lt;Bundling resin&gt; CO: Alicyclic olefin resin (ethylene-norbornene copolymer, manufactured by Tikona Co., Ltd., trade name: TOPAS COC, weight average molecular weight (Mw): 200,000, number average molecular weight (Mn): 5,000, Mw / Mn: 40) TPO: Olefin-based thermoplastic elastomer (quality component: polypropylene, soft component: ethylene-propylene rubber, melting point 155 ° C, manufactured by Idemitsu Petrochemical Co., Ltd., trade name: R110E) TPEE: polyester-based thermoplastic Elastomer (hard component: polybutylene terephthalate, soft component: polyether, melting point 163 ° C, manufactured by Toray DuPont Co., Ltd., trade name: Hytrel 4057) &lt;Colorant&gt; PIG .: Cyan pigment for toner CI Pigment Blue 15: 3 (Clariant Japan Co., Ltd., trade name: Hostaperm Blue B2G) &lt;Charge control agent&gt; CCA: Zinc salt-based charge control agent (manufactured by Orient Chemical Industry Co., Ltd., trade name: BONTRON E-84) &lt;Release agent &gt; WAX: Carnauba wax (Hiroyuki Kato, trade name: Carnauba wax No. 2 powder)

[Toner evaluation method]

1. [Fixing characteristics]

A two-component developer was prepared by mixing 4 parts by weight of toner and 96 parts by weight of a non-coated ferrite carrier (manufactured by Powdertech Co., Ltd., trade name: FL-1020). Next, using this developer, a commercially available copying machine (SF-9800, manufactured by Sharp Corporation) was used to prepare a strip-shaped unfixed image of 3 cm in length and 6 cm in width on A4 transfer paper. The amount of toner adhering to the transfer paper is approximately 2.0 mg / cm depending on the toner concentration, surface potential of the photoconductor, development potential, exposure amount, transfer conditions, etc.²Adjusted to . Next, a fixing machine in which a heat fixing roll whose surface layer is made of polytetrafluoroethylene and a pressure fixing roll whose surface layer is made of silicone rubber rotate in pairs, with a roll pressure of 1 Kgf / cm.², Adjust the roll speed to 125 mm / sec, and gradually raise the surface temperature of the heat-fixed roll between 150 and 200 ° C at intervals of 10 ° C, and at each surface temperature, the above-mentioned unfixed image. The toner image of the transfer paper having the above was fixed. After fixing, it was observed whether or not toner stains were generated in the margin portion, and the temperature region where the stains did not occur was defined as the non-offset temperature region. In the non-offset temperature region, it is observed whether or not the transfer paper having the unfixed image is wrapped around the surface of the heat fixing roll, and the temperature region where wrapping does not occur is defined as the non-winding temperature region, and the non-winding temperature region. The upper limit temperature on the high temperature side of was confirmed.

2. [Fusion resistance]

The toner was put into a developing machine of a non-magnetic one-component QMS2200 printer (manufactured by Minolta QMS), and 5000 A4 originals with an image ratio of 5% were copied on A4 transfer paper. After copying 5000 sheets, it was visually confirmed whether toner fusion was observed on the charging member (charging blade) of the developing machine. : Toner is fused, ×: Toner is not fused

3. [Moldability]

The cross section of the plate-shaped resin composition (C) extruded by the twin-screw extruder in the direction perpendicular to the extrusion direction was observed with an optical microscope (magnification: 400 times), and the alicyclic olefin resin (A) was observed. , The kneadability (degree of dispersion) of each material such as thermoplastic elastomer (B), colorant, and wax was confirmed. : Each material is uniformly dispersed and finely dispersed. Δ: Each material is uniformly dispersed, but not finely dispersed. X: The dispersed state of each material is non-uniform.

[Making toner]

Examples 1 to 4 and Comparative Examples 1 to 4 As raw materials for the toner, a binder resin composed of an alicyclic olefin resin (A) and a thermoplastic elastomer (B), a colorant, and a charge control agent are used. And the release agent were used in the ratios shown in Tables 1 and 2. In Comparative Examples 1 to 3, only the alicyclic olefin resin (A) was used as the binder resin without using the thermoplastic elastomer (B), and in Comparative Example 4, the thermoplastic elastomer was used as the binder resin. Only (B) was used. Each of the above materials is melt-kneaded using a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Corp.) at a temperature of 160 ° C to 200 ° C, a discharge rate of 3.5 kg / hr, and a rotation speed of 250 rpm to obtain a thickness. A plate-shaped melt-kneaded product having a thickness of 2 to 3 mm was obtained. The cross section of the obtained plate-shaped melt-kneaded product was observed, and the moldability of each of the above materials was evaluated. Then, the melt-kneaded product was pulverized by a jet mill and then classified by a dry air flow classifier to obtain toner particles having a volume average particle size of 8.5 μm. Next, with respect to the obtained toner particles, hydrophobic silica having a volume average particle diameter of 40 nm (RY-50, manufactured by Nippon Aerodil Co., Ltd.) was added to 0.3% by weight, and hydrophobic silica having a volume average particle diameter of 10 nm (RY-50, manufactured by Nippon Aerodil Co., Ltd.) was added. Add 1.0% by weight of H2000 / 4M (manufactured by Wacker Chemical Co., Ltd.) and stir and mix with a Henshell mixer at a peripheral speed of 40 m / sec for 10 minutes to obtain toners of Examples 1 to 4 and Comparative Examples 1 to 4. It was. The fixing characteristics and fusion resistance of the obtained toner were evaluated, and the results are shown in Tables 1 and 2.

<tables num="1"><img file="JP2005292362A_D0001.tif" /></tables>

<tables num="2"><img file="JP2005292362A_D0002.tif" /></tables>

As is clear from Tables 1 and 2, the toners of Examples 1 to 4 according to the present invention are excellent in various properties such as fixability, fusion resistance, and moldability. On the other hand, since the toner of Comparative Example 1 does not contain the thermoplastic elastomer (B), the upper limit temperature for non-wrapping is lower than that of Examples. Since the toner of Comparative Example 2 does not contain the thermoplastic elastomer (B) and has a lower wax content than the toner of Comparative Example 1, it has good fusion resistance and moldability, but has a non-winding upper limit temperature. It is declining. Since the toner of Comparative Example 3 has a higher wax content than the toner of Comparative Example 1, the upper limit temperature for non-wrapping is higher, but the fusion resistance and moldability are lowered. Since the toner of Comparative Example 4 does not contain the alicyclic olefin resin (A), an offset occurs at 150 ° C. and the fusion resistance is inferior.