JP4322740B2 - Resin production method, resin fine particle production method, resin fine particle - Google Patents

Description

  The present invention relates to a resin or resin fine particles having a low odor, and a product made from them. Specifically, a new resin and its sheet that are excellent in the balance of molding processability, productivity, appearance of molded product, rigidity, surface hardness, and heat resistance, and optimal for uses such as food packaging containers with little odor, Heavy duty used in rear projection screens for display, film viewing, magnetic recording media, liquid crystal display spacers, light diffusing agents for various lighting fixtures, column fillers or carriers for diagnostic agents, drug delivery systems, bioreactors, etc. Polymer fine particles and image formation that are most suitable for use as seed particles (monodispersed fine particles) in the production of coalesced fine particles, and image forming particles used in electrophotography, electrostatic recording, electrostatic printing, etc. Particles, an efficient production method thereof, a developer using the image forming particles, an image forming method using the developer, a container containing the image forming particles, and an image forming apparatus , And a process cartridge.

  Styrenic resins, polymethacrylic acid ester resins, and their copolymers are excellent in transparency, rigidity, moldability, etc., and are inexpensive, so that they are cheaper than household goods, toys, OA equipment housing materials, food packaging containers In addition, as a polymer fine particle, a light projection agent such as a display, a rear projection screen for viewing a film, a magnetic recording medium, a liquid crystal display spacer, various lighting fixtures, a column filler or a carrier for a diagnostic agent, Used in a wide range of applications, such as for use in drug delivery systems and bioreactors, for seed particles (monodispersed fine particles), etc., for electrophotographic imaging particle matrix and external additives Yes.

  In order to give viscosity and elasticity suitable for the application to these resins, there is a method of lowering the melt viscosity of the resin by adding a lubricant or a plasticizer. However, when a lubricant or a plasticizer is added to the resin, there is a possibility that problems may occur in the properties and processability of the resulting resin. For example, when manufacturing a sheet for food packaging, a lubricant and a plasticizer bleed out on the surface of the sheet at the time of manufacturing the sheet to contaminate the sheet surface and the roll, so that the sheet appearance is inferior and the frequency of roll cleaning is increased. Further, when the sheet is molded, mold contamination and transfer of the contaminants to the molded product occur, the frequency of cleaning the mold is high, and the appearance of the molded product is inferior, and productivity is impaired. The same is true at the time of injection molding, and the injection mold is contaminated, contaminants adhere to the molded product, the frequency of mold cleaning is high, and the appearance of the molded product is inferior, and the productivity is impaired.

  For this reason, there is a method of controlling the molecular weight of a resin using a chain transfer agent to give the resin viscosity and elasticity suitable for the application. The amount of chain transfer agent added is much less than when a lubricant or plasticizer is added. For this reason, the resin obtained using the chain transfer agent is imparted with viscosity and elasticity suitable for the application without adversely affecting the properties and processability of the resin. However, mercaptans used as suitable chain transfer agents, especially dodecyl mercaptan, have a specific odor, and when heated, the remaining chain transfer agent volatilizes and has the problem of generating odors. ing. In particular, when a food packaging container or sheet is heated in a microwave oven or the like, the influence of volatilization of the chain transfer agent remaining in the resin due to heat fixing of electrophotography is serious. Since the odor generated in the food packaging container or sheet is related to food, odor at a lower concentration than the odor at the time of heat fixing of electrophotography becomes a problem.

  As a countermeasure for this problem, a resin production method (see Patent Documents 1 and 2) in which the amounts of styrene monomer, methacrylic acid ester monomer and chain transfer agent are defined and the temperature during the polymerization reaction is controlled, α- In a method for producing monodisperse fine particles that are polymerized using methylstyrene dimer as a chain transfer agent (see Patent Document 3) and a method for producing image forming particles for electrophotography, a method using a chain transfer agent having a specific molecular structure (Patent Document) 4-8), a method of adding an additive during the cleaning process (see Patent Documents 9 to 15), a method of adding a deodorant (see Patent Documents 16 and 17), etc. However, it is not sufficient to remove the compounds that cause the problem, and no technology that can sufficiently solve the problem has yet been provided.

JP 2001-026619 A, JP 2001-031046 A JP-A-11-292907 JP 2001-281931 A, JP 2002-040711 A JP 2002-091067 A JP 2002-091070 A JP 2003-330226 A JP 2002-131981 Japanese Patent Laid-Open No. 2002-131982 Japanese Patent Laid-Open No. 2002-131983 Japanese Patent Laid-Open No. 2002-131985 JP 2002-139863 A JP 2003-098744 A Japanese Patent Laid-Open No. 2003-149861 JP 2002-108015 A JP 2003-098745 A

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, the present invention provides a chain for removing a chain transfer agent from a resin obtained by polymerizing a radical polymerizable monomer containing at least a chain transfer agent using at least one of a supercritical fluid and a subcritical fluid. Resin and resin fine particles having excellent transparency, rigidity, moldability, and the like, by efficiently removing a chain transfer agent due to malodor by a resin production method characterized by including at least a transfer agent removal step, and its Manufacturing method that is efficient and has a low environmental impact, image forming particles using the resin fine particles, a developer capable of improving image quality using the image forming particles, an image forming method using the developer, and an image It is an object to provide a container with formed particles, an image forming apparatus, and a process cartridge.

As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge.
That is, a resin obtained by polymerizing a radically polymerizable monomer containing at least a chain transfer agent is subjected to contact treatment for a certain period of time using at least one of a supercritical fluid and a subcritical fluid. The present invention has been completed based on the knowledge that the chain transfer agent present in the resin can be selectively and efficiently removed without deterioration.

The said subject of this invention is achieved by following (1)-( 16 ).
(1) "at least a radical polymerizable monomer containing a chain transfer agent to the resin obtained by polymerizing, to come in contact with the supercritical fluid or subcritical flow body, a chain transfer in the supercritical fluid or subcritical fluid A resin characterized by comprising a chain transfer agent removing step of dissolving the agent to remove the chain transfer agent from the resin , wherein the chain transfer agent dissolved in the supercritical fluid or subcritical fluid is precipitated and recovered Manufacturing method. "
(2) “The method for producing a resin according to (1) above, wherein the polymerizable monomer is one or more vinyl monomers”.
(3) “The method for producing a resin according to (1) or (2) above, wherein at least styrene and an acrylic acid derivative or a methacrylic acid derivative are used as the polymerizable monomer.”
(4) In any one of the above (1) to (3), at least one of the supercritical fluid and the subcritical fluid can dissolve the chain transfer agent without dissolving the resin. The manufacturing method of the resin as described. "
(5) “The method for producing a resin according to any one of (1) to (4) above, wherein at least one of the supercritical fluid and the subcritical fluid is either a simple substance or a mixture. "
(6) “The method for producing a resin according to any one of (1) to (5) above, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide.”
(7) “The method for producing a resin according to any one of (1) to (6) above, wherein at least one of the supercritical fluid and the subcritical fluid contains an organic solvent.”
(8) "in the resin particles obtained by polymerizing a radical polymerizable monomer containing at least the chain transfer agent, to come in contact with the supercritical fluid or subcritical flow body, linked to a supercritical fluid or subcritical fluid A chain transfer agent removing step of dissolving the transfer agent to remove the chain transfer agent from the resin fine particles , wherein the chain transfer agent dissolved in the supercritical fluid or subcritical fluid is precipitated and recovered. Manufacturing method of resin fine particles to be performed. "
( 9 ) "The method for producing resin fine particles according to ( 8 ) above, wherein a ratio of a median diameter to a mode diameter of the resin fine particles is 1.10 or less."
( 10 ) “In the aqueous medium in which the polymerization initiator is dissolved, at least a radically polymerizable monomer dissolved in the aqueous medium and a chain transfer agent dissolved in the aqueous medium are supplied for polymerization. The method for producing resin fine particles according to (8) or (9) , wherein polymerized particles are formed.
( 11 ) “In the organic medium, the polymer that is dissolved in the organic medium is polymerized by adding an insoluble or hardly soluble radically polymerizable monomer to the organic medium. In the step of forming polymer particles, a chain transfer agent is added at least once during the step, the method for producing resin fine particles according to (8) or (9) above.
( 12 ) “At least a polymerizable mixture containing a polymerizable monomer and a polymerization initiator is put into an aqueous dispersion medium containing a suspension stabilizer, and polymerized by stirring to form polymer particles. The method for producing resin fine particles according to (8) or (9) above, wherein the chain transfer agent is added at least once during the step.
( 13 ) “Seed polymerization step of performing polymerization in a solution dispersed in an aqueous or organic solvent using the resin fine particles obtained by the production method according to any one of (10) to (12) as seed particles, A method for producing resin fine particles, which is performed at least once. "
( 14 ) “The method for producing resin fine particles according to any one of (8) to (13) , wherein the resin fine particles are used during production of image-forming particles.”
( 15 ) "The method for producing resin fine particles according to any one of (8) to (14) , wherein the resin fine particles are a part or the whole of the image forming particles."
(16) "the (8) to (15) of any characterized in that it is produced by the production method of the resin fine particles according to the resin fine particles."

This invention is based on the said knowledge of the present inventors, and the means for solving the said subject has the following characteristics and effects. That is,
According to the present invention , the chain transfer agent present in the resin is removed by at least one of the supercritical fluid and the subcritical fluid. As a result, the odor generated when the resin receives heat can be improved.
Moreover, it is possible to obtain a resin that is excellent in transparency, rigidity, moldability, and the like and that has improved odor generated when it receives heat.
Moreover, it is excellent in transparency, rigidity, moldability, etc., and the odor generated when receiving heat is improved, and an inexpensive resin can be obtained.
In addition, a resin with improved odor generated when receiving heat can be obtained without adversely affecting the properties and processability of the resin.
Further, since at least one of the supercritical fluid and the subcritical fluid is either a simple substance or a mixture, preferably containing at least carbon dioxide having a low critical temperature, the supercritical fluid of the resin after treatment and The subcritical fluid removal step can be omitted, and the handleability is excellent.
In addition, since at least one of the supercritical fluid and the subcritical fluid contains the organic solvent, the removal of the chain transfer agent from the resin is performed more efficiently.
Further, since the removal is performed by precipitation of the chain transfer agent, it becomes easy to take out the chain transfer agent from the supercritical fluid and the subcritical fluid, and the supercritical fluid and the subcritical fluid can be reused. It becomes easy.
In addition, the step of granulating resin fine particles from the resin can be omitted, and the resin fine particles granulated by various polymerization methods are generated when subjected to heat without adversely affecting the properties and processability. Odor can be improved.
Moreover, the resin fine particle whose ratio of the median diameter and mode diameter of the resin fine particles is 1.10 or less can be manufactured.
Further , the present invention is a method for producing resin fine particles in which resin fine particles having a uniform particle diameter are obtained. In the production method, it is not easy to remove the chain transfer agent, but at least one of a supercritical fluid and a subcritical fluid is used. As a result, resin fine particles with improved odor generated upon receiving heat can be obtained without adversely affecting the properties and processability.
Further, even when the resin fine particles remain in the image forming particles, the odor at the time of heat fixing can be improved.
Further, Ru can improve the odor generated when resin fine particles are thermally fixed.

  According to the present invention, various problems in the prior art can be solved, and by removing the chain transfer agent with at least one of a supercritical fluid and a subcritical fluid, the generation of odor when receiving heat can be improved. Can provide a resin or resin fine particles and a production method thereof that is efficient and has a low environmental impact. Further, the image forming particles using the resin fine particles, and further the image quality improvement using the image forming particles can be provided. The image forming method using the developer, the container containing the image forming particles, the image forming apparatus loaded with the image forming particles, and the process cartridge can be provided.

(Resin and production method thereof)
The resin constituting the image-forming particles of the present invention is obtained by the resin production method of the present invention. The method for producing a resin of the present invention includes at least a chain transfer agent removing step, and includes other steps appropriately selected as necessary.
The resin here refers to a single substance or a mixture containing a polymer obtained by radical polymerization in the presence of at least a radical polymerizable monomer, a polymerization initiator, and a chain transfer agent. Therefore, the polymer itself, a polymer including a mixture, and a polymer that is coated, unevenly distributed, or adhered to a metal, an inorganic compound, or an organic compound are also included.
Hereafter, the manufacturing method of resin of this invention and resin obtained by it are demonstrated in detail.

-Polymerizable monomer-
As the polymerizable monomer in the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Monofunctional polymerizable monomers include styrene, α-methyl styrene, β-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl styrene. , P-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p- Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate , N-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Class: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n- Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate; vinyl esters such as methylene aliphatic monocarboxylic acid ester, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinylmethyl And vinyl ethers such as ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2'-bis {4- (acryloxydiethoxy) phenyl} propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Methacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis {4- (methacryloxydiethoxy) phenyl} propane, 2,2′-bis {4- (methacryloxypolyethoxy) phenyl} propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinyl ether and the like can be mentioned.

  The above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. Among the above-mentioned monomers, styrene and (meth) acrylic acid or their derivatives (for example, methyl (meth) acrylate, ethyl (meth) acrylate, etc.) are used alone or in combination, or with other units. It is desirable to use it mixed with a monomer.

-Polymerization initiator-
In the present invention, the polymerization initiator mixed with the polymerizable monomer is added for the purpose of polymerizing the polymerizable monomer.
Examples of the polymerization initiator that can be preferably used in the present invention include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis ( Cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo-based polymerization initiators such as azobismethylbutyronitrile; benzoyl peroxide, lauroyl peroxide, di -Α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) ) Cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy) isophthalate, methyl ethyl ketone Organic peroxide-based polymerization initiators such as hydrogen peroxide, tert-butylperoxy-2-ethylhexanoate, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide; Inorganic peroxides such as sulfates (sodium salts, potassium salts, ammonium salts, etc.) and oxidizing substances such as oxidizing metal salts such as tetravalent cerium salts and divalent iron salts, monovalent copper salts, 3 Reducing metal salts such as valent chromium salts; ammonia, lower amines (amines having about 1 to 6 carbon atoms such as methylamine and ethylamine), amino compounds such as hydroxylamine, sodium thiosulfate, sodium hydrosulfite, hydrogen sulfite Reduction of sodium, sodium sulfite, sodium formaldehyde sulfoxylate, etc. A redox initiator comprising a combination of a sulfur compound, a lower alcohol (about 1 to 6 carbon atoms), ascorbic acid or a salt thereof, and a reducing substance such as a lower aldehyde (about 1 to 6 carbon atoms) can be mentioned. .

  The initiator is selected with reference to the 10-hour half-life temperature, and is used alone or in combination. The addition amount of the polymerization initiator varies depending on the desired degree of polymerization, but is generally 0.1 to 20%, preferably 0.5 to 5%, based on the weight of the polymerizable monomer.

-Chain transfer agent-
In the present invention, the chain transfer agent for polymerizing the polymerizable monomer is added for the purpose of adjusting the degree of polymerization of the polymer obtained by polymerizing the polymerizable monomer.
Examples of the chain transfer agent include compounds represented by the following general formula (i) and general formula (ii).

〔式中、Ｒ^１は、置換基を有してもよい炭素数が１〜１０の炭化水素基であり、Ｒ^２は、置換基を有してもよい炭素数が２〜２０の炭化水素基を示す。また、Ｒ^１およびＲ^２は、互いに同一であっても、異なっていてもよい。〕

[Wherein, R ¹ is an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and R ² is an optionally substituted hydrocarbon group having 2 to 20 carbon atoms. Indicates a group. R ¹ and R ² may be the same as or different from each other. ]

〔式中、Ｒ^３は、置換基を有してもよい炭素数が１〜２０の炭化水素基を示す。〕

Wherein, R ³ is carbon atoms, which may have a substituent exhibits an 1-20 hydrocarbon group. ]

Specific examples of the specific compound represented by the general formula (i) include thioglycolic acid esters and 3-mercaptopropionic acid esters. Specifically, as thioglycolic acid esters, ethyl thioglycolate, n-butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, thioglycolic acid Decyl, dodecyl thioglycolate, ethylene glycol thioglycolate, neopentyl glycol thioglycolate, trimethylolpropane thioglycolate, pentaerythritol thioglycolate, sorbitol thioglycolate be able to. Examples of 3-mercaptopropionic acid esters include 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid octyl ester, 3-mercaptopropionic acid decyl ester, 3-mercaptopropionic acid dodecyl ester, 3-mercaptopropionic acid pentaerythritol tetrakis Esters, ethylene glycol 3-mercaptopropionate, neopentyl glycol 3-mercaptopropionate, trimethylolpropane 3-mercaptopropionate, pentaerythritol 3-mercaptopropionate, sorbitol 3-mercaptopropionate An acid ester etc. can be mentioned.
Examples of the specific compound represented by the general formula (ii) include n-octyl mercaptan, 2-ethylhexyl mercaptan, n-dodecyl mercaptan, sec-dodecyl mercaptan, t-dodecyl mercaptan, and the like.

  Other chain transfer agents include disulfides such as diisopropyl xanthogen disulfide, carbon tetrachloride, carbon tetrabromide, ethyl dibromide acetate, ethyl tribromide acetate, ethyl dibromide benzene, ethane dibromide, dichloride. Examples thereof include halogenated hydrocarbons such as ethane, hydrocarbons such as diazothioether, benzene, ethylbenzene, and isopropylbenzene.

  It is preferable that the addition amount (use amount) of a chain transfer agent is 0.01-10 mass% with respect to a polymer, More preferably, it is 0.05-5 mass%. Thereby, the molecular weight of a polymer can be adjusted reliably.

-Crosslinking agent-
In the polymerization of the polymerizable monomer, the following crosslinking agent may be present to carry out the polymerization to form a crosslinked polymer in the image-forming particles.
Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinyl ether, divinyl sulfone, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4-methacryloxydiethoxyphenyl) Propane, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, Trimethylolpropane trimethacrylate, trimethylol propane triacrylate, tetra methylol methane tetraacrylate, dibromo neopentyl glycol dimethacrylate, can be used allyl phthalate, a general crosslinking agent as appropriate.

-Manufacturing method of resin-
In the present invention, a method for producing a polymer which is the whole or part of the resin will be described.
The polymer (resin) of the present invention is not particularly limited as long as it is produced by a radical polymerization reaction of a radical polymerizable monomer, and can be appropriately selected according to the purpose. Specifically, suspension polymerization, bulk polymerization, solution polymerization and the like, preferably suspension polymerization and the like. The resin of the present invention can also be obtained as resin fine particles. Details of the resin fine particles will be described later.

  The resin of the present invention includes an antioxidant, a lubricant, a release agent, a plasticizer, a pigment, a pigment dispersant, a dye, a dyeing assistant, a discoloration inhibitor, a foaming agent, a foaming nucleating agent, an inorganic filler, as necessary. Known additives such as a charge control agent, an antistatic agent, a sliding agent, a pore forming agent, a pharmaceutical composition, an enzyme, a coenzyme, an antibody, a binding protein, a lectin, and a hormone receptor can also be contained. Furthermore, the resin of the present invention can be used in combination with known resins such as GP-PS, HI-PS, MS resin, MBS resin, AS resin, ABS resin, PE, PP, and PPO.

As a means for adding a known additive or a known resin to the polymer, a known additive or a known resin that is desired to be contained during the polymerization reaction is dispersed, or a known additive or a known resin is added to the obtained polymer. For example, or a combination thereof.
As a method of adding and mixing a known additive or a known resin to the obtained polymer, a method of kneading the obtained polymer with a known additive or a known resin, preferably the obtained polymer and a known additive Alternatively, there is a method of kneading after mixing a known resin, and if necessary, a kneading step, a molding step, and a classification step can be added after kneading.
For example, after the obtained polymer and known additives and known resins are sufficiently mixed by a mixer such as a Henschel mixer, a batch-type two-roll, Banbury mixer or continuous twin-screw extruder such as Kobe Steel KTK type twin screw extruder manufactured by Tokoro Co., Ltd., TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd., TEX type twin screw extruder manufactured by Nihon Steel Works, Ltd., PCM type twin screw extruder manufactured by Ikekai Tekko Co., Ltd. The components are well kneaded using a mold twin screw extruder or a continuous single screw kneader, for example, a heat kneader such as Bush's co-kneader. By molding and cooling, the resin can contain a known additive or a known resin. If necessary, the resin is coarsely pulverized using a hammer mill or the like, and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier using a swirl stream or classification using the Coanda effect It can also be classified to a predetermined particle size by a machine.

<Chain transfer agent removal step>
The chain transfer agent removal step is a step of removing the resin chain transfer agent using at least one of a supercritical fluid and a subcritical fluid.

-Supercritical fluid and subcritical fluid-
The supercritical fluid exists as a non-condensable high-density fluid in a temperature / pressure region that exceeds the limit (critical point) where gas and liquid can coexist, does not cause condensation even when compressed, and exceeds the critical temperature. And, as long as the fluid is in a state of a critical pressure or higher, there is no particular limitation, preferably those that do not dissolve the resin and dissolve the chain transfer agent, can be appropriately selected depending on the purpose, Are preferred. The subcritical fluid is not particularly limited as long as it exists as a high-pressure liquid in the temperature / pressure region near the critical point, and can be appropriately selected according to the purpose.
Suitable examples of these fluids include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, methanol, ethanol, ethane, propane, 2,3-dimethylbutane, benzene, chlorotrifluoromethane, and dimethyl ether. . Among these, carbon dioxide is particularly preferable in that the critical temperature is close to room temperature and the handleability is excellent. It is desirable to use a supercritical fluid having a critical temperature of 30 to 40 ° C. and close to normal temperature, such as supercritical carbon dioxide and supercritical carbon monoxide, at a temperature of 25 to 100 ° C. and a pressure of 5 to 50 MPa. This is because carbon dioxide and nitrous oxide are unlikely to be in a supercritical state at a temperature lower than 25 ° C. or a pressure lower than 5 MPa. Further, at a temperature exceeding 100 ° C., gas may be generated depending on the type of polymer used for the resin, or the polymer may be inadvertently decomposed into a polymerizable monomer or the like. Furthermore, if the pressure exceeds 50 MPa, the operation of the apparatus including the fluid pump or the like may be hindered. Incidentally, carbon dioxide has a critical temperature of 31 ° C. and a critical pressure of 7.53 MPa, and carbon monoxide has a critical temperature of 37 ° C. and a critical pressure of 7.26 MPa.
The various materials mentioned as the supercritical fluid can also be suitably used as a subcritical fluid having a temperature slightly lower than the temperature in the supercritical state or a pressure slightly lower than the pressure in the supercritical state. That is, even when a subcritical fluid such as subcritical carbon dioxide is brought into contact with the resin, the chain transfer agent of the resin can be extracted and removed. In the case of a supercritical fluid, it may be preferable to use a subcritical fluid instead of the supercritical fluid when the resin composition or shape is inadvertently changed.
Various materials mentioned as the supercritical fluid can be preferably used as the subcritical fluid.
The supercritical fluid and the subcritical fluid may be used alone or as a mixture of two or more.

  The critical temperature and critical pressure of the supercritical fluid are not particularly limited and may be appropriately selected depending on the intended purpose. The critical temperature is preferably −273 to 400 ° C., particularly preferably 0 to 200 ° C. preferable. At this time, the critical pressure is not particularly limited as long as it is a pressure that forms a supercritical fluid, but is preferably 1 MPa or more, more preferably 7.2 MPa or more.

In addition to the supercritical fluid and the subcritical fluid, other fluids can be used in combination. The other fluid is preferably one having a high affinity with the low softening point substance (chain transfer agent) to be removed. When the image-forming particles have a core-shell structure, the substance constituting the shell is not dissolved. Those are preferred. Specifically, nitric oxide, ethane, propane, ethylene and the like are preferable.
The mixing ratio of the other fluid and at least one of the supercritical fluid and the subcritical fluid is not particularly limited and may be appropriately selected depending on the purpose.

Furthermore, an organic solvent can be added in addition to the supercritical fluid and the subcritical fluid. By adding the organic solvent, the chain transfer agent described later can be removed more easily.
There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably, For example, methanol, ammonia, melamine, urea, thiodiethylene glycol etc. are mentioned. Specifically, a removal aid such as chloroform having high solubility of the polymerizable monomer is particularly preferable. Addition of the chloroform increases the effect of removing the chain transfer agent.

-Removal of chain transfer agent-
The removal of the chain transfer agent is performed on the chain transfer agent present in the resin. In addition, in order to change the site | part which performs the said removal, and the degree of a process, it can carry out by changing suitably types, such as temperature, a pressure, a supercritical fluid, for example.
The removal method is not particularly limited as long as at least one of the supercritical fluid and the subcritical fluid is brought into contact with the resin, and can be appropriately selected according to the purpose.
As an operation of bringing at least one of the supercritical fluid and the subcritical fluid into contact with the resin, the container in which the supercritical fluid and the subcritical fluid circulate but the resin is not discharged is filled with the resin, The operation of circulating the critical fluid and the subcritical fluid, the fluid medium of the supercritical fluid and the subcritical fluid and the resin are filled in a closed system, and the fluid medium is heated and pressurized to bring the fluid medium into the supercritical state and the subcritical fluid. There are operations to make it critical.
Further, the shape of the resin to be treated is appropriately selected from, for example, (fine) particles, powders, granules, pellets, spheres, plates, sheets, rods, columns, polygonal columns, indefinite shapes, etc. In view of ensuring uniformity of the removal process and ease of handling in the process, a (fine) particulate form or a pellet form is preferable.

  The apparatus used for the removal is not particularly limited and may be appropriately selected depending on the purpose. For example, a pressure vessel for removing the resin and a pressure for supplying the supercritical fluid The apparatus provided with the separation tank which has a pump and the pressure-reduction valve which isolate | separates the gas containing the chain transfer agent removed from the said resin into a chain transfer agent and a solvent is mentioned suitably.

  As a processing method using the apparatus, first, the resin is charged into the pressure vessel, the supercritical fluid is supplied into the pressure vessel by a pressure pump, and the supercritical fluid is brought into contact with the resin. The chain transfer agent is removed, and the supercritical fluid containing the chain transfer agent is discharged. When the supercritical fluid is returned to room temperature and normal pressure, the supercritical fluid becomes a gas, so that removal of the solvent becomes unnecessary. Further, at this time, in the separation tank, the pressure may be reduced by the pressure reducing valve, the chain transfer agent and the supercritical fluid may be separated, and the supercritical fluid may be reused.

  The temperature at which the removal is performed is not particularly limited as long as it is equal to or higher than the critical temperature of the supercritical fluid or the subcritical fluid to be used, and can be appropriately selected according to the purpose. Is preferably equal to or lower than the melting point of the substance forming the resin, and more preferably a temperature at which aggregation such as adhesion between the resins does not occur. The lower limit of the critical temperature is preferably a temperature at which the other fluid that can be added to the supercritical fluid can exist as a gas.

  Through the above steps, the resin chain transfer agent is removed using at least one of the supercritical fluid and the subcritical fluid.

(Resin fine particles and production method thereof)
The resin can also be obtained as resin fine particles. There is no restriction | limiting in particular as a manufacturing method of the said resin fine particle, According to the objective, it can select suitably. Examples thereof include pulverized resin fine particles, resin fine particles obtained by polymerization, and resin fine particles obtained by a microencapsulation method (spray drying method, coacervation method, etc.). Among them, a polymerization method in a liquid solvent, in particular, an aqueous medium in which a polymerization initiator is dissolved, at least a radically polymerizable monomer dissolved in the aqueous medium is supplied to form polymer particles. Method (hereinafter referred to as emulsion polymerization method), at least a polymerizable mixture containing a polymerizable monomer and a polymerization initiator is put into an aqueous dispersion medium containing a suspension stabilizer and stirred to polymerize particles. A polymer that is dissolved in the hydrophilic organic liquid and added to the hydrophilic organic liquid, and is dissolved in the hydrophilic organic liquid. The resin fine particles obtained by a method of forming polymer particles by adding a radical polymerizable monomer that swells but hardly dissolves in the hydrophilic organic liquid (hereinafter referred to as dispersion polymerization method) are obtained. preferable. If necessary, the obtained resin fine particles can be used as seed particles, dispersed in an aqueous or organic solvent, and polymerization can be performed in the presence of the seed particles.
The median diameter is a particle diameter with a cumulative number distribution of 50%, and the mode diameter is the most frequent particle diameter in the number distribution. It can be said that the closer the ratio of the median diameter to the mode diameter in the resin fine particles is to 1, the more monodispersed, and the less variation among the particles, and it is considered that a certain function can be exhibited. Preferably, the ratio of median diameter to mode diameter of the resin fine particles is 1.10 or less, and more preferably 1.05 or less. The median diameter and mode diameter were measured using a laser diffraction particle size distribution analyzer SALD-2000 manufactured by Shimadzu Corporation.

  The resin fine particles include, as necessary, an antioxidant, a lubricant, a release agent, a plasticizer, a pigment, a pigment dispersant, a dye, a dyeing assistant, a discoloration inhibitor, a foaming agent, a foam nucleating agent, an inorganic filler, a charge Known additives such as a control agent, an antistatic agent, a sliding agent, a pore-forming agent, a pharmaceutical composition, an enzyme, a coenzyme, an antibody, a binding protein, a lectin, and a hormone receptor can also be contained. Furthermore, the resin of the present invention can be used in combination with known resins such as GP-PS, HI-PS, MS resin, MBS resin, AS resin, ABS resin, PE, PP, and PPO.

  The use of the obtained resin fine particles is not limited, and can be appropriately selected according to the purpose, such as a display, a rear projection screen for viewing a film, a magnetic recording medium, a liquid crystal display spacer, various lighting fixtures, etc. Seed particles (monodispersed fine particles) used in the production of polymer fine particles for use in light diffusing agents, column packing materials, carrier / drug delivery systems for diagnostic agents, bioreactors, etc., as well as electrophotography and electrostatic recording methods -It can also be used as polymer fine particles that are optimal for the use of image-forming particles used in electrostatic printing and the like. The resin fine particles can be used as they are, and if necessary, are mixed with an additive to modify the surface, and further, a process for fixing the additive, in the presence of a supercritical fluid and a subcritical fluid. It is also possible to add treatments such as immersion, extraction, and coating with the additive.

Next, the emulsion polymerization method, suspension polymerization method, and dispersion polymerization method will be described.
Hereinafter, the emulsion polymerization method will be described.
The resin fine particles obtained by the emulsion polymerization method are prepared by forming polymer particles by supplying at least a radically polymerizable monomer dissolved in the aqueous medium to the aqueous medium in which the polymerization initiator is dissolved. can get. In addition, the aqueous medium as used in the field of this invention shows what contained 50 mass% or more of water at least.

  Although this method is not particularly limited, for example, U.S. Pat. No. 4,247,434, U.S. Pat. No. 4,339,337, U.S. Pat. No. 4,358,388, U.S. Pat. No. 5,496,897, U.S. Pat. No. 4,336,173. Journal of Applied Polymer Science Vol. 51 1-11 (1994). This includes a method of producing resin fine particles having a desired particle diameter in combination with seed polymerization described later.

-Surfactant-
In the present invention, a surfactant can be used for the purpose of promoting emulsification.
It is preferable to use a surfactant in the range of 0.001 to 0.1% by weight based on the weight of the polymerizable monomer. Although it does not specifically limit as surfactant which can be used, The following ionic surfactant can be mentioned as an example of a suitable thing.

  Examples of ionic surfactants include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6 Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, etc.), sulfuric acid Ester salt (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salt (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, stearic acid) Potassium, calcium oleate), and the like.

  Nonionic surfactants can also be used. Specifically, polyethylene oxide, polypropylene oxide, combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, sorbitan ester Etc.

In addition, when water-soluble to easily soluble monomers are used, emulsion polymerization occurs simultaneously in water, and the resulting suspension polymer is contaminated with small emulsion polymerization particles. Etc. may be added to prevent emulsion polymerization in the aqueous phase. In order to increase the viscosity of the continuous phase (dispersion medium) and prevent coalescence of particles, a polyhydric alcohol such as glycerin or glycol may be added to water. Also, because of the solubility decreases in water readily soluble monomer, it is also possible to use NaCl, KCl, and salts such as _Na 2 SO _4.

Subsequently, the suspension polymerization method will be described below.
The resin fine particles obtained by the suspension polymerization method are prepared by adding at least a polymerizable mixture containing a polymerizable monomer and a polymerization initiator into an aqueous dispersion medium system containing a suspension stabilizer and stirring. It can be produced by forming polymer particles. This method corresponds to resin fine particles produced by a known suspension polymerization method.

-Dispersion stabilizer-
A dispersion stabilizer for satisfactorily dispersing the polymerizable monomer composition in the aqueous dispersion medium may be used. These may be used individually by 1 type and may use 2 or more types together.
For example, in the case of a dispersion stabilizer of an inorganic compound, a metal such as cobalt, iron, nickel, aluminum, copper, tin, lead, magnesium or an alloy thereof (particularly 1 μm or less is preferable), tricalcium phosphate, magnesium phosphate, Aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, titania, iron oxide, copper oxide, Examples thereof include fine inorganic powders of oxides such as nickel oxide and zinc oxide, pigments such as carbon black, nigrosine dye, aniline blue, chrome yellow, phthalocyanine blue, and rose bengal, and dyes.

  Examples of dispersion stabilizers for organic compounds include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or hydroxyl groups. Acrylic monomers containing, for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxy methacrylate Propyl, acrylic acid, 3-chloro-2-hydroxypropyl, methacrylic acid, 3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin Monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or vinyl alcohol and carboxyl group Esters of compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone , Homopolymers or copolymers such as those having a nitrogen atom such as vinylimidazole or ethyleneimine or a heterocyclic ring thereof, polyoxyethylene, polyoxy Lopylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene Nonoxyphenyl esters and other polyoxyethylenes, celluloses such as methylcellulose and hydroxypropylcellulose, or those having a hydrophilic monomer and a benzene nucleus such as styrene, α-methylstyrene, vinyltoluene, or derivatives thereof, acrylonitrile, methacrylate Copolymers with acrylic acid or methacrylic acid derivatives such as nitrile and acrylamide, as well as crosslinkable monomers such as ethyl Examples thereof include copolymers with lenglycol dimethacrylate, diethylene glycol methacrylate, allyl methacrylate, divinylbenzene and the like.

It is also possible to use resin fine particles as a dispersion stabilizer.
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc. These may be used individually by 1 type and may use 2 or more types together.

Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

  Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

The volume average particle size of the resin fine particles is not particularly limited as long as it is a resin fine particle size that can ensure emulsifiability, and is preferably 1 nm to 1 μm, and more preferably 10 nm to 500 nm.
The dispersion stabilizer is preferably used in an amount of 0.2 to 10.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Commercially available dispersion stabilizers may be used as they are, but when the above inorganic compound is used as a dispersion stabilizer, an inorganic compound is produced under stirring in a dispersion medium in order to obtain dispersed particles having a fine uniform particle size. It can also be made. For example, in the case of tricalcium phosphate, a dispersant suitable for the suspension polymerization method can be obtained by charging and mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution into water under stirring.

-Surfactant-
Further, for the fine dispersion of the inorganic dispersant, a surfactant in the range of 0.001 to 0.1% by weight with respect to the weight of the polymerizable monomer may be used. This surfactant is for accelerating the intended action of the dispersion stabilizer. Although it does not specifically limit as surfactant which can be used, The following ionic surfactant can be mentioned as an example of a suitable thing.

  Examples of ionic surfactants include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6 Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, etc.), sulfuric acid Ester salt (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salt (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, stearic acid) Potassium, calcium oleate), and the like.

  Nonionic surfactants can also be used. Specifically, polyethylene oxide, polypropylene oxide, combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, sorbitan ester Etc.

In addition, when a water-soluble monomer is used, emulsion polymerization occurs simultaneously in water, and the resulting suspension polymer is contaminated with small emulsion polymerization particles. Therefore, a water-soluble polymerization inhibitor such as a metal salt is added. It is also possible to prevent emulsion polymerization in the aqueous phase. In order to increase the viscosity of the continuous phase (dispersion medium) and prevent coalescence of particles, a polyhydric alcohol such as glycerin or glycol may be added to water. Also, because of the solubility decreases in water readily soluble monomer, it is also possible to use NaCl, KCl, and salts such as _Na 2 SO _4. In the present invention, these are mainly used as an emulsifier at the time of emulsification, but they may be used for other processes or purposes.

Subsequently, the dispersion polymerization method will be described below.
The fine resin particles obtained by the dispersion polymerization method dissolve in the organic medium in the organic medium, but the resulting polymer is a radical polymerizable monomer that is insoluble or hardly soluble in the organic medium. It can manufacture by adding a body and a polymerization initiator, and forming a polymer particle.

  This method is not particularly limited, but is described in, for example, “Kinetics of Polymerization in Dispersed Systems” (Levy et al.), Impac Macro (1982), p. 76. Dispersion polymerization of styrene and methyl methacrylate, “Monodisperse Polymeric Spheres in the Micron Size Range by a Single Step Process”, The British Polymer Journal (December 1982) See pages 131-136 for the production of monodisperse polystyrene spheres in the micron-size region by a one-step process, “Polyelectrolyte Stabilized Latices Part 1, Preparation” (Corner) Elsvier Scientific Publishing Compary, ( 1981), pp. 119-129, stabilized latexes of certain polyelectrolytes, especially polyacrylic Polystyrene latex dispersion prepared by polymerizing styrene in alcohol / water mixture containing polyelectrolyte such as acid, “Absorption of Low Molecular Weight in aqueous dispersion by polymer oligomer particles” Compounds in Aquesns Dispersions by Polmer-Oligomer Particles) "2a, Makromol Chem. 180, (1979), pages 737-744, two-stage swelling to produce polymer particles with increasing absorption capacity Examples of the method include a resin fine particle produced by a known suspension polymerization method.

-Organic media-
A nonpolar solvent such as hexane or cyclohexane can be used for the organic medium of the present invention, but a hydrophilic organic liquid is preferable. This is because when the hydrophilic organic solvent is used, resin fine particles having a large particle diameter can be obtained with higher accuracy than when a nonpolar solvent is used.

  Examples of the hydrophilic organic liquid include methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol, 3-pentanol, Octyl alcohol, benzyl alcohol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, alcohols such as ethylene glycol, glycerin, diethylene glycol, methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Ether alcohols such as ether, and the like. These organic liquids can be used singly or as a mixture of two or more.

  In addition, by using together with alcohols and ether alcohols, various SP values are changed under conditions that do not have solubility in the generated polymer particles of the organic liquid, and the polymerization conditions are changed between the seed particles. An organic liquid capable of suppressing coalescence and generation of new particles can be used in combination. These organic liquids used in combination include hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, tetrabromoethane, ethyl ether, Ethers such as dimethyl glycol, trioxane and tetrahydrofuran, acetals such as methylal and diethyl acetal, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexane, esters such as butyl formate, butyl acetate, ethyl propionate and cellosolve acetate Acids such as formic acid, acetic acid, propionic acid, sulfur such as nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylsulfoxide, dimethylformamide, nitrogen Containing organic compounds, other water is also included.

Polymerization in the presence of SO ₄ ²⁻ , NO ₂ ⁻ , PO ₄ ³⁻ , Cl ⁻ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , and other inorganic ions in a solvent mainly composed of the above hydrophilic organic liquid May be performed.
Moreover, in order to disperse | distribute a polymerizable monomer composition favorably in an aqueous dispersion medium, you may add the said dispersion stabilizer and the said surfactant as needed.

  The polymerization conditions are determined according to the target average particle size and target particle size distribution of the polymer particles, and the concentration and mixing ratio of the dispersion stabilizer, the surfactant and the polymerizable monomer in the organic medium are determined. The In general, if the average particle size of the polymer particles is to be reduced, the concentration of the dispersion stabilizer and the surfactant is increased, and if the average particle size is to be increased, the dispersion stabilizer and the surfactant are used. The concentration of is set low. On the other hand, if the particle size distribution is to be made very sharp, the polymerizable monomer concentration is low, and if a relatively wide distribution is acceptable, the polymerizable monomer concentration is set high.

  In general, when the amount of the dispersion stabilizer used is 1/50 times (2%) or more of the weight of the polymerizable monomer, 90% by weight of particles having a mean particle size within ± 25%. It is difficult to obtain what has a distribution of more than%. The amount of the dispersion stabilizer used varies depending on the type of the polymerizable monomer for forming the desired polymer particles, but is preferably 0.1% by weight to 10% by weight with respect to the hydrophilic organic liquid. More preferred is 5% by weight to 5% by weight. When the concentration of the dispersion stabilizer is low, the produced polymer particles have a relatively large diameter, and when the concentration is high, small particles are obtained. There is little effect on conversion.

Furthermore, polymerization is performed in the presence of the polymerizable monomer and the polymerization initiator in a solution dispersed in the aqueous medium or the organic medium using the resin fine particles obtained above as seed particles. Is also possible (seed polymerization).
In carrying out seed polymerization, the dispersion stabilizer and the surfactant may be used for the purpose of improving emulsifying properties.
In the seed polymerization method, if the particle diameter of the seed particles is within a narrow range, the particle diameters of the resin particles obtained are well aligned. That is, by performing polymerization using seed particles having a uniform particle size in advance, resin particles having a desired particle size according to the application, for example, 0.3 to 0.5 mm, 0.5 to 0.7 mm, It can be divided into narrow ranges such as 0.7 to 1.2 mm, 1.2 to 1.5 mm, and 1.5 to 2.5 mm, and can be obtained with a yield of almost 100% for each section.

The seed particles can be used, if necessary, by once sieving or classifying and adjusting the particle size so that it is in the range of ± 20% of the average particle size.
The amount of seed particles used is preferably 10 to 75% by weight, more preferably 15 to 50% by weight, based on the total amount of the polymer at the end of polymerization (including seed particles). When the amount of seed particles used is less than 10% by weight, it is difficult to control the polymerization rate of the resin fine particles within an appropriate range when supplying the polymerizable monomer, and the resulting particles have a high molecular weight or fine powder. It is industrially disadvantageous because it occurs in large quantities and as a result, the production efficiency decreases. Conversely, when it exceeds 75% by weight, it becomes difficult to obtain excellent moldability.

  In the seed polymerization method, when the polymerization initiator is added directly into an aqueous suspension, it becomes difficult to be uniformly absorbed by the seed particles. Therefore, it is added in a state suspended or emulsified in an aqueous medium, or a small amount of the polymerization initiator is added. It is desirable to dissolve in a polymerizable monomer, add an inorganic suspension stabilizer and an anionic surfactant and add as an aqueous suspension. It is important in terms of reaction or quality to diffuse the polymerization initiator not only to the surface layer of the seed particles but also to the inside as much as possible. By allowing the polymerization initiator to diffuse into the seed particles, a substantially uniform reaction is performed between the particle surface layer and the inside of the particles, and resin particles having a uniform weight average molecular weight are obtained. In order to diffuse the polymerization initiator to the inside of the seed particles, it is effective to absorb an appropriate amount of the polymerizable monomer in the seed particles and soften the seed particles appropriately. By appropriately softening the seed particles, absorption of the polymerizable monomer containing the polymerization initiator is promoted, and absorption of the polymerization initiator can be promoted. As a result, the production of fine powder can be suppressed. When the ratio of the total amount of polymerizable monomers added before the start of polymerization is less than 25% by weight based on the total amount of the seed particles and the added polymerizable monomer, the seed particles are not sufficiently softened and the polymerization is performed. The rate of absorption of the polymerizable monomer suspension containing the initiator into the seed particles becomes slow, and the absorption of the polymerization initiator is delayed. In this case, an excessive amount of the polymerizable monomer containing the polymerization initiator adheres to the seed particle surface layer, and adhesion to the particle surface and aqueous suspension before the polymerization initiator is absorbed into the seed particles. The release to the liquid is repeated, and the generation of fine powder increases. Further, when the seed particles are insufficiently softened, the weight average molecular weight distribution in the resin particles obtained in terms of quality and the uniformity of the surface of the generated resin fine particles are lacking. Therefore, the addition amount of the polymerizable monomer is preferably 25% by weight or more from the viewpoint of using the polymerization initiator.

In the seed polymerization method of the present invention, an additive used when producing expandable resin particles such as a plasticizer, a foamed cell nucleating agent, a filler, a flame retardant, a flame retardant aid, a lubricant, and a colorant is necessary. You may use suitably according to.
In the present invention, when the diameter of the seed particles is increased, the absorption efficiency and internal diffusion of the polymerization initiator are decreased, and the molecular weight tends to be increased, and the use amount of the seed particles is small with respect to the resin particles after the completion of the polymerization. In addition, it is difficult to control the polymerization rate when supplying the polymerizable monomer, the reaction time is extended, and the molecular weight adjustment tends to be difficult. In order to adjust the weight average molecular weight of the resin particles to a range suitable for normal molding, it is important to make the polymerization initiator work efficiently, and polymerization initiation that prevents unnecessary decomposition and generates radicals throughout the polymerization process. It is preferable to control the distribution of the agent, the polymerization temperature program, the monomer supply rate, the polymerization rate adjustment during the polymerization, and the like.

  The distribution of the polymerization initiator, the polymerization temperature program, and the monomer supply rate are interrelated, and if these are balanced, it is possible to prevent the polymerization time from being extended due to excessive decrease in the polymerization rate, Generation | occurrence | production in large quantities can be prevented and the fall of the efficiency of a polymerization initiator can be prevented. When the entire amount of the polymerization initiator required for polymerization of the polymerizable monomer is added before the start of polymerization, the polymerization monomer starts to be supplied from a relatively low temperature in order to increase the efficiency of the polymerization initiator, and the polymerization starts. It is desirable to supply continuously or intermittently while heating with a temperature gradient so that radicals of the agent are appropriately generated. At the time when the supply of the polymerizable monomer is completed, the temperature is relatively high, the remaining polymerization initiator is appropriately consumed, and the molecular weight of the resin particles can be appropriately adjusted.

Then, the manufacturing method of the polymerization method in a liquid solvent is demonstrated.
When granulating the monomer composition in an aqueous dispersion medium, for example, a normal stirrer or T.W. K. Disperse the polymerizable composition by dispersing means such as homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Claremix (manufactured by M Technique Co., Ltd.) or the like with a high shearing force such as an agitator or ultrasonic disperser. Use liquid. The stirring blade of the stirrer is preferably a turbine type rather than a paddle type. Alternatively, a polymerizable composition dispersion can be obtained by using a porous material such as a porous glass and press-fitting the dispersed phase into the continuous phase. In the case of dispersion by shearing force, it is preferable to adjust the stirring speed and time so that the monomer composition has a particle size of 30 μm or less. More specifically, the rotational speed is preferably used so that the weekly speed of the turbine is 10 to 30 m / sec, and the granulation time is not particularly limited, but is preferably 5 to 60 minutes. The ratio of the monomer composition to the dispersion medium is preferably 200 to 3,000 parts by weight of the dispersion medium with respect to 100 parts by weight of the monomer composition. In the polymerization, it is necessary to expel oxygen in the reaction vessel sufficiently with an inert gas such as nitrogen gas or argon gas. If the oxygen purge is insufficient, fine particles are likely to be generated.

  By further polymerizing the granulated polymerizable composition, the resin fine particles used in the present invention are suitably obtained. In this polymerization, the polymerization reaction proceeds, but stirring may be performed to such an extent that the dispersion state is maintained by the action of the dispersion stabilizer and the precipitation of the particles is prevented. The polymerization is preferably carried out by setting the polymerization temperature to a temperature of 40 ° C. or higher (more preferably 60 to 90 ° C.). The polymerization time may be set so that the polymerization is completed. Specifically, the polymerization time is preferably 2 to 48 hours. If necessary, the polymerization can be stopped in the state of a desired particle size and particle size distribution, or a polymerization initiator can be sequentially added to increase the polymerization rate.

  In order to remove the dispersant, the particles obtained by the polymerization may be treated with acid or alkali, or other methods (or the dispersant is removed by washing or the like without treatment) as necessary.

(Image-forming particles using resin fine particles from which chain transfer agent has been removed)
Image-forming particles can also be produced using the resin fine particles from which the chain transfer agent has been removed. The purpose of the fine particles from which the chain transfer agent has been removed includes an adhesive substrate, a colorant, a release agent, a charge control agent, a fluidity improver, and a cleaning property improver for adhesion to a recording medium such as paper. , Magnetic materials, and the like that exhibit one or more of these functions, and emulsion stabilizers. As long as it is used to produce image forming particles, it does not matter whether or not the resin particles after removal of the chain transfer agent are finally present in the image forming particles. For example, an emulsion stabilizer that is used during granulation of image-forming particles and that is removed in a later step so that no resin fine particles remain as image-forming particle particles is also included in the present invention.

  The component that can be contained in the resin fine particles from which the chain transfer agent has been removed is not particularly limited and can be appropriately selected according to the purpose. For example, an adhesive base material for the purpose of adhesion to a recording medium such as paper , Coloring agents, mold release agents, charge control agents, fluidity improvers, cleaning improvers, magnetic materials, and the like that exhibit one or more of these functions. If necessary, the resin fine particles from which the chain transfer agent has been removed may be added to a colorant, a release agent, inorganic fine particles, resin fine particles, a charge control agent, a polymer polymer particle, a fluidity improver, a cleaning property improver, a magnetic agent. A process of mixing with an additive such as a material and dispersing on the surface, a process of fixing the additive, and the resin fine particles from which the chain transfer agent has been removed are dissolved in an additive-containing solution or dispersion; Alternatively, the additive may be subjected to a treatment such as dipping and coating in the presence of a supercritical fluid and a subcritical fluid.

  Details of the components contained in, dispersed in, immobilized on, or immersed in, the surface of the image-forming particles produced using the resin fine particles from which the chain transfer agent has been removed will be described.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, pyridian, emerald green, pigment green B, naphthol green B, green gold, reed De green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide, lithopone, and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular in content in the said image forming particle of the said coloring agent, Although it can select suitably according to the objective, 1-15 mass% is preferable and 3-10 mass% is more preferable. When the content is less than 1% by mass, a reduction in coloring power of the image-forming particles is observed, and when the content exceeds 15% by mass, poor pigment dispersion occurs in the image-forming particles, resulting in a reduction in coloring power. In addition, the electrical characteristics of the image-forming particles may be deteriorated.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polymer of styrene or a substituted product thereof include polystyrene, poly p-chlorostyrene, and polyvinyl toluene. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.
The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three roll mill is preferably used.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably. Examples of the waxes include low molecular weight polyolefin waxes, synthetic hydrocarbon waxes, natural waxes, petroleum waxes, higher fatty acids and metal salts thereof, higher fatty acid amides, and various modified waxes thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the low molecular weight polyolefin wax include low molecular weight polyethylene wax and low molecular weight polypropylene wax. Examples of the synthetic hydrocarbon wax include Fischer-Tropsch wax. Examples of the natural waxes include beeswax, carnauba wax, candelilla wax, rice wax, and montan wax. Examples of the petroleum waxes include paraffin wax and microcrystalline wax. Examples of the higher fatty acid include stearic acid, palmitic acid, myristic acid, and the like.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability. If it exceeds 160 ° C., it may easily cause a cold offset when fixing at a low temperature. May occur.
There is no restriction | limiting in particular as content in the said image forming particle of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass parts is preferable with respect to 100 weight part of image forming particles, 3 -30 mass parts is more preferable. When the content exceeds 40 parts by mass, the low-temperature fixability may be impaired and the image quality may be deteriorated (glossiness is too high).

-Inorganic fine particles-
The inorganic fine particles are not particularly limited and can be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the image-forming particles is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.
The inorganic fine particles can be suitably used as an external additive for the image forming particles. Details will be described later.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferred examples include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides And a simple substance of phosphorus or a compound thereof, a simple substance of tungsten or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. Among these, salicylic acid metal salts and metal salts of salicylic acid derivatives are preferred. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a metal of the said metal salt, According to the objective, it can select suitably, For example, aluminum, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. are mentioned.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, cal Examples thereof include polymer compounds having a functional group such as a boxyl group and a quaternary ammonium salt.

  The charge control agent may be melted and kneaded together with the master batch and then dissolved or dispersed, or may be added together with the components of the image-forming particles when directly dissolved or dispersed in the organic solvent. Alternatively, it may be fixed on the surface of the image-forming particles after production of the image-forming particles.

  The content of the charge control agent in the image-forming particles varies depending on the type of binder resin, the presence or absence of an additive, a dispersion method, and the like, and cannot be specified in general. On the other hand, 0.1-10 mass parts is preferable, and 1-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charging characteristics of the image-forming particles may be deteriorated. When the content exceeds 10 parts by mass, the chargeability of the image-forming particles becomes too high, and the main charging By reducing the effect of the control agent, the electrostatic attraction force with the developing roller may increase, leading to a decrease in developer fluidity and a decrease in image density.

-Polymer polymer particles-
The polymer polymer particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polystyrene, methacrylic acid obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, etc. Examples thereof include particles formed of esters, acrylic acid ester copolymers, silicone resins, polycondensation resins such as benzoguanamine, nylon, and thermosetting resins. These may be used individually by 1 type and may use 2 or more types together.

-Fluidity improver-
The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. These may be used individually by 1 type and may use 2 or more types together.

-Cleaning improver-
The cleaning improver is added to the image-forming particles in order to remove the transferred developer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid or the like. And polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. These may be used individually by 1 type and may use 2 or more types together.
The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

-Magnetic material-
The magnetic material is iron oxide such as magnetite, hematite, ferrite, etc., metal such as iron, cobalt, nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium And alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

  These magnetic materials preferably have an average particle size of 2 μm or less, more preferably about 0.1 to 0.5 μm. The content of the magnetic substance in the image-forming particles is preferably about 20 to 200 parts by mass, particularly preferably 40 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer. 150 parts by mass is preferable.

  In addition, the magnetic properties of the magnetic material when 800 kA / m is applied are as follows: coercive force (Hc) 1.6 to 24 kA / m, saturation magnetization (σs) 50 to 200 Am2 / kg, residual magnetization (σr) 2 to 20 Am2 / kg. Are preferred.

  In order to improve the dispersibility of these magnetic materials in the image-forming particles, it is also preferable to subject the surface of the magnetic material to a hydrophobic treatment. For the hydrophobization treatment, coupling agents such as a silane coupling agent and a titanium coupling agent are used, and among them, a silane coupling agent is preferably used. As silane coupling agents, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyl Examples include diethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane.

(Method for producing image-forming particles using resin fine particles from which chain transfer agent has been removed)
A method for producing image-forming particles using the resin fine particles from which the chain transfer agent has been removed obtained by the above method will be described.
In the case where the resin fine particles from which the chain transfer agent has been removed already contain at least an adhesive base material and a colorant for the purpose of adhesion to a recording medium such as paper, the resin fine particles themselves from which the chain transfer agent has been removed are imaged. Can be used as formed particles, but if necessary, adhesive substrates, colorants, mold release agents, charge control agents, fluidity improvers, and cleaning properties for adhesion to recording media such as paper An image forming particle can also be obtained by adding an agent, a magnetic material, or the like that exhibits one or more of these functions.

A specific example of a method for producing image forming particles using resin fine particles from which the chain transfer agent has been removed will be described.
-Emulsion aggregation method-
Image-forming particles can be produced by a method in which resin fine particles from which the chain transfer agent has been removed are produced, and then an organic solvent, an aggregating agent, and the like are added and associated. A method of preparing by agglomeration or fusion by mixing with a dispersion of a release agent or a colorant necessary for the formation of image-forming particles at the time of agglomeration or fusion, or a release agent or coloration in a monomer And a method of emulsion polymerization after dispersing image forming particle constituents such as an agent. Here, the aggregation or fusion means that a plurality of resin particles and colorant particles are associated. In addition, the aqueous medium as used in the field of this invention shows what contained 50 mass% or more of water at least.

  The method is not particularly limited, and examples thereof include methods disclosed in JP-A-5-265252, JP-A-6-329947, and JP-A-9-15904. That is, a method of associating a plurality of fine particles composed of resin particles and colorants, etc., or particles composed of resin and colorant, in particular, after dispersing them in water using an emulsifier, the critical aggregation concentration The above flocculant is added for salting out, and at the same time, the formed polymer itself is heated and fused at a temperature higher than the glass transition temperature to gradually grow the particle size while forming fused particles. Then, a large amount of water is added to stop the particle size growth, and the shape is controlled by smoothing the particle surface while heating and stirring, and the particles are heated and dried in a fluid state while containing water. Inventive image-forming particles can be formed. Here, an organic solvent that is infinitely soluble in water may be added simultaneously with the flocculant.

  The particle size of the resin fine particles from which the chain transfer agent has been removed may be any particle size as long as it is equal to or smaller than the target non-spherical particle size, but the particle size of commonly used fine polymer particles Is preferably in the range of 0.01 to 10 μm.

  The flocculant is not particularly limited, but one selected from metal salts is preferably used. Specifically, as a monovalent metal, for example, an alkali metal salt such as sodium, potassium or lithium, as a divalent metal, for example, an alkaline earth metal salt such as calcium or magnesium, or a divalent metal such as manganese or copper. And salts of trivalent metals such as iron and aluminum, and specific salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, etc. Can be mentioned. These may be used in combination.

These flocculants are preferably added in an amount equal to or higher than the critical aggregation concentration. The critical flocculation concentration is an index relating to the stability of the aqueous dispersion, and indicates a concentration at which flocculation occurs when a flocculant is added. This critical aggregation concentration varies greatly depending on the emulsified components and the dispersant itself. For example, it is described in Seizo Okamura et al., “Polymer Chemistry 17, 601 (1960) edited by Japan Society of Polymer Science”, and the like, and a detailed critical aggregation concentration can be obtained. As another method, a desired salt is added to the target particle dispersion at different concentrations, the ζ (zeta) potential of the dispersion is measured, and the salt concentration at which this value changes is defined as the critical aggregation concentration. You can ask for it.
The addition amount of the flocculant may be not less than the critical aggregation concentration, but is preferably 1.2 times or more, more preferably 1.5 times or more the critical aggregation concentration.

The solvent that dissolves infinitely means a solvent that dissolves infinitely in water, and in the present invention, a solvent that does not dissolve the formed resin is selected. Specific examples include alcohols such as methanol, ethanol, propanol, isopropanol, t-butanol, methoxyethanol, and butoxyethanol, nitriles such as acetonitrile, and ethers such as dioxane. In particular, ethanol, propanol, and isopropanol are preferable.
The addition amount of the infinitely soluble solvent is preferably 1 to 100% by volume with respect to the polymer-containing dispersion to which the flocculant is added.

  In order to make the shape uniform, it is preferable to fluidly dry a slurry in which 10% by mass or more of water is present after preparing and filtering colored particles. Those having a polar group are preferred. The reason for this is considered to be that it is particularly easy to make the shape uniform, in order to exhibit the effect that the water present is somewhat swollen with respect to the polymer in which the polar group is present. .

  In the association of the finely divided polymer particles in the emulsion aggregation method, an ordinary stirrer or T.W. K. Disperse the finely divided polymer particles with a high shearing stirrer such as Homomixer (made by Tokushu Kika Kogyo Co., Ltd.), Claremix (made by M Technique Co., Ltd.), etc., and add colorant, mold release agent and flocculant. By adding, associated particles are formed. In order to adjust the particle size of the associated particles, it is necessary to adjust the temperature, pH, stirrer rotation speed, and the like in the system. The granulation time is not particularly limited, but is preferably 5 to 60 minutes.

-Additive immobilization treatment-
In the present invention, the resin fine particles from which the chain transfer agent has been removed are bonded to a recording medium such as paper, an adhesive substrate, a colorant, a release agent, a charge control agent, a fluidity improver, and a cleaning agent. The image quality, durability, and reliability of the image forming particles can be improved by firmly adding an additive such as a property improver or a magnetic material.
As a method of immobilizing the additive on the resin fine particles from which the chain transfer agent has been removed, there is a method in which the additive is attached to the surface of the resin fine particles from which the chain transfer agent has been removed, and heat treatment or mechanical energy is applied. .

Examples of methods for applying mechanical energy include a method in which an impact force is applied to the mixture by blades rotating at high speed, a method in which the mixture is injected into a high-speed air stream and accelerated, and resin particles or resin particles collide with an appropriate collision plate. There is. Specific apparatuses used here include an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and the like. (Manufactured by Nara Machinery Co., Ltd.), kryptron system / KOSMOS (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.
Further, in the present invention, in order to adhere the additive to the liquid in the liquid, the fixing treatment may be performed with the apparatus as described above after drying, but the fixing treatment may be performed in the drying process. For example, in addition to an ordinary spray dryer, drying and immobilization can be simultaneously performed using a medium fluidized drying device MSD (manufactured by Nara Machinery Co., Ltd.), a fluidized bed drying device slurry dryer (manufactured by Okawara Seisakusho), or the like.

(Image-forming particle characteristics)
The image forming particles are image forming particles made using the resin fine particles from which the chain transfer agent has been removed. As a result, since the chain transfer agent that should originally remain in the image-forming particles is removed, the odor during heat fixing caused by the chain transfer agent is improved, which is preferable.
In addition, the image-forming particles obtained in this manner have the chain transfer agent removed from the image-forming particles, so that drying treatment, washing treatment and the like are unnecessary. Further, after the chain transfer agent removal step, the process is completed by simply degassing carbon dioxide and the like by depressurizing the reaction vessel containing the supercritical fluid. For this reason, image-forming particles can be produced efficiently in a very short time, waste liquid processing and the like are unnecessary, and the burden on the environment is reduced.

  The image forming particles have the following volume average particle diameter, ratio of volume average particle diameter to number average particle diameter (volume average particle diameter / number average particle diameter), molecular weight, glass transition temperature, penetration, low temperature It preferably has fixability, thermal characteristics, image density, average circularity, and the like.

-Volume average particle size, ratio of volume average particle size to number average particle size (volume average particle size / number average particle size)-
In the present invention, the volume average particle diameter (Dv) of the image-forming particles is preferably at least 0.1 to 10 μm, more preferably 2 to 8 μm. The ratio (Dv / Dn) to the number average particle diameter (Dn) is preferably 1.25 or less, more preferably 1.05 to 1.20. With such dry image-forming particles, it has excellent heat-resistant storage, low-temperature fixability, and hot-offset resistance, especially when used in full-color copiers, etc., and in two-component developers Even if the balance of image-forming particles is performed over a long period of time, the fluctuation of the particle diameter of the image-forming particles in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Further, even when used as a one-component developer, even if the balance of the image forming particles is performed, the fluctuation of the particle diameter of the image forming particles is reduced, and the filming of the image forming particles on the developing roller and the image The image forming particles are not fused to a member such as a blade for thinning the formed particles, and good and stable developability and images can be obtained even in the long-term use (stirring) of the developing device.

  In general, it is said that the smaller the particle diameter of the image-forming particles, the more advantageous it is to obtain a high-resolution and high-quality image. It is disadvantageous. Further, when the volume average particle diameter is smaller than the range of the present invention, in the two-component developer, the image-forming particles are fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced. When used as a component developer, filming of image forming particles to the developing roller and fusing of image forming particles to a member such as a blade for thinning the image forming particles are likely to occur. Further, these phenomena are the same for image forming particles having a fine powder content higher than the above range of the present invention.

  Conversely, when the particle diameter of the image-forming particles is larger than the above range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of the image-forming particles in the developer is performed. In many cases, the variation in the particle diameter of the image-forming particles increases. It was also clarified that the same is true when the volume average particle diameter / number average particle diameter (Dv / Dn) is larger than 1.25. In addition, when the volume average particle size / number average particle size (Dv / Dn) is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the image forming particles and uniforming the charge amount. In some cases, the formed particles cannot be sufficiently charged or the cleaning property is deteriorated.

  The volume average particle size and the ratio of the volume average particle size to the number average particle size (volume average particle size / number average particle size) are, for example, a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics. Can be measured.

-Molecular weight-
There is no restriction | limiting in particular as a weight average molecular weight of the said image forming particle, According to the objective, it can select suitably, For example, 1,000 or more are preferable, 2,000-10,000,000 are more preferable, 3 1,000 to 1,000,000 is particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

-Glass transition temperature-
There is no restriction | limiting in particular as glass transition temperature (Tg) of the adhesive base material of the said image forming particle, According to the objective, it can select suitably, For example, 30-70 degreeC is preferable and 40-65 degreeC is more. preferable. When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the image-forming particles may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

-Penetration depth-
As the penetration, for example, the penetration measured by a penetration test (JIS K2235-1991) is preferably 15 mm or more, and more preferably 20 to 30 mm. When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated. The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with image-forming particles and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the image-forming particles to room temperature and conducting a penetration test.
In addition, it has shown that the said heat-resistant preservation | save property is excellent, so that the said penetration value is large.

-Low temperature fixability-
As the low temperature fixability, from the viewpoint of achieving both a reduction in the fixing temperature and the occurrence of no offset, it is preferable that the lower limit temperature for fixing is lower, and more preferable that the temperature at which no offset is generated is higher. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 150 ° C., and the non-offset temperature is 200 ° C. or more. The fixing minimum temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The fixing roll temperature is the lower limit fixing temperature. The offset non-occurrence temperature is set by, for example, using an image forming apparatus, setting a transfer paper, and each monochrome color of yellow, magenta, cyan, and black, and solid images of red, blue, and green as intermediate colors in each monochrome color. It can be determined by adjusting the toner image to be developed, adjusting the temperature of the fixing belt to be variable, and measuring the temperature at which no offset occurs.

-Thermal characteristics-
The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like. These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 50 degreeC or more is preferable and 80-120 degreeC is more preferable. When the softening temperature (Ts) is less than 50 ° C., at least one of heat resistant storage stability and low temperature storage stability may be deteriorated.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 60 degreeC or more is preferable and 70-150 degreeC is more preferable. When the outflow start temperature (Tfb) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 ° C. or higher is preferable, and 80 to 170 ° C. is more preferable. If the 1/2 method softening point (T1 / 2) is less than 60 ° C., at least one of heat-resistant storage stability and low-temperature storage stability may deteriorate.

-Image density-
The image density is preferably 1.90 or more, more preferably 2.00 or more, and particularly preferably 2.10 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). preferable. If the image density is less than 1.90, the image density may be low and high image quality may not be obtained.

The image density is, for example, imagio Neo 450 (manufactured by Ricoh Co., Ltd.), and the amount of developer attached to copy paper (TYPE6000 <70W>; manufactured by Ricoh Co., Ltd.) is 1.00 ± 0.05 mg / cm ^2. The solid roller image was formed at a surface temperature of the fixing roller of 160 ± 2 ° C., and the image density at any six positions in the obtained solid image was measured using a spectrometer (938 Spectrodensitometer manufactured by X-Light). It can be measured by measuring and calculating the average value.

-Average circularity-
The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected area as the shape of the image-forming particle by the perimeter of the actual particle, and is preferably 0.900 to 1.000, for example, 0.950. -0.990 is more preferable. The particles having an average circularity of less than 0.94 are preferably 15% or less. If the average circularity is less than 0.900, there may be a case where satisfactory transferability and high-quality images free from dust may not be obtained.

  The average circularity is determined by, for example, an optical detection band method in which a suspension containing image forming particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.) or the like.

The image forming particles are formed by the following steps.
(Mixed external additives)
As the external additive for assisting fluidity, developability and chargeability to the image-forming particles, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m <2> / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5.0% by weight, particularly preferably 0.01 to 2.0% by weight, based on the image forming particles.

  Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles, for example, polycondensation systems such as polystyrene, methacrylic acid ester, acrylic acid ester copolymer, silicone resin, benzoguanamine resin, nylon obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, thermosetting Polymer particles made of a functional resin.

Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
Further, it is more preferable that the inorganic fine particles used as the external additive are the same type as the inorganic fine particles added in the organic solvent.

  In order to remove the transferred developer remaining on the photoreceptor or the primary transfer medium, a cleaning property improving agent may be added. Examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. it can. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  A mixer that mixes image-forming particles and external additives can seal the shaft with gas, and the equipped stirring blade can rotate at high speed, and the entire container can be cooled or heated. If it is a certain apparatus, it will not specifically limit. Examples of the mixer satisfying such a point include a Henschel mixer (manufactured by Mitsui Mining) and a super mixer (manufactured by Kawata). The sealing gas is not particularly limited, but usually a rare gas such as helium or argon, nitrogen, dry air, or the like can be used.

  In the method for producing image-forming particles of the present invention, the amount ratio of the colored particles to be mixed with respect to the unit internal volume of the mixer is preferably 0.05 to 0.4 kg / l, preferably 0.1 to 0.3 kg / l. More preferably. If this amount is small, productivity will be low, while if it is large, colored particles and / or image-forming particles may be discharged out of the mixer and the yield of image-forming particles may be reduced. In the method for producing image-forming particles of the present invention, the amount of the external additive mixed with the colored particles is not particularly limited, but is usually 0.1 to 6 parts by weight, preferably 100 parts by weight of the colored particles. 0.3 to 5 parts by weight, more preferably 0.5 to 3 parts by weight.

  After mixing the external additive, the obtained image-forming particles can be passed through a sieve for the purpose of removing coarse particles, fused coarse particles due to mechanical heat generation, re-aggregates due to van der Waals force, and the like. For example, a step of passing a sieve having an opening of 100 to 250 μm is performed. As an apparatus having a sieve, for example, there is a multistage gyro shifter, and examples of the vibration method include mechanical vibration and ultrasonic vibration.

(Developer)
The developer of the present invention contains at least the image-forming particles of the present invention and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer containing a carrier, but when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed. The two-component developer is preferable in terms of improving the life.
In the case of the one-component developer using the image-forming particles as the image-forming particles of the present invention, even if the balance of the image-forming particles is performed, the variation in the particle diameter of the image-forming particles is small, and the image on the developing roller There is no filming of formed particles and no fusing of image forming particles to a member such as a blade for thinning the image forming particles, and good and stable developability even in long-term use (stirring) of a developing device. And an image is obtained. Further, in the case of the two-component developer using the image-forming particles of the present invention, even if the image-forming particle balance is performed over a long period of time, there is little variation in the particle diameter of the image-forming particles in the developer, and the developing device Good and stable developability can be obtained even with long-term stirring.

-Career-
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. Further, weakness such as a copper-zinc (Cu—Zn) system (30 to 80 emu / g) is advantageous in that the contact with the photoconductor in which the image forming particles are in a spiked state can be weakened and it is advantageous for high image quality. Magnetized materials are preferred. These may be used alone or in combination of two or more.

  The core material has a volume average particle diameter of preferably 10 to 150 μm, more preferably 40 to 100 μm. When the average particle diameter (volume average particle diameter (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If it exceeds 150 μm, the specific surface area may be reduced, and image-forming particles may be scattered. In the case of a full color having a large solid portion, the reproduction of the solid portion may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And fluorinated terpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, and silicone resins. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

  Since the developer of the present invention contains the image-forming particles, it is possible to suppress the generation of odor during image formation, and it is excellent in low-temperature fixability and releasability, and stably forms high-quality images. can do. The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for a container containing particles, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

(Container with image forming particles)
The container with image-forming particles of the present invention comprises the image-forming particles as the toner of the present invention or the developer containing the image-forming particles contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, the thing etc. which have a container main body and cap with image forming particle are mentioned suitably. The size, shape, structure, material and the like of the container body containing image forming particles are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. In addition, spiral irregularities are formed on the inner peripheral surface, and the image forming particles as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function. And the like are particularly preferred.

(Image forming particle cartridge)
The container with image-forming particles of the present invention can also be made into an image-forming particle cartridge by making the container itself detachable from the image-forming apparatus and storing the image-forming particles therein.

The material for the image-forming particle-containing container and the image-forming particle cartridge main body is not particularly limited and is preferably a material having good dimensional accuracy, for example, a resin is preferable. Among them, for example, a polyester resin, a polyethylene resin, Preferable examples include polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.
The image forming particle-containing container and the image forming particle cartridge of the present invention are easy to store and transport, have excellent handling properties, and are detachably attached to the process cartridge, image forming apparatus, etc. of the present invention described later to form an image. It can be suitably used for replenishing particles.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image, a charging unit, and the electrostatic latent image carried on the electrostatic latent image carrier using a developer. Of the developing means for forming a visible image and other means such as a cleaning means appropriately selected as necessary, a means including at least the developing means is integrally supported. As the developing means, a developer storage container that stores the image forming particles as the toner of the present invention or the developer, and the image forming particles or the developer stored in the developer storage container are carried and transported. It may have at least a developer carrier, and may further include a layer thickness regulating member for regulating the thickness of the image forming particle layer to be carried. The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably detachably provided in the electrophotographic apparatus of the present invention described later.

(Image forming device)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention is performed using such an image forming apparatus. 1 to 4 show schematic views of examples of the image forming apparatus of the present invention.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon and the like are preferable in terms of long life.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. I have.

  The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger. The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons, corotrons and scorotrons.

  The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device. The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the image-forming particles or the developer of the present invention to form a visible image. The visible image can be formed, for example, by developing the electrostatic latent image using the image-forming particles or the developer of the present invention, and can be performed by the developing unit. The developing means is not particularly limited as long as it can be developed using, for example, the image-forming particles or the developer of the present invention, and can be appropriately selected from known ones. Preferred examples include those having at least a developing unit that accommodates the image-forming particles or the developer and can apply the image-forming particles or the developer to the electrostatic latent image in a contact or non-contact manner. More preferably, the image forming particle-containing container, a developing device including an image forming particle cartridge, and the like.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a preferable example includes a stirrer that frictionally stirs and charges the image forming particles or the developer, and a rotatable magnet roller.

  In the developing unit, for example, the image-forming particles and the carrier are mixed and stirred, and the image-forming particles are charged by friction at that time, and are held in a stand-up state on the surface of the rotating magnet roller. Is formed. Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photosensitive member), a part of the image forming particles constituting the magnetic brush formed on the surface of the magnet roller is electrically It moves to the surface of the electrostatic latent image carrier (photosensitive member) by a strong attraction force. As a result, the electrostatic latent image is developed by the image forming particles, and a visible image is formed by the image forming particles on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the image-forming particles of the present invention, and the developer may be a one-component developer or a two-component developer. . The image forming particles contained in the developer are the image forming particles of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image to a recording medium. The intermediate transfer member may or may not be used, but the intermediate transfer member is used and the visible image is transferred onto the intermediate transfer member. A mode in which the visible image is secondarily transferred onto the recording medium after the primary transfer is preferable, and two or more colors, preferably full-color image-forming particles are used as the image-forming particles, and the visible image is transferred onto the intermediate transfer member. An embodiment including a primary transfer step of transferring to form a composite transfer image and a secondary transfer step of transferring the composite transfer image onto a recording medium is more preferable.
The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoconductor) with a transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred. The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

  The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the image forming particles of each color are transferred to the recording medium, or images of each color. You may carry out simultaneously at the time of the state which laminated | stacked this with respect to the forming particle. There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

-Static elimination process and static elimination means-
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit. The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

-Cleaning process and cleaning means-
The cleaning step is a step of removing the electrophotographic image forming particles remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit. The cleaning means is not particularly limited as long as it can remove the electrophotographic image forming particles remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include magnetic brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, and web cleaners.

-Recycling process and recycling means-
The recycling step is a step of recycling the electrophotographic (color) image forming particles removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

-Control process and control means-
The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

One mode of carrying out the image forming method of the present invention by the image forming apparatus of the present invention (for example, the image forming apparatus shown in FIGS. 1 to 4) will be described with reference to FIG.
An image forming apparatus 100 shown in FIG. 1 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer member 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and transfers (secondary transfer) a developed image (image-forming particle image) onto a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as the transfer unit to which a transfer bias for applying the transfer bias can be applied. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the image forming particle image on the intermediate transfer member 50 is arranged in the rotational direction of the intermediate transfer member 50 with the photosensitive member 10 and the intermediate transfer member 50. And the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 1, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying image forming particles from the developing device 40 to form a visible image (image forming particle image). The visible image (image-forming particle image) is transferred (primary transfer) onto the intermediate transfer body 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The remaining image forming particles on the photoconductor 10 are removed by the cleaning device 60, and the charge on the photoconductor 10 is once removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 illustrated in FIG. 2 does not include the developing belt 41 in the image forming apparatus 100 illustrated in FIG. 1, and the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan are disposed around the photoconductor 10. Except that the developing units 45C are directly opposed to each other, the configuration is the same as that of the image forming apparatus 100 shown in FIG. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 120 shown in FIG. 3 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400. The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer body cleaning device 17 for removing residual image forming particles on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 120, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And image forming particle images of black, yellow, magenta and cyan are formed in each image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120 is a partially enlarged schematic view of FIG. As shown in FIG. 4, each of the photoconductors 10 (the black photoconductor 10K, the yellow photoconductor 10Y, the magenta photoconductor 10M, and the cyan photoconductor 10C) and a charger that uniformly charges the photoconductors. 59, and exposing the photoconductor to each color image corresponding to each color image based on each color image information (L in FIG. 4), and forming an electrostatic latent image corresponding to each color image on the photoconductor And developing the electrostatic latent image with each color image forming particle (black image forming particle, yellow image forming particle, magenta image forming particle and cyan image forming particle). A developing unit 61 for forming an image-forming particle image, a transfer charger 62 for transferring the image-forming particle image onto the intermediate transfer member 50, a photoconductor cleaning device 63, and a static eliminator 64. Each single-color image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred onto the black photoconductor 10K on the intermediate transfer member 50 that is rotated by the support rollers 14, 15, and 16 in FIG. The black image formed on the yellow image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred ( Primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual image forming particles on the intermediate transfer member 50 after the image transfer are cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus of the present invention, since the image forming particles of the present invention are used, there is no odor during heat fixing, and a high-quality image can be obtained efficiently.

FIG. 5 shows a schematic diagram of an image forming apparatus equipped with the process cartridge of the present invention.
In the image forming apparatus equipped with the process cartridge having the developing means holding the image forming particles or the developer of the present invention, the photosensitive member is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging unit, and then image exposure light from an image exposure unit such as slit exposure or laser beam scanning exposure. In this way, an electrostatic latent image is sequentially formed on the peripheral surface of the photoreceptor, and the formed electrostatic latent image is developed with image forming particles by a developing unit. Then, the transfer unit sequentially transfers the transfer material fed between the photoconductor and the transfer unit in synchronization with the rotation of the photoconductor. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing the transfer residual toner by a cleaning means, and after being further neutralized, it is repeatedly used for image formation.

  Since the process cartridge of the present invention holds the image forming particles or developer of the present invention, the process cartridge has the above-described effects and can be mounted on the image forming apparatus. It is possible to provide an image forming apparatus with improved performance.

<About amorphous silicon photoconductor>
As described above, the amorphous silicon photoconductor is preferable as the electrophotographic photoconductor used in the present invention. For example, the photosensitive member is heated at 50 ° C. to 400 ° C. on a conductive support, and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. It is preferable to use an amorphous silicon photoconductor (hereinafter referred to as “a-Si-based photoconductor”) having a photoconductive layer made of a-Si by the film forming method. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferably used.

<About layer structure>
FIG. 6 shows the layer structure of the amorphous silicon photoconductor. The layer structure is as follows, for example.
FIG. 6 is a schematic configuration diagram for explaining a layer configuration. In the electrophotographic photoreceptor 500 shown in FIG. 6A, a photoconductive layer 502 made of a-Si: H and having photoconductivity is provided on a support 501. An electrophotographic photoreceptor 500 shown in FIG. 6B is formed of a photoconductive layer 502 made of a-Si: H and having photoconductivity on a support 501, and an amorphous silicon-based surface layer 503. ing. An electrophotographic photoreceptor 500 shown in FIG. 6C has a photoconductive layer 502 made of a-Si: H and having photoconductivity, an amorphous silicon-based surface layer 503, and amorphous silicon on a support 501. And a system charge injection blocking layer 504. In the electrophotographic photoreceptor 500 shown in FIG. 6D, a photoconductive layer 502 is provided on a support 501. The photoconductive layer 502 includes a charge generation layer 505 and a charge transport layer 506 made of a-Si: H, and an amorphous silicon-based surface layer 503 is provided thereon.

<About support>
The support for the photoreceptor may be conductive or electrically insulating. Examples of the conductive support include metals such as Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Also, at least the surface on the side where the photosensitive layer is to be formed of an electrically insulating support such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide or other synthetic resin film or sheet, glass or ceramic. A conductively treated support can also be used.
The shape of the support can be a cylindrical or plate-like or endless belt with a smooth or uneven surface, and the thickness thereof is appropriately determined so that a desired photoreceptor for an image forming apparatus can be formed. When flexibility as a photoreceptor for an image forming apparatus is required, it can be made as thin as possible within a range where the function as a support can be sufficiently exhibited. However, the support is usually 10 μm or more in view of mechanical strength and the like in manufacturing and handling.

<Injection prevention layer>
In the amorphous silicon photoconductor that can be used in the present invention, a charge injection blocking layer that functions to block charge injection from the conductive support side is provided between the conductive support and the photoconductive layer as necessary. It is more effective to provide this (FIG. 6C). That is, the charge injection blocking layer has a function of blocking charge injection from the support side to the photoconductive layer side when the photosensitive layer is subjected to a charging process with a certain polarity on its free surface. When charged, it has a so-called polarity dependency that does not exhibit such a function. In order to provide such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer.
The layer thickness of the charge injection blocking layer is preferably from 0.1 to 5 μm, more preferably from 0.3 to 4 μm, and most preferably from 0.5 to 0.5 in view of obtaining desired electrophotographic characteristics and economic effects. 3 μm is desirable.

<About photoconductive layer>
The photoconductive layer is formed on the undercoat layer as necessary, and the layer thickness of the photoconductive layer 502 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, preferably It is desirable that the thickness is 1 to 100 μm, more preferably 20 to 50 μm, and most preferably 23 to 45 μm.

<About the charge transport layer>
The charge transport layer is a layer mainly having a function of transporting charges when the photoconductive layer is functionally separated. The charge transport layer includes at least silicon atoms, carbon atoms, and fluorine atoms as constituent elements, and is formed of a-SiC (H, F, O) including hydrogen atoms and oxygen atoms as required. It has conductive properties, particularly charge retention properties, charge generation properties, and charge transport properties. In the present invention, it is particularly preferable to contain an oxygen atom.
The layer thickness of the charge transport layer is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. The charge transport layer is preferably 5 to 50 μm, more preferably 10 to 40 μm, Optimally, the thickness is desirably 20 to 30 μm.

<About the charge generation layer>
The charge generation layer is a layer mainly having a function of generating charges when the photoconductive layer is functionally separated. This charge generation layer is composed of a-Si: H containing at least silicon atoms as components and substantially no carbon atoms and, if necessary, hydrogen atoms, and has desired photoconductive properties, particularly charge generation properties. , Has charge transport properties.
The layer thickness of the charge generation layer is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, etc., preferably 0.5 to 15 μm, more preferably 1 to 10 μm, optimally 1 ˜5 μm.

<About surface layer>
If necessary, the amorphous silicon photoreceptor that can be used in the present invention can be provided with a surface layer on the photoconductive layer formed on the support as described above. It is preferable to form a surface layer. This surface layer has a free surface, and is provided to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.
The thickness of the surface layer in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to wear or the like during use of the photoreceptor, and if it exceeds 3 μm, electrophotographic characteristics such as an increase in residual potential are observed.

  Amorphous silicon photoconductors have high surface hardness, high sensitivity to long-wavelength light such as semiconductor lasers (770 to 800 nm), etc., and almost no deterioration due to repeated use. Therefore, high-speed copying machines and laser beam printers are used. It is preferably used as an electrophotographic photoreceptor such as (LBP).

The electric field when developing the image forming particles by the developing means in the image formation of the present invention is preferably an alternating electric field.
FIG. 7 is a schematic view of an image forming apparatus provided with a developing unit that applies an alternating electric field.
In the developing device 1 shown in FIG. 7, during development, a vibration bias voltage in which an AC voltage is superimposed on a DC voltage is applied to the developing sleeve 2 as a developing bias by the power source 3. The background portion potential and the image portion potential are located between the maximum value and the minimum value of the vibration bias potential. As a result, an alternating electric field whose direction changes alternately is formed in the developing portion. In this alternating electric field, the developer image-forming particles and the carrier vibrate vigorously, and the image-forming particles fly off to the photosensitive drum 4 by shaking off the electrostatic binding force to the developing sleeve 2 and the carrier, and the latent image on the photosensitive drum. It adheres corresponding to the image.

  The difference (maximum peak voltage) between the maximum value and the minimum value of the vibration bias voltage is preferably 0.5 to 5 KV, and the frequency is preferably 1 to 10 KHz. As the waveform of the vibration bias voltage, a rectangular wave, a sine wave, a triangular wave, or the like can be used. As described above, the DC voltage component of the vibration bias is a value between the background part potential and the image part potential, but the value closer to the background part potential than the image part potential is more likely to cover the background part potential region. This is preferable for preventing adhesion of image forming particles.

  When the vibration bias voltage waveform is a rectangular wave, the duty ratio is preferably 50% or less. Here, the duty ratio is the ratio of the time during which image forming particles are directed to the photoreceptor during one period of vibration bias. By doing so, it is possible to increase the difference between the peak value at which the image-forming particles are directed to the photoconductor and the time average value of the bias, so that the movement of the image-forming particles is further activated and the image-forming particles are activated. Adheres faithfully to the potential distribution on the latent image surface, thereby improving the roughness and improving the resolving power. In addition, since the difference between the peak value of the carrier having a charge opposite to that of the image forming particle and the time average value of the bias toward the photoconductor can be reduced, the movement of the carrier is calmed down, and the latent image The probability that the carrier adheres to the background portion can be greatly reduced.

  As described above, when developing the latent image on the image carrier by the developing device, a high-definition image without roughness is obtained by applying the vibration bias voltage in which the AC voltage is superimposed on the DC voltage.

  The fixing step in the image formation of the present invention includes a heating body having a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, It is preferable to use a fixing device that heats and fixes a recording material on which an unfixed image is formed between the pressure members.

As shown in FIG. 8, the fixing device is a so-called surf fixing device that rotates and fixes a fixing film. The details will be described below.
The fixing film is an endless belt-like heat-resistant film, and is disposed by being fixedly supported by being held by a driving roller that is a supporting rotating body of the film, a driven roller, and a heater support provided below the two rollers. It is stretched around the heating element.

The driven roller also serves as a tension roller for the fixing film, and the fixing film is rotationally driven in the clockwise direction by the rotational driving of the driving roller in the clockwise direction in the drawing. This rotational driving speed is adjusted to a speed at which the transfer material and the fixing film are equal in the fixing nip region L where the pressure roller and the fixing film are in contact with each other.
Here, the pressure roller is a roller having a rubber elastic layer having good releasability, such as silicon rubber, and a contact pressure of 4 to 10 kg of total pressure against the fixing nip region L while rotating counterclockwise. With pressure contact.
The fixing film preferably has excellent heat resistance, releasability and durability, and a thin film having a total thickness of 100 μm or less, preferably 40 μm or less is used. For example, at least an image of a single layer film of a heat-resistant resin such as polyimide, polyetherimide, PES (polyether sulfide), PFA (tetrafluoroethylene barfluoroalkyl vinyl ether copolymer resin), or a composite layer film, for example, a 20 μm thick film The contact surface is coated with a release coating layer of PTFE (tetrafluoroethylene resin), PFA or other fluororesin added with a conductive material to a thickness of 10 μm, or an elastic layer such as fluororubber or silicon rubber. It is a thing.

In FIG. 8, the heating body of the present embodiment is composed of a planar substrate and a fixing heater, and the planar substrate is made of a material having high thermal conductivity and high electrical resistivity such as alumina, and is a surface in contact with the fixing film. Has a fixing heater formed of a resistance heating element in the longitudinal direction. Such a fixing heater is formed by coating an electric resistance material such as Ag / Pd or Ta ₂ N in a linear or belt shape by screen printing or the like. In addition, electrodes (not shown) are formed at both ends of the fixing heater, and the resistance heating element generates heat when energized between the electrodes. Furthermore, a fixing temperature sensor constituted by a thermistor is provided on the surface of the substrate opposite to the surface provided with the fixing heater.
The temperature information of the substrate detected by the fixing temperature sensor is sent to a control unit (not shown), and the amount of electric power supplied to the fixing heater is controlled by the control unit, and the heating body is controlled to a predetermined temperature.
By using the fixing device, it is possible to obtain an image forming apparatus capable of realizing fixing that is efficient and can shorten the rise time.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

-Production of resin-
Production Example 1
100 parts by weight of ion-exchanged water and 0.10 parts by weight of polyvinyl alcohol were added to an 8 L internal volume autoclave (manufactured by Toyo High Pressure Co., Ltd.) and stirred. Next, 77 parts by weight of styrene, 21 parts by weight of methyl methacrylate, 2 parts by weight of methacrylic acid, 0.10 parts of tert-butylperoxy-2-ethylhexanoate, and 0.05 parts by weight of t-dodecyl mercaptan were charged at 90 ° C. The temperature was raised to 10 hours for polymerization. The conversion rate when polymerized at 95 ° C. for 12 hours was 97%. Furthermore, it hold | maintained at 130 degreeC for 6 hours, and superposition | polymerization was completed. The beads obtained by polymerization were washed, dehydrated and dried, and then a pellet-shaped resin [Resin 1] was obtained using an extruder.

-Chain transfer agent removal step-
Production Example 2-1
A pellet-shaped resin [resin 1] was placed in a pressure vessel, carbon dioxide was selected as a supercritical fluid, and the treatment was performed under the following conditions.
At normal temperature and 0.10 MPa (1 atm), +2 to 3 ° C./min. +0.2 MPa / min. To 40 ° C. and 7.09 MPa (70 atm). Here, the flow rate is 5.0 L / min. (Standard state conversion value) and +2 to 3 ° C./min. +10 MPa / min. And heated to a supercritical state of 80 ° C. and 40.52 MPa (400 atm). The flow rate is 5.0 L / min. The treatment was performed for 6 hours while maintaining the (standard state converted value). Thereafter, the flow rate was adjusted to 1.0 to 3.0 L / min. (Standard state converted value), -2 to 3 ° C / min. -3 to 5 MPa / min. Then, the pressure was reduced to room temperature and the pressure was returned to 0.10 MPa (1 atm) to obtain [Chain Transfer Agent Removal Process Resin 1].

-Molding process-
Example 1
[Chain transfer agent removing step completed resin 1] was kneaded with a uniaxial kneader, and then a sheet with a thickness of 0.5 mm was obtained with a biaxial stretching machine. Using the biaxially stretched sheet, [food packaging container 1] (170 mm length × 120 mm width × 60 mm height) was obtained by a vacuum / pressure forming method.

Comparative Example 1
[Resin 1] was kneaded with a uniaxial kneader, and then a sheet with a thickness of 0.5 mm was obtained with a biaxial stretching machine. Using the biaxially stretched sheet, [food packaging container 2] (170 mm length × 120 mm width × 60 mm height) was obtained by a vacuum / pressure forming method.

In [Food Packaging Container 1] and [Food Packaging Container 2], there was almost no difference in the degree of contamination of the roll during stretching, the uneven thickness of the sheet, the brittleness and impact strength of the molded product.
However, while [Food Packaging Container 1] did not feel odor, [Food Packaging Container 2] felt a specific odor.
In addition, each of [Food Packaging Container 1] and [Food Packaging Container 2] was charged with 50 g of cooked white rice that had been allowed to cool, and heated in a commercially available microwave oven for 2 minutes. Felt a unique odor attributed to the chain transfer agent.

-Production of resin fine particle solution-
Production Example 3-1
A surfactant solution (7.0 parts by weight of sodium dodecylbenzenesulfonate dissolved in 2400 parts by weight of ion-exchanged water in a 3.0 L separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen introducing device ( The internal temperature was raised to 80 ° C. while stirring in a nitrogen stream. On the other hand, 108 parts by weight of styrene, 41 parts by weight of n-butyl acrylate, and 10 parts by weight of methacrylic acid were heated and dissolved at 80 ° C. to prepare a monomer solution. The monomer solution (80 ° C.) is mixed and dispersed in the surfactant solution (80 ° C.) contained in a separable flask by a mechanical disperser having a circulation path, and has a uniform dispersed particle size. A dispersion of emulsified particles (oil droplets) was prepared. An initiator solution in which 0.8 part by weight of potassium persulfate was dissolved in 200 parts by weight of ion-exchanged water was added to this dispersion, and the system was heated and stirred at 80 ° C. for 4 hours to polymerize (first step). An initiator solution in which 7.8 parts by weight of potassium persulfate was dissolved in 280 parts by weight of ion-exchanged water was added to this solution that had been subjected to one-stage polymerization), and after sufficient stirring, 380 wt. A monomer mixture consisting of 17.5 parts by weight, 137.5 parts by weight of n-butyl acrylate, 36 parts by weight of methacrylic acid, and 14.5 parts by weight of t-dodecyl mercaptan was added dropwise over 2 hours. After completion of dropping, the mixture was heated and stirred for 60 minutes to perform polymerization (second stage polymerization), and then cooled to 40 ° C. to obtain [resin fine particle solution 1].

Production Example 3-2
12 parts by weight of styrene and 1 part by weight of a charge control agent (product name: Spiron Black TRH, manufactured by Hodogaya Chemical Co., Ltd.) are mixed and dispersed for 12 hours using a sand mill (manufactured by Kansai Paint Co., Ltd.), and then 90 weight of styrene. Part, n-butyl acrylate 27 parts by weight, divinylbenzene 0.45 parts by weight, t-dodecyl mercaptan 1.0 part by weight, using a homomixer capable of mixing with a high shearing force (manufactured by Koki Kogyo Co., Ltd., TK type) The mixture was stirred and mixed at a rotational speed of 11000 rpm to perform uniform dispersion to prepare [polymerizable monomer composition for core (mixed solution)]. On the other hand, 5 parts by weight of methyl methacrylate and 100 parts by weight of water were finely dispersed using an ultrasonic emulsifier (TK machine, TK Homomixer). Dispersion] was prepared.
In addition, an aqueous solution obtained by dissolving 35 parts by weight of magnesium chloride in 500 parts by weight of ion-exchanged water and 12 parts by weight of sodium hydroxide in 50 parts by weight of ion-exchanged water were stirred. By adding gradually, [aqueous dispersion medium] was prepared.
In [Aqueous dispersion medium], [Polymerizable monomer composition for core (mixed solution)] was added and mixed, and then 4 parts by weight of t-butylperoxy-2-ethylhexanoate was added, and TK type homopolymer was added. Using a mixer, high shear stirring was performed at a rotational speed of 14,000 rpm to granulate droplets of the polymerizable monomer composition for the core. When the aqueous dispersion of the granulated monomer composition was put into a polymerization reactor equipped with a stirring blade, the polymerization reaction was started at 90 ° C., and when the polymerization conversion reached almost 100%, Polymeric monomer aqueous dispersion for shell] and 1 part by weight of 1% aqueous potassium persulfate solution were added and the reaction was continued for 5 hours. Then, the reaction was stopped, and an aqueous dispersion of core / shell type polymer particles. Was prepared. While stirring the aqueous dispersion of the obtained core-shell type polymer particles, the system was acid-washed (25 ° C., 10 minutes) with sulfuric acid to a pH of 4 or less, and water was separated by filtration. 500 parts by mass of ion-exchanged water was added to form a slurry again and washed with water. Thereafter, again, dehydration and water washing were repeated several times, and the solid content was separated by filtration, followed by drying at 45 ° C. for 24 hours with a dryer to obtain [resin fine particle solution 2].

Production Example 3-3
1840 parts by weight of methanol, 160 parts by weight of ion-exchanged water, and 75 parts by weight of polyvinylpyrrolidone are placed in a sealable reaction vessel that rotates in a constant temperature water bath, and the vessel is stirred at room temperature for about 1 hour. ] Was obtained. At this time, it was confirmed that polyvinylpyrrolidone was completely dissolved. On the other hand, 250 parts of a methanol solution in which a dispersion stabilizer is dissolved is transferred into a sealable reaction vessel that rotates in a constant temperature bath, and 53 parts by weight of styrene, 43 parts by weight of methyl acrylate, and 1,3-butanediol dimethacrylate. 0 parts by weight and 0.5 parts by weight of t-dodecyl mercaptan were added. While mixing by rotating the container, N ₂ gas was blown into the container to completely expel air, and the container was sealed. After rotating the container at 120 rpm for 1 hour in a 60 ° C. constant temperature water bath, 0.8 part by weight of 2,2′-azobisisobutyronitrile was added while blowing N ₂ gas into the container, The container was sealed, and the container was rotated at 120 rpm for 6 hours in a constant temperature water bath at 60 ° C. Further, while blowing N ₂ gas into the container, 8 parts by weight of methanol, 1.5 parts by weight of 1,3-butanediol dimethacrylate and 0.35 parts by weight of t-dodecyl mercaptan were added, and the container was sealed, 60 ° C. The container was rotated at 120 rpm for 18 hours in a constant temperature water bath to obtain [resin fine particle solution 3].

Production Example 3-4
2000 parts by weight of methanol and 100 parts by weight of polyvinyl pyrrolidone were placed in a sealable reaction vessel rotating in a constant temperature water bath, and the vessel was stirred at room temperature for about 1 hour to obtain [hydrophilic organic liquid]. At this time, it was confirmed that polyvinylpyrrolidone was completely dissolved. On the other hand, 250 parts of a methanol solution in which a dispersion stabilizer is dissolved is transferred into a sealable reaction vessel that rotates in a constant temperature bath, and 53 parts by weight of styrene, 43 parts by weight of methyl acrylate, and 1,3-butanediol dimethacrylate. 0 parts by weight and 0.5 parts by weight of t-dodecyl mercaptan were added. While mixing by rotating the container, N ₂ gas was blown into the container to completely expel air, and the container was sealed. After rotating the container at 120 rpm for 1 hour in a 60 ° C. constant temperature water bath, 0.8 part by weight of 2,2′-azobisisobutyronitrile was added while blowing N ₂ gas into the container, The container was sealed, and the container was rotated at 120 rpm for 6 hours in a constant temperature water bath at 60 ° C. Further, while blowing N ₂ gas into the container, 8 parts by weight of methanol, 1.5 parts by weight of 1,3-butanediol dimethacrylate, and 0.35 parts by weight of t-dodecyl mercaptan were added, and the container was sealed, 60 ° C. The container was rotated at 120 rpm for 18 hours in a constant temperature water bath to obtain [resin fine particle solution 4].

-Manufacture of resin fine particles-
Production Example 4-1
The obtained [resin fine particle solution 1] is separated into a solid content and a solution, the solid content is dehydrated and washed with water several times, and the obtained solid content is dried in a dryer at 45 ° C. for 24 hours. [Resin fine particles 1] were obtained.

Production Example 4-2
Except having changed [resin fine particle solution 1] of manufacture example 4-1 to [resin fine particle solution 2], it processed similarly to manufacture example 4-1, and obtained [resin fine particle 2].

Production Example 4-3
Except having changed [resin fine particle solution 1] of manufacture example 4-1 to [resin fine particle solution 3], it processed similarly to manufacture example 4-1, and obtained [resin fine particle 3].

Production Example 4-4
Except having changed [resin fine particle solution 1] of manufacture example 4-1 to [resin fine particle solution 4], it processed similarly to manufacture example 4-1, and obtained [resin fine particle 4].

-Chain transfer agent removal step-
Production Example 2-2
[Resin fine particle 1] was put in a pressure vessel, carbon dioxide was selected as a supercritical fluid, and the treatment was performed under the following conditions.
At normal temperature and 0.10 MPa (1 atm), +2 to 3 ° C./min. +0.2 MPa / min. To 40 ° C. and 7.09 MPa (70 atm). Here, the flow rate is 5.0 L / min. (Standard state conversion value) and +2 to 3 ° C./min. +10 MPa / min. The mixture was heated and pressurized at 70 ° C. and 45.59 MPa (450 atm) to obtain a supercritical state. The flow rate is 5.0 L / min. The treatment was performed for 6 hours while maintaining the (standard state converted value). Thereafter, the flow rate was adjusted to 1.0 to 3.0 L / min. (Standard state converted value), -2 to 3 ° C / min. -3 to 5 MPa / min. The pressure was reduced under reduced pressure and the temperature was returned to room temperature and 0.10 MPa (1 atm) to obtain [resin fine particles 5].

Production Example 2-3
Except having changed [resin fine particle 1] of manufacture example 2-2 to [resin fine particle 2], it processed like manufacture example 2-3 and obtained [resin fine particle 6].

Production Example 2-4
Except having changed [resin fine particle 1] of manufacture example 2-2 to [resin fine particle 3], it processed like manufacture example 2-3 and obtained [resin fine particle 7].

Production Example 2-5
Except having changed [resin fine particle 1] of manufacture example 2-2 to [resin fine particle 4], it processed like manufacture example 2-3 and obtained [resin fine particle 8].

Examples 2-5 and Comparative Examples 2-5
[Resin fine particles 5] to [resin fine particles 8] (Examples 2 to 5) and [Resin fine particles 1] to [Resin fine particles 4] (Comparative Examples 2 to 5) were placed on a hot plate, and 100 ° C, 140 ° C. Heating was performed at 1 ° C. and 180 ° C., respectively, and the shape of fine particles and the generated odor were evaluated.
The shape of the fine particles was obtained by placing a weight on the heated resin fine particles and observing the shape of the obtained resin fine particles with an electron microscope. The shape of the fine particles was ranked according to “no deformation, deformation, melting”, and the rank having the highest ratio among the observed particles (at least 100 particles or more) was used as the evaluation result. As for the generated odor, a cylindrical container having an inner diameter of 6 cm and a height of 30 cm, which is open at both ends, was placed so as to surround the heated resin fine particles, and the odor rising from the upper part of the container was subjected to sensory evaluation. The odor is an observation of the odor derived from the chain transfer agent and does not include the odor derived from the monomer. The results are shown in Table 1.

-Production of resin fine particle solution-
Production Example 3-5
64 parts by weight of carnauba wax was added to a monomer mixture consisting of 83 parts by weight of styrene, 31 parts by weight of n-butyl acrylate, and 8.8 parts by weight of methacrylic acid, and the monomer was heated to 80 ° C. and dissolved. A solution was prepared. On the other hand, a surfactant solution (aqueous medium) prepared by dissolving 4.8 parts by weight of sodium dodecylbenzenesulfonate in 1600 parts by weight of ion-exchanged water was charged into an 8 L internal volume autoclave, and the internal temperature was raised to 90 ° C. while stirring. The temperature was raised. Thereto was added an initiator solution prepared by dissolving 0.8 part by weight of potassium persulfate in 200 parts by weight of ion-exchanged water, and the temperature was raised to 90 ° C. to polymerize for 10 hours to prepare [resin fine particle solution 5].

-Production of colorant dispersion-
Production Example 5-1
To a solution obtained by dissolving 9.6 parts by weight of sodium n-dodecyl sulfate in 160 parts by weight of ion-exchanged water, 20 parts by weight of carbon black (product name: # 25B, manufactured by Mitsubishi Chemical Corporation) is gradually added with stirring. Then, [Colorant Dispersion Liquid 1] was prepared by performing a dispersion treatment using a homomixer that can be mixed with a high shearing force (manufactured by Special Machine Chemical Co., Ltd., TK type).

-Production of image-forming particles-
Production Example 6-1
[Resin fine particle solution 5] In a mixed solution of 835 parts by weight, ion-exchanged water 2159 parts, and sodium dodecylbenzenesulfonate 4.2 parts by weight, [resin fine particle 5] 200 parts by weight, [colorant dispersion 1] 200 parts by weight Were placed in a 5 L four-necked flask equipped with a temperature sensor, a condenser, a nitrogen introducing device, and a stirring device, and sufficiently dispersed by applying high shear.
After adjusting the liquid temperature to 30 ° C., 5N aqueous sodium hydroxide solution was added to the solution to adjust the pH to 10.0. Next, an aqueous solution in which 52.5 parts by weight of magnesium chloride hexahydrate was dissolved in 72 parts by weight of ion-exchanged water was added over 10 minutes with stirring at 30 ° C. After standing for 5 minutes, the temperature increase was started, and the system was heated to 90 ° C. over 10 minutes (temperature increase rate = 10 ° C./min). In this state, the particle size of the associated particles was measured with “Coulter Counter TA-II”, and when the volume average particle size became 5.8 to 6.2 μm, 115 parts by weight of sodium chloride was added to ion-exchanged water 700 The aqueous solution dissolved in parts by weight was added to stop particle growth, and the fusion was continued by stirring for 6 hours while maintaining the liquid temperature at a liquid temperature of 90 ° C. ± 2 ° C. Then, it cooled to 30 degreeC on 6 degree-C / min conditions. While stirring the resulting aqueous dispersion of associated particles, the pH of the system is adjusted to 4 or lower with sulfuric acid, and acid washing (25 ° C., 10 minutes) is performed. Water is separated by filtration, and then ion-exchanged water 500 is newly added. Part by weight was added to reslurry and washed with water. Thereafter, again, dehydration and water washing were repeated several times, and the solid content was filtered and separated, followed by drying at 45 ° C. for 24 hours with a dryer to obtain [Image-forming particles 1]. [Image-forming particles 1] had a Dv of 6.0 μm and a Dv / Dn of 1.20.

Production Example 6-2
Except having changed [resin fine particle 5] of manufacture example 6-1 to [resin fine particle 6], it processed similarly to manufacture example 6-1, and obtained [image forming particle 2]. [Image-forming particles 2] had a Dv of 5.8 μm and a Dv / Dn of 1.24.

Production Example 6-3
Except having changed [resin fine particle 5] of manufacture example 6-1 to [resin fine particle 7], it processed similarly to manufacture example 6-1, and obtained [image forming particle 3]. [Image forming particle 3] had a Dv of 6.1 μm and a Dv / Dn of 1.18.

-Production of colorant dispersion-
Production Example 5-2
30.0 parts by weight of oil black 860 and 20 parts by weight of methanol were added and dissolved by heating, then cooled and filtered through a 1 μm microfilter to prepare 10 parts by weight of [Colorant Dispersion Liquid 2].

-Production of colored resin particles-
Production Example 7-1
After adding 50 parts by weight of methanol, 50 parts by weight of water, and 10 parts by weight of [Colorant Dispersion Liquid 2] to 12 parts by weight of [Resin Fine Particles 8] and dispersing by high shear, the mixture was stirred at 50 ° C. for 1 hour. The dispersion was then cooled to room temperature. The obtained solid content was subjected to centrifugal sedimentation, the supernatant was removed, and the operation of redispersing in a mixed solvent of 50 parts by weight of methanol and 50 parts by weight of water was performed three times. After separation by filtration, it was air-dried and dried under reduced pressure at 40 ° C. for 6 hours to obtain [Colored resin particles 1].

-Production of image-forming particles through a charge control agent immobilization step-
Production Example 8-1
[Colored resin particles 1] After stirring 100 parts by weight of Spiron Black THR (manufactured by Hodogaya Chemical Co., Ltd.) and 0.5 parts by weight with a Henschel mixer (manufactured by Mitsui Miike Chemical Industries) for 5 minutes, hybridization NHS-1 (manufactured by Nara Machinery Co., Ltd.) ) At a rotational speed of 7000 rpm for 5 minutes to obtain [Image-forming particles 4]. [Image-forming particles 4] had a Dv of 6.2 μm and a Dv / Dn of 1.02.

-Production of image-forming particles-
Production Example 6-4
Except having changed [resin fine particle 5] of manufacture example 6-1 to [resin fine particle 1], it processed like manufacture example 6-1, and obtained [image forming particle 5]. [Image-forming particles 5] had a Dv of 6.0 μm and a Dv / Dn of 1.20.

Production Example 6-5
Except having changed [resin fine particle 5] of manufacture example 6-1 to [resin fine particle 2], it processed similarly to manufacture example 6-1, and obtained [image forming particle 6]. [Image-forming particles 6] had a Dv of 5.8 μm and a Dv / Dn of 1.24.

Production Example 6-6
Except having changed [resin fine particle 5] of manufacture example 6-1 to [resin fine particle 3], it processed similarly to manufacture example 6-1, and obtained [image forming particle 7]. [Image-forming particles 7] had a Dv of 6.1 μm and a Dv / Dn of 1.18.

-Production of colored resin particles-
Production Example 7-2
The process was performed in the same manner as in Production Example 7-1 except that [Resin fine particles 8] in Production Example 7-1 was changed to [Resin fine particles 4] to obtain [Colored resin particles 2].

-Production of image-forming particles through a charge control agent immobilization step-
Production Example 8-2
Except having changed [colored resin particle 1] of manufacture example 8-1 to [colored resin particle 2], it processed like manufacture example 8-1, and obtained [image forming particle 8]. [Image-forming particles 8] had a Dv of 6.2 μm and a Dv / Dn of 1.02.

Examples 6-9 and Comparative Examples 6-9
[Image forming particles 1] to [image forming particles 4] (Examples 6 to 9) and [Image forming particles 5] to [Image forming particles 8] (Comparative Examples 6 to 9) evaluated.
First, to 100 parts by weight of the obtained image-forming particles, 0.8 part by weight of silica having an average particle diameter of 12 nm (trade name “RX200”, manufactured by Nippon Aerosil Co., Ltd.) that has been subjected to a hydrophobic treatment is added, and a Henschel mixer is used. Using the surface treatment, a developer is prepared by a conventional method, and for each developer, a tandem color electrophotographic apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.) is used to copy paper (TYPE6000 <70W>, Co., Ltd.). A solid image having an adhesion amount of each developer of 1.00 ± 0.05 mg / cm ² was formed on Ricoh. The solid image was repeatedly formed on 20000 copies of the copy paper. The obtained solid image was fixed using a fixing device. Adjustment was made so that the temperature of the fixing belt was variable, and heat fixing was performed at a temperature 15 ° C. lower than the temperature at which the copy paper offset occurs.
Thermal fixing was performed in a sealed room with a floor area of 100 m ² (10 m × 10 m) and a height of 2 m and no air circulation, and the odor generated at that time was evaluated by 20 evaluators.
Odor evaluation is as follows.
The evaluator evaluated the odor when entering the room after thermal fixing as follows.
Evaluation was made in four stages: no odor, odor, strong odor, very strong odor.
The evaluation results are shown in Table 2.

Is a schematic diagram showing an example of an image forming apparatus for carrying out the images forming method. It is a schematic diagram showing another example of the image forming apparatus for carrying out the images forming method. It is a schematic diagram showing an example of an image forming apparatus for carrying out the images forming method (tandem type color image forming apparatus). FIG. 4 is a partially enlarged schematic view of the image forming apparatus shown in FIG. 3. It is a schematic view of an image forming apparatus equipped with a profile processes cartridge. Is a diagram showing the layer structure of the amorphous silicon photosensitive member which constitutes the images forming apparatus. It is a schematic view of an image forming apparatus having a developing means for applying the exchange互電field. It is a schematic view of an image forming apparatus including a service-safe fixing means.

Explanation of symbols

(Figs. 1-4)
10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Development roller 45K Black developer (unit)
45Y Yellow developer unit
45M Magenta developer unit
45C Cyan developer (unit)
49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 59 Charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning Device 64 Static eliminator 70 Static eliminator lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 110 Belt-type fixing device 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed Path 147 conveying roller 148 sheet feeding path 150 copying apparatus main body 200 sheet feeding table 300 scanner 400 automatic document feeder (ADF)
(Fig. 6)
500 Amorphous silicon photoreceptor 501 Support 502 Photoconductive layer 503 Amorphous silicon surface layer 504 Amorphous silicon charge injection blocking layer 505 Charge generation layer 506 Charge transport layer (FIG. 7)
1 Developing Device 2 Developing Sleeve 3 Power Supply 4 Photosensitive Drum

Claims (16)

A resin obtained by polymerizing a radical polymerizable monomer containing at least the chain transfer agent, to come in contact with the supercritical fluid or subcritical flow body, dissolving the chain transfer agent in the supercritical fluid or subcritical fluid And a chain transfer agent removing step of removing the chain transfer agent from the resin , wherein the chain transfer agent dissolved in the supercritical fluid or subcritical fluid is precipitated and recovered . The method for producing a resin according to claim 1, wherein the polymerizable monomer is one or more vinyl monomers. The method for producing a resin according to claim 1 or 2, wherein at least styrene and an acrylic acid derivative or a methacrylic acid derivative are used as the polymerizable monomer. The method for producing a resin according to any one of claims 1 to 3, wherein at least one of the supercritical fluid and the subcritical fluid can dissolve the chain transfer agent without dissolving the resin. The method for producing a resin according to any one of claims 1 to 4, wherein at least one of the supercritical fluid and the subcritical fluid is either a simple substance or a mixture. 6. The method for producing a resin according to claim 1, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide. The method for producing a resin according to any one of claims 1 to 6, wherein at least one of the supercritical fluid and the subcritical fluid contains an organic solvent. The resin particles obtained by polymerizing a radical polymerizable monomer containing at least the chain transfer agent, to come in contact with the supercritical fluid or subcritical flow body, dissolving the chain transfer agent in the supercritical fluid or subcritical fluid And a chain transfer agent removing step for removing the chain transfer agent from the resin fine particles , wherein the chain transfer agent dissolved in the supercritical fluid or subcritical fluid is precipitated and recovered . Production method. The method for producing resin fine particles according to claim 8 , wherein a ratio of a median diameter to a mode diameter of the resin fine particles is 1.10 or less. In the aqueous medium in which the polymerization initiator is dissolved, at least a radically polymerizable monomer dissolved in the aqueous medium and a chain transfer agent dissolved in the aqueous medium are supplied to be polymerized, and polymerized particles are obtained. The method for producing resin fine particles according to claim 8 or 9 , wherein the resin fine particles are formed. Although dissolved in the organic medium, the resulting polymer is polymerized by adding an insoluble or poorly soluble radically polymerizable monomer to the organic medium to form polymer particles. The method for producing resin fine particles according to claim 8 or 9 , wherein in the step, a chain transfer agent is added at least once during the step. In a step of forming polymer particles by introducing a polymerizable mixture containing at least a polymerizable monomer and a polymerization initiator into an aqueous dispersion medium containing a suspension stabilizer and polymerizing by stirring, The method for producing resin fine particles according to claim 8 or 9 , wherein the chain transfer agent is added at least once during the step. A seed polymerization step of performing polymerization in a solution dispersed in an aqueous or organic solvent using the resin fine particles obtained by the production method according to claim 10 as seed particles is performed at least once. A method for producing fine resin particles. The method for producing resin fine particles according to claim 8 , wherein the resin fine particles are used at the time of producing image forming particles. The resin fine particles, method for producing fine resin particles according to any one of claims 8 to 14, characterized in that a part or the whole of the image forming grains child. A resin fine particle produced by the method for producing a resin fine particle according to claim 8 .

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