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WO2002077071A1 - Organopolysiloxane cireux et composition de toner le contenant - Google Patents

Organopolysiloxane cireux et composition de toner le contenant Download PDF

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Publication number
WO2002077071A1
WO2002077071A1 PCT/JP2002/002420 JP0202420W WO02077071A1 WO 2002077071 A1 WO2002077071 A1 WO 2002077071A1 JP 0202420 W JP0202420 W JP 0202420W WO 02077071 A1 WO02077071 A1 WO 02077071A1
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WIPO (PCT)
Prior art keywords
group
toner
weight
organopolysiloxane
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2002/002420
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English (en)
Japanese (ja)
Inventor
Takakazu Hino
Takatoshi Toyama
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NUC Corp
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Nippon Unicar Co Ltd
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Application filed by Nippon Unicar Co Ltd filed Critical Nippon Unicar Co Ltd
Priority to DE10296506T priority Critical patent/DE10296506T5/de
Publication of WO2002077071A1 publication Critical patent/WO2002077071A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08773—Polymers having silicon in the main chain, with or without sulfur, oxygen, nitrogen or carbon only

Definitions

  • the present invention relates to waxy organopolysiloxanes. More specifically, according to the present invention, in an endothermic curve obtained when the endothermic characteristic is measured by a differential scanning calorimeter, the endothermic peak area of the fraction melting at 50 ° C or lower is 50% of the total peak area. % Or less of a waxy organopolysiloxane.
  • the present invention also relates to a toner composition for developing an electrostatic charge image, comprising such a hexagonal organopolysiloxane.
  • Electrophotography is disclosed in U.S. Pat.No. 2,297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 432-2474S, Generally, an electrostatic latent image is formed on a photosensitive material containing a photoconductive substance, and then the latent image is developed as a powder image with a toner, and the image is transferred to paper or the like as necessary. It is a technique that takes root afterwards.
  • This fixing means includes heating, pressurizing, and application of a solvent vapor. The most widespread is a heat fixing method using a heating roller. In this heating roller fixing method, the toner image and the surface of the fixing roller come into pressure contact with each other in a heated and molten state.
  • a surface of the mouth is formed of a material such as silicon rubber or a fluorine-based resin which is excellent in releasability from toner.
  • the surface has good release properties such as silicone oil Application of liquids has been performed. This method does not provide sufficient fixability at both low and high temperatures.
  • Japanese Patent Publication No. 52-334 and Japanese Patent Publication No. 60-171109 propose the use of various resins as internal release agents.
  • Japanese Patent Application Laid-Open No. 7-244398 an organopolysiloxane compound having a monovalent organic group having an amide, carboxylate, or alkoxy group of a long-chain fatty acid having 18 or more carbon atoms is disclosed.
  • an internal release agent a modified polysiloxane having a hydrocarbon group having an average carbon number of 6 to 200 has been proposed as an internal release agent in Japanese Patent Application Laid-Open No. 11-136472. ing.
  • An object of the present invention is to provide a toner which does not cause an offset phenomenon and a winding phenomenon of a sheet even at a high speed when fixing is performed by a fixed fixing method of a heating roller, and has good fixability from a low temperature to a high temperature. I do. Disclosure of the invention
  • the present inventors have found that the above object can be achieved by including a specific novel modified polysiloxane as an internal release agent in a toner for developing an electrostatic image.
  • the present invention is based on the finding that if a low-temperature melting component is large in the internal release agent, the blocking resistance of the toner is deteriorated, and an offset phenomenon and a sheet winding phenomenon are generated.
  • the present invention provides a compound represented by the general formula (1): RRR
  • R represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms; R ′ and R ′′ each independently represent R,
  • n an integer of 3 to 200.
  • the endothermic peak area of the fraction that melts at 50 ° C or less is the total peak area. 50% or less of the waxy organopolysiloxane.
  • the present invention also provides a toner composition for developing an electrostatic image comprising the waxy organopolysiloxane.
  • This toner composition for developing an electrostatic image has a wide range of fixing speed, excellent blocking resistance and fluidity, and has hot offset resistance in oilless fixing.
  • the present invention further provides a method for improving the releasability of an electrostatic image developing toner, comprising internally adding the waxy organopolysiloxane to an electrostatic image developing toner.
  • the present invention further provides a method for producing a toner composition for electrostatic image development, (a) preparing a mixture comprising at least a waxy organopolysiloxane and a binder resin monomer;
  • FIG. 1 shows a DSC chart of compound A prepared in Example 1.
  • FIG. 2 shows a DSC chart of compound B prepared in Example 2.
  • FIG. 3 shows a DSC chart of compound C prepared in Example 3.
  • FIG. 4 shows a GPC chart of hydromethylpolysiloxane 2 prepared in Example 4.
  • FIG. 5 shows a DSC chart of compound D prepared in Example 4.
  • R of the waxy organopolysiloxane represented by the general formula (1) of the present invention is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms or 6 carbon atoms. ⁇ 10 aryl groups.
  • the alkyl group may be linear or branched, and specifically, includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. And a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
  • the aryl group includes a phenyl group and a naphthyl group, and a phenyl group is particularly preferable.
  • % Is a long-chain alkyl group having 16 to 300 carbon atoms of the above (a) or a long-chain organic group having 16 to 300 carbon atoms containing 1 to 10 hetero atoms.
  • C 2 15 alkylene or c 2 - 15 alkylene one C ⁇ one, preferably C 2 - 12 alkylene or c 2 - 12 alkylene one C 0- a through polysiloxane chains bonded to hetero atom-containing long-chain organic groups to have the
  • long-chain alkyl group and “heteroatom-containing long-chain organic group” are sometimes collectively referred to simply as “long-chain organic group”).
  • the “waxy” property referred to in the present specification is provided by having the long-chain organic group in the above-described ratio.
  • the hetero atom of the hetero atom-containing long-chain organic group may be any atom other than carbon.
  • various types of hetero atoms may be mixed, and their positions may be any positions.
  • heteroatom-containing long-chain organic groups to this, C 2 - 15 ⁇ alkylene or C 2 - 15 alkylene - CO- binds to the organopolysiloxane via.
  • the total number of heteroatoms in the heteroatom-containing long-chain organic group is 1 to 10, preferably 1 to 5, and more preferably 1 to 3.
  • the heteroatoms are selected from oxygen atoms or nitrogen atoms.
  • the carbon number of the long-chain organic group including the long-chain alkyl group is 16 to 300, preferably 18 to 200, more preferably 20 to 100, and most preferably 20 to 50. It is.
  • This long-chain organic group may be linear or branched.
  • the average carbon number of the long-chain organic group is less than 16, it becomes oily at normal temperature, and when used as an internal release agent for toner for developing electrostatic images, the toner becomes blocked or the fluidity of the toner decreases. descend.
  • the average number of carbon atoms is larger than 300, the maximum endothermic peak temperature becomes too high, and it becomes difficult to produce a waxy organopolysiloxane and to mix the toner for developing an electrostatic image.
  • Such long chain organic groups include straight or branched,
  • Alkoxycarbonylalkyl group [CH 3 (CH 2 ) D 0 C 0) (CH 2 ) q —]; alkylaminocarbonylalkyl group [CH 3 (CH 2 ) P NHC ⁇ (CH 2 ) Q —]; alkyl Carbonyloxyalkyl group [CH 3 (CH 2 ) p COO (CH 2 ) q —]; alkoxyalkyl group [CH 3 (CH 2 ) p O (CH 2 ) q —];
  • Alkylcarbonylaminoalkyl group [ ⁇ 11 3 ( ⁇ ⁇ ) 1) j0] ⁇ ] 3 ⁇ 4 ( ⁇ 1 2 ). ⁇ ];
  • An alkylaminocarbonylaminoalkyl group [CH 3 (CH 2 ) P NH C 0 NH (CH 2 ) Q- ];
  • Alkoxycarbonylaminoalkyl group (CH 3 (CH 2 ) P 0 (C 0) NH
  • Alkylcarbonylamino alkylaminoalkyl group [CH 3 (CH 2) P C ON H (CH 2) Q NH (CH 2) R - is included.
  • q and r are each independently an integer of 2 to 15, preferably 2 to 12, and p is a total of 16 to 300 carbon atoms of the long-chain organic group, It is preferably an integer of 18 to 200, more preferably 20 to 100, and most preferably 20 to 50.
  • branched carbon chains are not shown, but the long-chain organic groups of the present invention include those.
  • Linear long-chain alkyl group alkoxyl carbonyl alkyl group, alkoxycarbonylaminoalkyl group, alkylcarbonylaminoalkyl group, alkylcarbonyloxyalkyl group, alkylcarbonyloxy (2-hydroxy) propyloxyalkyl Groups, alkylcarbonylaminoalkylaminoalkyl groups, and alkylaminocarbonylalkyl groups are preferred.
  • the proportion of this group in the total number of R ' is preferably 0 to 10%, more preferably 0 to 5%, most preferably 0%.
  • the type of this group will be referred to again when explaining the method for producing the waxy organopolysiloxane of the general formula (1).
  • n represents an integer of 3 to 200 on average, preferably 5 to 150 on average, more preferably 5 to 100 on average, and most preferably 5 to 100 on average. ⁇ 50.
  • n is greater than 200, the blocking resistance becomes insufficient when used as an internal release agent for the toner for developing electrostatic images.
  • a differential scanning calorimeter is a calorimeter called so-called DSC.
  • the endothermic peak area in the present specification refers to a DSC-6200 (manufactured by Seiko Electronic Industry Co., Ltd.) of measuring 5 mg of a sample at 10 °. This is the area surrounded by the baseline and endothermic peak of the DSC chart where the heat of fusion was measured in the second heating step by heating at a constant heating rate of C / 'minute.
  • the endothermic peak area of the fraction that melts at 50 ° C or lower is 50% or less of the entire endothermic peak area. If this ratio is more than 50%, the offset phenomenon and the sheet wrapping phenomenon cannot be sufficiently prevented when used as an internal release agent for the toner for developing electrostatic images. Preferably, this proportion is at most 40%, more preferably at most 35%. Further, from the viewpoint of the storage stability of the toner, the ratio of the endothermic peak area of the fraction that melts at 35 ° C or less to the total area is preferably 30% or less, more preferably 15% or less, and most preferably.
  • the ratio of the endothermic peak area of the fraction that melts at 25 ° C or less to the whole is preferably 10% or less, more preferably 5% or less.
  • the maximum endothermic peak temperature is typically 40 to 150 ° C., and 50 ° C. To 130 ° C., more preferably 50 to 110 ° C., and particularly preferably 60 to 100 ° C.
  • the maximum endothermic peak temperature is low, the blocking resistance of the toner is insufficient, and when it is high, the low-temperature fixability and the releasing effect become insufficient.
  • the proportion of the group (a) in the total number of R's is increased; (2) (a) (3) narrow the molecular weight distribution of the group (a); and / or (4) make the group (a) have a polar group such as an amide group. It can be obtained by doing.
  • R is methyl, and 40 to 60%% of the total number of R ′ present is R, that is, methyl; 35 to 70% of the total number of R's has a long-chain alkyl group of 20 to 50 carbon atoms, an alkoxycarbonylalkyl group, an alkylcarbonylaminoalkyl group, an alkylcarbonyloxyalkyl group, an alkylcarbonylaminoalkyl group.
  • endothermic maximum Temperature of chromatography click is Olga Bruno polysiloxane is 6 0 ⁇ 1 0 0 ° C.
  • the long-chain organic group of the waxy organopolysiloxane of the general formula (1) is a long-chain alkyl group.
  • R is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms
  • p is a long-chain organic group. It is an integer such that the total number of carbon atoms of the group is 16 to 300.
  • the hydroorganopolysiloxane of the general formula (2) is obtained by reacting tetraalkyldisiloxane and octaalkylcyclotetrasiloxane for several hours at room temperature in the presence of an acid catalyst such as sulfuric acid. By ring-opening polymerization, it can be obtained in various degrees of polymerization.
  • the long-chain 11-argen may be produced by a conventional method or a commercially available product.
  • a long-chain 1-alkene available from Mitsubishi Chemical Corporation under the trade name Dialen 30 has an average carbon number of 30.
  • long-chain 11-argen available from Idemitsu Petrochemical Co., Ltd. under the trade name Linearen 18 has an average carbon number of 18.
  • the low molecular weight component in these commercially available long-chain 1-argens may be removed by a thin film distillation apparatus or the like to increase the average molecular weight before use.
  • This hydrosilylation reaction can be carried out in the presence of a catalyst at a temperature from room temperature to about 150 ° C, preferably about 40 ° C to 120 ° C.
  • the catalyst include compounds such as platinum, ruthenium, rhodium, palladium, osmium, and iridium, and platinum compounds are particularly effective because of their high catalytic activity.
  • platinum compounds include: Chloroplatinic acid; metallic platinum; alumina, silica, carbon black, etc., with metallic platinum supported thereon; and platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, Platinum complexes such as a platinum alcohol catalyst are exemplified. When a platinum catalyst is used, the amount of the catalyst is about 0.001 to 0.1 weight as platinum metal.
  • a solvent may be used if necessary.
  • usable solvents include sulfur compounds such as thiophene and getyl sulfide; nitrogen compounds such as acetonitrile, methylamine, and aniline; fatty acids such as acetic acid and butyric acid; and anhydrides of these acids; ethers; Ketones such as xanone; esters; phenols; hydrocarbons; halogenated hydrocarbons; and dimethylpolysiloxane.
  • Introduction of a long-chain organic group into an organopolysiloxane chain by this hydrosilylation reaction is not limited to the case of using a long-chain mono-argen, but may include an ethylenic double bond in a compound used for introduction.
  • the present invention can be applied to the introduction of any long-chain organic group.
  • the long-chain organic group containing a hetero atom of the waxy organopolysiloxane represented by the general formula (1) of the present invention is bonded to the organopolysiloxane chain via an alkylene group or an alkylene carboxy group constituting a part thereof.
  • the ethylene group in the long-chain organic group which constitutes the alkylene group or alkylene carboxy group, is converted into an ethylenic double bond, which is then converted into a hydrophile of the general formula (2).
  • the hydrosilyl group of the organopolysiloxane By reacting with the hydrosilyl group of the organopolysiloxane, all waxy organopolysiloxanes of the general formula (1) can be synthesized using a hydrosilylation reaction. Methods for forming ethylenic double bonds are well known in the art.
  • an alkylene group or an alkylene carbonyl group having a hetero atom at the other end is introduced by a hydrosilylation reaction, followed by esterification and amide.
  • the chain can also be extended using reactions known to those skilled in the art, such as alkylation, etherification, and N-alkylation.
  • R is an ester-forming group
  • R, a, b, p and Q are as defined above.
  • ester group-containing organopolysiloxane By subjecting the ester group-containing organopolysiloxane to a transesterification reaction with a long-chain alcohol [CH 3 (CH 2 ) P COOH].
  • Organopolysiloxane of the formula (1) can be obtained by subjecting an organopolysiloxane of the formula (1) to an amidation reaction between an ester group-containing organopolysiloxane of the general formula (3) and a long-chain alkylamine [CH 3 (CH 2 ) P NH 2 ]. .
  • human mud organopolysiloxanes of the general formula (2) After subjecting it to a hydrosilylation reaction with siloxane, the following general formula (4) is obtained:
  • organopolysiloxane of formula (4) with the long-chain alkyl halide [CH 3 (CH 2 ) P X (X represents a halogen atom)] Can be obtained.
  • an activated derivative such as a long-chain carboxylic acid [CH 3 (CH 2 ) P COOH] or an acid chloride thereof.
  • long-chain organic groups can be introduced by Ami de reaction of this kind, alkylaminocarbonyl ⁇ aminoalkyl group [CH 3 (CH 2) P NH C ONH (CH 2) q - ] and, alkoxycarbonyl ⁇ Mino There is an alkyl group [CH 3 (CH 2 ) P 0 (CO) NH (CH 2 ) q —].
  • alkyl group [CH 3 (CH 2 ) P 0 (CO) NH (CH 2 ) q —].
  • a long-chain organic group containing a large number of bond-forming groups is obtained by sequentially bonding a fragment of the long-chain organic group to the amino group of the amino-organopolysiloxane of the general formula (6). May be formed on an organopolysiloxane.
  • aminoorganopolysiloxanes represented by the general formula (6) for example, those whose length is an alkyl group include, for example, tetraalkyl (tetraaminoalkyl) cyclotetrasiloxane, octaalkylcyclotetrasiloxane and tetraalkyl.
  • alkyleneaminoalkyleneaminoorganopolysiloxane represented by the following formula is obtained. If this is alkyloxycarbonylated with a long-chain alkyl haloformate [XCOOCH 3 (CH 2 ) p ], the general formula (1h):
  • alkylcarbonyl ⁇ Minoan Le kills aminoalkyl group [CH 3 (CH 2) P C ONH (CH 2) q NH (CH 2) r one] is Chikaraku.
  • the reactive groups may be blocked or inactivated with a suitable compound.
  • suitable compound Good.
  • Methods for capping or inactivating include alkoxylation of hydrosilyl groups, esterification of carboxylic acid groups, and acylation of hydroxy and diamino groups.
  • Alcohols used for alkoxylation of the hydrosilyl group include alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, propanol, butanol, hexanol, and octanol. Thus, the resulting alkoxy group has 1 to 8 carbon atoms.
  • the esterifying agent used for the esterification of the remaining carboxylic acid group includes, in addition to the alcohol that can be used for the alkoxylation of the above-mentioned hydrosilyl group, an alkyl halide such as methyl iodide.
  • the acylating agent used for the acylation of the remaining hydroxy group and amino group includes an anhydride capable of producing an acyl group having 2 to 7 carbon atoms, such as acetic anhydride, propionic anhydride, and benzoic anhydride. Included are acyl halides, such as rubonic acid, acetyl chloride and benzoyl chloride, and sulfonyl halides, such as methyl sulfonyl chloride and toluenesulfonyl chloride. These reactions can be performed by a conventional method.
  • the C 2 1 5 alkylene or C 2 - 1 5 alkylene - and C 0-, heteroatoms present in the other end of the polysiloxane bond end includes a hydrosilyl group and a carboxylic acid, including an intermediate reactive group generated during a chain extension reaction as described above. It is intended to include reactive groups such as carboxylic acid ester groups, hydroxy groups, epoxy groups and amino groups, and groups resulting from blocking or inactivating these reactive groups. Such groups include:
  • Alkoxycarbonylalkyl group [CH 3 (CH 2) s O (CO) (CH 2) q - ]; hydroxycarboxylic alkyl group [HO (CH 2) q -];
  • Alkylcarbonyloxyalkyl group [CH 3 (CH 2 ) S C 00 (CH 2 ) q —]; alkoxyalkyl group [CH 3 (CH 2 ) s O (CH 2 ) q —];
  • Epoxypropyl O alkoxyalkyl group [CH 2 (0) CHCH 2 0 (CH 2) q - ]; alkylcarbonyl O alkoxy (2-arsenate Dorokishi) propyl O alkoxyalkyl group [C
  • Aminoalkyl group [NH 2 (CH 2 ). One];
  • Alkylcarbonyl ⁇ amino ⁇ Le Kill group [CH 3 (CH 2) s CONH (CH 2) q - ]; alkyl ⁇ iminocarbonyl aminoalkyl group [CH 3 (CH 2) s NHCONH (C
  • Aminoalkyl aminoalkyl group [NH 2 (CH 2) q NH (CH 2) r - ]; alkoxycarbonylamino alkylaminoalkyl group [CH 3 (CH 2) s O (C
  • Alkylcarbonylaminoalkylaminoalkyl group [CH 3 (CH 2 ) s CON H (CH 2 ) q NH (CH 2 ) r ⁇ ; Wherein s is an integer from 0 to 13, preferably from 0 to 2, and q and r are as defined above. However, the total number of carbon atoms of these groups is 2 to 15. .
  • the present invention also provides a toner composition for developing an electrostatic charge image, comprising a waxy organopolysiloxane of the general formula (1).
  • the waxy organopolysiloxane is added to the toner composition for developing an electrostatic image as an internal release agent. It is essential to use the waxy organopolysiloxane in the toner composition for developing an electrostatic image, but another internal release agent is used in combination within a range where the effects of the present invention can be obtained. It is also possible. In this case, it is preferable to use one or both of the internal release agents having a melting point of about 100 ° C. or higher or about 30 to 100 ° C. in combination.
  • aliphatic hydrocarbon resins such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax
  • aliphatic hydrocarbon resins such as polyethylene oxide
  • Hydrogen-based oxides and their block copolymers Boxes mainly containing fatty acid esters such as carnaubax, Sazox, and montsuccinate esters; Some fatty acid esters such as deoxidized carnaubax Or those obtained by deoxidizing all; saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as pramic acid, eleostearic acid, and norinalic acid; stearyl alcohol , Aralkyl alcohol, behenyl alcohol, carnauville Saturated alcohols such as rucol, seryl alcohol, and mesyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and radium phosphoric acid amide; Saturated fatty acid bisamides such as acid amide, ethylenebiscapric acid amide, ethylene bislauric acid amide, hexam
  • Components other than the internal release agent of the toner composition for developing an electrostatic image of the present invention are not particularly limited, and are generally a binder resin, a coloring agent, and, if necessary, a charge control agent, and other optional components. Can be included.
  • binder resin examples include polyester resin, acrylic resin, styrene resin, acrylic styrene resin, styrene monovinyl acetate resin, styrene monochlorostyrene resin, styrene-propylene copolymer resin, and styrene butadiene copolymer.
  • Colorants include Rippon Bon Black, Nig Mouth Shin, Anilin Bleu, Phthalocyanine Bleu, Phthalocyanine Green, Hanseero I, Rhodamine Dyes, Krommeello, Kinacridone, Benzi Jin Iero, Rose Bengal, Triari Any known dyes and pigments such as methane dyes, monoazo dyes, disazo dyes and integrated azo dyes can be used alone or in combination.
  • yellow is benzidine yellow
  • magenta is quinacridone
  • rhodamine dyes monoazo dyes
  • cyan is yellow. Evening Russian Nimble is preferably used.
  • the charge control of the toner may be performed by the binder resin or the colorant itself, but may be performed in combination with a charge control agent if necessary.
  • Quaternary ammonium salts, basic and electron-donating organic substances can be used as positive charge control agents, and metal chelates, alloy dyes, acid or electron withdrawing agents can be used as negative charge control agents.
  • Organic substances and the like can be used.
  • the quaternary ammonium salt compound is desirable as the positive charge
  • the negative charge Sex is salicylic acid or a Salts / complexes of rukylsalicylic acid with chromium, zinc, aluminum, etc.
  • metal salts / complexes of benzylic acid, amide compounds, phenol compounds, naphthol compounds and the like are desirable.
  • inorganic particles such as metal oxides and inorganic substances surface-treated with the organic substances may be used.
  • Optional components other than the above include fine powders such as silica, alumina, titania and other fluidity improvers, magnetite, graphite, cerium oxide, strontium titanate, and inorganic fine powders such as conductive titania, styrene resin, An internal additive or an external additive such as a resistance controlling agent such as an acrylic resin or a lubricant is included.
  • the internal release agent is preferably added in an amount of 0.1 to 35 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the binder resin. Is particularly preferred.
  • the waxy organopolysiloxane of the present invention is preferably used in an amount of 100 to 3% by weight of the total internal release agent for obtaining the effects of the present invention, and more preferably 100 to 5% by weight. , 100 to 10% by weight is particularly preferred. If the content of the internal release agent is too small, the releasability, offset resistance, and low-temperature fixability become insufficient.If the content is too large, the blocking resistance of the toner decreases, and the toner is fixed at a high temperature. The performance also decreases.
  • the waxy organopolysiloxane of the present invention may be used in combination of two or more.
  • the colorant is generally used in an amount of 1 part by weight or more, preferably 3 parts by weight or more, based on 100 parts by weight of the binder resin. It is more preferably used in an amount of 1 to 30 parts by weight, even more preferably in an amount of 3 to 30 parts by weight, particularly preferably in an amount of 1 to 20 parts by weight and most preferably in an amount of 3 to 20 parts by weight. Used in
  • the amount of the charge control agent added depends on the chemical and physical properties of the toner to be produced and the method of producing the toner, as well as the properties of each component of the toner composition and the method of producing them. It can be determined in consideration of the chargeability of the resin, the production method including the colorant addition amount / dispersion method, and the chargeability of other additives, but it is usually 100 parts by weight of the binder resin. On the other hand, it is used in an amount of at least 0.1 part by weight, preferably at least 0.1 part by weight.
  • the binder resin is more preferably used in an amount of from 0.1 to 15 parts by weight, even more preferably in an amount of from 0.1 to 10 parts by weight, particularly preferably from 0.1 to 15 parts by weight, most preferably from 0.1 to 15 parts by weight. Suitably it is used in an amount of up to 10 parts by weight.
  • the amount of the optional additive used may be appropriately selected depending on the desired performance. Usually, the amount is preferably about 0.05 to 10% by weight based on 100 parts by weight of the binder resin.
  • the method of adding the internal release agent to the toner for developing an electrostatic image differs depending on the toner production method.In the case of the pulverization method, it may be dissolved or dispersed in the binder resin in advance. It may be added at the same time as the colorant or the like is kneaded.
  • As a method of adding the internal release agent in advance there is a method in which the binder resin and the internal release agent are dissolved or suspended in an organic solvent, and then the solvent is removed by vacuum distillation or the like.
  • the internal release agent is added to the monomer during the polymerization process of the binder resin to carry out polymerization.
  • the toner composition for developing an electrostatic image of the present invention is produced by polymerization.
  • a mixture containing at least a waxy organopolysiloxane and a binder resin monomer is prepared, the monomers in the mixture are subjected to a polymerization reaction, and the obtained polymer is recovered. By doing so, a toner composition for developing an electrostatic image is manufactured.
  • binder resin monomer examples include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and gay cinnamate; monomers having a sulfonic acid group such as vinylsulfonic acid; and Brenstead acid.
  • a monomer having an amino group such as aminostyrene and dimethylaminoethyl acrylate; a monomer having a nitrogen-containing heterocyclic ring such as vinyl pyridine; and a radical polymerization of a monomer having a Blensted basic group.
  • monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and gay cinnamate
  • monomers having a sulfonic acid group such as vinylsulfonic acid
  • Brenstead acid a monomer having an amino group such as aminostyrene and dimethylaminoethyl acrylate
  • Monofunctional monomers which can be used in combination with these include styrenes such as styrene, methylstyrene and chlorostyrene; butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate and methyl methacrylate. (Meth) acrylates such as butyl acrylate; and acrylamides such as dimethylamide acrylate.
  • the resin may be crosslinked by using a polyfunctional monomer together with these monomers.
  • the degree of crosslinking is preferably controlled so that the tetrahydrofuran insoluble content is 0.5 to 80%. Tetrahydrofuran-insoluble matter is further 1-8 0% is rather preferred, especially 1. 5 ⁇ 8 0. ⁇ ⁇ are preferred. Tetrahydrofuran insolubles are It is an index indicating the degree of crosslinking, and the larger the value, the higher the degree of crosslinking. If the degree of bridging is too low, the offset is likely to occur. If the degree of cross-linking is too high, the transparency of the toner deteriorates.
  • a polyfunctional monomer means a monomer having at least two polymerizable ethylenic double bonds in the molecule.
  • divinylbenzene, hexanediol diacrylate, ethylene glycol diacrylate and the like can be mentioned.
  • the polymerization can be carried out by any method such as bulk polymerization, precipitation polymerization, suspension polymerization, or emulsion polymerization or emulsion polymerization aggregation.
  • a suspension polymerization method and an emulsion polymerization method in which the polymer is obtained in powder form are preferred.
  • the final toner composition is obtained by the suspension polymerization method
  • a colorant, a charge control agent, a polymerization initiator, and other additives are added to the monomer at the same time as an internal release agent, and a homogenizer or the like is added.
  • the mixture obtained by uniformly dissolving or dispersing the above in a dispersion medium is dispersed in an aqueous medium containing a dispersion stabilizer using a homomixer or the like, and the mixture is heated and polymerized.
  • polymer primary particles are produced by emulsion polymerization, and a colorant, and, if necessary, a charge controlling agent and a fluidizing agent are added to the polymer primary particles. And other additives such as coagulation to form a particle aggregate.
  • the internal release agent used in the present invention is prepared by emulsifying the internal release agent dispersion with at least one emulsifier selected from among known cationic surfactants, anionic surfactants, and nonionic surfactants. May be added to the polymerization system or may be added when the polymer primary particles after polymerization and the colorant or the like are aggregated.
  • the chargeability and the aggregation of the obtained toner can be improved. Stability can also be adjusted.
  • the degree of polymerization of the resulting polymer can be controlled by adding a chain transfer agent such as bromotrichloromethane and 2-merbutoethanol to the polymerization system.
  • the toner for developing an electrostatic image of the present invention can be used for both dry one-component developer and two-component developer.
  • the magnetic material used in the one-component developer includes, for example, phenylite, magnetite, and the like. Or other ferromagnetic alloys such as iron, cobalt, nickel, etc. Compounds or alloys that do not contain ferromagnetic elements but become ferromagnetic when appropriately heat-treated, such as Heusler alloys containing manganese and copper, such as manganese-copper-aluminum or manganese-copper-tin Alloys or chromium dioxide.
  • the magnetic material is uniformly dispersed in the binder resin in the form of a fine powder having an average particle size of 0.3 to 30 / m.
  • the content of the magnetic particles is preferably from 20 to 70 parts by weight, more preferably from 40 to 70 parts by weight, based on 100 parts by weight of the binder resin.
  • the carrier may be a magnetic substance such as iron powder, magnetite powder, or fly powder, or a substance obtained by applying a resin coating on the surface thereof or a magnetic carrier. Known ones can be used.
  • coating resins for resin coating carriers generally known styrene resins, acrylic resins, styrene acryl copolymer resins, silicone resins, modified silicone resins, Fluorinated resins or mixtures of these resins can be used.
  • the toner for developing an electrostatic image to which the internal release agent of the present invention is blended does not cause an offset phenomenon or a sheet wrapping phenomenon at the time of high-speed fixing by a heating roller fixing method. It has good fixability up to high temperatures, and is also excellent in gloss, transparency, and fluidity.
  • the molecular weights of the binder resin and the internal release agent are as follows, respectively. Was measured.
  • Detector Refractive index (R I) Detector RL540R (GL Science Co., Ltd.) Calibration curve: 10 types of standard polystyrene (Molecular weight 1.2 X manufactured by Showa Denko KK)
  • Endothermic peak area ratio The part surrounded by the DSC line and endothermic peak obtained by measuring the maximum endothermic peak temperature is 25 ° C or less and 35 ° C or less with respect to the entire area. , And the area ratio of the portion at 50 ° C or lower was calculated.
  • Offset resistance Unfixed images were created using an electrophotographic copying machine using an organic photoconductor as a photoconductor. The amount of toner attached was 0.7 mg./cm 2 . The unfixed image was transferred to paper, and the surface was made of fluororesin. Using a 58 mm-diameter heating port fixed machine, the nip width was 4 mm, and the fixing speed was 100 mm. In fixing, no offset prevention liquid such as silicone oil was supplied to the roller. The temperature of the surface of the fixing roller was changed in increments of 5 ° C, and the non-offset area was visually evaluated. .
  • Blocking resistance After applying a constant load to the toner and leaving it for 24 hours in an environment of 50 ° C, the presence or absence of aggregation was checked, and the quality of the blocking property was judged.
  • Compound A A DSC chart of Compound A is shown in FIG.
  • the endothermic peak area ratio of this polymer is 0% at 25 ° C or less, 0.85% at 35 ° C or less, and 7.32% at 50 ° C or less. there were.
  • the endothermic maximum peak temperature was ⁇ 0 ° C.
  • FIG. 2 shows a DSC chart of Compound B.
  • the endothermic peak area ratio of this polymer is 0.05% for those below 25 ° C, 0.81% for those below 35 ° C, and 4.83 for those below 50 ° C. %Met.
  • the maximum endothermic peak temperature was 87 ° C.
  • Figure 3 shows the DSC chart of Compound C.
  • the endothermic peak area ratio of this polymer is less than 25 ° C, less than 0.380 35 ° C, 3.55%, and less than 50 ° ⁇ , 33. It was 0.
  • the maximum endothermic peak temperature was 62 ° C.
  • the endothermic peak area ratio of Compound E is 0.30% at 25 ° C or lower, 6.18% at 35 ° C or lower, and 17% at 50 ° C or lower. It was 10%.
  • the maximum endothermic peak temperature was 69 ° C.
  • the endothermic peak area ratio of this compound F is less than 25 ° C, 1.0% 2% 35 ° C or less, 3.57 ° C, and 50 ° C or less, 9.0%. 1%.
  • the maximum endothermic peak temperature was 81 ° C.
  • Hydrochloric acid water was added to methyl carboxylate-containing methylpolysiloxane 2 obtained in Example 6, and the mixture was stirred at 120 ° C for 3 hours to obtain a hydrolyzate having the following structure.
  • the compound G has an endothermic peak area ratio of 0.1% at 25 ° C or lower, 5.89% at 35 ° C or lower, and 50%. C following ones were 3 0.5 0. The maximum endothermic peak temperature was 69 ° C.
  • Example 8
  • the endothermic peak area ratio of this waxy organopolysiloxane is 25% or less, preferably 1,50%, that of 35 ° C or less is 15.2%, and 50%. Those with C or less were 35.0%.
  • the maximum endothermic peak temperature was 60 ° C.
  • the methyl carboxylate-containing methylpolysiloxane 1 obtained in Example 2 was hydrolyzed. To 35 g of this hydrolyzate is added 65 g of benzylamine and 100 g of xylene. Len was added, and the mixture was refluxed (135 ° C) for 10 hours. After the reaction, xylene was removed under reduced pressure to obtain a waxy organopolysiloxane having the following structure.
  • the endothermic peak area ratio of the waxy organopolysiloxane is 0.02% at 25 ° C or lower, 2.8 2 at 35 ° C or lower, and 21 ° at 50 ° C or lower. 9%.
  • the maximum endothermic peak temperature was 75 ° C.
  • the endothermic peak area ratio of this waxy organopolysiloxane is 1.06% at 25 ° C or lower, 5, 21% at 35 ° C or lower, and 1 at 50 ° C or lower. It was 5.6%.
  • the maximum endothermic peak temperature was 75 ° C.
  • Table 1 below shows the endothermic maximum peak temperature and the endothermic peak area ratio for compounds H and I represented by
  • Example 1 2 100 parts by weight of styrene-acrylic resin (haima-TB-900; Sanyo Chemical Industries, Ltd.) with a glass transition point of 68 ° C, 5 parts by weight of carbon black (MA-600: Mitsubishi Chemical) 1 part by weight of methyltriphenylphosphonium tosylate (charge control agent) and 5 parts by weight of compound A were dispersed and mixed, and then melt-kneaded using a twin-screw extruder. After cooling, it was pulverized by a hammer mill and finely pulverized by a supersonic jet mill. The obtained powder was classified by an air classifier to obtain a fine black powder toner having an average particle diameter of 11 m.
  • Example 1 2 100 parts by weight of styrene-acrylic resin (haima-TB-900; Sanyo Chemical Industries, Ltd.) with a glass transition point of 68 ° C, 5 parts by weight of carbon black (MA-600: Mitsubishi Chemical) 1 part by weight of
  • a fine black powder toner having an average particle diameter of 11 was obtained in the same manner as in Example 11 except that Compound B was used instead of Compound A used in Example 11.
  • Example 1 Example 1 except that compound C was used instead of compound A used in 1. In the same manner as in 1, a fine powder black toner having an average particle diameter of 11 m was obtained.
  • a fine black powder toner having an average particle diameter of 11 m was obtained in the same manner as in Example 11 except that Compound D was used instead of Compound A used in Example 11.
  • Example 15
  • a fine black powder toner having an average particle diameter of 11 m was obtained in the same manner as in Example 11 except that Compound F was used instead of Compound ⁇ used in Example 11.
  • a fine black powder toner having an average particle size of 11 ⁇ was obtained in the same manner as in Example 11 except that Compound G was used instead of Compound A used in Example 11. Comparative Example 1
  • a fine powder black toner having an average particle diameter of m was obtained in the same manner as in Example 11, except that Compound H was used instead of Compound A used in Example 11. Comparative Example 2
  • a fine powder black toner having an average particle diameter of 11 m was obtained in the same manner as in Example 11 except that Compound I was used in place of Compound A used in Example 11.
  • the offset resistance and blocking resistance of the toners obtained in Examples 11 to 16 and the toners obtained in Comparative Examples 1 and 2 were evaluated, and the results are shown in Tables 2 and 3, respectively. did.
  • the toner containing the compounds A to D and F to G, which are the internal release agents of the present invention is fixed to the heating roller without supplying an anti-offset liquid such as silicone oil.
  • the method has a sufficient non-offset area in the method, and has good blocking resistance and fluidity.
  • the toners of Comparative Examples 1 and 2 containing the internal release agent H or I were inferior in offset resistance and blocking resistance to the toner composition of the present invention.
  • the above-mentioned colorant-dispersed monomer composition is poured into a suspension bath containing 4 times the amount of the suspending agent slurry, and then the mixture is homogenized by a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was dispersed at 0 rpm for 3 minutes to form suspended fine particles of the monomer composition. Microscopic observation showed that the particle size was less than about 10 ⁇ m.
  • a fine powder black toner having an average particle diameter of 11 m was obtained in the same manner as in Example 17 except that Compound B was used instead of Compound A used in Example 17.
  • a fine black powder toner having an average particle diameter of 11 m was obtained in the same manner as in Example 17 except that Compound C was used instead of Compound A used in Example 17.
  • Example 20
  • a fine powder black toner having an average particle size of 11 zm was obtained in the same manner as in Example 17 except that Compound D was used instead of Compound A used in Example 17.
  • Example 2 1 A fine powder black toner having an average particle size of 11 zm was obtained in the same manner as in Example 17 except that Compound D was used instead of Compound A used in Example 17.
  • Example 2 1 A fine powder black toner having an average particle size of 11 zm was obtained in the same manner as in Example 17 except that Compound D was used instead of Compound A used in Example 17.
  • Example 1 Except that Compound F was used instead of Compound A used in Example 7 In the same manner as 7, a fine powder black toner having an average particle diameter of 11 m was obtained.
  • a fine powder black toner having an average particle diameter of 11 // m was obtained in the same manner as in Example 17 except that Compound G was used instead of Compound A used in Example 17. Comparative Example 3
  • a fine powder black toner having an average particle diameter of 11 / m was obtained in the same manner as in Example 17 except that Compound I was used instead of Compound A used in Example 17.
  • the offset resistance and blocking resistance of the toners obtained in Examples 17 to 22 were evaluated. The results are shown in Table 4.
  • the toners obtained in Comparative Examples 3 and 4 were evaluated, and the results are shown in Table 5.
  • the toner containing the compounds A to D and F to G which are the internal release agents of the present invention, can be used even in the heating roller fixing method without supplying an offset prevention liquid such as silicone oil. It has a sufficient non-offset area, and has good blocking resistance and fluidity.
  • the toners of Comparative Examples containing Compounds H to I were inferior in offset resistance and blocking resistance to the toner composition of the present invention.
  • Example Example 1 7 Example 1 8 Example 1 9
  • Example 23 the average particle size, weight average molecular weight, fixing temperature range, and blocking resistance of the toner were measured as follows.
  • volume average particle size (proportion of toner particles of 5 m or less and 15 am or more):
  • GPC gel permeation chromatography
  • the fixing temperature area is defined as a temperature area where toner offset does not occur on the heating roller during fixing and the toner on the recording paper after fixing is sufficiently adhered to the recording paper.
  • the soft roller is made of aluminum as the core metal and the elastic layer is a dimethyl-based low-temperature vulcanized silicone rubber with a rubber hardness of 3 ° according to JIS-A standard 1.5 mm thick, release layer PFT (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) 50 zm thickness is used, the diameter is 30 mm, and it conforms to the Japan Rubber Association Standard SRIS 0101.
  • the rubber hardness of the fixing roller surface measured by the method is 80.
  • the evaluation with a soft roller was performed with a nip width of 4 mm or 3 lmm without applying silicone oil.
  • the fixing speed was 120 mm / s or 30 mm / s.
  • toner for development in a cylindrical container Apply a load of 2 Og, leave it in a 50 ° C environment for 5 hours, remove the toner from the container, and apply a load from above. The degree of aggregation was determined.
  • Neogen SC a 65% aqueous solution of sodium dodecylbenzenesulfonate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • Neogen SC a 65% aqueous solution of sodium dodecylbenzenesulfonate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • a milky white polymer primary particle dispersion A was obtained.
  • the weight average molecular weight of the tetrahydrofuran-soluble portion of the polymer was 66, 946, and the average particle size measured by UPA was 1775 nm.
  • a reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and a raw material charging device was charged with 6 parts by weight of an aqueous solution of 10% neogen SC and 372 parts by weight of demineralized water as an emulsifier. After the temperature was raised to 90 ° C. under a nitrogen stream, 1.6 parts by weight of an 8% aqueous hydrogen peroxide solution and 1.6 parts by weight of an 8-ascorbic acid aqueous solution were added as polymerization initiators.
  • a milky white resin particle dispersion A was obtained.
  • the weight average molecular weight of the tetrahydrofuran-soluble component of the polymer was 57,000, and the average particle size measured by UPA was 56 nm.
  • Pigmentable—15 3 aqueous dispersion (EP-700 Blue GA; manufactured by Dainichi Seika; solid content: 35%).
  • the average particle size measured by UPA was 150 nm.
  • Toner 1 To 100 parts by weight of Toner 1, 1 part by weight of silica subjected to hydrophobic surface treatment was mixed and stirred to obtain Toner 1 for development. Evaluation of toner 1 for development
  • the volume average particle size of the developing toner 1 measured by the Coulter Counter was 7.9 / m, and the ratio of the volume average particle size to the number average particle size was 1.12.
  • the developing toner 1 was fixed at 160 to 210 ° C. at a fixing speed of 12 O mms, and was fixed at 130 to 170 ° C. at a fixing speed of 3 O mmZs.
  • Example 2 4
  • a milky white polymer primary particle dispersion B was obtained.
  • the weight average molecular weight of the tetrahydrofuran-soluble component of the polymer was 70,903, and the average particle size measured by UPA was 203 nm.
  • toner 1-2 One hundred parts by weight of toner 1-2 was mixed with 1 part by weight of silica having been subjected to a hydrophobic surface treatment, followed by stirring to obtain toner 2 for development.
  • the volume average particle diameter of the developing toner 2 as measured by Coulter and Counter was 7.4, and the ratio of the volume average particle diameter to the number average particle diameter was 1.13.
  • Developing toner 2 fixed at 160 to 210 at 'fixing speed of 120 mm /' s, and at 130 to 170 ° C at fixing speed of 30 mm / s .
  • Example 2 5
  • a milky white polymer primary particle dispersion C was obtained.
  • the weight-average molecular weight of the tetrahydrofuran-soluble component of the polymer was 64,902, and the average particle size measured by UPA was 168 nm.
  • toner 3 One hundred parts by weight of toner 3 and 1 part by weight of silica subjected to hydrophobic surface treatment were mixed and stirred to obtain toner 3 for development.
  • the volume average particle diameter of the developing toner 3 measured by a Coulter counter was 7.6; m, and the ratio of the volume average particle diameter to the number average particle diameter was 1.11.
  • Developing toner 3 was fixed at 160 to 210 ° C at a fixing speed of 120 mm / s, and was fixed at 130 to 170 ° C at a fixing speed of 30 mmZs. .
  • Example 26
  • a milky white polymer primary particle dispersion D was obtained.
  • the weight average molecular weight of the tetrahydrofuran-soluble component of the polymer was 53, 716, and the average particle size measured by UPA was 191.4 nm.
  • toner 4 One hundred parts by weight of toner 4 and one part by weight of silica subjected to a hydrophobic surface treatment were mixed and stirred to obtain toner 4 for development. Evaluation of developing toner 4
  • the volume average particle size of the developing toner 4 measured by a Coulter counter was 7.0 / zm, and the ratio of the volume average particle size to the number average particle size was 1.17.
  • the developing toner 4 is fixed at a fixing speed of 120 mm, '' s at 180 to 220 ° C or higher, and at a fixing speed of 30 mms at 140 to 220 ° C or higher. Established.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Physics & Mathematics (AREA)
  • Silicon Polymers (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

L'invention concerne un organopolysiloxane cireux présentant un groupe alkyle à longue chaîne ou un groupe organique à longue chaîne contenant un hétéroatome. Dans une courbe d'absorption thermique obtenue par mesurage des caractéristiques d'absorption thermique au moyen d'un calorimètre à balayage différentiel, la zone d'une pointe d'absorption thermique pour une fraction fondant dans une gamme de température inférieure ou égale à 50 °C, représente au maximum 50 % de la zone de la pointe totale. L'incorporation de l'organopolysiloxane cireux dans un toner pour développer une image de charge électrostatique, peut produire un toner exempt de la survenue d'un phénomène de décalage ou d'enroulement de feuille, même dans le cas où une image est fixée à grande vitesse selon le procédé de fixation par rouleau chauffant.
PCT/JP2002/002420 2001-03-15 2002-03-14 Organopolysiloxane cireux et composition de toner le contenant Ceased WO2002077071A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004099290A1 (fr) * 2003-05-12 2004-11-18 Shin-Etsu Chemical Co., Ltd. Cire au silicone
WO2006028265A1 (fr) * 2004-09-06 2006-03-16 Dow Corning Toray Co., Ltd. Cires organopolysiloxanes pour cosmétiques et produits cosmétiques les contenant
KR101294554B1 (ko) 2008-04-02 2013-08-07 와커 헤미 아게 왁스-유사 β-케토카르보닐-작용성 유기규소 화합물

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JPS56123551A (en) * 1980-03-05 1981-09-28 Hitachi Metals Ltd Toner for developing electrostatic charge
JPS63189438A (ja) * 1986-11-03 1988-08-05 ゼネラル・エレクトリツク・カンパニイ シリコーン−エステルワツクス
JPH06322356A (ja) * 1993-05-12 1994-11-22 Toshiba Silicone Co Ltd 表面保護剤
JPH07145242A (ja) * 1993-08-02 1995-06-06 Dow Corning Corp プリスチン アルキルシロキサン類およびそれらの製造方法
JPH07244398A (ja) * 1994-03-03 1995-09-19 Shin Etsu Chem Co Ltd トナー用内添離型剤及びそれを用いたトナー
GB2299024A (en) * 1995-03-24 1996-09-25 Unilever Plc Antiperspirant containing an alkyl ester siloxane
JPH08311204A (ja) * 1995-05-03 1996-11-26 Dow Corning Corp 線状のトリオルガノシロキシ末端キャップメチル水素ポリシロキサンの製造方法
JPH09190009A (ja) * 1996-01-09 1997-07-22 Kao Corp 静電荷像現像用トナー
JPH1180366A (ja) * 1997-05-13 1999-03-26 Lexmark Internatl Inc シリコーン共重合体の製造方法
JPH11316472A (ja) * 1998-03-03 1999-11-16 Mitsubishi Chemical Corp 静電荷像現像用トナー
JP2000314982A (ja) * 1999-04-28 2000-11-14 Shin Etsu Chem Co Ltd 静電荷画像形成用トナー
JP2002029918A (ja) * 2000-07-12 2002-01-29 Shin Etsu Chem Co Ltd 固形化粧料
JP2002069193A (ja) * 2000-08-31 2002-03-08 Nippon Unicar Co Ltd ポリエチレンワックス変性オルガノポリシロキサン及びそれを含有するトナー組成物
JP2002069190A (ja) * 2000-08-31 2002-03-08 Nippon Unicar Co Ltd 長鎖アルキル変性オルガノポリシロキサン及びそれを含有するトナー組成物

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Publication number Priority date Publication date Assignee Title
JPS56123551A (en) * 1980-03-05 1981-09-28 Hitachi Metals Ltd Toner for developing electrostatic charge
JPS63189438A (ja) * 1986-11-03 1988-08-05 ゼネラル・エレクトリツク・カンパニイ シリコーン−エステルワツクス
JPH06322356A (ja) * 1993-05-12 1994-11-22 Toshiba Silicone Co Ltd 表面保護剤
JPH07145242A (ja) * 1993-08-02 1995-06-06 Dow Corning Corp プリスチン アルキルシロキサン類およびそれらの製造方法
JPH07244398A (ja) * 1994-03-03 1995-09-19 Shin Etsu Chem Co Ltd トナー用内添離型剤及びそれを用いたトナー
GB2299024A (en) * 1995-03-24 1996-09-25 Unilever Plc Antiperspirant containing an alkyl ester siloxane
JPH08311204A (ja) * 1995-05-03 1996-11-26 Dow Corning Corp 線状のトリオルガノシロキシ末端キャップメチル水素ポリシロキサンの製造方法
JPH09190009A (ja) * 1996-01-09 1997-07-22 Kao Corp 静電荷像現像用トナー
JPH1180366A (ja) * 1997-05-13 1999-03-26 Lexmark Internatl Inc シリコーン共重合体の製造方法
JPH11316472A (ja) * 1998-03-03 1999-11-16 Mitsubishi Chemical Corp 静電荷像現像用トナー
JP2000314982A (ja) * 1999-04-28 2000-11-14 Shin Etsu Chem Co Ltd 静電荷画像形成用トナー
JP2002029918A (ja) * 2000-07-12 2002-01-29 Shin Etsu Chem Co Ltd 固形化粧料
JP2002069193A (ja) * 2000-08-31 2002-03-08 Nippon Unicar Co Ltd ポリエチレンワックス変性オルガノポリシロキサン及びそれを含有するトナー組成物
JP2002069190A (ja) * 2000-08-31 2002-03-08 Nippon Unicar Co Ltd 長鎖アルキル変性オルガノポリシロキサン及びそれを含有するトナー組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004099290A1 (fr) * 2003-05-12 2004-11-18 Shin-Etsu Chemical Co., Ltd. Cire au silicone
US7354983B2 (en) 2003-05-12 2008-04-08 Shin-Etsu Chemical Co., Ltd. Silicone wax
WO2006028265A1 (fr) * 2004-09-06 2006-03-16 Dow Corning Toray Co., Ltd. Cires organopolysiloxanes pour cosmétiques et produits cosmétiques les contenant
KR101294554B1 (ko) 2008-04-02 2013-08-07 와커 헤미 아게 왁스-유사 β-케토카르보닐-작용성 유기규소 화합물

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