JP4746289B2 - Resin particles for toner and method for producing the same - Google Patents

Description

  The present invention relates to resin particles for toner used for electrophotography, electrostatic recording, electrostatic printing, and the like.

Conventionally, a resin solution obtained by dissolving a resin in a solvent in advance is dispersed in an aqueous medium in the presence of a dispersing agent (auxiliary) such as a surfactant or a water-soluble polymer, and the solvent is removed by heating or decompression. There are known resin particles for toner produced by the above (solution resin suspension method). It is difficult to control the shape of the resin particles for toner obtained by the solution resin suspension method, and the shape is generally spherical.
When the spherical resin particles are used, there is a problem that the cleaning property becomes poor when the toner remaining on the photoreceptor without being transferred to the paper surface is cleaned with a blade. In order to solve such a problem, there is a method in which the particle surface is appropriately elasticized before the volume of the particle shrinks due to solvent removal, and the surface area reduction rate is made smaller than the volume shrinkage rate to form resin particles having irregularities on the surface. As a means for elasticizing the particle surface, a method of forming a shell material on the surface of a resin particle by an interfacial polymerization method or an in-situ polymerization method (see Patent Document 1) has been proposed. Due to the influence, there is a problem that the low-temperature fixing property and the hot-off-setting property are lowered, and the fixing temperature range is remarkably narrowed.
JP-A-4-209630

  The present invention has been made in view of the above circumstances in the prior art, and an object of the present invention is to obtain toner resin particles having excellent blade cleaning properties and a wide fixing temperature range.

The inventors of the present invention have reached the present invention as a result of intensive studies to achieve the above object.
That is, the present invention comprises (1) a filler (D0) in a dispersion (D0) comprising a resin (a) and / or a precursor (a0) thereof in a solvent (s) having a solubility in water of 80% or less. An oil-in- water dispersion (D1) in which the filler-containing dispersion (D) in which b) is dispersed is dispersed in the aqueous medium (W ) and the oil droplets (A0) containing the filler (b) are dispersed. The concentration of at least a part (b *) of the filler (b) in the oil droplet (A0) is formed by the diffusion of the filler (b) in the oil droplet (A0) to the surface of the oil droplet (A0). Forming an integrated layer (S0) with a high
(2) Resin particles for toner comprising resin (a) and filler (b) obtained by a production method including a step of removing the solvent from the oil-in-water dispersion (D1): resin (a ) Is one or more resins selected from the group consisting of urethane resins, epoxy resins, vinyl resins and ester resins; the filler (b) is a surface treatment agent selected from the group consisting of silane coupling agents and tertiary amine compounds. is silica treated with (d), the content of the filler (b) in the particles is 0.01 to 50 wt%; particle shape factor of the volume average particle diameter and 110-137 of 3~10μm (SF-2); the particle is an outer shell layer in which the filler (b) is present inside the surface and at least a part (b *) of the filler (b) is accumulated near the surface. Having (S); the layer (S) The thickness of the layer (S) is at least 0.01 μm and not more than ½ of the maximum inscribed circle radius of the cross section of the particle. in the cross-sectional image of the area is maximum, from the surface of the particles, within the cross section image, the entire area within a certain distance of the particles inside the vertical direction, the predetermined distance area of the filler (b) account for at least 50% Is the maximum distance (T).
. As well as
(1) One or more resins (a) selected from the group consisting of urethane resins, epoxy resins, vinyl resins and ester resins in a solvent (s) having a solubility in water of 80% or less and / or precursors thereof Resin (a) and Silica treated with a surface treatment agent (d) selected from the group consisting of a silane coupling agent and a tertiary amine compound in dispersion (D0) comprising body (a0) as filler (b) // Disperse the filler-containing dispersion (D) dispersed in an amount of 0.01 to 50% by mass with respect to the total amount with the precursor (a0) in the aqueous medium (W), and contain the filler (b). The oil droplets (A0) are dispersed to form an oil-in-water dispersion (D1), and the filler (b) in the oil droplets (A0) is diffused on the surface of the oil droplets (A0). At least one of the fillers (b) in (A0) (B *) concentration to form an integrated layer becomes higher (S0) of
(2) A step including removing the oil-in-water dispersion (D1) to obtain resin particles (A) having an outer shell layer (S) composed of at least a part (b *) of the filler (b). Item 5. A method for producing resin particles for toners (A) according to any one of Items 1 to 4 ;
It is.

The toner resin particles of the present invention have the following effects.
[1] Good blade cleaning properties.
[2] Excellent low-temperature fixability.
[3] Excellent hot offset resistance.

  The resin particle for toner of the present invention (hereinafter also referred to as (A)) contains the resin (a) and the filler (b), and is an outer shell layer (S) comprising at least a part of (b). [Hereinafter, (b) that forms the outer shell layer (S) is also referred to as (b *)]. Containing (b) is a state in which (b) is present inside the surface of the resin particles (A) and can be observed by a transmission electron microscope (TEM). When (b) is exposed to the outside of the resin particles (A) or adsorbed to the surface of (A), the surface and bulk properties of (A) are predominantly the properties of (b), and the resin (a ) Is less likely to be exhibited. On the contrary, when (b) is contained in the particles, the characteristics of (a) are easily developed. That is, since (a) is present on the surface of (A), and there is also a portion occupied by (a) in the outer shell layer (S) described later formed by (b *), the low temperature fixing Good. When (A) contains a wax, the wax oozes out from the portion occupied by (a) described above at the time of thermal fixing, so that the hot offset resistance is improved.

The thickness of the outer shell layer (S) formed of at least a part of the filler (b) formed in the vicinity of the surface of the resin particle (A) of the present invention is an image of a cross section of the resin particle by a transmission electron microscope (TEM). Can be measured by image analysis.
That is, resin particles are dispersed in a sucrose saturated solution (67% by mass solution) (hereinafter,% means mass% unless otherwise specified), frozen at −100 ° C., and then cryocooled. After slicing to a thickness of about 1000 angstroms and dyeing the filler (b) containing (b *) with ruthenium tetroxide, the resin particle cross-section was photographed with a transmission electron microscope at a magnification of 10,000 times, and an image analyzer [for example, , Nexus NEW CUBE ver. 2.5 (manufactured by NEXUS Co., Ltd.)], in the cross section where the cross-sectional area is maximum, in the area of a portion having a certain distance from the surface of the resin particle in the vertical direction inside the particle, (b *) is mainly The maximum distance (T) in which the area of (b) occupies 50% or more is defined as the thickness of the outer shell layer formed by (b *). In addition, the said measured value is taken as the average value which calculated each value about ten resin particles selected at random. FIG. 1 shows an example of (T).
In addition, when it is difficult to distinguish the outer shell layer (S) and the resin (a) from the observation of the TEM image, various apparatuses (for example, energy dispersive X) capable of composition mapping the resin particle cross section obtained by the above method. Mapping with a line spectrometer: EDX, electron energy loss spectrometer EELS, etc.), specifying the outer shell layer (S) from the composition distribution image obtained by the analysis, and calculating the outer shell layer thickness (T) by the above method can do.

  The lower limit of the thickness of the outer shell layer of the filler (b *) is usually 0.01 μm, preferably 0.02 μm, more preferably 0.03 μm. The upper limit of the thickness of the outer shell layer is usually ½, preferably ３, more preferably ¼, particularly preferably ５ of the inscribed circle radius of the resin particles (A). In order to bring the shape factor (SF-2) of (A) into the range described later, it is necessary to make the surface area reduction rate significantly slower than the volume shrinkage rate during volume shrinkage of the resin particles (A), It is important to make the surface of the resin particle elastic enough to make the resin particle surface more viscous than the inside of the resin particle. When the thickness of the outer shell layer of the filler (b *) is within the above range, the difference in viscosity between the resin particle surface and the resin particle inside becomes large, and unevenness is easily developed on the particle surface.

The volume average particle diameter of (A) is usually 3 to 10 μm. The upper limit is preferably 9 μm, more preferably 8 μm, particularly preferably 7 μm, most preferably 6.5 μm, and the lower limit is preferably 3.5 μm, more preferably 4 μm, particularly preferably 4.2 μm, most preferably 4.5 μm. When the thickness is less than 3 μm, transferability to paper and blade cleaning properties are deteriorated, and when it exceeds 10 μm, it is difficult to obtain a high-resolution image with high resolution.
The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of (A) is preferably 1.0 to 1.5, more preferably 1.0 to 1.4. is there. If Dv / Dn is 1.0 to 1.5, the resolution is good.

In the present invention, the degree of surface unevenness of the resin particles (A) can be evaluated by the shape factor (SF-2) and the ratio of the surface centerline average roughness to the volume average particle size.
(SF-2) of (A) is 110-300. The upper limit is preferably 250, more preferably 230, particularly preferably 200, and the lower limit is more preferably 115, particularly preferably 120, and most preferably 125.

The ratio of the surface centerline average roughness and the volume average particle size of (A) is preferably 0.001 to 0.1, more preferably 0.002 to 0.08, and particularly preferably 0.002 to 0.06. Most preferably, it is 0.003-0.05.
When it is in the above range, the blade cleaning property of the toner becomes good.

In the present invention, the resin particle (A) has a shape factor (SF-2) of 500 magnifications using an electron microscope (for example, FE-SEM (S-800) manufactured by Hitachi, Ltd., and so on). 100 images of the resin particles magnified twice are randomly sampled, and the image information is sent to an image analysis apparatus [for example, Nexus NEW CUBE ver. 2.5 (manufactured by NEXUS), Luzex III (manufactured by Nicole) and the like, and so on. It is a value obtained by introducing into and analyzing and calculating from equation (1).

(SF-2) = 100 × (P) ² / {4π × (Y)} (1)

[In the formula, (P) represents the perimeter of the resin particles, and (Y) represents the projected area of the resin particles. ]

  In the present invention, the surface centerline average roughness of the resin particles (A) can be measured by a scanning probe microscope system (AFM, for example, manufactured by Toyo Technica Co., Ltd.). The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the resin particles (A) are determined by a Coulter counter particle size measuring device [for example, trade name: Multisizer III (manufactured by Beckman Coulter)] or a laser particle size. It can be measured using a distribution measuring apparatus [for example, trade name: LA-920 (manufactured by Horiba)].

The upper limit of the ratio of the volume average particle diameter of the primary particles of the filler (b *) and the volume average particle diameter of the resin particles (A), which comprises at least part of the filler (b) described later and forms the outer shell layer (S) Is usually preferably 0.1, more preferably 0.01, and particularly preferably 0.005. The volume average particle size of the primary particles of the filler (b *) is preferably 0.001 to 0.5 μm, more preferably 0.001 to 0.1 μm, and particularly preferably 0.002 to 0.05 μm.
When the volume average particle size of the filler (b *) is 0.1 μm or more, it is preferable to measure using a laser-type particle size distribution measuring device. Is preferred. The BET specific surface area can be measured by using an apparatus based on a normal nitrogen adsorption method [for example, trade name: QUANTTASORB (manufactured by QUANTACHROME)]. The primary particle diameter of (b *) can be measured by dividing the reciprocal of the BET specific surface area of (b *) by the true specific gravity of (b *).

The content of (b) in (A) is preferably 0.01 to 50%, more preferably 0.05 to 45%, and particularly preferably 0.1 to 40%.
The content of (b *) in (A) is preferably 0.01 to 20%, more preferably 0.05 to 18%, and particularly preferably 0.1 to 15%.
Further, the ratio of (b *) in (b) is preferably 10% or more, more preferably 20% or more.

  The filler (b *) preferably has a high effect of thickening (S) during the formation of the outer shell layer (S). The viscosity when the filler (b *) alone is dispersed in the solvent (s) described later at a temperature of 25 ° C. and a filler volume fraction of 0.3 is preferably from 50 to 100,000 mPa · s, more preferably from 100 to 100 m. It is 50,000 mPa · s, particularly preferably 150 to 30,000 mPa · s.

  The higher the aspect ratio of the filler (b *), the higher the effect of thickening the outer shell layer (S), and the higher the effect of forming irregularities on the surface of the resin particles (A). Therefore, the higher the aspect ratio of (b *), the more the irregularities can be formed on the surface of the resin particles with a low addition amount. The aspect ratio is preferably 1.5 to 1000, more preferably 2 to 800, particularly preferably 2.5 to 600, and most preferably 3 to 500.

  The filler (b), at least a part of which becomes the filler (b *) forming the outer shell layer (S), is not particularly limited as long as it is an inorganic or organic particulate material that does not dissolve in the solvent (s) described later. However, it may be used alone or in combination of two or more depending on the purpose. That is, any of inorganic filler (b1), organic filler (b2), and a combination of (b1) and (b2) may be used. In (b2), colorants, waxes, charge control agents and the like generally used for resin particles for toner are included. Moreover, these can also be made into (b *) by the following filler surface treatment.

Examples of the inorganic filler (b1) include silica, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, Metal oxides such as samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, heavy Calcium carbonate, light calcium carbonate, metal carbonate such as zinc carbonate, barium carbonate, dosonite, hydrotalcite, metal sulfate such as calcium sulfate, barium sulfate, gypsum fiber, calcium silicate (wollastonite, zonotlite), kaolin, Kure , Talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass flakes and other metal silicates, aluminum nitride, boron nitride, silicon nitride and other metal nitrides, potassium titanate Metal titanates such as calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, metal borates such as zinc borate and aluminum borate, metal phosphoric acids such as tricalcium phosphate Examples thereof include salts, metal sulfides such as molybdenum sulfide, metal carbides such as silicon carbide, carbons such as carbon black, graphite, and carbon fiber, and other fillers.
Among these, a metal oxide is preferable as the filler (b *) forming the outer shell layer (S), and silica, alumina, and titania are more preferable.

Examples of the organic filler (b2) include vinyl resin, urethane resin, epoxy resin, ester resin, polyamide, polyimide, silicone resin, fluorine resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, aniline resin, and ionomer resin. Resin beads such as polycarbonate, cellulose and mixtures thereof. Also, ester wax (carnauba wax, montan wax, rice wax, etc.), polyolefin wax (polyethylene, polypropylene, etc.), paraffin wax, ketone wax, ether wax, long chain (C30 or higher) aliphatic alcohol, long chain (C30 or more) Fatty acids and organic waxes such as a mixture thereof can be used. In addition, various organic dyes or organic pigments such as azo, phthalocyanine, condensed polycyclic, dye lake and the like, which are generally used as colorants, and derivatives thereof can be used.
Among these, preferable as the filler (b *) for forming the outer shell layer (S) are various organic dyes or organic pigments such as azo, phthalocyanine, condensed polycyclic, and dyed lake, and these Is a derivative of

  In addition, colorants, waxes, and charge control agents that are generally used for toner resin particles may be used as the filler (b). Among the inorganic or organic fillers, examples of charge control agents include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, and quaternary ammonium salts. (Including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of 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-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfo group, a carboxyl group, and a quaternary ammonium salt.

  In order for the (b *) to form an outer shell layer in the vicinity of the surface of the resin particle (A), the surface property of (b *) is basically hydrophobic but slightly hydrophilic. It is preferable to have. (B) If the surface has no hydrophilic group and is highly hydrophobic, (b) is dispersed inside the resin particles (A). Further, if (b) the hydrophilicity of the surface is strong enough to disperse (b) alone in water, (b) is the (W) side when dispersing the dispersion liquid (D) described later in the aqueous medium (W). Will be detached.

  Therefore, in order to change the shape of the resin particles (A), the resin particles (A) can be deformed by the method described later for several levels of (b) having different hydrophilicity / hydrophobicity by the surface treatment described later (b). It is necessary to optimize the hydrophilic / hydrophobic balance on the surface (b) by confirming the shape of (A) and the outer shell layer (S).

  As a method for evaluating the hydrophilicity and hydrophobicity of the filler (b), the water-insoluble solvent dispersion of (b) or the water-insoluble solvent dilution of the dispersion (D) described later (both diluted 10,000 times) In addition, there is a method in which an amount of water equal to that of the liquid is added and forcibly stirred to observe the separation rate of the oil phase and the aqueous phase and the oil-water orientation of (b). As the water-insoluble solvent, for example, toluene, xylene, methyl ethyl ketone, ethyl acetate and the like can be used. When the total amount of (b) shifts to the aqueous phase, the surface hydrophilicity of (b) is too high, and therefore it is necessary to hydrophobize (b) by surface treatment. Further, when the total amount of (b) is transferred into the oil phase promptly (within 1 minute) after forced stirring, the surface hydrophobicity of (b) is too strong, so that it is necessary to impart hydrophilicity by surface treatment. After forced stirring, oil / water separation occurs gently, and the behavior in which the (b) is oriented in the vicinity of the oil / water interface is ideal, but the evaluation in this observation is only one standard.

  In order to optimize the surface hydrophilic / hydrophobic balance of the filler (b), silicone oil, coupling agents (for example, silane coupling agents, titanate coupling agents and aluminate coupling agents), amine compounds, commercially available The filler (b) is preferably surface-treated with a surface treatment agent (d) such as various pigment dispersants.

  Examples of silicone oil include straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, methacrylic acid modified silicone oil, epoxy modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, amino Examples include modified silicone oil such as modified silicone oil. Examples of the silane coupling agent include organoalkoxysilane, organochlorosilane, organosilazane, organodisilazane, organosiloxane, organodisiloxane, and organosilane.

As the amine compound, a compound that is compatible with the solvent (s) described later and has one or more of a primary amine group, a secondary amine group, and a tertiary amine group can be used. It is particularly preferable to use a compound having a tertiary amine group that does not contain active hydrogen.
Examples of the tertiary amine compound include triethylamine, N, N′-dimethylaminodiethyl ether, tetramethylhexamethylenediamine, tetramethylethylenediamine, dimethylethanolamine, and N-methyl-N ′-(2-dimethylamino) ethylpiperazine. 1,2-dimethylimidazole, triethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, tetramethylguanidine 1,8-diazabicyclo (5,4,0) undecene-7, bis (2-morpholinoethyl) ether, etc., and two or more of these may be used in combination. Of these, triethylamine, 1,8-diazabicyclo (5,4,0) undecene-7, and bis (2-morpholinoethyl) ether are particularly preferable.

The method for surface treatment of the filler (b) is not particularly limited, and known methods can be applied. For example, the following [1] to [5] and a combination thereof can be applied.
[1] A method in which the surface treatment agent (d) is added to the filler (b) and dry-treated with a Henschel mixer, a Laedige mixer or the like.
[2] A method in which the resin (a) and the filler (b) are melt-kneaded by a kneader in the presence of a solvent (s) as necessary. (Integral blend method)
[3] A method in which a filler (b), a surface treatment agent (d), and, if necessary, a resin (a) are dispersed in a solvent (s) by a bead mill or the like and wet-treated.
[4] A method in which the filler (b) is dispersed in water, the surface treatment agent (d) is added and wet processing is performed, and then the water and the solvent (s) are replaced.
[5] A method in which the surface treatment agent (d) is directly added to the dispersion liquid (D) containing the filler (b), and the dispersion treatment is performed by a disperser such as a homomixer or Ebara milder.

  The resin (a) in the present invention may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, urethane resin, epoxy resin, ester resin, polyamide, polyimide, silicone resin, phenol resin Melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate, and a mixture thereof can be used. Of these, vinyl resin, urethane resin, epoxy resin, ester resin, and mixtures thereof are preferable from the viewpoint that uniform fine spherical resin particles are easily obtained, and more preferably vinyl resin, urethane resin, ester resin, and these. And particularly preferred are vinyl resins, ester resins and mixtures thereof.

Among the resins (a), preferable resins, that is, vinyl resins, urethane resins, epoxy resins and ester resins will be described, but other resins can be used in the same manner.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers.
A known polymerization catalyst or the like can be used for the polymerization.
The following (1) to (10) can be used as the vinyl monomer.
(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbon: Alkene having 2 to 12 carbon atoms (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and α-olefin having 3 to 24 carbon atoms) Etc.); alkadienes having 4 to 12 carbon atoms (for example, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, etc.) and the like.

  (1-2) Alicyclic vinyl hydrocarbon: mono- or di-cycloalkene having 6 to 15 carbon atoms (for example, cyclohexene, vinylcyclohexene and ethylidenebicycloheptene), mono- or di- having 5 to 12 carbon atoms Cycloalkadienes (for example, (di) cyclopentadiene and the like); and terpenes (for example, pinene, limonene and indene) and the like.

  (1-3) aromatic vinyl hydrocarbon: styrene; hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 24 carbon atoms) substituted styrene (for example, α-methylstyrene, vinyltoluene, 2 , 4-dimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, and trivinyl benzene); and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and their salts:
C3-C30 unsaturated monocarboxylic acid (for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, cinnamic acid, etc.); C3-C30 unsaturated dicarboxylic acid or its anhydride (for example, (anhydrous)) Maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid and mesaconic acid, etc.); and monoalkyl (C1-24) esters of unsaturated dicarboxylic acids having 3 to 30 carbon atoms (e.g. Maleic acid monooctadecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester, itaconic acid glycol monoether and citraconic acid monoeicosyl ester).

  Examples of the salt of the carboxyl group-containing vinyl monomer include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, and quaternary ammonium salts. . The amine salt is not particularly limited as long as it is an amine compound. For example, a primary amine salt (ethylamine salt, butylamine salt, octylamine salt, etc.), secondary amine (diethylamine salt, dibutylamine salt, etc.), tertiary amine, etc. (Triethylamine salt, tributylamine salt, etc.). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, tributyllaurylammonium salt and the like.

  Specific examples of the carboxyl group-containing vinyl monomer salt include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, lithium acrylate, acrylic acid Examples include cesium, ammonium acrylate, calcium acrylate, and aluminum acrylate.

(3) Sulfo group-containing vinyl monomers and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfone) Acid etc .; C5-C18 sulfo (hydroxy) alkyl- (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyl) Oxyethanesulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, etc.); C5-C18 sulfo (hydroxy) alkyl (meth) acrylamide (for example, 2- (meth) acryloylamino-2, 2-dimethylethanesulfonic acid, 2- (meth) acrylic Amido-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid); alkyl (C3-C18) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2- Ethyl hexyl-allylsulfosuccinic acid); poly (n = 2 to 30) oxyalkylene (oxyethylene, oxypropylene, oxybutylene: single, random or block) mono (meth) acrylate sulfate ester [for example, poly (n = 5-15) oxyethylene monomethacrylate sulfate, poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.]; polyoxyethylene polycyclic phenyl ether sulfate (for example, general formula (1-1) or (1 -2) And the like; and the sulfonic acid represented by the general formula (1-3); and salts thereof.
In addition, as a salt, the counter ion etc. which are shown in "(2) Carboxyl group containing vinyl monomer and its salt" are used.

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different. Or Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.)

(4) Phosphono group-containing vinyl monomer and salts thereof:
(Meth) acryloyloxyalkyl phosphate monoester (alkyl group having 1 to 24 carbon atoms) (for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxy Alkylphosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid) and the like.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer:
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, amino Indole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.

(6-2) Amide group-containing vinyl monomer:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone and the like.

(6-3) Nitrile group-containing vinyl monomer having 3 to 10 carbon atoms:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(6-4) Vinyl monomer containing a group consisting of a quaternary ammonium cation:
Quaternized products of tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide and diallylamine (methyl chloride, dimethyl sulfate) Quaternized with a quaternizing agent such as benzyl chloride, dimethyl carbonate, etc. (eg, dimethyl diallyl ammonium chloride, trimethyl allyl ammonium chloride, etc.).
(6-5) Nitro group-containing vinyl monomer having 8 to 12 carbon atoms:
Nitrostyrene etc.

(7) C6-C18 epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.
(8) C2-C16 halogen-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(9) Vinyl ester, vinyl (thio) ether, vinyl ketone, vinyl sulfone:
(9-1) Vinyl ester having 4 to 16 carbon atoms:
Vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl Benzoate, ethyl α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eikoshi (Meth) acrylates, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups) Is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetra Allyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl Alcohol ethylene oxide (hereinafter abbreviated as EO) 10 mol adduct (meth) acrylic Rate, lauryl alcohol EO 30 mole adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].

(9-2) Vinyl (thio) ether having 3 to 16 carbon atoms:
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro 1,2 -Pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, and the like.

(9-3) Vinyl ketone having 4 to 12 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone and vinyl phenyl ketone):
C2-C16 vinyl sulfone (for example, divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide).

(10) Other vinyl monomers:
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.
Among these vinyl monomers, vinyl hydrocarbons, carboxyl group-containing vinyl monomers and salts thereof, sulfonic acid group-containing vinyl monomers and salts thereof, hydroxyl group-containing vinyl monomers, and nitrogen-containing vinyl monomers are preferable, and vinyl is more preferable. Hydrocarbons, carboxyl group-containing vinyl monomers and their salts, sulfonic acid group-containing vinyl monomers and their salts, particularly preferably aromatic vinyl hydrocarbons, carboxyl group-containing vinyl monomers and their salts, sulfonic acid group-containing vinyl monomers And their salts.

  Among the vinyl resins, as a polymer obtained by copolymerizing vinyl monomers (copolymer of vinyl monomers), any one of the above monomers (1) to (10) may be binary or more in any proportion. For example, styrene- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-acrylonitrile copolymer Polymer, styrene- (maleic anhydride) copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, and styrene-styrenesulfonic acid- (meth) acrylic acid ester A copolymer etc. are mentioned.

As the ester resin, a polycondensate of a polyol and a polycarboxylic acid, this acid anhydride or this lower alkyl (carbon group having 1 to 4 carbon atoms) ester can be used.
A known polycondensation catalyst or the like can be used for the polycondensation reaction.
As the polyol, diol (11) and trivalent to hexavalent or higher polyol (12) are used.
As polycarboxylic acid, this acid anhydride or this lower alkyl ester, dicarboxylic acid (13), tri- or hexavalent or higher polycarboxylic acid (14), these acid anhydrides and these lower alkyl esters are used. It is done.

Diol (11) includes alkylene glycol having 4 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octane). Diol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol, etc .; alkylene ether glycols having a molecular weight of 50 to 10,000 (for example, diethylene glycol, triethylene glycol, dipropylene glycol) Polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol); alicyclic diols having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedimethanol and hydrogenation) Sphenol A and the like; alkylene oxide of the above alicyclic diol having a molecular weight of 100 to 10,000 (hereinafter abbreviated as AO) [EO, propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO). Etc.] Adducts (addition mole number 2 to 100) (for example, EO 10 mole addition product of 1,4-cyclohexanedimethanol, etc.); bisphenols having 15 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol S, etc.) or AO (EO, PO, BO, etc.) adducts of polyphenols having 12 to 24 carbon atoms (eg, catechol, hydroquinone, resorcin, etc.) (addition moles of 2 to 100) (eg, bisphenol A / EO 2 mol adduct, bisphenol A)・ EO4 mol adduct, bisphenol A ・ PO Mole adducts, bisphenol A · PO 3 mol adducts, bisphenol A · PO 4 mol adducts, etc.); Examples thereof include polybutadiene diol.
Of these, an AO adduct of alkylene glycol and bisphenol is preferred, and an AO adduct of bisphenol and a mixture of this with an alkylene glycol are more preferred.

Examples of the trivalent to hexavalent or higher polyol (12) include trivalent to hexavalent or higher aliphatic polyhydric alcohols having 3 to 8 carbon atoms (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, Sorbitan, sorbitol, etc.); alkylene (2-4 carbons) oxide adduct (2-100 added moles) of trisphenol having 25 to 50 carbon atoms (for example, trisphenol PA) (for example, trisphenol PA · EO 2) Mol adduct, trisphenol PA / EO4 mol adduct, trisphenol PA / PO2 mol adduct, trisphenol A / PO3 mol adduct, trisphenol PA / PO4 mol adduct, etc.); (For example, phenol novolac and cresol novolac ) Alkylene (carbon number 2-4) oxide adduct (addition mole number 2-100) (phenol novolac PO 2 mol adduct, phenol novolac EO 4 mol adduct, etc.); polyphenols having 6-30 carbon atoms (for example, pyrogallol, Phloroglucinol and 1,2,4-benzenetriol etc.) alkylene (2 to 4 carbon atoms) oxide adduct (2 to 100 addition moles) (pyrogallol EO 4 mol adduct etc.); Acrylic polyol [hydroxyethyl (meth) acrylate and other vinyl monomers (for example, copolymers of styrene, (meth) acrylic acid, (meth) acrylic acid ester, etc.), etc.].
Of these, AO adducts of aliphatic polyhydric alcohols and novolak resins are preferred, and AO adducts of novolak resins are more preferred.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 32 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid); 4 to 32 alkene dicarboxylic acids (for example, maleic acid, fumaric acid, citraconic acid and mesaconic acid); branched alkene dicarboxylic acids having 8 to 40 carbon atoms [for example, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadece Nyl succinic acid, octadecenyl succinic acid, etc.); branched alkane dicarboxylic acids having 12 to 40 carbon atoms [eg, alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.); aromatics having 8 to 20 carbon atoms Group dicarboxylic acids (eg phthalic acid, isophthalic acid) Acid, terephthalic acid and naphthalene dicarboxylic acid) and the like.
Of these, alkene dicarboxylic acids and aromatic dicarboxylic acids are preferred, and aromatic dicarboxylic acids are more preferred.

Examples of the tri- or tetravalent or higher polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid).
Examples of the acid anhydride of the dicarboxylic acid (13) or the tri- or tetravalent or higher polycarboxylic acid (14) include trimellitic acid anhydride and pyromellitic acid anhydride. Alternatively, these lower alkyl esters include methyl esters, ethyl esters, and isopropyl esters.

As ester resin, diol, 3-6 valence or more polyol, dicarboxylic acid, 3-4 valence or more polycarboxylic acid, and mixtures thereof can be used in arbitrary ratios. The equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1. 3/1 to 1.02 / 1.
Further, the ester group equivalent (molecular weight per equivalent of ester group) in the ester resin is preferably 50 to 2000, more preferably 60 to 1000, and particularly preferably 70 to 500.

As the urethane resin, polyisocyanate (15) and active hydrogen-containing compound (a021) {for example, water, diol (11), trivalent to hexavalent or higher polyol (12), dicarboxylic acid (13), 3-4 A polyaddition product with a polycarboxylic acid (14), polyamine (16), polythiol (17) or the like having a valence of 1 or more can be used.
A known polyaddition reaction catalyst or the like can be used for the polyaddition reaction.

  As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (excluding carbon in NCO group, the same shall apply hereinafter) Formula polyisocyanate, araliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products, etc.) and mixtures of two or more of these.

  Examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- or 4,4 ′. Diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20%) of a trifunctional or higher polyamine] A polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate and These mixtures etc. are mentioned

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and these And the like.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanate). Natoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and mixtures thereof.

Examples of the araliphatic polyisocyanate include m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and mixtures thereof.
Examples of modified polyisocyanates include urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, and / or oxazolidone groups. Modified MDI (such as urethane-modified MDI, carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, and mixtures thereof [for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)] and the like.
Of these, aromatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates are preferred, and TDI, MDI, HDI, hydrogenated MDI and IPDI are more preferred.

As a polyamine (16), a C2-C18 aliphatic polyamine, an aromatic polyamine (C6-C20), etc. can be used.
Examples of aliphatic polyamines having 2 to 18 carbon atoms include [1] aliphatic polyamines, [2] these alkyl (C1 to C4) or hydroxyalkyl (C2 to C4) substitutes, [3] alicyclic rings Formula or heterocyclic ring-containing aliphatic polyamines and [4] aromatic ring-containing aliphatic amines (8 to 15 carbon atoms) are used.

  [1] Aliphatic polyamines include alkylene diamines having 2 to 12 carbon atoms (ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and polyalkylene (2 to 6 carbon atoms) polyamines [diethylene triamine, Iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.

  [2] As these alkyl (carbon number 1 to 4) or hydroxyalkyl (carbon number 2 to 4) substitution products, dialkyl (carbon number 1 to 3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, Examples include 2,5-dimethyl-2,5-hexamethylenediamine and methyliminobispropylamine.

[3] As the alicyclic or heterocyclic-containing aliphatic polyamine, an alicyclic polyamine having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (Hydrogenated methylenedianiline) and 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane etc.} and a heterocyclic polyamine having 4 to 15 carbon atoms {Piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.} and the like.
[4] Examples of the aromatic ring-containing aliphatic amine (having 8 to 15 carbon atoms) include xylylenediamine and tetrachloro-p-xylylenediamine.

  Aromatic polyamines (6-20 carbon atoms) include: [1] unsubstituted aromatic polyamines, [2] nuclear substituted alkyl groups [methyl, ethyl, n- or i-propyl, butyl, etc. An aromatic polyamine having an alkyl group), [3] an aromatic polyamine having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I and F; an alkoxy group such as methoxy and ethoxy; a nitro group) and the like [4] An aromatic polyamine having a secondary amino group can be used.

  [1] Unsubstituted aromatic polyamines include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylene). Polyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, Examples thereof include naphthylenediamine and a mixture thereof.

  [2] As an aromatic polyamine having a nucleus-substituted alkyl group (an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n- or i-propyl and butyl), for example, 2,4- or 2,6- Tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1, 3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3 5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3, 5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetraisopropylbenzidine, 3,3 ′, 5,5 ′ -Tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraiso Propyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetrabutyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3, , 5-diisopropyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 3, 3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraisopropyl-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraethyl -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone and the same And the like.

  [3] As an aromatic polyamine having a nuclear substitution electron withdrawing group (halogen such as chlorine atom, bromine atom, iodine atom and fluorine atom; alkoxy group such as methoxy and ethoxy; nitro group etc.), for example, methylenebis-o- Chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1 , 4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane, 3, , 3′-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bi (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-amino) Phenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′-methylenebis (2-bromoaniline) ), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline and the like.

[4] As the aromatic polyamine having a secondary amino group, a part or all of —NH ₂ of the aromatic polyamine of the above [1] to [3] is —NH—R ′ (R ′ is an alkyl group, for example, Or a lower alkyl group having 1 to 4 carbon atoms such as methyl and ethyl) [for example, 4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene Polyamide polyamines: low molecular weight polyamide polyamines obtained by condensation of dicarboxylic acids (such as dimer acids) and excess (more than 2 moles per mole of acid) polyamines (such as alkylene diamines, polyalkylene polyamines, etc.) Polyether polyamine: hydride of cyanoethylated polyether polyol (polyalkylene glycol and the like).

As polythiol (17), C2-C24 dithiol and 3-6 valence or more, C5-C30 polythiol, etc. can be used.
Examples of the dithiol include ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.
Examples of the polythiol include Capcure 3800 (manufactured by Japan Epoxy Resin Co., Ltd.), polyvinyl thiol and the like.

  Of the active hydrogen-containing compounds (a021), water, diol (11), polyol (12), dicarboxylic acid (13) and polyamine (16) are preferred, and water, diol (11), polyol (12) and Polyamine (16), particularly preferably diol (11), polyol (12) and polyamine (16).

Examples of the epoxy resin include a ring-opening polymer of polyepoxide (18), a polyaddition product of polyepoxide (18) and active hydrogen-containing compound (a021), and polyepoxide (18) and dicarboxylic acid (13) or 3 to 4 valences or higher. A cured product of the above polycarboxylic acid (14) with an acid anhydride can be used.
A known catalyst or the like can be used for the ring-opening polymerization reaction, polyaddition reaction and curing reaction.

The polyepoxide (18) is not particularly limited as long as it has two or more epoxy groups in the molecule, but has 2 to 6 epoxy groups in the molecule from the viewpoint of the mechanical properties of the cured product. Those are preferred.
The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (18) is preferably 65 to 1,000. The upper limit is more preferably 500, particularly preferably 300, and the lower limit is more preferably 70, particularly preferably 90. If the epoxy equivalent exceeds this range, the crosslinked structure tends to be loose, and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product tend to deteriorate, while those having an epoxy equivalent less than this range It tends to be difficult to obtain (including synthesis).

As the polyepoxide (18), aromatic polyepoxide, heterocycle-containing polyepoxide, alicyclic polyepoxide, aliphatic polyepoxide, and the like are used.
Examples of the aromatic polyepoxide include polyhydric phenol glycidyl ether, polyhydric phenol glycidyl ester, glycidyl aromatic polyamine, and glycidylated product of aminophenol.

  Examples of the polyhydric phenol glycidyl ether include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycid Ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4'-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether Glycidyl ether of phenol or cresol novolac resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde condensation reaction And polyglycidyl ether of polyphenol obtained by the condensation reaction of resorcin and acetone.

Examples of the polyhydric phenol glycidyl ester include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and the like.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. It is done.
Further, as the epoxide, diglycidyl urethane compound obtained by addition reaction of p-aminophenol triglycidyl ether, tolylene diisocyanate or diphenylmethane diisocyanate and glycidol, and bisphenol A AO (EO or PO 2 to 20 mol) adduct di Glycidyl ethers (for example, diglycidyl ethers of bisphenol AEO 4 mol adducts) can also be used.

Examples of the heterocyclic polyepoxide include trisglycidyl melamine.
Examples of the alicyclic polyepoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6. -Methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) ) Nuclear hydrogenated products of butylamine, dimer acid diglycidyl ester and aromatic polyepoxide (for example, water additive of bisphenol F diglycidyl ether, water additive of bisphenol A diglycidyl ether, etc.).

Examples of the aliphatic polyepoxide include polyglycidyl ethers of aliphatic polyhydric alcohols, polyglycidyl esters of polyvalent fatty acids, glycidyl aliphatic amines, and the like.
Examples of polyglycidyl ethers of aliphatic polyhydric alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene. Glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, etc. Is mentioned.

Examples of polyglycidyl esters of polyvalent fatty acids include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, and diglycidyl pimelate.
Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine, N, N, N ′, N′-tetraglycidylethylenediamine, and the like.
Aliphatic polyepoxides also include (co) polymers of diglycidyl ether and glycidyl (meth) acrylate.
Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

The resin (a) is a resin constituting the resin particles (A), and the number average molecular weight (Mn), peak molecular weight, glass transition point (Tg), SP value, hydroxyl value, and acid value of the resin (a) are as follows. It is preferable that it exists in the range.
That is, the number average molecular weight (Mn) of (a) is preferably 1000 to 20000, more preferably 1500 to 17500, and particularly preferably 1750 to 15000, from the viewpoints of heat resistant storage stability, low temperature fixability, and hot offset resistance. Most preferably, it is 2000-12500. The peak molecular weight is preferably 1000 to 30000, more preferably 1500 to 10000, and particularly preferably 2000 to 8000. When it is 1000 or more, the heat resistant storage stability is improved, and when it is 10,000 or less, the low-temperature fixability is better. In the above and below, Mn and Mw of the resin (a) are measured by gel permeation chromatography (GPC) (THF solvent, reference material polystyrene).

The Tg of (a) is preferably 30 to 80 ° C., more preferably 35 to 75 ° C., and particularly preferably 40 to 70 ° C. from the viewpoints of heat resistant storage stability and low temperature fixability.
In the above and below, Tg is obtained from DSC (differential scanning calorimetry, temperature rising rate 20 ° C./min).
Moreover, 7-18 are preferable, as for SP value of (a), More preferably, it is 8-16, Most preferably, it is 9-14.
In the above and the following, the SP value is determined according to Polymer Engineering and Science, February, 1974, Vol. 14, no. 2, calculated by the method described on pages 147 to 154.
The hydroxyl value of (a) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is 5 or more, it is advantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (a) is preferably 1-30, more preferably 5-20. By having an acid value, it tends to be negatively charged. Also, those having an acid value and a hydroxyl value that are less than or equal to the upper limit of this range are not easily affected by the environment in a high temperature and high humidity environment and a low temperature and low humidity environment, and there is no risk of image deterioration.

  As a method for producing the resin particles (A), for example, the filler (b) is dispersed in the dispersion liquid (D0) composed of the resin (a) and / or its precursor (a0) in the solvent (s). When the filler-containing dispersion (D) is dispersed in the aqueous medium (W) and the precursor (a0) is used, the resin (a) is formed by reaction to form an oil-in-water dispersion (D1). Thereafter, a method of removing the aqueous medium from the aqueous dispersion containing the resin particles (A) obtained by removing the solvent can be mentioned.

  The production method of the aqueous dispersion containing the resin particles (A) is not particularly limited, but for example, a dispersion liquid (a) comprising a precursor (a0) of the resin (a), a filler (b), and a solvent (s) described later ( After D) is dispersed in the aqueous medium (W) and the precursor is reacted in the aqueous medium, the dead polymer of the resin (a) is produced and the filler (b) and the solvent (s) described later are added , A method of dispersing in an aqueous medium (W), and a resin (a) in a state where a dead polymer of the resin (a), a filler (b), and a solvent (s) described later are dispersed in the aqueous medium (W). And a method of reacting the precursor (a0).

As a method of dispersing a dispersion (D) composed of a precursor (a0) of a resin (a), a filler (b), and a solvent (s) described later in an aqueous medium, and reacting the precursor in the aqueous medium. The following [1] and [2] are mentioned.
[1] In the case of a vinyl resin, using a monomer as a starting material, a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method in the presence of a polymerization catalyst, a filler (b), and a solvent (s) described later A method for producing an aqueous dispersion of resin particles (A) by a polymerization reaction such as

[2] In the case of a polyaddition resin or a condensation resin such as an ester resin, a urethane resin and an epoxy resin, an appropriate dispersion of the solvent solution of the precursor (a0) or (a0) of the resin (a) and the filler (b) Resin particles (A) dispersed in an aqueous medium in the presence of an agent and then cured by heating or adding a curing agent (a compound having at least two functional groups capable of reacting with a precursor in the molecule). ) Aqueous dispersion.

  The following [3] and [4] can be mentioned as a method for producing a resin (a) dead polymer and dispersing it in an aqueous medium.

[3] Resin (a), filler (b) prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation and condensation polymerization); A dispersion comprising the solvent (s) is dispersed in an aqueous medium in the presence of a suitable dispersant, and the solvent is removed by heating or decompression.

[4] Resin (a), filler (b) prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation and condensation polymerization) A method in which a suitable emulsifier is dissolved in a dispersion comprising the solvent (s), and then water is added for phase inversion emulsification, and the solvent is removed by heating or decompression.

  Of the above [1] to [4], [1], [2], [3] and combinations thereof are preferable, and [2], [3] and combinations thereof are more preferable.

The method for reacting the precursor of the resin (a) in an aqueous medium will be described in more detail.
The precursor (a0) of the resin (a) is not particularly limited as long as it can be converted into the resin (a) by a chemical reaction. For example, when the resin (a) is a vinyl resin, the vinyl monomer (single Or may be used by mixing them) and their solutions.

  When a vinyl monomer is used as the precursor (a0), the method of reacting the precursor (a0) to form the resin (a) includes, for example, an oil-soluble initiator, a monomer, a filler (b), and a solvent described later. From a method in which an oil phase comprising (s) is dispersed and suspended in water in the presence of a synthetic polymer dispersant (h) and a radical polymerization reaction is carried out by heating (so-called suspension polymerization method), monomer and solvent (s) And a method of emulsifying the resulting oil phase in water containing an emulsifier and a water-soluble initiator and performing a radical polymerization reaction by heating (so-called emulsion polymerization method).

  As the oil-soluble initiator and the water-soluble initiator, a peroxide polymerization initiator, an azo polymerization initiator, and the like can be used. Further, a peroxide polymerization initiator and a reducing agent can be used in combination as a redox polymerization initiator. Furthermore, you may use 2 or more types together from these.

As the peroxide polymerization initiator, an oil-soluble peroxide polymerization initiator and a water-soluble peroxide polymerization initiator are used.
Examples of the oil-soluble peroxide polymerization initiator include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, and t-butyl peroxide. Oxybivalate, 3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butylperoxyisobuty T-butyl peroxymaleic acid, t-butyl peroxylaurate, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, t- Butyl peroxyacetate, t-butyl peroxybenzoate, diisobutyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butyl cumylper Oxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide, 2,5-dimethylhexane-2,5- Hydroperoxide and cumene peroxide.

  Examples of the water-soluble peroxide polymerization initiator include hydrogen peroxide, peracetic acid, ammonium persulfate, potassium persulfate, and sodium persulfate.

As the azo polymerization initiator, an oil-soluble azo polymerization initiator and a water-soluble azo polymerization initiator can be used.
Examples of the oil-soluble azo polymerization initiator include 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane 1-carbonitrile, and 2,2′-azobis-4-methoxy-2,4. -Dimethylvaleronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2'-azobis (2-methylpropionate), 1,1'-azobis (1-acetoxy-1- Phenylethane) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile).

  Examples of the water-soluble azo polymerization initiator include azobisamidinopropane salt, azobiscyanovaleric acid (salt), and 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]. Is mentioned.

As the redox polymerization initiator, an oil-soluble redox polymerization initiator, a water-soluble redox polymerization initiator, and the like are used.
Examples of the oil-soluble redox polymerization initiator include hydroperoxide (tret-butylhydroxyperoxide, cumenehydroxyperoxide, etc.), dialkyl peroxide (e.g., lauroyl peroxide), and diacyl peroxide (e.g., benzoyl peroxide). Oil-soluble peroxides and oil-soluble properties of tertiary amines (triethylamine, tributylamine, etc.), naphthenates, mercaptans (mercaptoethanol, lauryl mercaptan, etc.), organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.) What uses a reducing agent together, etc. are mentioned.

  Examples of water-soluble redox polymerization initiators include water-soluble peroxides such as persulfates (potassium persulfate, ammonium persulfate, etc.), hydrogen peroxide, and hydroperoxides (tret-butylhydroxyperoxide, cumenehydroxyperoxide, etc.). And a water-soluble inorganic or organic reducing agent (divalent iron salt, sodium hydrogen sulfite, alcohol, dimethylaniline, etc.).

When the resin (a) is a condensation resin (for example, urethane resin, epoxy resin, and ester resin), the precursor (a0) includes a reactive group-containing prepolymer (a01) and a curing agent (a02) described later. Combinations and the like can also be used.
Here, the “reactive group” means a group capable of reacting with the curing agent (a02).

In this case, examples of the method for forming the resin particles (A) by reacting the precursor (a0) include the following [1] to [3].
[1] An oil phase containing a reactive group-containing prepolymer (a01), a curing agent (a02), a filler (b), and a solvent (s) is dispersed in an aqueous medium, and the reactive group-containing prepolymer is heated. (A01) and the hardening | curing agent (a02) are made to react and the resin particle (A) which consists of resin (a) is formed.

[2] A solution comprising a reactive group-containing prepolymer (a01), a filler (b), and a solvent (s) is dispersed in an aqueous medium, and a water-soluble curing agent (a02) is added and reacted therewith, The method of forming the resin particle (A) which consists of resin (a).
[3] When the reactive group-containing prepolymer (a01) is cured by reacting with water, a dispersion comprising the reactive group-containing prepolymer (a01), the filler (b), and the solvent (s) is prepared. A method of forming resin particles (A) comprising (a) by reacting with water by dispersing in an aqueous medium.

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (a01) and the curing agent (a02) include the following combination [1] and combination [2].
Combination [1]: A combination comprising a reactive group-containing prepolymer (a011) having a functional group capable of reacting with an active hydrogen-containing group and an active hydrogen-containing compound (a021).
Combination [2]: A combination comprising a reactive group-containing prepolymer (a012) having an active hydrogen-containing group and a curing agent (a022) having a functional group capable of reacting with the active hydrogen-containing group.
Among these, the combination of [1] is preferable from the viewpoint of the reaction rate in water.

  Examples of the functional group capable of reacting with the active hydrogen-containing group include an isocyanate group, a blocked isocyanate group, an epoxy group, a group composed of an acid anhydride, and a group composed of an acid halide (acid chloride, acid bromide, etc.).

Among these, an isocyanate group, a blocked isocyanate group, and an epoxy group are preferable, and an isocyanate group and a blocked isocyanate group are more preferable.
The blocked isocyanate group means an isocyanate group blocked with a blocking agent.

As the blocking agent, known blocking agents can be used, for example, oximes [acetooxime, methylisobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactam [γ-butyrolactam, ε-caprolactam and γ-valerolactam, etc.]; C1-C20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; active methylene compounds [acetylacetone, malon Ethyl acetate and ethyl acetoacetate and the like]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine and the like]; Beauty, etc. of two or more of these mixtures thereof.
Of these, oximes are preferred, and methyl ethyl ketoxime is more preferred.

As the skeleton of the reactive group-containing prepolymer (a01), polyether, ester resin, epoxy resin, urethane resin, or the like can be used.
Of these, ester resins, epoxy resins, and urethane resins are preferable, and ester resins and urethane resins are more preferable.

Examples of the polyether include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetramethylene oxide.
Examples of the ester resin include a polycondensate of diol (11) and dicarboxylic acid (13), polylactone (such as a ring-opening polymer of ε-caprolactone), and the like.
Examples of the epoxy resin include addition condensates of bisphenol (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin.
Examples of the urethane resin include a polyaddition product of diol (11) and polyisocyanate (15), a polyaddition product of ester resin and polyisocyanate (15), and the like.

There is no restriction | limiting in particular as a method of making an ester resin, an epoxy resin, or a urethane resin contain a reactive group, For example, the following methods [1] and [2] are applicable.
[1] A method of leaving a reactive group of a constituent component by using one of the constituent components constituting an ester resin, an epoxy resin, or a urethane resin in excess.
[2] Among the components constituting the ester resin, epoxy resin, urethane resin, etc., the functional group of the component remains by using one of the components in excess, and further a functional group (reaction that can react with the remaining functional group) A compound containing a functional group).

  In the method of [1], a hydroxyl group-containing ester resin prepolymer, a carboxyl group-containing ester resin prepolymer, an ester resin prepolymer containing a group consisting of an acid halide, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, A hydroxyl group-containing urethane resin prepolymer, an isocyanate group-containing urethane resin prepolymer, and the like are obtained.

In the method of [1], the ratio of each constituent component is exemplified. For example, in the case of a hydroxyl group-containing ester resin prepolymer, an alcohol component (diol (11), polyol (12), etc.) and a carboxylic acid component (dicarboxylic acid (13) ) And polycarboxylic acid (14) and the like are preferably 2/1 to 1/1, more preferably 1 as the equivalent ratio [OH] / [COOH] of hydroxyl group [OH] to carboxyl group [COOH] 0.5 / 1 to 1/1, particularly preferably 1.3 / 1 to 1.02 / 1.
For the carboxyl group-containing ester resin prepolymer, the ester resin prepolymer containing a group consisting of an acid halide, the hydroxyl group-containing urethane resin prepolymer, the isocyanate group-containing urethane resin prepolymer, etc. It is the same.

  In the method [2], the prepolymer obtained by the method [1] is reacted with a polyisocyanate to obtain an isocyanate group-containing prepolymer, and the blocked polyisocyanate is reacted to contain a blocked isocyanate group. A prepolymer is obtained, and an epoxy group-containing prepolymer is obtained by reacting a polyepoxide, and a prepolymer containing a group consisting of an acid anhydride is obtained by reacting a compound having two or more groups consisting of an acid anhydride. can get.

In the method [2], the amount of the compound having a reactive group is exemplified. For example, when a hydroxyl group-containing ester resin is reacted with a polyisocyanate to obtain an isocyanate group-containing ester resin prepolymer, The ratio with isocyanate is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, as an equivalent ratio [NCO] / [OH] of isocyanate group [NCO] to hydroxyl group [OH]. Especially preferably, it is 2.5 / 1 to 1.5 / 1.
In the case of other prepolymers, the preferred ratio is the same as the constituent components are changed.

  The average number of reactive groups contained in the reactive group-containing prepolymer (a01) per molecule is preferably 1 to 3, more preferably 1.5 to 3, particularly preferably 1.8 to 2.5. It is. Within this range, the mechanical strength of the resin (a) obtained by reacting with the curing agent (a02) tends to increase.

The Mn of the reactive group-containing prepolymer (a01) is preferably 500 to 30,000. The upper limit is more preferably 20,000, particularly preferably 10,000, and the lower limit is more preferably 1,000, particularly preferably 2,000.
The Mw of the reactive group-containing prepolymer (a01) is preferably 1,000 to 50,000. The upper limit is more preferably 40,000, particularly preferably 20,000, and the lower limit is more preferably 2,000, particularly preferably 4,000.

  Examples of the active hydrogen group-containing compound (a021) include water, diol (11), trivalent to hexavalent or higher polyol (12), dicarboxylic acid (13), trivalent to tetravalent or higher exemplified above. In addition to polycarboxylic acid (14), polyamine (16), polythiol (17), etc., polyamine which may be blocked with a detachable compound, and may be blocked with a detachable compound A polyol etc. are mentioned.

  Polyamines blocked with a detachable compound include ketimine compounds, polyamines (polyamines (16) obtained by dehydration reaction of C3-8 ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) 16) and an aldimine compound obtained by a dehydration reaction between an aldehyde compound having 2 to 8 carbon atoms (for example, formaldehyde, acetaldehyde), and a polyamine (16) and a ketone having 3 to 8 carbon atoms or an aldehyde having 2 to 8 carbon atoms And enamine compounds or oxazolidine compounds.

  Of these, an optionally blocked polyamine, an optionally blocked polyol, and water are preferred, and an optionally blocked polyamine and water, particularly preferably a polyamine, ketimine compound and water. Most preferred are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, ketimine compounds obtained from these and ketones, and water.

  In producing the resin particles (A), a reaction terminator (a02s) can be used together with the active hydrogen group-containing compound (a021). By using the reaction terminator together with (a021) at a certain ratio, it is easy to adjust the molecular weight of the resin (a) constituting the resin particles (A).

  As the reaction terminator (a02s), monoamines having 1 to 40 carbon atoms (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); blocked monoamines having 3 to 40 carbon atoms (ketimine compounds, etc.) ); Monools having 1 to 40 carbon atoms (such as methanol, ethanol, isopropanol, butanol and phenol); monocaptans having 2 to 40 carbon atoms (such as butyl mercaptan and lauryl mercaptan); monoisocyanates having 5 to 40 carbon atoms (butyl) Isocyanate, lauryl isocyanate, and phenyl isocyanate); monoepoxides having 2 to 40 carbon atoms (such as butyl glycidyl ether) and the like.

In the above combination [2] (reactive group-containing prepolymer (a012) having an active hydrogen-containing group and a curing agent (a022) having a functional group capable of reacting with the active hydrogen-containing group)). The active hydrogen-containing group of the containing prepolymer (a01) is blocked with an amino group, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), a mercapto group, a carboxyl group, and a compound (such as a ketone and an aldehyde) from which these can be removed. Organic groups (such as ketimine-containing groups, aldimine-containing groups, oxazolidine-containing groups, enamine-containing groups, acetal-containing groups, ketal-containing groups, thioacetal-containing groups, and thioketal-containing groups).
Among these, an amino group, a hydroxyl group, and an organic group blocked with a compound from which these groups can be removed are preferable, and a hydroxyl group is more preferable.

As the curing agent (a022) having a functional group capable of reacting with an active hydrogen-containing group, a group consisting of polyisocyanate (15), polyepoxide (18), dicarboxylic acid (13), polycarboxylic acid (14), and acid anhydride And compounds having two or more groups consisting of acid halides.
Of these, polyisocyanates and polyepoxides are preferable, and polyisocyanates are more preferable.

Examples of the compound having two or more groups made of acid anhydride include pyromellitic acid anhydride and polymaleic anhydride (co) polymer.
Examples of the compound having two or more groups consisting of acid halides include acid halides (acid chloride, acid bromide, acid iodide, etc.) of dicarboxylic acid (13) or polycarboxylic acid (14).
When producing the resin particles (A), a reaction terminator (a02s) can be used together with a curing agent (a022) having a functional group capable of reacting with an active hydrogen-containing group, if necessary. By using the reaction terminator together with (a022) at a certain ratio, it is easy to adjust the molecular weight of the resin (a) constituting the resin particles (A).

The amount of the curing agent (a02) used is the ratio of the equivalent [a01] of the reactive group in the reactive group-containing prepolymer (a01) to the equivalent [a02] of the active hydrogen-containing group in the curing agent (a02). [A01] / [a02] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. is there.
When the curing agent (a02) is water, water is handled as a compound having a divalent active hydrogen-containing group.

The reaction time of the reactive group-containing prepolymer (a01) and the curing agent (a02) is selected depending on the reactivity of the combination of the type of the reactive group possessed by the prepolymer (a01) and the curing agent (a02). Is preferably 10 minutes to 40 hours, more preferably 30 minutes to 24 hours, and particularly preferably 30 minutes to 8 hours.
Moreover, 0-150 degreeC of these reaction temperature is preferable, More preferably, it is 50-120 degreeC.
Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate in the case of a reaction between an isocyanate and an active hydrogen compound.

As the emulsifier and dispersant in the methods [1] to [4] for obtaining an aqueous dispersion containing the resin particles (A), known surfactants (k) and synthetic polymer dispersants (h) Etc. can be used.
When the surfactant (k) is used, the amount used is preferably 0.0001 to 50%, more preferably 0.0005, based on the masses of (a), (a0), and filler (b). It is -0.4%, Most preferably, it is 0.001-0.3%.

  When the synthetic polymer dispersant (h) is used, the amount used is preferably 0.005 to 0.6%, more preferably based on the mass of (a) and (a0), the filler (b). Is 0.01 to 0.4%, particularly preferably 0.02 to 0.3%.

  As surfactant (k), anionic surfactant (k-1), cationic surfactant (k-2), amphoteric surfactant (k-3), nonionic surfactant (k-4), etc. Is used. In addition, surfactant (k) can use 2 or more types of surfactant together. In addition to those exemplified below, those described in International Publication WO 03/037964 can also be used.

  As the anionic surfactant (k-1), a carboxylic acid or a salt thereof, a sulfate ester salt, a salt of a carboxymethylated product, a sulfonate salt, a phosphate ester salt, or the like is used.

As the carboxylic acid or a salt thereof, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms or a salt thereof can be used. For example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and ricinol Examples thereof include a mixture of acids and higher fatty acids obtained by saponifying palm oil, palm kernel oil, rice bran oil, beef tallow and the like.
Examples of the salt include salts such as sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, and alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.).

The sulfate ester salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms), higher alkyl ether sulfate esters salts (EO or PO 1 to 10 mol of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated oils having 12 to 50 carbon atoms or unsaturated waxes that have been neutralized by sulfation), sulfated fatty acid esters (unsaturated fatty acids (carbon number) 6-40) lower alcohols (one obtained by sulfating and neutralizing esters of 1 to 8 carbon atoms) and sulfated olefins (one obtained by sulfating and neutralizing olefins having 12 to 18 carbon atoms) can be used.
Examples of the salt include sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.

  Examples of the higher alcohol sulfate ester salt include octyl alcohol sulfate ester salt, lauryl alcohol sulfate ester salt, stearyl alcohol sulfate ester salt, alcohol synthesized using Ziegler catalyst (for example, trade name: ALFOL 1214: manufactured by CONDEA) Sulfates and alcohols synthesized by the oxo method (for example, trade names: Dovanol 23, 25, 45, Diadol 115-L, 115H, 135: manufactured by Mitsubishi Chemical Corporation, trade name: tridecanol: manufactured by Kyowa Hakko Name: Oxocol 1213, 1215, 1415: manufactured by Nissan Chemical Co., Ltd.) and the like.

Examples of the higher alkyl ether sulfate ester salt include lauryl alcohol EO 2 mol adduct sulfate ester salt and octyl alcohol EO 3 mol adduct sulfate ester salt.
Examples of the sulfated oil include a salt of sulfate such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow and sheep fat.
Examples of sulfated fatty acid esters include sulfate salts such as butyl oleate and butyl ricinoleate.
Examples of the sulfated olefin include trade name: TEPOL (manufactured by Shell).

  Examples of the carboxymethylated salt include a carboxymethylated salt of an aliphatic alcohol having 8 to 16 carbon atoms, an EO of an aliphatic alcohol having 8 to 16 carbon atoms, or a carboxymethylated salt of an adduct having 1 to 10 moles of PO. Can be used.

  Examples of carboxymethylated salts of aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, and tridecanol carboxymethylated sodium salt. .

  Examples of carboxymethylated salts of EO 1 to 10 mol adducts of aliphatic alcohols include, for example, octyl alcohol EO3 mol adduct carboxymethylated sodium salt, lauryl alcohol EO4 mol adduct carboxymethylated sodium salt and dovanol 23 EO3 mol adduct. Examples thereof include carboxymethylated sodium salt.

As the sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, sulfosuccinic acid diester salt, α-olefin sulfonate, igepon T-type and other sulfonates of aromatic ring-containing compounds can be used.
Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate.

Examples of the alkyl naphthalene sulfonate include sodium dodecyl naphthalene sulfonate and the like.
Examples of the sulfosuccinic acid diester salt include sulfosuccinic acid di-2-ethylhexyl ester sodium salt.
Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether and styrenated phenol sulfonate.

As the phosphate ester salt, a higher alcohol phosphate ester salt, a higher alcohol EO adduct phosphate ester salt and the like can be used.
Examples of the higher alcohol phosphate salt include lauryl alcohol phosphate monoester disodium salt and lauryl alcohol phosphate diester sodium salt.
Examples of the higher alcohol EO adduct phosphate ester salt include oleyl alcohol EO 5 mol adduct phosphate monoester disodium salt.

As the cationic surfactant (k-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.
Examples of the quaternary ammonium salt type surfactant include tertiary amines having 3 to 40 carbon atoms and quaternizing agents (for example, alkylating agents such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride and dimethyl sulfate, and EO). For example, lauryltrimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, polyoxyethylenetrimethylammonium chloride, and the like. Examples include stearamide ethyl diethyl methylammonium methosulfate.

As amine salt type surfactants, primary to tertiary amines are inorganic acids (eg hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, phosphoric acid and perchloric acid) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid , Gluconic acid, adipic acid, alkylphosphoric acid having 2 to 24 carbon atoms, malic acid, citric acid, etc.).
Examples of the primary amine salt type surfactant include inorganic acid salts or organic compounds of aliphatic higher amines having 8 to 40 carbon atoms (for example, higher amines such as laurylamine, stearylamine, hardened tallow amine, and rosinamine). Examples thereof include salts of higher fatty acids (8 to 40 carbon atoms, stearic acid, oleic acid, etc.) of acid salts and lower amines (2 to 6 carbon atoms).

Examples of the secondary amine salt type surfactant include inorganic acid salts or organic acid salts such as EO adducts of aliphatic amines having 4 to 40 carbon atoms.
Examples of the tertiary amine salt type surfactant include aliphatic amines having 4 to 40 carbon atoms (for example, triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), EO (2 mol or more) adduct of aliphatic amine (2 to 40 carbon atoms), alicyclic amine having 6 to 40 carbon atoms (for example, N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine and 1,8-diazabicyclo (5,4,0) -7-undecene, etc.), nitrogen-containing heterocyclic aromatic amines having 5 to 30 carbon atoms (for example, 4-dimethylaminopyridine, N-methylimidazole) And 4,4′-dipyridyl) and inorganic acid salts or organic acid salts and triethanolamine monostearate, stearamide ethyl diethyl methyl ester Such as tertiary inorganic or organic acid salts of amines such as Noruamin the like.

  Examples of the amphoteric surfactant (k-3) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric surfactant. Can be used.

  As the carboxylate type amphoteric surfactant, an amino acid type amphoteric surfactant, a betaine type amphoteric surfactant, an imidazoline type amphoteric surfactant and the like are used. The amino acid type amphoteric surfactant is an amphoteric surfactant having an amino group and a carboxyl group in the molecule, and examples thereof include a compound represented by the general formula (2).

_{[R-NH- (CH 2)} n-COO] mM (2)
[Wherein R is a monovalent hydrocarbon group; n is 1 or 2; m is 1 or 2; M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium cation, an amine cation, an alkanolamine cation, etc. It is. ]

  Examples of the double-sided active agent represented by the general formula (2) include alkyl (carbon number 6 to 40) aminopropionic acid type amphoteric surfactants (eg, sodium stearylaminopropionate, sodium laurylaminopropionate); alkyl ( Examples thereof include C4-C24) aminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate).

  The betaine-type amphoteric surfactant is an amphoteric surfactant having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule, for example, alkyl (having 6 to 40 carbon atoms) dimethyl betaine. (Stearyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, etc.), C6-C40 amide betaines (coconut oil fatty acid amidopropyl betaine, etc.), alkyls (C6-C40) dihydroxyalkyls (C6-C40) Examples include betaine (such as lauryl dihydroxyethyl betaine).

  The imidazoline type amphoteric surfactant is an amphoteric surfactant having a cation part having an imidazoline ring and a carboxylic acid type anion part. For example, 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoli Examples include nitrobetaine.

  Other amphoteric surfactants include, for example, glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; sulfobetaines such as pentadecyl sulfotaurine Examples include amphoteric surfactants, sulfonate amphoteric surfactants, and phosphate ester type amphoteric surfactants.

As the nonionic surfactant (k-4), an AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant can be used.
AO addition-type nonionic surfactants can be obtained by directly applying AO (2 to 20 carbon atoms) to higher alcohols having 8 to 40 carbon atoms, higher fatty acids having 8 to 40 carbon atoms or alkylamines having 8 to 40 carbon atoms. AO is added to the esterified product obtained by adding a higher fatty acid or the like to a polyalkylene glycol obtained by adding AO to glycol or by reacting a higher fatty acid with a polyhydric alcohol. It is obtained by adding or adding AO to a higher fatty acid amide.

Examples of AO include EO, PO, and BO.
Preferred among these are EO and random or block adducts of EO and PO.
The number of moles of AO added is preferably 10 to 50 moles, and 50 to 100% of the AO is preferably EO.

  As the AO addition type nonionic surfactant, for example, oxyalkylene alkyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon number 8 to 40) (for example, octyl alcohol EO 20 mol adduct, stearyl alcohol EO 10 mol) Adduct, oleyl alcohol EO 5 mol adduct, lauryl alcohol EO 10 mol PO 20 mol block adduct, etc.); polyoxyalkylene higher fatty acid ester (alkylene having 2 to 24 carbon atoms, higher fatty acid having 8 to 40 carbon atoms) (for example, stearyl) Acid EO 10 mol adduct, lauric acid EO 10 mol adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (carbon number 2-24 of alkylene, carbon number 3-4 of polyhydric alcohol, carbon number of higher fatty acid) 8-40) (for example, polyethylene glycol Lauric acid diester having a polymerization degree of 20 and oleic acid diester having a polyethylene glycol degree of polymerization of 20; polyoxyalkylene alkylphenyl ether (alkylene having 2 to 24 carbon atoms and alkyl having 8 to 40 carbon atoms) (for example, Nonylphenol EO 4 mol adduct, bisphenol A · EO 10 mol adduct, styrenated phenol EO 20 mol adduct, etc.); polyoxyalkylene alkylamino ether (alkylene having 2 to 24 carbon atoms, alkyl having 8 to 40 carbon atoms) And (for example, laurylamine EO 10 mole adduct, stearylamine EO 10 mole adduct, etc.); polyoxyalkylene alkanolamide (carbon number 2-24 of alkylene, carbon number 8-24 of amide (acyl moiety)) (for example, Hydroxypropyl olein EO20 mole adduct of amide, EO 10 mol adduct of dihydroxyethyl lauric acid amide, etc.) and the like.

  As the polyhydric alcohol type nonionic surfactant, polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid ester AO adduct, polyhydric alcohol alkyl ether, polyhydric alcohol alkyl ether AO adduct and the like can be used. The polyhydric alcohol has 3 to 24 carbon atoms, the fatty acid has 8 to 40 carbon atoms, and the AO has 2 to 24 carbon atoms.

  Examples of the polyhydric alcohol fatty acid ester include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan dioleate, and sucrose monostearate.

  Examples of polyhydric alcohol fatty acid ester AO adducts include ethylene glycol monooleate EO 10 mol adduct, ethylene glycol monostearate EO 20 mol adduct, trimethylolpropane monostearate EO 20 mol PO 10 mol random adduct, sorbitan monolaurate. EO 10 mol adduct, sorbitan distearate EO 20 mol adduct, sorbitan dilaurate EO 12 mol PO 24 mol random adduct and the like.

  Examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monostearyl ether, methyl glycoside and lauryl glycoside.

  Examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO 10 mol random adduct, methyl glycoside EO 20 mol PO 10 mol random adduct, stearyl glycoside EO 20 mol PO 20 mol random adduct, and the like.

  Examples of the synthetic polymer dispersant (h) include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, and a water-soluble urethane resin (such as a reaction product of polyethylene glycol, polycaprolactone diol, and polyisocyanate).

In the method [1] to [4] for obtaining the aqueous dispersion containing the resin particles (A), [3] or a combination of [2] and [3], and at least the dead polymer of (a) A method using organic fine particles (A2) as a part, that is, a method in which resin fine particles (A2) are added as a dispersion stabilizer in an aqueous medium (W), and a reaction of (a0) is performed in (W) as necessary. The (A) having a sharp particle size distribution can be obtained. That is, the resin (a) or its solvent solution or the resin (a) precursor (a0) or its solvent solution is dispersed in an aqueous dispersion of resin fine particles (A2) made of the resin (a2). When the precursor (a0) is reacted to form the resin particles (A), the resin fine particles (A2) are adsorbed on the surface of the resin particles (A1) having a larger particle diameter, thereby providing an oil-in-water type. In the dispersion (D1), the resin particles (A1) or the oil droplets (A0) are prevented from coalescing with each other, and the resin particles (A) are hardly broken under high shear conditions. Thereby, the particle diameter of the resin particle (A) is converged to a constant value, and the effect of improving the uniformity of the particle diameter is exhibited.
Therefore, as the resin fine particles (A2), the resin fine particles (A2) have a strength not to be destroyed by shearing at the temperature at the time of dispersion, are not easily dissolved or swelled in water, It is preferable that the resin (a) precursor (a0) or its solvent solution is hardly dissolved or swelled.

  Examples of the resin (a2) constituting (A2) include vinyl resin, urethane resin, epoxy resin, ester resin, polyamide, polyimide, silicone resin, fluorine resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, Examples thereof include aniline resin, ionomer resin, polycarbonate, cellulose, and a mixture thereof.

Although the method to make resin (a2) the aqueous dispersion liquid of resin microparticles | fine-particles (A2) is not specifically limited, The following [1]-[8] are mentioned.
[1] In the case of vinyl resin, an aqueous dispersion of resin fine particles (A2) is directly produced by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material. [2] In the case of polyaddition or condensation resin such as ester resin, urethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant. And a method of producing an aqueous dispersion of resin fine particles (A2) by heating or adding a curing agent thereafter [3] polyaddition or condensation resin of ester resin, urethane resin, epoxy resin, etc. In the case of a suitable milk in a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably a liquid. It may be liquefied by heating). After dissolving the agent, water is added to perform phase inversion emulsification, heating or curing by adding a curing agent [4] polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization) Any polymerization reaction mode may be used) and the resin prepared by pulverization using a mechanical pulverizer or jet pulverizer and then classified to obtain resin particles, and then dispersed appropriately. Dispersing in water in the presence of an agent [5] A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization) A method in which resin particles are obtained by spraying the dissolved resin solution in the form of a mist, and then the resin particles are dispersed in water in the presence of an appropriate dispersant. [6] Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) Addition, addition condensation, condensation The resin particles can be precipitated by adding a poor solvent to a resin solution prepared by dissolving a resin prepared in a solvent, or by cooling a resin solution previously dissolved in a solvent. Next, after removing the solvent to obtain resin particles, the resin particles are dispersed in water in the presence of an appropriate dispersant. [7] Polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) A resin solution prepared by dissolving a resin prepared by any polymerization reaction mode such as condensation and condensation polymerization in a solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant, and this is heated or reduced in pressure. Method for removing solvent [8] Dissolve a resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization). A method of dissolving a suitable emulsifier in a resin solution and then adding water to perform phase inversion emulsification The dispersant and emulsifier used in [1] to [8] are used in the resin particle (A) production method. The above-mentioned surfactant (k) can be used.

  The particle size of the resin fine particles (A2) is usually smaller than the particle size of the resin particles (A1). From the viewpoint of particle size uniformity, the particle size ratio [volume average particle size of the resin fine particles (A2)] / [ The value of the volume average particle size of the resin particles (A1)] is preferably in the range of 0.001 to 0.3. When the particle size ratio is larger than 0.3, (A2) is not efficiently adsorbed on the surface of (A1), so that the particle size distribution of the obtained resin particles (A) tends to be wide.

  The volume average particle diameter of the resin fine particles (A2) can be appropriately adjusted within the above range of particle diameter ratio so as to be a particle diameter suitable for obtaining the resin particles (A) having a desired particle diameter. For example, when it is desired to obtain resin particles (A) having a volume average particle diameter of 1 μm, the range is preferably 0.0005 to 0.3 μm, particularly preferably 0.001 to 0.2 μm, and 10 μm resin particles (A). In the case of obtaining particles (A) of preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm and 100 μm, preferably 0.05 to 30 μm, particularly preferably 0. 1-20 μm.

From the viewpoint of the particle size uniformity, powder flowability, storage stability, etc. of the resin particles (A), it is preferable that 5% or more of the surface of the resin particles (A1) is covered with the resin fine particles (A2). More preferably, 30% or more of the surface of (A1) is covered with (A2). The surface coverage can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = [area of the portion covered with the resin fine particles (A2) / area of the portion covered with the resin fine particles (A2) + area of the portion where the resin particles (A1) are exposed] × 100

  As the solvent (s) in the methods [1] to [4] for obtaining the aqueous dispersion containing the resin particles (A), an aromatic hydrocarbon solvent (for example, toluene, xylene, ethylbenzene, tetralin, etc.) Aliphatic or alicyclic hydrocarbon solvents (eg n-hexane, n-heptane, mineral spirits and cyclohexane); halogen solvents (eg methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride); Ester or ester ether solvents (eg, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate); ether solvents (eg, diethyl ether, tetrahydrofuran, dioxane, ethyl acetate) Sorb, butyl cellosolve and propylene glycol monomethyl ether); ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone); alcohol solvents (eg, methanol, ethanol, n-propanol, isopropanol, n) -Butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol); amide solvents (for example, dimethylformamide and dimethylacetamide); sulfoxide solvents (for example, dimethyl sulfoxide); heterocyclic solvent (for example, , N-methylpyrrolidone, etc.); and a mixed solvent of two or more of these.

The solubility of (s) in water is preferably 80% or less, more preferably 70% or less, and particularly preferably 50% or less. In the above range, since (s) is not instantaneously extracted into the aqueous phase when the resin particles (A) are formed, in the oil-in-water dispersion (D1), in the oil droplets (A0) , (B), an integrated layer (S0) having a high concentration of at least part (b *) is easily formed.
Further, the boiling point of (s) is preferably 120 ° C. or less, more preferably 100 ° C. or less, and particularly preferably 40 to 80 ° C. from the viewpoint of easy removal during solvent removal.

  The amount of the aqueous medium used is preferably 50 to 2000 parts, more preferably 100 to 1000 parts, and particularly preferably 100 to 500 parts, based on 100 parts by weight of the resin (a) (hereinafter, “part” means “parts by weight”). . If it is less than this range, the dispersion state of (a) tends to deteriorate, and if it exceeds this range, it tends to be economically undesirable.

The aqueous medium can be used without limitation as long as it is a liquid containing water as an essential constituent, and includes water, an aqueous solution of a solvent, an aqueous solution of a surfactant (k), an aqueous solution of a synthetic polymer dispersant (h), and these. A mixture of these can be used.
Examples of the solvent include, among the above solvents (s), an ester or ester ether solvent, an ether solvent, a ketone solvent, an alcohol solvent, an amide solvent, a sulfoxide solvent, a heterocyclic compound solvent, and a mixed solvent of two or more thereof. Etc.
When the solvent is contained, the content of the solvent is preferably 1 to 80% based on the mass of the aqueous medium. The upper limit is more preferably 70%, particularly preferably 30%, and the lower limit is more preferably 2%, particularly preferably 5%.

  When the surfactant (k) is used, the content is preferably 0.001 to 0.3%, more preferably 0.005 to 0.2%, particularly preferably based on the mass of the aqueous medium. 0.01 to 0.15%.

  When the synthetic polymer dispersant (h) is used, the content is preferably 0.0001 to 0.2%, more preferably 0.0002 to 0.15%, particularly based on the mass of the aqueous medium. Preferably it is 0.0005 to 0.1%.

When the resin (a) and / or the precursor (a0) is dispersed in an aqueous medium, it is preferable that (a) and (a0) are liquid. When the resins (a) and (a0) are solid at room temperature, a solution in which the resins (a) and (a0) are dispersed in a liquid state at a temperature higher than the melting point or dissolved in the solvent (s). May be used.
When the solvent (s) is used, a solvent having a SP value difference of 3 or less from (a) or (a0) is preferable, although it varies depending on the types of the resin (a) and the precursor (a0).
In the above and below, the melting point is measured by DSC (temperature increase rate: 20 ° C./min).

  The viscosity of the resin (a), the precursor (a0) and these solvent solutions is preferably 10 to 50,000 mPa · s, more preferably 100 to 30,000 mPa · s, particularly preferably 200 to 2 at 25 ° C. 10,000 mPa · s. Within this range, it is easy to form irregularities on the surface of the resin particles (A).

  The temperature at which the resin (a) and / or the precursor (a0) is dispersed in the aqueous medium is preferably 0 to 150 ° C, more preferably 5 to 98 ° C, and particularly preferably 10 to 60 ° C. In addition, when exceeding 100 degreeC, the temperature under pressure is shown.

  There are no particular limitations on the dispersion device used to disperse the resin (a) and / or the resin precursor (a0), the filler (b), and these solvent solutions in an aqueous medium. For example, a homogenizer (IKA Corporation) ), Polytron (manufactured by Kinematica), batch type emulsifiers such as TK auto homomixer (manufactured by Special Machine Industries), Ebara Milder (manufactured by Aihara Seisakusho), TK fill mix, TK pipeline homomixer (special Kika Kogyo Co., Ltd.), colloid mill (Shinko Pantech Co., Ltd.), slasher, trigonal wet milling machine (Mitsui Miike Kako Co., Ltd.), Cavitron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.) Continuous emulsifiers, such as microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), nanomizer (manufactured by Nanomizer), APV Gaurin High-pressure emulsifiers such as membrane emulsifiers (made by Chilling Industries Co., Ltd.), vibratory emulsifiers such as Vibro mixers (made by Chilling Industries Co., Ltd.), ultrasonic homogenizers (made by Branson), etc. An ultrasonic emulsifier is mentioned. Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

  In the present invention, in order to form the (S) in the (A), since the filler (b) needs to diffuse from the inside to the (A0) surface, in order to increase the diffusion coefficient of (b), It is preferable that at least a part of (b) is finely dispersed in (A0). A method for dispersing at least a part of the filler (b) is not particularly limited, and a known method can be applied. For example, the following [1] to [6] and a combination thereof can be applied.

[1] A master batch in which the resin (a) and the filler (b) are melt-kneaded by a kneader in the presence of a solvent (s) and / or a dispersant as necessary, and (b) is dispersed in (a). (M) is obtained, and this is dispersed in the solvent (s).
[2] After the filler (b) is dissolved or suspended in the solvent (s) together with the resin (a) and / or the precursor (a0) of the resin (a) as necessary, cooling crystallization, solvent crystal A method of depositing in the liquid by precipitation or the like.
[3] The filler (b) is dissolved or suspended in the solvent (s) together with the resin (a) and / or the precursor (a0) of the resin (a) as necessary, and is put into the gas phase by spray drying or the like. A method of mixing and dispersing in the solvent (s) after the precipitation.
[4] The filler (b) is dissolved or suspended in the solvent (s) together with the resin (a) and / or the precursor (a0) of the resin (a) as necessary, and then mechanically wet by a disperser. A method of crushing or crushing.
[5] A method of adding and mixing (b) synthesized in the solvent (s).
[6] A method in which the filler (b) dispersed in water is wet-treated by adding the surface treating agent (d), and then the solvent-substituted organosol is added and mixed in the dispersion (D0).

  Examples of the kneader used in the method [1] include batch kneaders such as roll mills and universal mixers, uniaxial or biaxial extrusion kneaders, continuous kneaders such as two rolls and three rolls. Can be mentioned.

  Examples of the above [2] include a method in which the filler (b) is heated and dissolved in a solvent and then cooled to crystallize the filler (b) particles, or the filler (b) is dissolved in a good solvent. And a method of crystallizing the filler (b) particles by adding it to a poor solvent. In these methods, batch operation may be performed with a stirred reactor, a universal mixer, etc., and it is used to obtain an aqueous dispersion containing resin particles (A) such as APV Gaurin, Nanomizer, High Pressure Homogenizer. Continuous operation may be performed by the high-pressure emulsifier.

  As an example of the above [3], after the filler (b) is heated and dissolved in a solvent, the filler (b) particles are crystallized in the gas phase by spray drying or the like, and then the method of the above [2]. The method of disperse | distributing in a solvent (s) with the illustrated disperser etc. is mentioned.

  As the disperser used in the above [4], in addition to the emulsifier used to obtain the aqueous dispersion containing the resin particles (A), dyno mill (manufactured by Shinmaru Enterprises), Ultraviscomil Media dispersers (bead mills) such as (Imex Co., Ltd.) and Pure Mill (Asada Tekko Co., Ltd.) can be used. Among these, preferred are cavitron, ebara milder, colloid mill, dyno mill, ultra visco mill, and pure mill from the viewpoint of pulverizability and pulverization of the filler (b).

Examples of the above [5] include a method of adding organic fine particles synthesized by a dispersion polymerization method or a precipitation polymerization method in a solvent as a filler (b).
Examples of the organosol of (b) synthesized by the wet method of [6] above include hydrogels of metal oxides synthesized by hydrothermal synthesis method, sol-gel method, emulsion polymerization, seed polymerization, An organic fine particle dispersion obtained by suspension polymerization or the like is hydrophobized with the surface treatment agent (d), and water is replaced with a solvent (s) (preferably methyl ethyl ketone, ethyl acetate, etc.). It is done. Commercially available organosols obtained by the above method (for example, organosilica sol [MEK-ST, MEK-ST-UP, etc.] manufactured by Nissan Chemical Industries, etc.) can be used.
From the viewpoint of dispersion stability, the methods [1], [4], [5] and [6] are particularly preferable.

  The content of (s) in the (D) is preferably 20 to 80%, more preferably 30 to 75%, and particularly preferably 40 to 70%. In order to deform the shape of the (A), the (A) needs to shrink in volume, and the content of (s) is preferably at least 20% or more.

The solvent removal method is not particularly limited, and a known method can be applied. For example, the following [1] to [3] and a combination of these can be applied.
[1] A method of removing a solvent by heating and / or reducing pressure in a general stirring / desolving tank or a film evaporator.
[2] A method of removing the solvent by air blowing on the liquid surface or in the liquid.
[3] A method of diluting the suspension of (D) and (W) with water and extracting (s) into a water continuous phase.
When the resin (a) is crystalline, the temperature at the time of heating by the method [1] is below the melting point (Tm), and when the resin (a) is amorphous, it is below the glass transition temperature (Tg). Preferably, the Tm or Tg is preferably 5 ° C. or less, more preferably 10 ° C. or less, and particularly preferably 20 ° C. or less. The degree of decompression (gauge pressure) during decompression is preferably −0.03 MPa or less, more preferably −0.05 MPa or less.
The method [3] is a preferable method when the solvent (s) has solubility in water. In general, the method [1] is preferable.

  If the solvent removal rate is high, the solvent on the surface of the resin particle (A) is rapidly removed, and the difference in viscosity between the inside and the surface of the resin particle (A) becomes large. And the shape factor (SF-2) increases. Therefore, by selecting a method having a high solvent removal rate, the amount of (b) added can be reduced.

As a method for removing the aqueous medium from the aqueous dispersion containing the resin particles (A), the following methods [1] to [3] and combinations thereof can be applied.
[1] A method of drying an aqueous dispersion under reduced pressure or normal pressure.
[2] A method of solid-liquid separation with a centrifuge, a spatula filter and / or a filter press, etc., adding water or the like as necessary, and repeating solid-liquid separation, and then drying the obtained solid.
[3] A method in which the aqueous dispersion is frozen and dried (so-called lyophilization).

In the above methods [1] and [2], the drying can be performed using known equipment such as a fluidized bed dryer, a vacuum dryer, and a circulating dryer.
Moreover, it classifies using an air classifier or a sieve as needed, and it can also be set as predetermined particle size distribution.

  The resin particles (A) of the present invention have a volume average particle diameter of 3 to 10 μm, a filler (b *) having a thickness of 0.01 μm or more near the surface and (A) 1/2 or less of the inscribed circle radius. ) And a shape factor (SF-2) of 110-300. As a result, a toner having good blade cleaning properties, low-temperature fixing properties, and hot offset resistance can be obtained.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

<Production Example 1>
A reaction vessel equipped with a stirrer and a dehydrator is charged with 218 parts of bisphenol A / EO 2 mol adduct, 537 parts of bisphenol A / PO 3 mol adduct, 213 parts of terephthalic acid, 47 parts of adipic acid, and 2 parts of dibutyltin oxide. Then, after dehydration reaction at 230 ° C. under normal pressure for 5 hours, dehydration reaction was performed under reduced pressure of 3 mmHg for 5 hours. The mixture was further cooled to 180 ° C., 43 parts of trimellitic anhydride was added, and the reaction was performed at normal pressure for 2 hours to obtain [Ester Resin 1]. [Ester resin 1] had a Tg of 44 ° C., a number average molecular weight of 2700, a weight average molecular weight of 6500, and an acid value of 25.

<Production Example 2>
In a reaction vessel equipped with a stirrer and a dehydrator, 681 parts of bisphenol A / EO 2 molar adduct, 81 parts of bisphenol A / PO2 molar adduct, 275 parts of terephthalic acid, 7 parts of adipic acid, 22 parts of trimellitic anhydride, dibutyl 2 parts of tin oxide was added and subjected to dehydration reaction at 230 ° C. under normal pressure for 5 hours, and then dehydration reaction was performed under reduced pressure of 3 mmHg for 5 hours to obtain [Ester Resin 2]. [Ester resin 2] had a Tg of 54 ° C., a number average molecular weight of 2200, a weight average molecular weight of 9500, an acid value of 0.8, and a hydroxyl value of 53.

<Production Example 3>
In an autoclave, 407 parts of [Ester resin 2] obtained in Production Example 2, 108 parts of IPDI, and 485 parts of ethyl acetate are added, and the reaction is carried out at 100 ° C. for 5 hours in a sealed state. Polymer solution 1] was obtained. [Prepolymer solution 1] had an NCO content of 1.7%.

<Production Example 4>
A reaction vessel equipped with a stirrer, a solvent removal device, and a thermometer was charged with 50 parts of isophoronediamine and 300 parts of methyl ethyl ketone, reacted at 50 ° C. for 5 hours, and then desolvated to form a ketimine compound [curing Agent 1] was obtained. The total amine value of [Curing Agent 1] was 415.

<Production Example 5>
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 139 parts of styrene, 138 parts of methacrylic acid, When 184 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of an aqueous 1% ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene / methacrylic acid / butyl methacrylate / methacrylic acid EO adduct sulfate). [Fine particle dispersion] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 0.15 μm.

<Production Example 6>
955 parts of water, 15 parts of [Fine Particle Dispersion 1] obtained in Production Example 5 and 30 parts of sodium dodecyl diphenyl ether disulfonate solution (Eleminol MON7, manufactured by Sanyo Chemical Industries) are put into a container equipped with a stir bar and milky white Liquid [aqueous phase 1] was obtained.

<Production Example 7>
[Aqueous Phase 2] was obtained in the same manner as in <Production Example 6> except that 15 parts of [Fine Particle Dispersion 1] was not added.

<Production Example 8>
300 parts of [Ester resin 1] obtained in Production Example 1, 500 parts of copper phthalocyanine 15: 3 (CI Pigment Blue 15: 3) (average primary particle size 25 nm), ester pigment dispersant (Solspurs 24000SC, 150 parts of Avicia) and 50 parts of a phthalocyanine pigment derivative (Solspers 5000, manufactured by Avisia) were mixed with a Henschel mixer and then kneaded with a twin-screw extrusion kneader to obtain [Masterbatch 1].

<Production Example 9>
150 parts of [Ester resin 1] obtained in Production Example 1, 50 parts of hydrophobic silica (Aerosil R974, average primary particle size 12 nm, manufactured by Nippon Aerosil), 5 parts of bis (2-morpholinoethyl) ether, 478 parts of ethyl acetate Were mixed in an agitating and mixing tank and then wet-dispersed with Ultra Viscomil (manufactured by IMEX) to obtain [Silica Dispersion 1].

<Production Example 10>
Add 50 parts of carnauba wax, 150 parts of [Ester resin 1] and 470 parts of ethyl acetate to a reaction vessel equipped with a stir bar and thermometer, and heat to 70 ° C to dissolve the carnauba wax, then cool to 30 ° C. The wax was crystallized to obtain [Wax Dispersion 1]. Furthermore, [Wax Dispersion 1] was wet-dispersed with Ultra Viscomil (manufactured by Imex) to obtain [Wax Dispersion 2]. The solid content concentration of [Wax Dispersion 2] was 30%.

<Production Example 11>
In an autoclave equipped with a stir bar and a thermometer, 24 parts of xylene were charged and glycidyl methacrylate / methyl methacrylate / styrene / 2-ethylhexyl acrylate (25 wt% / 33 wt% / 40 wt% / 2 wt%) 2,000 parts of the mixed monomer and 1 part of the polymerization catalyst were dropped at 170 ° C. over 3 hours. Volatilization was performed at normal pressure while raising the temperature to 180 ° C., and when the temperature reached 180 ° C., the pressure was switched to reduced pressure and devolatilization was performed over 2 hours to obtain [Vinyl Resin 1]. [Vinyl resin 1] had a number average molecular weight of 10,500, a weight average molecular weight of 120,000, and a glass transition temperature of 65 ° C.

<Production Example 12>
500 parts of [Ester resin 1] obtained in Production Example 1 and 500 parts of copper phthalocyanine 15: 3 (CI Pigment Blue 15: 3) (average primary particle size 25 nm) were mixed with a Henschel mixer and then biaxially extruded. The mixture was kneaded with a kneader to obtain [Masterbatch 2].

<Comparative Production Example 1>
[Silica dispersion 2] was obtained in the same manner as in Production Example 9 except that bis (2-morpholinoethyl) ether was not added in Production Example 9.

< Reference Example 1>
[Ester resin 1] 291 parts, [Wax dispersion 2] 325 parts, Ethyl acetate 213 parts, [Prepolymer solution 1] 119 parts, [Curing agent 1] 13 parts, and [Masterbatch 1] 39 parts in a beaker Was added and dissolved and mixed, and then 1500 parts of [Aqueous Phase 1] was added. Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the dispersion operation was carried out at 25 ° C. for 1 minute at a rotational speed of 12000 rpm. Then, the solvent was removed with a film evaporator at a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm for 30 minutes to obtain an aqueous dispersion (D1).
(D1) Centrifugation of 100 parts, addition of 60 parts of water, centrifugation and solid-liquid separation were repeated twice, followed by drying at 35 ° C. for 1 hour to obtain resin particles (P1). The characteristic values of (P1) are shown in Table 1.

<Example 2>
[Ester resin 1] 271 parts, [Wax dispersion 2] 330 parts, [Masterbatch 2] 39 parts, Ethyl acetate 142 parts, [Prepolymer 1] 116 parts, [Curing agent 1] 13 parts, Organo After adding 86 parts of silica sol (MEK-ST-UP, solid content concentration 20%, average primary particle size 15 nm, manufactured by Nissan Chemical Industries) and dissolving and mixing and homogenizing, 1500 parts of [Aqueous Phase 1] were added, Using a TK homomixer, the dispersion operation was performed at 12000 rpm for 1 minute at 25 ° C., and the solvent was removed with a film evaporator at a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation rate of 100 rpm for 30 minutes. As a result, an aqueous dispersion (D2) was obtained.
(D2) Centrifugating 100 parts, adding 60 parts of water, centrifuging and solid-liquid separation was repeated twice, followed by drying at 35 ° C. for 1 hour to obtain resin particles (P2). The characteristic value of (P2) is shown in Table 1, the SEM image is shown in FIG. 2, and the TEM image is shown in FIG. Only silica is accumulated on the surface to form an outer shell layer (as seen in FIG. 3 where the particle contour is in the form of a dark belt), and the resin particle surface is deformed into irregularities. (The particles can be seen from the appearance of “plum pickled” in FIG. 2).

<Example 3>
In the above <Example 2>, 86 parts of MEK-ST-UP were changed to 115 parts of MEK-ST (solid content concentration 30%, average primary particle size 15 nm, manufactured by Nissan Chemical Industries), and an aqueous dispersion was obtained in the same manner. (D3) and resin particles (P3) were obtained. The characteristic values of (P3) are shown in Table 1.

<Example 4>
[Ester resin 1] 223 parts, [Wax dispersion 2] 324 parts, [Masterbatch 2] 39 parts, Ethyl acetate 54 parts, [Prepolymer 1] 114 parts, [Curing agent 1] 13 parts, After adding 231 parts of silica dispersion 1] and dissolving and mixing and homogenizing, 1500 parts of [aqueous phase 1] was added, and dispersion operation was performed at 25 ° C. for 1 minute at a rotational speed of 12000 rpm using a TK homomixer. Further, the solvent was removed with a film evaporator under the conditions of a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm to obtain an aqueous dispersion (D4).
(D4) Centrifugating 100 parts, adding 60 parts of water, centrifuging and solid-liquid separation was repeated twice, followed by drying at 35 ° C. for 1 hour to obtain resin particles (P4). The characteristic values of (P4) are shown in Table 1.

<Example 5>
In <Example 4> above, [ester resin 1] was changed to [vinyl resin 1], and aqueous dispersion (D5) and resin particles (P5) were obtained in the same manner. Table 1 shows the characteristic values of (P5).

<Comparative Example 1>
An aqueous dispersion (CD1) and resin particles (CP1) were obtained in the same manner as in Example 2 except that no organosilica sol was added in Example 2. The characteristic value of (CP1) is shown in Table 1, and the SEM image is shown in FIG. FIG. 4 shows that (CP1) is a true spherical particle.

<Comparative example 2>
In the above <Example 5>, [Silica dispersion 2] was used instead of [Silica dispersion 1], and an aqueous dispersion (CD2) and resin particles (CP2) were obtained by the same method. The characteristic value of (CP2) is shown in Table 1.

<Comparative Example 3>
In Reference Example 1, [Masterbatch 2] was used instead of [Masterbatch 1], and otherwise, an aqueous dispersion (CD3) and resin particles (CP3) were obtained in the same manner as Reference Example 1. The characteristic value of (CP3) is shown in Table 1.

  With respect to the resin particles (P1) to (P5) and (CP1) to (CP3) obtained in the above Examples and Comparative Examples, 1 part of hydrophobic silica particles is added to 100 parts of the resin particles, and a Henschel mixer is used. By mixing, toners (T1) to (T5) and (CT1) to (CT3) were obtained.

A developer composed of 95% copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with 5% toner obtained by the above and a silicone resin was prepared, and RICOH made by Ricoh that can print 45 sheets of A4 size paper per minute. Using 450, continuous printing was carried out and evaluated according to the following criteria. The results are shown in Table 1.
(A) Fixability The toner amount is adjusted so that 1.0 ± 0.1 mg / cm 2 of toner is developed with a solid image on transfer paper (Ricoh type 6200), and the temperature of the fixing belt becomes variable. Thus, the minimum value and the maximum value of the temperature at which no offset occurs were measured. Further, the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad becomes 70% or more was determined as the minimum fixing temperature.
(B) Cleaning property The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.) and measured with a Macbeth reflection densitometer RD514. Those with 0.01 or less were evaluated as ◯ (good), and those exceeding it were evaluated as x (bad). Evaluation was performed after printing 5000 sheets.

  The resin particles of the present invention are excellent in blade cleaning properties, low-temperature fixability, and hot offset resistance, and are useful as toner resin particles.

It is a cross-sectional schematic diagram of resin particles for toner of the present invention having an outer shell layer thickness (T). 3 is a SEM image of resin particles obtained in Example 2. 2 is a TEM image of resin particles obtained in Example 2. FIG. 3 is a SEM image of resin particles obtained in Comparative Example 1.

Claims (11)

(1) The filler (b) is dispersed in the dispersion (D0) composed of the resin (a) and / or its precursor (a0) in the solvent (s) whose solubility in water is 80% or less. The filler-containing dispersion liquid (D) is dispersed in the aqueous medium (W) to form an oil-in- water dispersion liquid (D1) in which oil droplets (A0) containing the filler (b) are dispersed. An accumulation layer in which the concentration of at least a part (b *) of the filler (b) is increased in the oil droplet (A0) by the diffusion of the filler (b) in (A0) to the surface of the oil droplet (A0). (S0) is formed,
(2) Resin particles for toner comprising resin (a) and filler (b) obtained by a production method including a step of removing the solvent from the oil-in-water dispersion (D1): resin (a ) Is one or more resins selected from the group consisting of urethane resins, epoxy resins, vinyl resins and ester resins; the filler (b) is a surface treatment agent selected from the group consisting of silane coupling agents and tertiary amine compounds. is silica treated with (d), the content of the filler (b) in the particles is 0.01 to 50 wt%; particle shape factor of the volume average particle diameter and 110-137 of 3~10μm (SF-2); the particle is an outer shell layer in which the filler (b) is present inside the surface and at least a part (b *) of the filler (b) is accumulated near the surface. Having (S); the layer (S) The thickness of the layer (S) is at least 0.01 μm and not more than ½ of the maximum inscribed circle radius of the cross section of the particle. in the cross-sectional image of the area is maximum, from the surface of the particles, within the cross section image, the entire area within a certain distance of the particles inside the vertical direction, the predetermined distance area of the filler (b) account for at least 50% Is the maximum distance (T). Toner resin particles of claim 1, wherein the value of (volume average particle diameter / number average particle diameter) is 1.0 to 1.5. Filler (b) contains from 0.05 to 45 wt%, the layer toner resin particles of claim 1 or 2 wherein the filler constituting the (S) and (b) contains 0.05 to 18 wt%. Filler (b) is, the toner resin particles according to any one of claims 1 to 3 is organosilica sol synthesized by a wet method using a silane coupling agent. (1) One or more resins (a) selected from the group consisting of urethane resins, epoxy resins, vinyl resins and ester resins in a solvent (s) having a solubility in water of 80% or less and / or precursors thereof Silica treated with a surface treatment agent (d) selected from the group consisting of a silane coupling agent and a tertiary amine compound in a dispersion (D0) comprising the body (a0) is used as a filler (b) as a resin ( A filler-containing dispersion (D) dispersed in an amount of 0.01 to 50% by mass with respect to the total amount of a) and / or its precursor (a0) is dispersed in an aqueous medium (W), and filler ( forming an oil-in-water dispersion (D1) in which oil droplets (A0) containing b) are dispersed, and the filler (b) in the oil droplets (A0) diffuses to the surface of the oil droplets (A0) Accordingly, the filler (b) in the oil droplets (A0) small Also form part (b *) integrated layer density is higher in the (S0) and,
(2) A step including removing the oil-in-water dispersion (D1) to obtain resin particles (A) having an outer shell layer (S) composed of at least a part (b *) of the filler (b). Item 5. A method for producing a resin particle for toner (A) according to any one of Items 1 to 4 . The process according to claim 5 , wherein the content of the solvent (s) in the dispersion (D) is 20 to 80% by mass. By dispersing the master batch (m) obtained by melt-kneading the resin (a) and the filler (b) in the presence or absence of a solvent and / or a dispersant in the solvent (s), The manufacturing method of Claim 5 or 6 which obtains a dispersion liquid (D). The production according to claim 5 or 6 , wherein an organosilica sol synthesized by a wet method using a silane coupling agent is dispersed as a filler (b) in the dispersion (D0) to obtain the dispersion (D). Law. The production according to claim 5 or 6 , wherein in the solvent (s), at least a part of the filler (b) is pulverized or crushed in the presence or absence of the resin (a) and / or its precursor (a0). Law. The dispersion (D0) contains a precursor (a0) of the resin (a), the precursor (a0) having at least one reactive group, and a curing agent having reactivity therewith The production method according to claim 5 , comprising (a02). The process according to claim 10 , wherein the reactive group is selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group.

Images