JP5146670B2 - toner - Google Patents

Description

  The present invention relates to a toner used for electrophotographic image formation such as a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, and an image forming apparatus, an image forming method, and a process cartridge using the toner.

Conventionally, in an electrophotographic image forming apparatus, an electrostatic recording apparatus, or the like, an electrical or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating.
The toner used for developing an electrostatic image is generally colored particles containing a colorant, a charge control agent, etc. in a binder resin, and the production method is roughly divided into a pulverization method and a suspension polymerization method. There is.

  In the pulverization method, a toner is produced by pulverizing and classifying a toner composition obtained by uniformly dispersing a colorant, a charge control agent, an offset preventing agent and the like in a thermoplastic resin by melt mixing. According to this pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of materials. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this demand, the toner composition obtained by melt mixing must be made sufficiently brittle. When pulverizing such a toner composition, particles having a wide particle size distribution are likely to be formed. At this time, in order to obtain a copy image with good resolution and gradation, for example, fine powder having a particle size of 5 μm or less and coarse powder having a particle size of 20 μm or more must be removed by classification, yield. Is very low. In the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent and the like in the thermoplastic resin, and the obtained toner has an adverse effect on fluidity, developability, durability, image quality, and the like. There is a problem that arises.

Therefore, in Patent Documents 1 and 2, a resin solution in which a resin synthesized in advance by a polymerization reaction is dissolved is used as a dispersion (auxiliary) agent such as a surfactant or a water-soluble resin, and a dispersion stabilizer such as inorganic fine particles and resin fine particles. There has been proposed a dissolved resin suspension method in which a toner is obtained by dispersing in an aqueous medium in the presence of water and removing the solvent by heating, decompression or the like. According to this dissolved resin suspension method, a uniform toner can be obtained without classification.
In addition, in an electrophotographic image forming apparatus, in a fixing process by a contact heating method performed using a heating member such as a heat roller, releasability (hereinafter sometimes referred to as offset resistance) to the heating member is provided. Required. This offset resistance is solved by using a modified polyester resin in the dissolved resin suspension method (see Patent Document 3).

  By the way, most of the binder resin occupying 70% or more of the constituent components of the toner is made from petroleum resources. This is due to the problem of exhaustion of petroleum resources, large consumption of petroleum resources, and emission of carbon dioxide into the atmosphere. There are concerns about global warming. Therefore, if a plant-derived resin that grows by taking in carbon dioxide in the atmosphere is used as the binder resin, the resulting carbon dioxide will only circulate in the environment, which simultaneously raises the problem of global warming and the depletion of petroleum resources. Various toners using such plant-derived resins as binder resins have been proposed. For example, Patent Document 4 proposes using polylactic acid as a binder resin. However, when polylactic acid is used as it is as in this proposal, the concentration of the ester bond is higher than that of the polyester resin, so that the action as a thermoplastic resin is lowered during fixing. Further, since the toner becomes very hard, there is a problem that the grindability is poor and the productivity is inferior.

Further, Patent Document 5 proposes an electrostatic charge image developing toner containing a polyester resin obtained by dehydration polycondensation of a composition containing lactic acid and a tri- or higher functional oxycarboxylic acid, and a colorant. Yes. However, in this proposal, since the polyester resin is formed by dehydration polycondensation reaction between the hydroxyl group of lactic acid and the carboxyl group of oxycarboxylic acid, the molecular weight is increased, the sharp melt property is impaired, and the low-temperature fixing property is lacking. There's a problem.
Patent Document 6 discloses an electrophotographic toner containing a polylactic acid biodegradable resin and a terpene phenol copolymer in order to improve thermal characteristics. Sexuality cannot be satisfied at the same time.
Since all of the toners according to these prior art documents are obtained by a pulverization method, there is a problem of toner loss caused by classification and associated disposal. Further, since the amount of energy required for the pulverization method is relatively large, further reduction of the environmental load is required.

  Polylactic acid, which is widely available as a plant-derived resin, is synthesized by dehydration condensation of lactic acid or ring-opening polymerization of lactic acid cyclic lactide as described in Patent Documents 7 and 8. For this reason, when manufacturing a toner using polylactic acid, the dissolving resin suspension method like the said patent documents 1-3 can be used. However, since polylactic acid has high crystallinity only in the L-form or D-form, the solubility in an organic solvent is extremely low, and it is difficult to use the dissolved resin suspension method. For this reason, it is possible to improve the solubility to an organic solvent by mixing the L-form and D-form of polylactic acid to reduce crystallinity.

  On the other hand, polylactic acid is difficult to control the molecular weight and has ester bonds only through carbon atoms, so that it is difficult to achieve the physical properties necessary for the toner only with polylactic acid. On the other hand, it is conceivable to ensure the physical properties and thermal characteristics required for the toner by mixing polylactic acid and other resins as in the conventional methods. Since the compatibility and dispersibility with respect to a polyester resin and a styrene-acrylic copolymer, which are generally used for toner, are extremely poor, it is very difficult to produce a toner in this way.

  In addition, since the crystallization speed of polylactic acid is slow, it is difficult to control the crystalline state of polylactic acid in the toner produced using the dissolved resin suspension method, and the toner produced using the dissolved resin suspension method. May contain polylactic acid having high crystallinity and polylactic acid having low crystallinity. Therefore, there is a problem that the charge amount and the image density change over time due to the crystal growth of the portion having polylactic acid with low crystallinity over time.

Therefore, it is excellent in image density, fixability, and heat-resistant storage stability, and there is little change in fixability with time, and a toner containing polylactic acid and related technologies have not yet been obtained, and further improvement and development are desired. This is the current situation.
JP-A-9-319144 JP 2002-284881 A Japanese Patent No. 3640918 Japanese Patent No. 2909873 Japanese Patent Laid-Open No. 9-274335 JP 2001-166537 A JP 7-33861 A JP 59-96123 A

  The present invention has been made in view of the above circumstances in the prior art. That is, even when polylactic acid is used, a toner, an image forming apparatus, an image forming method, and a process cartridge including resin particles having a uniform particle size excellent in thermal characteristics, heat-resistant storage stability, and transparency are provided. To do.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is as follows.
(1) The resin particles (A) containing the first resin (a) or the coating (P) containing the resin (a) is on the surface of the resin particles (B) containing the second resin (b). A toner comprising resin particles (C) having an attached structure, wherein the resin (b) comprises a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than (b11). A polyester diol (b11) containing a linear polyester resin (b1) obtained by reacting with an extender and containing the polyhydroxycarboxylic acid skeleton, and a polyester diol (b12) other than (b11) The mass ratio is 31:69 to 90:10, and the monomer that forms the polyhydroxycarboxylic acid skeleton of (b11) is an optically active monomer; b) Resin (b1) content Y (mass%) in the optical component X (mol%) = | X (L form) −X (D form) | [where X (L form) ) Represents an L-form ratio (mol%) in terms of an optically active monomer, and X (D form represents a D-form ratio (mol%) in terms of an optically active monomer)] is Y ≦ −1.5X + 220 (80 < A toner satisfying X ≦ 100) .
(2) said resin (a) is a vinyl resin, a polyester resin, the toner of (1), wherein the at least one resin selected from polyurethane resins, and epoxy resins.

( 3 ) The toner according to (1) or (2) , wherein the polyhydroxycarboxylic acid skeleton of (b11) is a skeleton obtained by polymerizing a hydroxycarboxylic acid having 3 to 5 carbon atoms.
( 4 ) The toner according to any one of (1) to ( 3 ), wherein the polyhydroxycarboxylic acid skeleton is a polymer obtained by direct dehydration condensation of hydroxycarboxylic acid.
( 5 ) The monomer that forms the polyhydroxycarboxylic acid skeleton of (b11) is an optically active monomer, and optical purity X (%) = | X (L form) −X (D form) | , X (L isomer) represents the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) represents the D isomer ratio (mol%) in terms of optically active monomer]. The toner according to any one of (1) to ( 4 ), wherein:

( 6 ) The toner according to any one of (1) to ( 5 ), wherein the toner contains a charge control agent.
(7) The toner according to (6) of the charge controlling agent is characterized in that it is a fluorine-containing quaternary ammonium salt.
( 8 ) The toner according to any one of (1) to ( 7 ), wherein the toner contains a colorant.
( 9 ) The toner according to any one of (1) to ( 8 ), wherein the toner contains a release agent.
( 10 ) The toner according to any one of (1) to ( 9 ), wherein the toner has a layered inorganic mineral obtained by modifying at least a part of ions between layers of the layered inorganic mineral as a toner composition with organic ions. The toner described.
( 11 ) An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, and exposure means for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image. Developing means for developing the electrostatic latent image with toner to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit, wherein the toner is the image forming toner according to any one of (1) to ( 10 ).
( 12 ) A charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic latent image with toner. An image forming method comprising at least a developing step for developing a visible image by using the developing method, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium The image forming method, wherein the toner is the image forming toner described in any one of (1) to ( 10 ).
( 13 ) An electrostatic latent image carrier and at least developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and forming an image A process cartridge that is attachable to and detachable from an apparatus main body, wherein the toner is the image forming toner according to any one of (1) to ( 10 ).

The toner of the present invention has the following effects.
1. Excellent thermal properties (especially low-temperature fixability) and heat-resistant storage stability.
2. Excellent transparency and uniform particle size.
3. Since the toner can be obtained by dispersion in water, it can be manufactured at low cost.

The resin particles (A) containing the first resin (a) or the coating (P) containing the resin (a) of the present invention is a surface of the resin particles (B) containing the second resin (b). In the resin particles (C) having a structure attached to the resin, the resin (b) comprises a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than (b11) together with an extender. It contains a linear polyester resin (b1) obtained by reacting. In order to obtain a linear polyester, each of (b11), (b12) and the extender needs to be bifunctional. If any of them is trifunctional or more, a crosslinking reaction proceeds and a linear polyester cannot be obtained.
Linear polyesters have the advantages of high solvent solubility, viscoelasticity for toner, and excellent manufacturability compared to branched or network polyesters. ing.
In addition, linear polyester has a simple structure, and it is easy to control molecular weight and physical properties (thermal characteristics, compatibility with other resins, etc.) generated thereby. The linear polyester resin in the present invention is composed of the units (b11) and (b12), and the physical properties of (b1) can be controlled by the polyester type, molecular weight, and structure used in the unit (b12). This is a merit and is characterized in that a physical property control means is clearly provided for a conventional composition containing lactic acid.

The polyhydroxycarboxylic acid skeleton constituting (b11) has a skeleton obtained by polymerizing hydroxycarboxylic acid, and can be formed by a method of directly dehydrating and condensing hydroxycarboxylic acid or a method of ring-opening polymerization of a corresponding cyclic ester. From the viewpoint that the degree of freedom in composition design is high, a method of directly dehydrating and condensing hydroxycarboxylic acid is preferable. Examples of hydroxycarboxylic acids include aliphatic hydroxycarboxylic acids (such as glycolic acid, lactic acid, and hydroxybutyric acid), aromatic hydroxycarboxylic acids (such as salicylic acid, creosote acid, mandelic acid, burric acid, and syringic acid), or mixtures thereof. Corresponding cyclic esters include glycolide, lactide, γ-butyrolactone, 6-valerolactone and the like. Among these, from the viewpoint of the transparency and thermal characteristics of the resin particles (C), the monomer that forms the polyhydroxycarboxylic acid skeleton is preferably an aliphatic hydroxycarboxylic acid and a cyclic ester, more preferably 2 to 2 carbon atoms. 6 hydroxycarboxylic acids (including the corresponding cyclic esters), particularly preferably glycolic acid, lactic acid, glycolide, and lactide, and most preferably glycolic acid and lactic acid.
When the monomer that forms the polyhydroxycarboxylic acid skeleton is an optically active monomer such as lactic acid, particularly when only (b1) is used as (b), the optical purity X (%) = | X (L form) in terms of monomer component -X (D-form) | [wherein X (L-form) represents the L-form ratio (%) in terms of optically active monomer, and X (D-form) represents the D-form ratio (%) in terms of optically active monomer)] Is preferably 80% or less, more preferably 60% or less. Within this range, the solvent solubility is improved and the production method (I) described later, which is a preferred production method, can be easily applied.

  When forming the polyhydroxycarboxylic acid skeleton, a diol (11) described later is added and copolymerized to obtain a polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton as a polyhydroxycarboxylic acid skeleton. Preferred as diols are alkylene oxides of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (Alkylene oxide is hereinafter abbreviated as AO. Specific examples include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.) 2-30), and combinations thereof, more preferably 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and AO adducts of bisphenol A, particularly preferably With 1,3-propylene glycol That.

  The polyester diol (b12) other than (b11) can be the same as the reaction product of the diol (11) and the dicarboxylic acid (13) among the polyester resins described later, and charged with the diol and the dicarboxylic acid during the polymerization. It is obtained by adjusting the ratio to make the hydroxyl group excessive. Preferred as (b12) is 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.). One or more selected from AO (EO, PO, BO, etc.) adduct (number of added moles 2 to 30) and combinations thereof, and selected from terephthalic acid, isophthalic acid, adipic acid, succinic acid, and combinations thereof It is a reaction product with one or more kinds.

  The number average molecular weight (hereinafter abbreviated as Mn) of (b11) and (b12) is preferably from 500 to 30,000, more preferably from 1000 to 20,000, most preferably from 2000, from the viewpoint of adjusting the physical properties of (b1). 5000.

The extender used for the extension of (b11) and (b12) is not particularly limited as long as it has two functional groups capable of reacting with the hydroxyl groups contained in (b11) and (b12). However, among dicarboxylic acids (13) and their anhydrides, polyisocyanates (15) and polyepoxides (19) described later, bifunctional ones can be mentioned. Of these, from the viewpoint of compatibility with (b11) and (b12), preferred are diisocyanate compounds and dicarboxylic acid compounds, and more preferred are diisocyanate compounds. Specifically, succinic acid, adipic acid, maleic acid (and anhydride), fumaric acid (and anhydride), phthalic acid, isophthalic acid, terephthalic acid, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4 '-Diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), bisphenol A diglycidyl ether, etc., among which succinic acid, adipic acid, isophthalic acid, terephthalic acid, maleic acid (and anhydrous) Product), fumaric acid (and anhydride), and DI, is IPDI, most preferably maleic acid (and anhydride), fumaric acid (and anhydride), and IPDI.
The content of the extender in (b1) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, from the viewpoints of transparency and thermal characteristics.

The content of the linear polyester resin (b1) contained in the resin (b) may be appropriately adjusted within a preferable range depending on the use. From the viewpoint of transparency and thermal characteristics of the resin particles (C), , (B) is 40 to 100% by mass, more preferably 60 to 90% by mass. Even when the hydroxycarboxylic acid contained in the resin (b1) is an optically active monomer such as lactic acid, the same content is preferable from the viewpoint of solvent solubility, provided that the optical purity is 80% or less in terms of monomer components. . When the optical purity in terms of monomer component exceeds 80%, from the viewpoint of solvent solubility, the content of the resin (b1) in the resin (b) is the content Y of the resin (b1) in the resin (b). It is preferable that the relationship between (%) and X satisfies Y ≦ −1.5X + 220.
The mass ratio of the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than (b11) constituting the linear polyester is preferably 31:69 to 90:10, From the viewpoint of the transparency and thermal characteristics of the resin particles (C), it is more preferably 40:60 to 80:20.

  As the resin contained in the resin (b), any known resin may be used in addition to the linear polyester (b1), and specific examples thereof are the same as those described later in (a). Can be used. As the resin to be used in combination, a preferable resin can be appropriately selected according to the use and purpose. The resin used in combination may be a resin (b2) obtained by reacting the precursor (b0) in the resin particle forming step, and the precursor (b0) is used from the viewpoint of easy particle formation. Thus, a method of containing a resin to be used in combination is preferable. As the reaction method for obtaining (b2) from the precursor (b0) and (b0), those described later can be used.

In general, vinyl resins, polyester resins, polyurethane resins, epoxy resins, and combinations thereof are preferable as resins used in combination, and polyurethane resins and polyester resins are more preferable, and 1 is particularly preferable. Polyester resins and polyurethane resins containing 2-propylene glycol as structural units.
These preferable resins will be described in detail in the description of the resin (a). The content of the resin other than the linear polyester resin (b1) may be appropriately adjusted within a preferable range depending on the use, but from the viewpoint of the transparency and thermal characteristics of the resin particles (C), the content of (b) 0-60 mass% is preferable, More preferably, it is 10-40 mass%.

Number average molecular weight of resin (b) (measured by gel permeation chromatography, details of measurement method will be described later. Hereinafter, abbreviated as Mn), melting point (measured by DSC), glass transition temperature (Tg), sp value ( The calculation method of the sp value may be suitably adjusted within a preferable range depending on the application, according to Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154).
Tg in the present invention is a value obtained from DSC measurement or flow tester measurement (when measurement cannot be performed by DSC).
In the case of measurement by DSC, it is measured by a method (DSC method) prescribed in ASTM D3418-82 using DSC20 and SSC / 580 manufactured by Seiko Electronics Industry.
For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions.
(Flow tester measurement conditions)
Load: 30 kg / cm ² , heating rate: 3.0 ° C./min.
Die diameter: 0.50 mm, Die length: 10.0 mm

  The Mn of the resin (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of (b) is preferably 20 ° C to 300 ° C, more preferably 80 ° C to 250 ° C. The Tg of (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 200 ° C. The sp value of (b) is preferably 8-16, more preferably 9-14.

  The resin (a) may be any resin, and may be thermoplastic or thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin , Silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. As the resin (a), two or more of the above resins may be used in combination. Among these, a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin, and a combination thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained, and a vinyl resin is more preferable.

  Hereinafter, vinyl resin, polyester resin, polyurethane resin, and epoxy resin which are preferable resins as (a) will be described in detail. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).

(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, etc .; alkadienes such as butadiene, Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, etc .; terpenes such as pinene, limonene, indene etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitution products such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene , Isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomer and metal salt thereof:
C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (C1-24) esters thereof such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxylic group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid. In addition, the said (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used hereafter.

(3) Sulfone group-containing vinyl monomer, vinyl sulfate monoester product and salts thereof:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2 , 2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (Meth) acrylamide-2- Droxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random or block) sulfuric acid of mono (meth) acrylate Esters [poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and sulfates or sulfones represented by the following general formulas (1-1) to (1-3) Acid group-containing monomers; and salts thereof.

（式中、Ｒは炭素数１〜１５のアルキル基、Ａは炭素数２〜４のアルキレン基を示し、ｎが複数の場合同一でも異なっていてもよく、異なる場合はランダムでもブロックでもよい。Ａｒはベンゼン環を示し、ｎは１〜５０の整数を示し、Ｒ’はフッ素原子で置換されていてもよい炭素数１〜１５のアルキル基を示す。）

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block. 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) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate phenyl-2-acryloyloxyethyl phosphate (meth) acryloyloxyalkyl (C1-24) phosphonic acids For example, 2-acryloyloxyethylphosphonic acid.

  Examples of the salts (2) to (4) include metal salts, ammonium salts, and amine salts (including quaternary ammonium salts). Examples of the metal forming the metal salt include Al, Ti, Cr, Mn, Fe, Zn, Ba, Zr, Ca, Mg, Na, and K. Alkali metal salts and amine salts are preferred, and sodium wax and tertiary monoamine salts having 3 to 20 carbon atoms are more preferred.

(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, etc.

(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-vinylthio (6-2) Amido groups such as pyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and their salts Vinyl monomers: (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, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene (6-4) quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethyl Aminoethyl (meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomer: nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride chlorostyrene VI bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meta ) Acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate 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, eicosyl (meth) acrylate, etc.], dialkyl fumarate (dialkyl fumarate ester) (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms. Rudialkyl maleate (dialkyl maleate) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [ Vinyl monomers having a polyalkylene glycol chain, such as diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc. [polyethylene glycol (molecular weight 300) mono (Meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate Methyl alcohol EO 10 mol adduct (meth) acrylate lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] etc. (9-2) vinyl (thio) ether, such as vinyl methyl Ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-12-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. (9-3) vinyl ketones such as vinyl Methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfone, such as divinyl sulfide, p-vinyl diphenyl sulfide vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

(10) Other vinyl monomers:
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

  As the vinyl resin, the arbitrary monomers of the above (1) to (10) are binary or more, preferably the carboxyl group content in the resin particles (A) is 1 to 50%. Examples thereof include polymers copolymerized at an arbitrary ratio. For example, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-butadiene- (meth) acrylic acid copolymer, (meta ) Acrylic acid monoacrylic acid ester copolymer, styrene-acrylonitrile- (meth) acrylic acid monodivinylbenzene copolymer, styrene-styrenesulfonic acid mono (meth) acrylic acid ester copolymer and salts of these copolymers Etc. Among these, preferred is a copolymer containing 20 to 80% of an acrylate ester as a structural unit.

  In addition, when the resin (a) forms the resin particles (A) in the aqueous dispersion, it is necessary that the resin (a) is not completely dissolved in water at least under the conditions for forming the aqueous dispersion. Therefore, although the ratio of the hydrophobic monomer and the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, generally the hydrophobic monomer is preferably 10% or more, and more preferably 30% or more. When the ratio of the hydrophobic monomer is less than 10%, the vinyl resin becomes water-soluble, and the particle size uniformity 1 in (C) may be impaired. Here, the hydrophilic monomer means a monomer that dissolves in water at an arbitrary ratio, and the hydrophobic monomer means another monomer (a monomer that is basically not miscible with water).

Examples of the polyester resin include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. The polyol is a diol (11) and a polyol having 3 to 8 or more valences (12), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) and 3 to 6 or more valences. The above polycarboxylic acid (14) and these acid anhydrides or lower alkyl esters are mentioned.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1 to the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1/4, particularly preferably 1 / 1.3 to 1/3.
In order to keep the carboxyl group content within the above preferred range, the polyester having an excess of hydroxyl groups may be treated with polycarboxylic acid.

  Diol (11) includes alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol. , Decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc .: C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol, polytetramethylene ether glycol, etc.); C4-C36 alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); AO [EO, PO, BO, etc.] adduct of recall or alicyclic diol (addition mole number 1 to 120): AO (AO, PO, BO, etc.) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) Examples include adducts (addition mole number: 2 to 30); polylactone diols (poly ε-caprolactone diol and the like); and polybutadiene diols and the like.

As the diol, in addition to the diol having no functional group other than the hydroxyl group, a diol (11a) having another functional group may be used. Examples of (11a) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [things of C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolhebutane. Acid, 2,2-dimethylol octanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [NN-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (AO is EO or PO, Addition mole number of AO 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 mole adduct, etc.]: Bis (2-hydroxy Ethyl) phosphate and the like.
Examples of the neutralizing base of the diol having these neutralizing bases include the tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, AO adducts of diol bisphenols having a carboxyl group, and combinations thereof.

  Examples of the polyol (12) having 3 to 8 or more valences include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof such as glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; saccharides and derivatives thereof such as sucrose and methylglucoside); AO adducts of polyhydric aliphatic alcohols (addition mole number: 2-120) : AO adduct (addition mole number 2-30) of trisphenol (trisphenol PA, etc.); AO adduct (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [hydroxy Ethyl (meth) acrylate and others Such as copolymer of vinyl monomers]; and the like. Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acid (dodecenyl succinic acid, Pentadecenyl succinic acid, octadecenyl succinic acid, etc.); alicyclic dicarboxylic acids having 6 to 40 carbon atoms (dimer acid (dimerized linoleic acid) etc.), alkenedicarboxylic acids having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.): C8-36 aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and the like. Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the tri- or hexavalent or higher polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as dicarboxylic acid (13) or polycarboxylic acid (14) having 3 to 6 or more valences, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester) Etc.) may be used.

As the polyurethane resin, polyisocyanate (15) and active hydrogen-containing compound {water, polyol [diol (11) [including diol (11a) having a functional group other than hydroxyl group], and 3 to 8 or more valences] Polyol (12)] polycarboxylic acid [dicarboxylic acid (13) and polycarboxylic acid (14) having 3 to 6 or more valences], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, carbon number 6 to 12 lactone ring-opening polymer, polyamine (16), polythiol (17), and a combination thereof, and the like, and a terminal isocyanate group prepolymer obtained by reacting (15) with an active hydrogen-containing compound, , Equal amounts of primary and / or secondary monoamines (with respect to the isocyanate groups of the prepolymer) 8) and reacting the obtained, and amino group-containing polyurethane resins.
The content of carboxyl groups in the polyurethane resin is preferably 0.1 to 10%.

  Examples of the diol (11), 3 to 8 or more polyol (12), dicarboxylic acid (13), and 3 to 6 or more polycarboxylic acid (14) include those described above, and are preferable. The thing is the same.

  As polyisocyanate (15), C6-C20 aromatic polyisocyanate C2-C18 aliphatic polyisocyanate C4-C15 alicyclic poly (excluding carbon in NCO group) Isocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone groups And the like, and mixtures of two or more thereof.

  Specific examples of the aromatic polyisocyanate include 1,3- and / or 14-phenylene diisocyanate 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or Or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20%) of 3 Mixtures with functional or higher polyamines]: Polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanatophenyl Sulfonyl isocyanate Specific 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 lysine. Aliphatics such as diisocyanate 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4′-diisocyanate. Nate (hydrogenated MDI), cyclohexylene diisocyanate methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2, 6-norbornane diisocyanate, etc. Specific examples of the aromatic aliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α, α, -tetramethylxylylene diisocyanate ( Examples of the modified polyisocyanates include urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products, and the like. Is mentioned The Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included. Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI and HDI. , Hydrogenated MDI, and IPDI.

Examples of the polyamine (16) include aliphatic polyamines (C2 to Cl8): [1] aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc. ), Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1 C4) or hydroxyalkyl (C2-C4) substituted [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa [3] Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; [4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4 to C15): 1,3- Heterocyclic polyamines (C4-C15) such as diaminocyclohexaneisophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylbiperazine, 1,4 -Aromatic poly, such as diaminoethylbiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Mines (C6-C20): [1] Unsubstituted aromatic polyamines [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethane Diamine (polyphenyl polymethylene polyamine), diaminodiphenyl sulfone, benzidine, thiodianiline, bis (3,4-diaminophenol) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 "-triamine, naphthylenediamine and the like; [2] aromatic polyamines having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propylbutyl], for example 2.4 and 2 , 6-Tolylenediamine, Crudetolylenediamine, Diethyltolylenediamine 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (O-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2, , 3-Dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3,5,5-tetramethylbenzidine, 3,3,5,5-tetramethyl-4, 4'-diaminodiphenylmethane, 3,5-diethyl-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-tetraethyl-4,4′-diaminodiphenyl ether, 3, , 3,5,5-tetraisopropyl-4,4′-diaminodiphenylsulfone, etc.], and mixtures of these isomers in various proportions: [3] nuclear substituted electron withdrawing groups (Cl, Br, I, F, etc.) An aromatic polyamine having methylene bis-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, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3) -Methoxyphenyl) decane, bis (4-aminophenyl) sulfide bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4-methylenebis ( 2-iodoaniline), 4,4-methylenebis (2-bromoaniline), 4,4-methylene Bis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [in the above-mentioned [1] to [3] aromatic polyamines —NH ₂ Partially or entirely replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4-di (methylamino) diphenylmethane, 1-methyl-2 -Methylamino-4-aminobenzene, etc.], polyamide polyamine: by condensation of dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamine (such as alkylenediamine, polyalkylenepolyamine, etc.) Low molecular weight polyamide polyamines such as polyether polyamines: polyether polyols (polyalkylene glycols, etc.) Examples thereof include cyanoethyl hydride.

  Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

  Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (such as ethylamine, butylamine, and isobutylamine).

  Examples of the epoxy resin include a ring-opening polymer of polyepoxide (19), polyepoxide (19) and an active hydrogen group-containing compound {water, polyol [the diol (11) and a polyol having 3 to 8 or more valences (12)], The dicarboxylic acid (13), the trivalent to hexavalent or higher polycarboxylic acid (14), the polyamine (16), the polythiol (17), etc.}, or the polyepoxide (19) and the dicarboxylic acid (13) or a cured product of an acid anhydride of a polycarboxylic acid (14) having a valence of 3 to 6 or more, and the like.

  The polyepoxide (19) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. A thing preferable as a polyepoxide (19) has 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (19) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent exceeds 1000, the cross-linked structure becomes loose and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are deteriorated. On the other hand, it is difficult to synthesize an epoxy equivalent of less than 65. is there.

  Examples of the polyepoxide (19) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. The glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol, and A diglycidyl 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'-dihydroxybiphenyl Diglycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, 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 ethers of enol or cresol novolac resins, glycidyl ethers of limonene phenol novolak resins, diglycidyl ethers obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, condensation of phenol and glyoxal glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ether of polyphenol obtained by the reaction, polyglycidyl ether of polyphenol obtained by the condensation reaction of resorcin and acetone, and the like. Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and the like. Examples of the glycidyl aromatic polyamine include NN-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine: Examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, and 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) Examples include adipate and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate diglycidyl malate diglycidyl succinate diglycidyl glutarate, diglycidyl adipate diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic type also includes a (co) polymer 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.

  In the resin particles (C) of the present invention, the resin particles (A) containing the first resin (a) or the coating (P) containing the resin (a) contains the second resin (b). As long as it covers the surface of the resin particle (B), it may be obtained by any manufacturing method.

The resin particles (C) of the present invention may be resin particles produced by any method and process, but as a method for producing resin particles, the following production method (I) or (II), etc. Is mentioned.
(I): An aqueous dispersion (W) of resin particles (A) containing the resin (a) and [resin (b) or an organic solvent solution or dispersion thereof (hereinafter referred to as (O1)), or [ A precursor (b0) of resin (b) or an organic solvent solution or dispersion thereof (hereinafter referred to as (O2)) is mixed, and (O1) or (O2) is dispersed in (W); (W) A method of forming resin particles (B) containing (b) therein. In this case, simultaneously with the granulation of the resin particles (B), the resin particles (A) or the coating (P) adhere to the surface of (B) to form an aqueous dispersion (X) of the resin particles (C). Built by removing.

  (II): A method of producing resin particles (C) by coating resin particles (B) containing a resin (b) prepared in advance with a coating agent (W ′) containing a resin (a). In this case, the coating agent (W ′) may be liquid, solid, or any form, and after coating with the precursor (a ′) of (a), (a ′) is reacted (a ). Further, (B) to be used may be a resin particle produced by an emulsion polymerization aggregation method, a resin particle produced by a pulverization method, or any production method. . The coating method is not limited, and for example, a dispersion of resin particles (B) or (B) prepared in advance in an aqueous dispersion (W) of resin particles (A) containing resin (a) is dispersed. And a method of sprinkling (B) the solution of (a) as a coating agent. Among these, the production method (I) is preferable.

The resin particles (C) are more preferably obtained by the following production method because the resin particles have a uniform particle size.
Resin particle (A) aqueous dispersion (W) and (O1) (resin (b) or organic solvent solution or dispersion thereof), or (O2) (resin (b) precursor (b0) or organic thereof Solvent solution or dispersion) and (O1) or (O2) is dispersed in (W) to form resin particles (B) containing (b). ) Adsorb the resin particles (A) on the surface thereof to prevent the resin particles (C) from being united with each other, and (C) is less likely to be split under high shear conditions. Thereby, the particle diameter of (C) is converged to a constant value, and the effect of improving the uniformity of the particle diameter is exhibited. Therefore, the resin particles (A) have such a strength that they are not destroyed by shearing at the temperature at which they are dispersed, are not easily dissolved or swelled in water, and (b) or an organic solvent solution or dispersion thereof. It is preferable that it is difficult to dissolve in the liquid, (b0) or an organic solvent solution or dispersion thereof.
In addition, a colorant, a release agent, and a modified layered inorganic mineral that are toner components are included in the resin particles (B). For this reason, before mixing (W) and (O) (O1 or O2), it is dispersed in the solution of (O). The charge control agent may be included in the resin particles (B) or externally added. In the case of inclusion, it may be dispersed in the solution of (O) in the same manner as the colorant and the like, and in the case of external addition, it is externally added after the formation of the particles C.

  From the viewpoint of reducing dissolution or swelling of the resin particles (A) in water or a solvent used for dispersion, the molecular weight of the resin (a), the sp value (a method for calculating the sp value is Polymer Engineering and Science, February, 1974, VoL14, No. 2P, 147 to 154), crystallinity, molecular weight between cross-linking points, and the like are preferably adjusted as appropriate.

  The number average molecular weight (measured by gel permeation chromatography, hereinafter abbreviated as Mn) of the resin (a) is preferably from 1 to 5 million, more preferably from 2 to 5 million, particularly preferably from 500 to 500000, The sp value is preferably 7 to 18, and more preferably 8 to 14. The melting point (measured by DSC) of the resin (a) is preferably 50 ° C. or higher, more preferably 80 to 200 ° C.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of a resin other than a polyurethane resin such as a polyester resin are obtained by gel permeation chromatography (GPC) for tetrahydrofuran (THF) soluble matter. And measured under the following conditions.
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
: TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

Moreover, Mn and Mw of a polyurethane resin are measured on condition of the following using GPC.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

  The glass transition temperature (Tg) of the resin (a) is preferably 50 ° C. to 100 ° C. from the viewpoint of the particle size uniformity of the resin particles (C), powder flowability, heat resistance during storage, and stress resistance. More preferably, it is 51 to 90 degreeC, Most preferably, it is 52 to 75 degreeC. If the Tg is lower than the temperature at which the aqueous resin dispersion is produced, the effect of preventing coalescence or preventing splitting is reduced, and the effect of improving the uniformity of particle size is reduced. Moreover, Tg of the resin particle (A) containing the resin (a) and the coating (P) containing the resin (a) is preferably 20 to 200 ° C., more preferably 30 to 100 ° C. for the same reason. Especially preferably, it is 40-85 degreeC. In addition, Tg in this invention is a value calculated | required from DSC measurement or a flow tester measurement (when it cannot measure by DSC).

In the case of measurement by DSC, it is measured by the method (DSC method) defined in ASTM D3418-82 using DSC20 and SSC / 580 manufactured by Seiko Electronics Industry.
For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions.
(Flow tester measurement conditions)
Load: 30 kg / cm ² , temperature rising rate: 3.0 ° C./min,
Die diameter: 0.50 mm, tie length: 10.0 mm

  The resin (a) is selected from known resins as described above. When the glass transition temperature (Tg) of the resin (a) is adjusted, the molecular weight of (a) and / or the simple substance constituting (a) is selected. It can be easily adjusted by changing the mass composition. As a method for adjusting the molecular weight of (a) (the higher the molecular weight, these temperatures are higher), a known method may be used. For example, when polymerization is performed by a sequential reaction such as a polyurethane resin or a polyester resin. In the case of polymerizing by a chain reaction such as vinyl resin, adjustment of the polymerization initiator amount and chain transfer agent amount, reaction temperature, and reaction concentration can be mentioned.

  In the aqueous dispersion (W) of the resin particles (A), an organic solvent miscible with water (acetone, methyl ethyl ketone, etc.) may be contained in the organic solvent (u) described later in addition to water. At this time, if the organic solvent contained does not cause aggregation of the resin particles (A), does not dissolve the resin particles (A), and does not interfere with granulation of the resin particles (C) Any kind and any content may be used, but it is preferably 40% by mass or less of the total amount with water and not remaining in the resin particles (C) after drying.

The method for converting the resin (a) to the aqueous dispersion (W) of the resin particles (A) is not particularly limited, and the following [1] to [8] can be mentioned.
[1] In the case of vinyl resin, an aqueous dispersion of resin particles (A) 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 polyester resin, a precursor (monomer, oligomer, etc.) or an organic solvent solution or dispersion thereof in an aqueous medium in the presence of a suitable dispersant if necessary. In the case of polyaddition or condensation resin such as polyester resin, a method for producing an aqueous dispersion of resin particles (A) by heating or adding a curing agent and then curing the resin particle (A), An appropriate emulsifier was dissolved in a precursor (monomer, oligomer, etc.) or an organic solvent solution or dispersion thereof (preferably a liquid, which may be liquefied by heating). , A method of producing an aqueous dispersion of resin particles (A) by adding water to phase inversion emulsification and curing by adding a curing agent [4] polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, It may be any polymerization reaction mode such as addition condensation, condensation polymerization, etc. The same applies to the polymerization reaction in the following section), and the resin prepared by pulverization using a mechanical rotary type or jet type fine pulverizer, After obtaining resin particles by classification, a method of dispersing in water in the presence of a suitable dispersant [5] By spraying a resin solution prepared by previously polymerizing a resin solution in an organic solvent in a mist form After obtaining the resin particles, a method of dispersing the resin particles in water in the presence of a suitable dispersant [6] adding a poor solvent to a resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction in an organic solvent, or Arakaji A method of precipitating resin particles by cooling a resin solution heated and dissolved in an organic solvent, then removing the organic solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant [7] A method in which a resin solution obtained by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent is dispersed in an aqueous medium in the presence of a suitable dispersing agent, and the organic solvent is removed by heating or decompressing. A method in which a suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent, and then water is added to perform phase inversion emulsification.

  In the above methods [1] to [8], as the emulsifier or dispersant used in combination, a known surfactant (s), water-soluble polymer (t) and the like can be used. Moreover, an organic solvent (u), a plasticizer (V), etc. can be used together as an auxiliary agent for emulsification or dispersion.

  Examples of the surfactant (s) include an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3), and a nonionic surfactant (s-4). Is mentioned. The surfactant (s) may be a combination of two or more surfactants. Specific examples of (s) include those described below and JP-A-2002-284881.

  As the anionic surfactant (s-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, cabrynic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, olein Examples thereof include mixtures of acids, linoleic acid and ricinoleic acid, and higher fatty acids obtained by saponifying coconut 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 moles of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated fats and oils having a carbon number of 12 to 50 or neutralized by neutralization) and sulphated 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, decyl alcohol sulfate ester salt, lauryl alcohol sulfate ester salt, stearyl alcohol sulfate ester salt, and alcohol synthesized using a Ziegler catalyst (for example, trade name: ALFOL1214). : Manufactured by CONDEA) and alcohol synthesized by the oxo method (for example, trade names: Dovanol 23, 25, 45, Diadol 115, 115H, 135: manufactured by Mitsubishi Chemical Corporation, trade name: tridecanol: Kyowa Hakko) Manufactured by the trade name: Oxocol 1213, 1215, 1415: manufactured by Nissan Chemical Co., Ltd.).

  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 sulfated oils include sulfate salts 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 carboxymethylated salts of aliphatic alcohols having 8 to 16 carbon atoms and EO or carboxymethylated salts of 1 to 10 mol adducts of aliphatic alcohols having 8 to 16 carbon atoms. Can be used.

  Examples of the salt of the carboxymethylated product of the aliphatic alcohol include octyl alcohol carboxymethyl sodium salt, lauryl alcohol carboxymethyl sodium salt, carboxymethylated sodium salt of dovanol 23, tridecanol carboxymethyl sodium salt, and the like. Can be mentioned.

  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 tridecanol EO5 mol addition. Carboxymethylated sodium salt and the like.

  As sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid diester salts, α-olefin sulfonates, sulfonates of Igepon T-type and other 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 (s-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used. As the quaternary ammonium salt type surfactant, a tertiary amine having 3 to 40 carbon atoms and a quaternizing agent (for example, alkylating agents such as methyl chloride methyl bromide, ethyl chloride, benzyl chloride and dimethyl sulfate, EO, etc.) For example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide stearyl trimethyl ammonium bromide lauryl dimethyl benzyl ammonium chloride (benzalkonium chloride), cetyl pyridinium chloride, polyoxyethylene trimethyl Examples include ammonium chloride and stearamide ethyl diethyl methyl ammonium methosulfate.

  As the amine salt type surfactant, a primary to tertiary amine is converted into an inorganic acid (for example, hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, phosphoric acid and perchloric acid) or an organic acid (acetic acid, formic acid, glue acid, Lactic acid, gluconic acid, adipic acid, alkylphosphoric acid having 2 to 24 carbon atoms, malic acid, citric acid and the like). Examples of the primary amine salt type surfactant include inorganic acid salts of aliphatic higher amines having 8 to 40 carbon atoms (for example, higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine). Alternatively, organic acid salts and higher fatty acid (carbon number 8 to 40, stearic acid, oleic acid, etc.) salts of lower amines (having 2 to 6 carbon atoms) can be used.

  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), nitrogen-containing heteroaromatic amines having 5 to 30 carbon atoms (for example, 4-dimethylaminopyridine, N-methyl) Inorganic salts or organic salts of imidazole and 4,4′-dipyridyl) and triethanolamine monostearate, stearamide ethyl die Such as tertiary mineral or organic acid salts of amines such as methyl ethanolamine.

  Examples of the amphoteric surfactant (s-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 (s-4), an AO addition type nonionic surfactant and a polyhydric alcohol type nonionic surfactant can be used. The AO addition type nonionic surfactant directly adds AO (2 to 20 carbon atoms) to a higher alcohol having 8 to 40 carbon atoms, a higher fatty acid having 8 to 40 carbon atoms or an alkylamine having 8 to 40 carbon atoms. Or, a higher fatty acid or the like is reacted with a polyalkylene glycol obtained by adding AO to glycol, or AO is added to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or a higher fatty acid amide is added. It is obtained by adding AO.

  Examples of AO include EO, PO, and BO. Of these, EO and random or block adducts of EO and PO are preferred. 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, lauryl 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, lauryl acid EO 10 mol adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (alkylene having 2 to 24 carbon atoms, polyhydric alcohol having 3 to 40 carbon atoms, higher fatty acid) Carbon number -40) (for example, lauric acid diester of polyethylene glycol (polymerization degree 20), oleic acid diester of polyethylene glycol (polymerization degree 20), etc.); polyoxyalkylene alkylphenyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon) 8 to 40) (for example, nonylphenol EO 4 mol adduct, norphenol EO 8 mol PO 20 mol block adduct, octylphenol EO 10 mol adduct, bisphenol A · EO 10 mol adduct, styrenated phenol EO 20 mol adduct, etc.); polyoxy Alkylene alkyl amino ether (alkylene having 2 to 24 carbon atoms, alkyl carbon number of 8 to 40) and (for example, laurylamine EO 10 mol adduct, stearylamine EO 10 mol adduct, etc.): polyoxy Lukylene alkanolamide (2-24 carbon atoms of alkylene, 8-24 carbon atoms of amide (acyl moiety)) (for example, EO 10 mol adduct of hydroxyethyl lauric acid amide, EO 20 mol adduct of hydroxypropyl oleic acid amide, etc. ).

  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 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 dilaurate sorbitan diolate 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 monomethyl 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 adduct, methyl glycoside EO 20 mol PO 10 mol random adduct, lauryl glycoside EO 10 mol adduct and stearyl glycoside EO 20 mol PO 20 mol random adduct. Can be mentioned.

  Examples of the water-soluble polymer (t) include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin , Chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, in the sodium hydroxide part of polyacrylic acid) Sodium hydroxide, acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide Beam (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

  The organic solvent (u) used in the present invention may be added to an aqueous medium as necessary during emulsification and dispersion in the dispersion to be emulsified [the oil phase (O1) containing the resin (b) or (b0) or (O2) Medium] may be added. Specific examples of the organic solvent (u) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, and mineral spirit cyclohexane. Solvent: Halogen solvents such as methyl chloride, methyl bromide methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc .; Esters such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, or Ester ether solvents; ether solvents such as diethyl ether, tetrahydrofuran dioxane, ethyl cellosolve, ptyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl Ketone solvents such as ruketone, di-n-butylketone, cyclohexanone: alcohol solvents such as methanol, ethanol n-propanolisopropanol, n-butanol, isobutanol t-butanol, 2-ethylhexyl alcohol benzyl alcohol: dimethylformamide dimethylacetamide, etc. Amide solvents; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and mixed solvents of two or more of these.

Even if the plasticizer (v) is added to an aqueous medium as needed during emulsification and dispersion, it is contained in the dispersion to be emulsified [in the oil phase (O1) or (O2) containing the resin (b) or (b0)]. ] May be added. As a plasticizer (v), it is not limited at all, The following are illustrated.
(Vl) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate diisodecyl, etc.];
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.];
(V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.];
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.];
(V5) fatty acid ester [butyl oleate and the like];
(V6) and a mixture of two or more of these.

  The particle size of the resin particles (A) used in the present invention is usually smaller than the particle size of the formed resin particles (B). From the viewpoint of particle size uniformity, the particle size ratio [volume of the resin particles (A) The value of [average particle diameter] / [volume average particle diameter of resin particles (B)] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, and the upper limit is more preferably 0.25. When the particle size ratio is larger than 0.3, (A) is not efficiently adsorbed on the surface of (B), so that the obtained particle size distribution of (C) tends to be wide.

  The volume average particle size of the resin particles (A) can be appropriately adjusted within the above range of particle size ratios so as to be a particle size suitable for obtaining the resin particles (C) having a desired particle size. The volume average particle diameter of (A) is generally preferably 0.0005 to 1 μm. The upper limit is more preferably 0.75 μm, particularly preferably 0.5 μm, and the lower limit is further preferably 0.01 μm, particularly preferably 0.02 μm, and most preferably 0.04 μm. However, for example, when it is desired to obtain resin particles (C) having a volume average particle diameter of 1 μm, the range is preferably 0.0005 to 0.30 μm, particularly preferably in the range of 0.001 to 0.2 μm, and 10 μm resin particles ( When C) is obtained, it is preferably 0.005 to 0.8 μm, particularly preferably 0.05 to 1 μm. In addition, the volume average particle size is determined by laser type particle size distribution measuring device LA-920 (manufactured by Horiba), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using a laser Doppler method as an optical system, or the like. Can be measured. If there is a difference in the measured value of the particle diameter between the measuring devices, the measured value by ELS-800 is adopted. In addition, since the said particle size ratio is easy to obtain, 0.1-15 micrometers is preferable as the volume average particle diameter of the resin particle (B) mentioned later. More preferably, it is 0.5-10 micrometers, Most preferably, it is 1-8 micrometers.

  As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). In this case, as a method of forming the resin particles (B) containing the resin (b2) obtained by reacting the precursor (b0) in the step of forming the resin particles (C), a reactive group-containing prepolymer (α ) And a curing agent (β) and optionally an organic solvent (u) are dispersed in an aqueous dispersion of the resin particles (A), and the reactive group-containing prepolymer (α) and the curing agent ( a method of reacting β) to form resin particles (B) containing the resin (b2); a reactive group-containing prepolymer (α) or an organic solvent solution or dispersion thereof as an aqueous dispersion of resin particles (A) A method in which the resin particles (B) containing the resin (b2) are formed by dispersing in the resin and reacting with the water-soluble curing agent (β). The reactive group-containing prepolymer (α) is mixed with water. In the case of curing by reaction, a reactive group-containing prepolymer Resin (α) or an organic solvent solution or dispersion thereof is dispersed in an aqueous dispersion (W) of resin particles (A) to react with water to form resin particles (B) containing (b2). A method etc. can be illustrated.

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following [1] and [2].
[1] The reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1). The combination.
[2] A combination in which the reactive group of the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. .

  Among these, [1] is more preferable from the viewpoint of the reaction rate in water. In the combination [1], the functional group (α1) capable of reacting with the active hydrogen compound includes an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable. The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]: C1-20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; phenols [phenol, -cresol, xylenol, nonylphenol, etc.]; active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] ]; Basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]: and mixtures of two or more thereof . Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

  Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Among these, (αx), (αy) and (αz) are preferable, and (αx) and (αz) are particularly preferable. Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide and polytetramethylene oxide. Examples of polyester (αx) include polycondensates of diol (11) and dicarboxylic acid (13), polylactones (ring-opening polymerization products of ε-caprolactone), and the like. Examples of the epoxy resin (αy) include addition condensation products of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin. Examples of polyurethane (αz) include polyaddition product of diol (11) and polyisocyanate (15), polyaddition product of polyester (αx) and polyisocyanate (15), and the like.

As a method of adding a reactive group to polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1] A method of leaving a functional group of a constituent component at the terminal by excessively using one of two or more constituent components,
[2] A compound containing a functional group and a reactive group capable of reacting with the remaining functional group by leaving the functional group of the structural component at the terminal by excessively using one of the two or more structural components And the like.
In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained. For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of polyol (1) to polycarboxylic acid (2) is equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and 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. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.

  In the above method [2], an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in the above method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted to cause a blocked isocyanate group-containing prepolymer. A polymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride. The amount of the compound containing a functional group and a reactive group is used, for example, when a polyisocyanate is reacted with a hydroxyl group-containing polyester to obtain an isocyanate group-containing polyester prepolymer, the ratio of the polyisocyanate is an isocyanate group [NCO]. And the hydroxyl group [Om equivalent ratio [NCO] / [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and particularly preferably 2.5. / 1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

  The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high. The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000. The weight average molecular weight of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 4,000 to 20,000. The viscosity of the reactive group-containing prepolymer (α) is preferably 2,000 poise or less, more preferably 1,000 poise or less at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that a sharp resin particle (C) having a particle size distribution can be obtained with a small amount of an organic solvent.

  Examples of the active hydrogen group-containing compound (βl) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Among these, (β1a), (β1b) and (β1d) are preferable, and (β1a) and (β1d) are more preferable, and particularly preferable are blocked polyamines and (β1d). ). (Β1a) is exemplified by those similar to polyamine (16). Preferred as (β1a) are 4,4'-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine and mixtures thereof.

  Examples of the case where (β1a) is a polyamine blocked with a detachable compound include ketimine compounds obtained from the polyamines and ketones having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) And aldimine compounds, enamine compounds and oxazolidine compounds obtained from aldehyde compounds having 2 to 8 carbon atoms (formaldehyde, acetaldehyde).

  Examples of the polyol (β1b) are the same as the diol (11) and the polyol (12). Diol (11) alone or a mixture of diol (11) and a small amount of polyol (12) is preferred. Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

  If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). By using a reaction terminator in combination with (βl) at a certain ratio, it is possible to adjust (b2) to a predetermined molecular weight. As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.): monool (methanol, ethanol, isopropanol, butanol) , Phenol, etc.); monomercaptan (such as butyl mercaptan, lauryl mercaptan); monoisocyanate (such as lauryl isocyanate phenyl isocyanate): monoepoxide (such as butyl glycidyl ether).

  As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2], an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Of these, (α2a), (α2b) and an organic group (α2e) blocked with a compound capable of removing an amino group are preferred, and (α2b) is particularly preferred. Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polycarboxylic acid anhydride (β2d), and polyacid halide (β2e). Can be mentioned. Of these, (β2a) and (β2b) are preferable, and (β2a) is more preferable.

  Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (15), and preferred ones are also the same. Examples of the polyepoxide (β2b) are the same as those of the polyepoxide (19), and preferred ones are also the same.

  Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2). (Β2c-1) alone and (β2c-1) and a small amount of ( A mixture of β2c-2) is preferred. Examples of the dicarboxylic acid (β2c-1) include the dicarboxylic acid (13), and examples of the polycarboxylic acid include those similar to the polycarboxylic acid (5), and preferable ones are also the same.

  Examples of the polycarboxylic acid anhydride (β2d) include pyromellitic acid anhydride. Examples of the polyacid halides (β2e) include the acid halides (acid chloride, acid bromide acid iodide) of the above (β2c). Furthermore, a reaction terminator (βs) can be used together with (β2) if necessary.

  The ratio of the curing agent (β) is the ratio of the equivalent [α] of the reactive group in the reactive group-containing prepolymer (α) to the equivalent of the active hydrogen-containing group [β] in the curing agent (β) [α. ] / [Β] 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. When the curing agent (β) is water (β1d), water is treated as a divalent active hydrogen compound.

  Resin (b2) obtained by reacting a reactive group-containing prepolymer (α) and a precursor (b0) containing a curing agent (β) in an aqueous medium is a constituent of resin particles (B) and resin particles (C). It becomes. The weight average molecular weight of the resin (b2) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is preferably 3000 or more, more preferably 3,000 to 10,000,000, particularly preferably 5,000 to 5,000. One million.

  Further, during the reaction of the reactive group-containing prepolymer (α) and the curing agent (β) in the aqueous medium, the reactive group-containing prepolymer (α) such as the linear polyester resin (b1) and the curing agent. By including in the system a polymer that does not react with (β) [so-called dead polymer], the resin (b) reacts the reactive group-containing prepolymer (α) with the curing agent (β) in an aqueous medium. A mixture of the obtained resin (b2) and an unreacted resin such as a linear polyester-based resin (b1) is obtained.

  The amount of the aqueous dispersion (W) used with respect to 100 parts by mass of the resin (b) is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass. If it is 50 parts by mass or more, the dispersed state of (b) is good, and if it is 2,000 parts by mass or less, it is economical.

  The resin particles (C) include an aqueous dispersion (W) of the resin particles (A) containing the resin (a), an organic solvent solution or dispersion (O1) of the resin (b) or (b), or (b ) Precursor (b0) or an organic solvent solution or dispersion (02) of (b0) is mixed, and (O1) or (O2) is dispersed in (W). b0) is reacted to form a resin (b2), and an aqueous dispersion of resin particles (C) having a structure in which the resin (a) is adhered to the surface of the resin particles (B) containing the resin (b) ( X) is obtained and obtained by removing the aqueous medium from the aqueous resin dispersion (X). The state of the resin (a) adhering to the surface of the resin particle (B) may be either the resin particle (A) or the coating (P). Whether it is (A) or (P) depends on the Tg of the resin (a) and the production conditions (desolvent temperature, etc.) of the resin particles (C).

  The shape of the resin particles (C) obtained by the production method (I) is controlled by controlling the difference in sp value between the resin (a) and the resin (b) and the molecular weight of the resin (a). The surface property can be controlled. When the difference in sp value is small, irregularly-shaped and smooth surface particles are easily obtained, and when the difference in sp value is large, spherical particles having a rough surface are easily obtained. Further, when the molecular weight of (a) is large, particles having a rough surface are easily obtained, and when the molecular weight is small, particles having a smooth surface are easily obtained. However, if the difference in sp value between (a) and (b) is too small or too large, granulation becomes difficult. If the molecular weight of the resin (a) is too small, granulation becomes difficult. From this, the sp value difference between (a) and (b) is preferably 0.01 to 5.0, more preferably 0.1 to 3.0, and still more preferably 0.2 to 2.0. The weight average molecular weight of the resin particles (a) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 500,000, still more preferably from 2,000 to 200,000, particularly preferably from 3,000 to 100,000.

  In the case of the production method (II), the shape of the resin particles (C) greatly affects the shape of the resin particles (B) prepared in advance, and the resin particles (C) have almost the same shape as the resin particles (B). become. However, when (B) is distorted, if more coating agent (W ′) is used in the production method (II), it becomes spherical.

  In the present invention, from the viewpoints of particle size uniformity, storage stability and the like of the resin particles (C), the resin particles (C) are resin particles (A) containing 0.01 to 60% by mass of the resin (a). Or it is preferable to consist of the film (P) containing resin (a) and the resin particle (B) containing 40-99.99 mass% resin (b), More preferably, it is 0.1-50 mass%. (A) or (P) and 50 to 99.9% by weight (B), particularly preferably 1 to 45% by weight (A) or (P) and 55 to 99% by weight (B). is there. When (A) or (P) is 0.01% by mass or more, the blocking resistance is good, and when it is 60% by mass or less, the fixing characteristics, particularly the low temperature fixability is good.

Further, from the viewpoint of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (C), in the resin particles (C), 5% or more of the surface of the resin particles (B), preferably 30%. More preferably, 50% or more, particularly preferably 80% or more, is covered with the resin particles (A) containing the resin (a) or the coating (P) containing the resin (a). The surface coverage of (C) 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 (A) or (P) / area of the portion covered with (A) or (P) + resin particle (B) is exposed Area of part] × 100

  From the viewpoint of particle size uniformity, the coefficient of variation of the volume distribution of the resin particles (C) is preferably 30% or less, and more preferably 0.1 to 15%. Further, from the viewpoint of particle size uniformity, the value of [volume average particle size / number average particle size] of the resin particles (C) is preferably 1.0 to 1.4, preferably 1.0 to 1.2. More preferably. The volume average particle size of (C) varies depending on the application, but is generally preferably 0.1 to 16 μm. The upper limit is more preferably 11 μm, particularly preferably 9 μm, and the lower limit is further preferably 0.5 μm, particularly preferably 1 μm. The volume average particle size and the number average particle size can be measured simultaneously with Multisizer III (manufactured by Coulter).

The resin particle (C) of the present invention changes the particle size of the resin particle (A) and the resin particle (B) and the coverage of the surface of the resin particle (B) with the coating (P) containing the resin (a). Thereby, desired unevenness | corrugation can be provided to the particle | grain surface. When it is desired to improve the powder fluidity, the BET specific surface area of (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area of the present invention is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measuring gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen). . Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of (C) is preferably 0.01 to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (C) is preferably spherical from the viewpoint of powder flowability, melt leveling properties and the like. In that case, the resin particles (B) are also preferably spherical. The average circularity of (C) is preferably 0.95 to 1.00. The average circularity is more preferably 0.96 to 1.0, and particularly preferably 0.97 to 1.0. The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 ml of water from which impure solids have been removed in advance is added, and 0.1 to 0.5 ml of a surfactant (dry well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) for about 1 to 3 minutes to obtain a dispersion concentration of 3,000 to 10,000 / μl. To measure the shape and distribution of the resin particles.

(CCA)
The toner of the present invention can contain a charge control agent in the toner as needed.
For example, nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes such as C.I. I. Basic Yellow 2 (C.I. 41000), C.I. I. Basic Yellow 3, C.I. I. Basic Red 1 (C.I. 45160), C.I. I. Basic Red 9 (C.I. 42500), C.I. I. Basic Violet 1 (C.I. 42535), C.I. I. Basic Violet 3 (C.I. 42555), C.I. I. Basic Violet 10 (C.I. 45170), C.I. I. Basic Violet 14 (C.I. 42510), C.I. I. Basic Blue 1 (C.I. 42025), C.I. I. Basic Blue 3 (C.I. 51005), C.I. I. Basic Blue 5 (C.I. 42140), C.I. I. Basic Blue 7 (C.I. 42595), C.I. I. Basic Blue 9 (C.I. 52015), C.I. I. Basic Blue 24 (C.I. 52030), C.I. I. Basic Blue 25 (C.I. 52025), C.I. I. Basic Blue 26 (C.I. 44045), C.I. I. Basic Green 1 (C.I. 42040), C.I. I. Basic Green 4 (C.I. 42000) and the like and lake pigments of these basic dyes, C.I. I. Solvent Black 8 (C.I. 26150), quaternary ammonium salts such as benzoylmethyl hexadecyl ammonium chloride, decyl trimethyl chloride, or dialkyl tin compounds such as dibutyl or dioctyl, dialkyl tin borate compounds, guanidine derivatives, containing amino groups Polyamine resins such as vinyl polymers, condensation polymers containing amino groups, Japanese Patent Publication No. 41-20153, Japanese Patent Publication No. 43-27596, Japanese Patent Publication No. 44-6397, Japanese Patent Publication No. 45-26478 Metal complex salts of monoazo dyes described, Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 59-7385, salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr , Fe, etc. Metal complex, a copper phthalocyanine pigment obtained by sulfonation, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. Naturally, color toners other than black should avoid the use of charge control agents that impair the target color, and white metal salts of salicylic acid derivatives are preferably used.

  The toner of the present invention preferably has a layered inorganic mineral obtained by modifying at least part of ions between layers of the layered inorganic mineral as a toner composition with organic ions. The layered inorganic mineral modified in the present invention is preferably a layered inorganic mineral having a smectite basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.

  Examples of the organic cation modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  As the organic anion modifier, branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, etc. Sulfates, sulfonates, carboxylates, or phosphates having A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least part of the layered inorganic mineral with organic ions, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, and the toner is deformed Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with an organic cation include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. The following general formula (1) is, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
General formula (1)
R1 (OR2) nOSO ₃ M
[Wherein R 1 represents an alkyl group having 13 carbon atoms, and R 2 represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]

(Coloring agent)
As the colorant used in the toner of the present invention, known pigments and dyes capable of obtaining toners of yellow, magenta, cyan and black colors can be used.
Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG and Tartrazine Lake. Can be mentioned.
Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.
Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B.
Examples of purple pigments include fast violet B and methyl violet lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC.
Examples of the green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
These can use 1 type (s) or 2 or more types.

(Release agent)
As the release agent used for the toner in the present invention, all known ones can be used, and in particular, the free fatty acid type carnauba wax, polyethylene wax, montan wax and oxidized rice wax can be used alone or in combination. . The carnauba wax is preferably a microcrystalline one, having an acid value of 5 or less and a particle size of 1 μm or less when dispersed in a toner binder. The montan wax generally refers to a montan wax refined from minerals, and like a carnauba wax, it is microcrystalline and preferably has an acid value of 5 to 14. The oxidized rice wax is obtained by air-oxidizing rice bran wax, and the acid value is preferably 10-30. The reason is that these waxes are finely dispersed in the toner binder resin of the present invention, so that it is easy to obtain a toner excellent in offset prevention, transferability and durability as described later. These waxes can be used alone or in combination of two or more.

As other mold release agents, any conventionally known mold release agents such as solid silicone wax, higher fatty acid higher alcohol, montan ester wax, polyethylene wax and polypropylene wax can be mixed and used.
The Tg of the release agent used in the toner of the present invention is preferably 70 to 90 ° C. If it is less than 70 ° C., the heat-resistant storage stability of the toner is deteriorated, and if it exceeds 90 ° C., the releasability at a low temperature is not expressed, the cold offset resistance is deteriorated, and the paper is wound around the fixing machine. The amount of these release agents used is 1 to 20% by mass, preferably 3 to 10% by mass, based on the toner resin component. If it is less than 1% by mass, the effect of preventing offset is insufficient, and if it exceeds 20% by mass, transferability and durability are deteriorated.

(Developer)
The developer contains at least the toner of the present invention, and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

(Career)
There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.

  The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (weight average particle diameter (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

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

The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the silicone resin or the like in an organic solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core by a known coating method, drying, and baking. Can be formed. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.

The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.
The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, for example, 90 to 98 mass. % Is preferable, and 93 to 97% by mass is more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

The toner for image formation of the present invention can be used by being housed in a process cartridge having at least the electrostatic latent image carrier and a developing unit and detachable from the main body of the image forming apparatus.
FIG. 1 shows a schematic configuration of an image forming apparatus provided with a process cartridge having the image forming toner of the present invention.
In the figure, reference numeral 1 denotes the entire process cartridge, 2 denotes a photosensitive member, 3 denotes charging means, 4 denotes developing means, and 5 denotes cleaning means.
In the present invention, a plurality of components such as the photosensitive member 2, the charging unit 3, the developing unit 4, and the cleaning unit 5 described above are integrally coupled as a process cartridge, and this process is performed. The cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

The operation of the image forming apparatus provided with the process cartridge having the image forming toner of the present invention will be described as follows.
The photoreceptor 2 is driven to rotate at a predetermined peripheral speed. In the rotating process, the photosensitive member 2 is uniformly charged with a positive or negative predetermined potential on the peripheral surface thereof by the charging unit 3, and then an image from the image exposure unit such as slit exposure or laser beam scanning exposure. In response to the exposure light, an electrostatic latent image is sequentially formed on the circumferential surface of the photoreceptor, and the formed electrostatic latent image is then toner developed by the developing means 4, and the developed toner image is fed. The transfer unit sequentially transfers the image to the transfer material fed in synchronization with the rotation of the photoconductor between the photoconductor and the transfer unit. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing the transfer residual toner by a cleaning means, and after being further neutralized, it is repeatedly used for image formation.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, “parts” indicates parts by mass.

Production Example A (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stir bar and thermometer, 680 parts of water, 139 parts of styrene, 99 parts of methacrylic acid, 49 parts of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminor JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 15 minutes, 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 a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and then an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid monobutyl methacrylate-alkylallylsulfosuccinate sodium salt) [fine particle dispersion W1] was obtained. The volume average particle diameter of [fine particle dispersion W1] measured by ELS-800 was 0.09 μm. A part of [fine particle dispersion W1] was dried to isolate the resin component, and the glass transition temperature measured by a flow tester was 76 ° C.

Production Examples 1 to 13 (Production of resin (b1))
In an autoclave reaction vessel equipped with a thermometer, a stirring frame, and a nitrogen insertion tube, the raw materials shown in the polyester diol (b11) in Table 1 and 2 parts of 2-ethylhexylate were placed, and 160 ° C. for 3 hours at normal pressure. Ring-opening polymerization was conducted, and the reaction was further carried out at 130 ° C. at normal pressure. The taken-out resin was cooled to room temperature, and then pulverized into polyester diols (b11) -1 to 13 containing a polyhydroxycarboxylic acid skeleton. Polyester diols (b12) -1 to 13 obtained by dehydrating and condensing raw materials shown in the polyester diol (b12) in Table 1 and polyester diols (b11) -1 to 13 obtained previously in methyl ethyl ketone. It melt | dissolved, followed by adding IPDI as an extending | stretching agent, extending | stretching reaction was performed at 50 degreeC for 6 hours, the solvent was distilled off, and the [polyester b1-1-13] of manufacture examples 1-13 was obtained.

-Preparation of aqueous medium-
An aqueous medium phase was prepared by mixing and stirring uniformly 300 parts by mass of ion-exchanged water, 300 parts by mass of [fine particle dispersion W1], and 0.2 parts by mass of sodium dodecylbenzenesulfonate.

-Synthesis of polyester prepolymer-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 680 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 80 parts by mass of bisphenol A propylene oxide 2 mol adduct, 282 parts by mass of terephthalic acid, anhydrous 22 parts by mass of trimellitic acid and 2 parts by mass of dibutyltin oxide were added, reacted at 230 ° C. for 7 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 to 15 mmHg to synthesize intermediate polyester resin 2. The obtained intermediate polyester resin 2 has a number average molecular weight (Mn) of 2,300, a weight average molecular weight (Mw) of 9,900, a peak molecular weight of 3,100, a glass transition temperature (Tg) of 55 ° C., an acid The value was 0.4 mgKOH / g, and the hydroxyl value was 51 mgKOH / g.
Next, 395 parts by mass of the intermediate polyester resin 2, 91 parts by mass of isophorone diisocyanate, and 550 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. [Polyester prepolymer] was synthesized by reacting for a period of time. The obtained polyester prepolymer had a free isocyanate content of 1.47% by mass.

-Preparation of master batch-
1,000 parts by mass of water, 530 parts by mass of carbon black (Printex 35, manufactured by Degussa) having a DBP oil absorption of 42 ml / 100 g and a pH of 9.5, and 1200 parts by mass of resin were added to a Henschel mixer (Mitsui Mining Co., Ltd.). And mixed). The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

-Synthesis of ketimine compounds-
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The obtained ketimine compound had an amine value of 423 mgKOH / g.

Examples 1-9, Comparative Examples 1-4
-Preparation of toners 1-13-
[Polyester b1-1 to 13], [Polyester prepolymer], and 80 parts by mass of ethyl acetate were added to the reaction vessel in the number of parts shown in Table 2 and stirred to prepare resin solutions 1 to 13.

Next, 5 parts by mass of carnauba wax (molecular weight 1,700, acid value 2.8 mgKOH / g, penetration 1.6 mm (40 ° C.)) and 5 parts by mass of the master batch were charged into the resin solutions 1 to 13, Using a bead mill, Ultra Visco Mill (manufactured by Imex), three passes were performed under conditions where the liquid feed speed was 1 kg / hour, the disk peripheral speed was 6 m / second, and 80% by volume of 0.5 mm zirconia beads were filled. Further, 2.5 parts by mass of a ketimine compound was added and dissolved to obtain a toner material liquid.
Next, 150 parts by mass of an aqueous medium is put in the container, and 100 parts by mass of the toner material liquid is added while stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Emulsified slurry was obtained by mixing for a minute. Furthermore, 100 parts by mass of the emulsified slurry was charged into a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.

  Next, 100 parts by mass of the dispersed slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed at 12,000 rpm for 10 minutes using a TK homomixer, followed by filtration. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, it mixed for 10 minutes at 12,000 rpm using the TK type | mold homomixer, and it filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake. Using the circulating dryer, the obtained filter cake was dried at 45 ° C. for 48 hours, and sieved with a mesh having an opening of 75 μm to prepare toner base particles 1-13.

-Preparation of toner-
100 parts by mass of the obtained toner base particles 1 to 13 and 1.0 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were used using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Then, the mixture was mixed for 30 seconds at a peripheral speed of 30 m / second and rested for 1 minute for 5 cycles, and then sieved with a mesh having an opening of 35 μm to prepare toners 1 to 13.

-Production of carrier-
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (organostraight silicone), 5 parts by mass of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black are added and dispersed for 20 minutes with a homomixer. To prepare a resin layer coating solution. Using a fluidized bed type coating apparatus, the resin layer coating solution was applied to the surface of 1,000 parts by mass of spherical magnetite having a volume average particle size of 50 μm to prepare a carrier.

-Production of developer-
Each developer of Examples 1 to 9 and Comparative Examples 1 to 4 was prepared by mixing 5 parts by mass of each of the toners 1 to 13 and 95 parts by mass of the carrier.

  Next, the fixability, the heat resistant storage stability, and the haze degree were evaluated using the obtained developers as follows. The results are shown in Table 3.

In addition, 3 parts of a layered inorganic mineral montmorillonite (manufactured by Kraton APA Southern Clay Products) at least partially modified with a quaternary ammonium salt having a benzyl group was added to the resin solutions 1 and 2 in Production Examples 1 and 2. T. T. et al. K. [Polyester b1-14-15] of Production Examples 14 and 15 was obtained in the same manner as in Production Examples 1 and 2, except that the mixture was stirred for 30 minutes using a homodisper (made by Koki Kogyo Co., Ltd.). Toners 14 and 15 were obtained in the same manner as in Examples 1 and 2, using polyesters b1-14 and b1-15.
The evaluation results of this toner are shown in Table 3 as Examples 10 and 11.

<Fixability>
As a fixing roller, an electrophotographic copying machine using a Teflon (registered trademark) roller (MF-200, manufactured by Ricoh Co., Ltd.) is used to change the temperature of the fixing belt, by changing the fixing unit. A solid image having a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was formed on a paper and cardboard transfer paper type 6200 (manufactured by Ricoh Co., Ltd.) and copy printing paper <135> (manufactured by NBS Ricoh Co., Ltd.). . At this time, the upper limit temperature at which hot offset does not occur on plain paper was taken as the fixing upper limit temperature. Further, the lower limit temperature at which the residual ratio of the image density after rubbing the solid image with a pad was 70% or more was defined as the minimum fixing temperature.
[Evaluation criteria for maximum fixing temperature]
A: Fixing upper limit temperature is 190 ° C. or higher B: Fixing upper limit temperature is 180 ° C. or higher and lower than 190 ° C. C: Fixing upper limit temperature is 170 ° C. or higher and lower than 180 ° C. D: Fixing upper limit temperature is lower than 170 ° C.
A: The lower limit fixing temperature is less than 135 ° C. B: The lower limit fixing temperature is 135 ° C. or more and less than 145 ° C.

<Heat resistant storage stability (Penetration)>
A 50 ml glass container is filled with toner, left in a thermostatic bath at 50 ° C. for 24 hours, then cooled to 24 ° C., and the penetration (mm) is measured by a penetration test (JIS K2235-1991). The heat resistant storage stability was evaluated according to the following criteria. In addition, the greater the penetration, the better the heat-resistant storage stability. If the penetration is less than 5 mm, there is a high possibility that a problem will occur in use.
〔Evaluation criteria〕
A: Needle penetration is 25 mm or more B: Needle penetration is 15 mm or more and less than 25 mm C: Needle penetration is 5 mm or more and less than 15 mm D: Needle penetration is less than 5 mm

<Haze degree>
As a fixing color evaluation image sample, a single color image sample was developed on an OHP sheet type PPC-DX (manufactured by Ricoh Co., Ltd.) with a fixing belt temperature of 160 ° C., and a direct reading haze degree computer (HGM) -2DP type, manufactured by Suga Test Instruments Co., Ltd.). The haze degree is also referred to as haze and is measured as a measure of the transparency of the toner. The lower this value, the higher the transparency and the better the color developability when an OHP sheet is used.
〔Evaluation criteria〕
A: Haze degree is less than 20% B: Haze degree is 20% or more and less than 30% C: Haze degree is 30% or more

  The toners using the polyester diol containing the polyhydroxycarboxylic acid skeleton and the diol not containing it in an appropriate ratio range all showed excellent fixing properties, heat-resistant storage stability, and haze (Examples 1 to 9). When the optical purity is high (Examples 7 to 9), the fixing minimum temperature is slightly high. However, when the ratio of the polyester diol and the prepolymer are used within an appropriate range, no major problem occurs. When a diol having a polyhydroxycarboxylic acid skeleton is not used (Comparative Example 1), or when a diol having a polyhydroxycarboxylic acid skeleton is used, the ratio with other components is not appropriate (Comparative Examples 2 to 4) However, the low-temperature fixability deteriorated, and a good image could not be formed.

  The toner for image formation of the present invention is excellent in both thermal properties (particularly low-temperature fixability) and heat-resistant storage stability, and can be produced at low cost because it is a toner that can be obtained by dispersion in water. Therefore, it can be suitably used as a toner used for electrophotographic image formation such as copying machines, electrostatic printing, printers, facsimiles, and electrostatic recording.

It is the schematic which shows the structure of a process cartridge.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Process cartridge 2 Photoconductor 3 Charging means 4 Developing means 5 Cleaning means

Claims (13)

The resin particles (A) containing the first resin (a) or the coating (P) containing the resin (a) are attached to the surface of the resin particles (B) containing the second resin (b). A toner comprising resin particles (C) having a structure, wherein the resin (b) comprises a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than (b11) A linear polyester resin (b1) obtained by reacting together with the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than (b11). 31:69 to 90:10, and the monomer that forms the polyhydroxycarboxylic acid skeleton of (b11) is an optically active monomer, and the resin (b) Content Y (mass%) of the resin (b1) and optical purity X (mol%) in terms of monomer component = | X (L form) −X (D form) | [where X (L form) is optical The relationship of L isomer ratio (mol%) in terms of active monomer and X (D isomer represents D isomer ratio (mol%) in terms of optically active monomer)] is Y ≦ −1.5X + 220 (80 <X ≦ 100 A toner characterized by satisfying   The toner according to claim 1, wherein the resin (a) is at least one resin selected from a vinyl resin, a polyester resin, a polyurethane resin, and an epoxy resin. The toner according to claim 1 or 2 , wherein the polyhydroxycarboxylic acid skeleton of (b11) is a skeleton obtained by (co) polymerizing a hydroxycarboxylic acid having 3 to 5 carbon atoms. The toner according to any one of claims 1 to 3, wherein the polyhydroxycarboxylic acid skeleton is (co) polymer obtained by combined direct dehydration condensation of a hydroxycarboxylic acid. The monomer that forms the polyhydroxycarboxylic acid skeleton of (b11) is an optically active monomer, and optical purity X (%) = | X (L form) −X (D form) | [where X ( L-form) is an L-form ratio (mol%) in terms of optically active monomer, and X (D-form is a D-form ratio (mol%) in terms of optically active monomer)] is 80% or less. the toner according to any one of claims 1 to 4. The toner according to any one of claims 1 to 5, characterized in that the toner contains a charge control agent. The toner according to claim 6 , wherein the charge control agent is a fluorine-containing quaternary ammonium salt. The toner according to any one of claims 1 to 7, characterized in that said toner contains a colorant. The toner according to claim 1-8, wherein the toner contains a release agent. The toner according to any one of claims 1 to 9, wherein the toner is characterized by having a layered inorganic mineral at least part of the interlayer ions modified with organic ions layered inorganic mineral has a toner composition. An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the static Developing means for developing an electrostatic latent image with toner to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; and at least having an image forming apparatus, the toner, the image forming apparatus, characterized in that the image forming toner according to any one of claims 1-10. A charging process for charging the surface of the electrostatic latent image carrier, an exposure process for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and developing the electrostatic latent image using toner. An image forming method including at least a developing step for forming a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. an image forming method, wherein the toner is the image forming toner according to any one of claims 1-10. The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A process cartridge that is detachable, wherein the toner is the image forming toner according to any one of claims 1 to 10 .

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