JP2010235948A - Dispersion liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersion liquid having excellent affinity with a silicone oil, giving steric stabilization action to dispersed particles and having enhanced dispersibility to the silicone oil. <P>SOLUTION: In the dispersion liquid including a particle component insoluble in at least the silicone oil and a polymer formed by polymerizing a (meth)acrylate monomer having a dimethyl siloxane unit having recurring units of a natural number in the silicone oil, the polymer is formed by further including and polymerizing a (meth)acrylate monomer having a polyalkylene ether unit having recurring units of a natural number equal to or smaller than 25. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dispersed dispersion, and specifically includes treatment agents for fibers, paper, plastic surfaces, metal surfaces, and the like, mold release agents using them, printing inks, inkjet inks, adhesives, dry toners, and wet toners. The present invention relates to a dispersion useful for toner for electrophotography, paint, electrodeposition paint, display, magnetic fluid, rubber roller coating material, cosmetics and the like.

  In a dispersion liquid in which particles of resin, pigment, magnetic substance and the like are dispersed in an appropriate solvent, the stability of the dispersed particles is an important problem in both non-aqueous solvent systems and aqueous solvent systems.

  It is known that the stability of such dispersed particles is generally obtained by the action of electrostatic effect or steric effect (also called adsorption layer effect).

  The DLVO theory has been established for the electrostatic effect. In this theory, the spread of the electric double layer and the interface potential (so-called ζ potential) are important factors. Therefore, the presence of ions that form these is required, and several studies have been made on aqueous solvent systems in which the presence of ions is clear.

  On the other hand, the steric effect that corresponds to the DLVO theory has not yet been established, but the following studies are known for non-aqueous solvent systems (mainly petroleum solvents).

  That is, the research described in Non-Patent Document 1 relates to a basic method for producing a stable non-aqueous solvent dispersion, and this method is compatible with particles dispersed in a solvent (insoluble in a solvent) in the solvent. A block or graft copolymer containing a certain component and a component dissolved in the solvent is produced.

  As a method using this method, Patent Document 1 describes a method of radically polymerizing methyl methacrylate (MMA) in a hydrocarbon solvent in the presence of degradable rubber to obtain a stable polymethyl methacrylate (PMMA) dispersion. ing. It is unlikely that the degraded rubber is adsorbed on the PMMA particles by this method, and it is considered that MMA is graft-polymerized on the degraded rubber from the fact that the PMMA particles are dispersed and stabilized. This graft polymer is considered to have an insoluble part associated with the particle surface, and the dissolved part has a steric effect, and as a result, maintains the dispersion stability of the particle.

  Regarding the above, Patent Document 2, Patent Document 3, and the like can be cited as disclosures of aqueous solvent dispersion techniques.

  Further, Patent Literature 4, Patent Literature 5, and the like can be cited as disclosures of non-aqueous solvent dispersion techniques.

  In addition, unlike conventional non-aqueous solvents, it is disclosed that the dispersion technology in silicone oil has various characteristics such as excellent heat resistance, cold resistance, and chemically inert. 6, Patent Document 7 and the like.

  However, conventionally, it has not been known to disperse solid particles sufficiently in a non-aqueous solvent dispersion such as a petroleum solvent, that is, a nonpolar aprotic solvent, by charging them clearly with ions, For this reason, the life of the electrodeposition paint, electrophotographic liquid developer or dispersion for display is particularly limited.

  In recent years, hydrocarbon solvents with a certain degree of viscosity have been used for dispersions from the viewpoint of easy handling, low volatility, and odorlessness. The liquid developer or the dispersion for display is disadvantageous in terms of fluid resistance, and has limited application in both dispersion stability and electrophoretic characteristics. Therefore, a technique for dispersing and stabilizing solid particles by ion charging is required even in a nonpolar solvent having viscosity.

  In addition, silicone oil solvents, unlike nonpolar aprotic solvents represented by conventional petroleum solvents, do not dissolve or disperse polymers stably. That is, it is very difficult to stabilize a dispersion using silicone oil, and it is difficult to produce a dispersion that is stable for a long period of time.

  The present invention has been made in view of the above problems, and provides a hydrocarbon solvent dispersion having excellent affinity with a hydrocarbon solvent, providing steric stability to the dispersed particles, and excellent dispersion stability. The first purpose is to provide it.

  The second object of the present invention is to provide a dispersion having excellent affinity with silicone oil, providing a steric stabilizing action to the dispersed particles, and improving the degree of dispersion in silicone oil. .

  The dispersion of the reference invention for explaining the present invention is at least a particle component insoluble in the hydrocarbon solvent and is compatible with the hydrocarbon solvent, and is at least represented by the following general formula (I). Monomer

［式中、Ｒ_１は水素原子またはメチル基、Ｒ_２は水素原子または炭素数１〜４のアルキル基、ｘは１〜３の整数、ｙは２５以下の自然数を表す。］を重合した重合体とを含有することを特徴とする。

[Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, x represents an integer of 1 to 3, and y represents a natural number of 25 or less. And a polymer obtained by polymerizing].

  Thereby, it is possible to provide a hydrocarbon solvent-based dispersion having excellent affinity with a hydrocarbon solvent, imparting a steric stabilizing action to the dispersed particles, and excellent dispersion stability.

  The dispersion of the reference invention for explaining the present invention is a polymer in which the polymer further contains at least one of a monomer having an acidic group and a monomer having a basic group. It is characterized by that.

  Thereby, it is possible to provide a hydrocarbon solvent-based dispersion system in which the interaction between the dispersed particles and the polymer is strong and the affinity with the hydrocarbon solvent is excellent.

  The dispersion of the reference invention for explaining the present invention is characterized in that the particle component has at least one of a basic group and an acidic group on at least the surface.

  As a result, it is possible to provide a hydrocarbon solvent dispersion that imparts electric charges to the dispersed particles, improves dispersibility by electrostatic repulsion, and is capable of electrophoresis.

  As a result, it is possible to provide a hydrocarbon solvent-based dispersion liquid that is more stable and excellent in electrophoretic characteristics due to a synergistic effect of steric stabilization action and stabilization action by electrostatic repulsion.

  The dispersion of the reference invention for explaining the present invention contains at least a hydrocarbon solvent having a viscosity of 10 mPa · s or more at room temperature, a particle component insoluble in the solvent, and a resin soluble in the solvent. It is characterized by.

  Thereby, the dispersion system excellent in affinity with a hydrocarbon solvent can be provided.

  Thereby, the dispersion liquid with a good dispersibility with respect to a hydrocarbon solvent can be provided.

  The dispersion of the reference invention for explaining the present invention is characterized in that at least the surface of the particle component has an acidic group or a basic group.

  Accordingly, it is possible to provide a dispersion liquid that imparts electric charges to the dispersed particles, improves dispersibility by electrostatic repulsion, and enables electrophoresis.

  In addition, the dispersion of the reference invention for explaining the present invention is characterized in that at least one of the resin and the particle component has a nonionic polar group.

  As a result, it is possible to provide a dispersion liquid having better dispersion stability and further excellent charge amount of particles.

  The dispersion of the present invention is characterized in that the silicone oil contains at least a particle component insoluble in the silicone oil and a polymer obtained by polymerizing at least the monomer represented by the following general formula (II).

［式中、Ｒは水素原子またはメチル基を表し、ｎは自然数を表す。］
これにより、シリコーンオイルとの親和性に優れた分散系を提供することができる。

[Wherein, R represents a hydrogen atom or a methyl group, and n represents a natural number. ]
Thereby, the dispersion system excellent in affinity with silicone oil can be provided.

  And the dispersion liquid of this invention is a monomer in which the polymer is represented by the following general formula (III):

［式中、Ｒ_１は水素原子またはメチル基、Ｒ_２は水素原子または炭素数１〜４のアルキル基、ｘは１〜３の整数、ｙは２５以下の自然数を表す。］
をさらに含んで重合したものであることを特徴とする。

[Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, x represents an integer of 1 to 3, and y represents a natural number of 25 or less. ]
It is characterized by being further polymerized.

  As a result, it is possible to provide a dispersion-stable silicone oil dispersion that is excellent in affinity with silicone oil and imparts a steric stabilizing action to the dispersed particles.

  The dispersion of the present invention is characterized by containing a copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group or a basic group.

  As a result, it is possible to provide a dispersion system that has a strong interaction with the dispersed particles and an excellent affinity with silicone oil.

  In addition, the dispersion of the present invention comprises a copolymer of a monomer represented by the general formula (II) and a monomer having an acidic group, and a monomer represented by the general formula (II) and a basic property. It contains a copolymer with a monomer having a group.

  As a result, it is possible to provide a dispersion liquid that imparts an electric charge to the dispersed particles, improves dispersibility by electrostatic repulsive force, and enables electrophoresis.

  The dispersion of the present invention is a copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group or the monomer represented by the general formula (II) and a basic compound. A copolymer with a monomer having a group is insoluble in the silicone oil.

  As a result, it is possible to provide a dispersion liquid that is more stable and excellent in electrophoretic properties due to the synergistic effect of the steric stabilization action and the stabilization action due to electrostatic repulsion.

  In addition, the dispersion of the present invention comprises a copolymer of a monomer represented by the general formula (II) and a monomer having an acidic group, and a monomer represented by the general formula (II) and a basic property. It is characterized in that at least one of the copolymer with a monomer having a group is a copolymer with a monomer having a polar group.

  Thereby, it is possible to provide a dispersion in which the charge amount related to the charging of the particles is improved.

  In the dispersion of the present invention, the particle component can have at least a basic group or an acidic group on the surface.

  As a result, it is possible to provide a dispersion liquid that imparts an electric charge to the dispersed particles, improves dispersibility by electrostatic repulsive force, and enables electrophoresis.

  In the dispersion of the present invention, at least one of the particle component and at least one of the polymers can have a nonionic polar group.

  As a result, it is possible to provide a dispersion liquid that is more stable and excellent in electrophoretic properties due to the synergistic effect of the steric stabilization action and the stabilization action due to electrostatic repulsion.

  In the dispersion of the present invention, the silicone oil has a viscosity of 200 cSt (centistokes) or less.

  Thereby, a silicone oil dispersion having excellent storage characteristics can be provided.

  The dispersion of the present invention is characterized in that the content of the particle component is 0.1 to 20% by mass.

  Thereby, it is possible to provide a silicone oil dispersion having a low price and excellent storage characteristics.

  Conventionally, the presence of ions or charges has been unclear in non-aqueous solvents, particularly nonpolar aprotic solvent dispersions. This is presumably because interaction (solvation) between ions and solvent molecules hardly occurs in this type of solvent.

  Therefore, the present inventors have (1) an organic substance having an acidic group but not having a basic group, (2) an organic substance having a basic group but having no acidic group, and (3) a phase compatible with the solvent. Contains three components of organic substances that are soluble and have non-ionic polar components [any of components (1) and (2) may be present as a copolymer with component (3)] As a result of various experiments on the hydrocarbon solvent dispersion, it was found that the components (1) and (2) cause acid-base ion dissociation in the solvent. It was also suggested that ion-dipole interaction, or solvation, exists. Thus, the present inventors, when the three components (1), (2), (3) are present in the solvent, cause ion-dissociation between the acid and the base via the solvation of the polar group in the component (3). It was found that ions can exist stably even in a hydrocarbon solvent. This fact was similarly observed whether both (1) and (2) components were soluble or insoluble in the solvent.

  In addition, when the present inventors coexist with fixed particles such as pigments and metal oxides in a system containing the three components (1), (2) and (3), the components (1) or (2) It was found that an acid group or a basic group was fixed by chemical bonding, adsorption, or the like, and ionic dissociation occurred at the interface between the solid particle surface and the solvent via the solvation of component (3).

  Moreover, the dispersion stability of the particle | grains considered to be based on the steric effect of a polyoxyalkylene group was confirmed. As a result, the solid particles are uniformly charged to a positive or negative polarity, and the solid particles are more stably dispersed than before due to the synergistic effect of this electrostatic effect and further the steric effect.

  Furthermore, the present inventors have found that the amount of ions and the amount of charge can be controlled by the type and amount of each component (1), (2), (3). The present invention is based on the above findings.

  According to the dispersion liquid of the present invention, at least the particle component insoluble in the hydrocarbon solvent and the monomer represented by the general formula (I) are compatible with the hydrocarbon solvent. It is possible to provide a hydrocarbon solvent dispersion having excellent affinity with a hydrocarbon solvent, providing a steric stabilizing action to the dispersed particles, and excellent dispersion stability. it can.

  Further, according to the dispersion of the invention of the present reference, the polymer is a polymer further containing at least one of a monomer having an acidic group and a monomer having a basic group, A hydrocarbon solvent-based dispersion system in which the interaction between the dispersed particles and the polymer is strong and the affinity with the hydrocarbon solvent is excellent can be provided.

  Further, according to the dispersion liquid of the present invention, the particle component has at least one of a basic group and an acidic group on the surface, thereby imparting electric charge to the dispersed particles and electrostatic repulsion. It is possible to provide a hydrocarbon solvent-based dispersion capable of improving the dispersibility by force and allowing electrophoresis.

  Further, according to the dispersion of the present invention, at least one of the particle component and the polymer has a nonionic polar group, so that the dispersed particles are stabilized by steric stabilizing action and electrostatic repulsion. It is possible to provide a hydrocarbon solvent dispersion that is more stable and has excellent electrophoretic properties due to a synergistic effect of action.

  In addition, according to the dispersion of the invention of the present reference, by containing a hydrocarbon solvent having a viscosity of at least 10 mPa · s at room temperature, a particle component insoluble in the solvent, and a resin soluble in the solvent, A dispersion system excellent in affinity with a hydrocarbon solvent can be provided.

  Moreover, according to the dispersion liquid of this reference invention, since the resin has any one of an acidic group and a basic group, a dispersion liquid having good dispersibility in a hydrocarbon solvent can be provided.

  Further, according to the dispersion liquid of the present invention, the particle component has any one of an acidic group and a basic group, thereby imparting electric charge to the dispersed particles and improving dispersibility by electrostatic repulsion. And a dispersion capable of electrophoresis can be provided.

  Further, according to the dispersion of the invention of the present reference, since any one of the resin and the particle component has a nonionic polar group, the dispersion stability is further improved, and the charge amount of the particles is further increased. Can provide an excellent dispersion.

  According to the dispersion of the present invention, the silicone oil contains at least a particle component insoluble in the silicone oil and a polymer obtained by polymerizing at least the monomer represented by the general formula (II). Dispersion-stable silicone oil dispersion with excellent compatibility with silicone oil and steric stabilization effect on dispersed particles by further polymerization of monomer represented by general formula (III) A liquid can be provided.

  In addition, according to the dispersion of the present invention, by containing a copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group or a basic group, interaction with the dispersed particles is achieved. In addition, it is possible to provide a dispersion system that is strong and has excellent affinity with silicone oil.

  The dispersion of the present invention comprises a copolymer of a monomer represented by the general formula (II) and a monomer having an acidic group, and a monomer represented by the general formula (II) and a basic group. It contains a copolymer with the monomer it has.

  As a result, it is possible to provide a dispersion liquid that imparts an electric charge to the dispersed particles, improves dispersibility by electrostatic repulsive force, and enables electrophoresis.

  Further, according to the dispersion of the present invention, the copolymer of the monomer represented by the general formula (II) and the monomer having an acidic group, and the monomer represented by the general formula (II) and the basic Since any one of the copolymers with a monomer having a group is insoluble in silicone oil, the dispersed particles are more stable and electrophoretic characteristics due to a synergistic effect of steric stabilization action and stabilization action by electrostatic repulsion. An excellent dispersion can be provided.

  Further, according to the dispersion of the present invention, the copolymer of the monomer represented by the general formula (II) and the monomer having an acidic group, and the monomer represented by the general formula (II) and the basic Provided is a dispersion in which at least one of the copolymer with a monomer having a group is a copolymer with a monomer having a polar group, thereby improving the charge amount related to charging of particles. be able to.

  Further, according to the dispersion of the present invention, the particle component has at least a basic group or an acidic group on the surface, thereby imparting electric charge to the dispersed particles, improving dispersibility by electrostatic repulsion, and A dispersion capable of electrophoresis can be provided.

  In addition, according to the dispersion of the present invention, since at least one of the particle component and the polymer has a nonionic polar group, the dispersed particles have a synergistic effect between the steric stabilizing action and the stabilizing action by electrostatic repulsion. Thus, it is possible to provide a dispersion that is more stable and excellent in electrophoretic properties.

  Moreover, according to the dispersion liquid of this invention, when the viscosity of a silicone oil is 200 cSt or less, the silicone oil dispersion liquid excellent in the storage characteristic can be provided.

  Moreover, according to the dispersion liquid of this invention, the content of a particle component is 0.1-20 mass%, and can provide the silicone oil dispersion liquid which was cheap and excellent in the storage characteristic.

  Hereinafter, reference examples of the invention for explaining the present invention and first to fourth dispersions according to embodiments of the present invention will be described in order.

(First dispersion)
The first dispersion as a reference invention for explaining the present invention relates to a dispersion in a hydrocarbon solvent system.

  In the dispersion of the invention of this reference, by containing a monomer compatible with a hydrocarbon solvent and a polymer obtained by polymerizing the monomer represented by the general formula (I) as a constituent requirement, carbonization is performed. Dispersion stability of the dispersed particles increases due to excellent affinity with a hydrogen solvent and the steric effect of the (poly) oxyalkylene group.

  Further, in the dispersion of the invention of this reference, a monomer having compatibility with a hydrocarbon solvent, a monomer represented by the general formula (I), and a monomer having an acidic group were polymerized as constituents. By containing the polymer, the interaction between the polymer and the particles is increased, and a dispersion having excellent affinity with the hydrocarbon solvent is obtained.

  In addition, in the dispersion liquid of the invention of this reference, a monomer having compatibility with a hydrocarbon solvent, a monomer represented by the general formula (I), and a monomer having a basic group are included as constituent requirements. By containing the polymerized polymer, the interaction between the polymer and the particles by adsorption increases, and a dispersion having excellent affinity with the hydrocarbon solvent is obtained.

  In addition, in the dispersion of the invention of this reference, the particle component insoluble in the hydrocarbon solvent has a basic group on at least the surface, thereby imparting a positive charge to the dispersed particles by acid-base dissociation and electrostatic repulsion. Improves dispersibility and enables electrophoresis.

  Further, in the dispersion of the invention of the present reference, at least the particle component insoluble in the hydrocarbon solvent has a nonionic polar group other than the (poly) oxyalkylene group, so that a solvation effect on acid-base dissociation is expressed. It is possible to improve dispersibility due to electrostatic repulsion of dispersed particles and electrophoretic characteristics.

  In addition, in the dispersion of the invention of the present reference, at least a monomer compatible with a hydrocarbon solvent, a monomer represented by the general formula (I), and a monomer having an acidic group are included as constituent requirements. The polymerized polymer has a nonionic polar group other than the (poly) oxyalkylene group, thereby exhibiting a solvation effect on acid-base dissociation and improving dispersibility due to electrostatic repulsion of dispersed particles and electrophoretic characteristics. It becomes possible.

  Further, in the dispersion of the invention of this reference, the particle component insoluble in the hydrocarbon solvent, the monomer compatible with the hydrocarbon solvent, the monomer represented by the general formula (I), and the acid It is possible to further improve the charge amount related to the charging of the particles by having both non-polar polar groups other than the (poly) oxyalkylene group as the polymer obtained by polymerizing the monomer having a group as a constituent requirement. Become.

  In the dispersion of the invention of this reference, the particle component insoluble in the hydrocarbon solvent has an acidic group on at least the surface, thereby giving a negative charge to the dispersed particles by acid-base dissociation, and by electrostatic repulsion. Improves dispersibility and enables electrophoresis.

  Further, in the dispersion of the invention of the present reference, at least the particle component insoluble in the hydrocarbon solvent has a nonionic polar group other than the (poly) oxyalkylene group, so that a solvation effect on acid-base dissociation is expressed. It is possible to improve dispersibility due to electrostatic repulsion of dispersed particles and electrophoretic characteristics.

  Further, in the dispersion of the invention of this reference, at least a monomer compatible with a hydrocarbon solvent, a monomer represented by the general formula (I), and a monomer having a basic group are included as constituent requirements. As a polymer polymerized as a non-polar polar group other than (poly) oxyalkylene group, solvation effect on acid-base dissociation is exhibited, and dispersibility due to electrostatic repulsion of dispersed particles and electrophoretic characteristics are improved. It becomes possible to make it.

  In the dispersion of the present invention, the particle component insoluble in the hydrocarbon solvent, the monomer compatible with the hydrocarbon solvent, the monomer represented by the general formula (I), and the base The amount of charge related to the charging of particles can be further improved by having both non-polar polar groups other than (poly) oxyalkylene groups in both polymers polymerized with monomers having functional groups. It becomes.

  In the following, the configuration of the above-described reference invention will be described in more detail.

  Examples of the hydrocarbon solvent used as a dispersion medium in the present invention include paraffinic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, and dodecane, isoparaffinic hydrocarbons such as isohexane, isooctane, and isododecane, and fluid. Examples include alkyl naphthenic hydrocarbons such as paraffin, and aromatic hydrocarbons such as benzene, toluene, xylene, alkyl benzene, and solvent naphtha.

  The polymer in the invention of this reference has a monomer having high affinity with a hydrocarbon solvent, an acrylic monomer having a (poly) oxyalkylene group, and an acidic group or a basic group as necessary. A monomer or a monomer having a polar group is copolymerized. Hereinafter, the monomer polymerizable in the present invention will be further described.

  First, a monomer having a high affinity with a hydrocarbon solvent gives a polymer soluble in the hydrocarbon solvent when the polymer composed of such a monomer is a single polymer, and other monomers In the case of a copolymer with a body, even if it is soluble or insoluble, it has a high affinity with a hydrocarbon solvent and can provide a stable dispersion.

  Examples of such monomers include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, vinyl Laurate, lauryl methacrylamide, stearyl methacrylamide, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Examples include hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, styrene, vinyl toluene, and vinyl acetate.

  Next, the acrylic monomer having a (poly) oxyalkylene group is a monomer represented by the general formula (I), and has a polyethylene glycol chain having a repeating unit of oxyethylene group of 25 or less. The copolymer having the monomer as a constituent element is adsorbed to particles insoluble in a solvent, and the dispersion of the particles is stabilized by the steric effect expressed by the polyethylene glycol chain.

Next, examples of monomers that can be copolymerized with the above monomers include the following.
(A) Examples of monomers having an acidic group:
These monomers include at least one of vinyl group, —COOH group, —SO ₃ H group, —SO ₂ H group, —CH ₂ NO ₂ group, —CHRNO ₂ group, —ArOH group, —ArSH group and the like. (Wherein R is an alkyl group and Ar is an allyl group). Specifically, (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, cinnamic acid, crotonic acid, vinyl benzoic acid, 2-methacryloxyethyl succinic acid, 2-methacryloxy Ethyl maleic acid, 2-methacryloxyethyl hexahydrophthalic acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2-sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, 3-chloroamidophosphoxypropyl Methacrylate, 2-methacryloxyethyl acid phosphate and the like.
(B) Examples of monomers having a basic group:
These monomers include those having at least one of vinyl group, —NH ₂ group, —NHR group, —NRR ′ group, pyridyl group, piperidyl group and the like (where R and R ′ are alkyl groups). Group or allyl group). Specifically, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl acrylate, N-phenylaminoethyl methacrylate, N, N-diphenylaminoethyl methacrylate, aminostyrene, dimethylaminostyrene, N-methylaminoethylstyrene, dimethylaminoethoxystyrene, diphenylaminoethylstyrene, N-phenylaminoethyl styrene, 2-N-piperidylethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine and the like can be mentioned.
(C) Examples of monomers having a polar group:
2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-propyl methacrylate, 2-chloroethyl (meth) acrylate, 2,3- Dibromopropyl (meth) acrylate, (meth) acrylonitrile, isobutyl-2-cyanoacrylate, 2-cyanoethyl acrylate, ethyl-2-cyanoacrylate, methacrylacetone, vinylpyrrolidone, N-acryloylmorpholine, tetrahydrofurfuryl methacrylate, trifluoroethyl Examples include methacrylate, p-nitrostyrene, acrylamide, methacrylamide, N, N-dimethylmethacrylamide, N, N-dibutylmethacrylamide and the like.
(D) Examples of polyfunctional monomers:
Divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol tri (meth) acrylate, butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolhexane tri (meth) acrylate, bentaerythritol tetra (meth) acrylate 1,3-dibutylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, and the like.

  As a polymer used in one embodiment (A) of the present invention, a copolymer having a high affinity with a hydrocarbon solvent and a monomer represented by the general formula (I) Coalescence is mentioned.

  In addition, particle components insoluble in hydrocarbon solvents include various insoluble resins, generally known inorganic or organic pigments, metals, metal oxides, magnetic powders, waxy substances (for example, low molecular polyolefins, waxes), chemical products (For example, agricultural chemicals), swelling agents and the like.

  More specifically, for example, carbon black, lamp black, ultramarine blue, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, rake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, tri Any conventionally known dyes and pigments such as dyes and pigments such as allylmethane dyes can be used alone or in combination. Also, iron oxides such as magnetite, hematite, ferrite, metals such as iron, carbonyl iron powder, cobalt, nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium of these metals And alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof, glass beads, and the like. Examples of the resin particles include homopolymers of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and the like; and styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyl. Toluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene -Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether Copolymer, styrene-vinylethyl Ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Examples thereof include styrene copolymers such as copolymers.

  Moreover, the copolymer of the monomer with high affinity with a hydrocarbon solvent at least and the monomer of said (d) is mentioned. However, in this case, the ratio of using these monomers cannot be uniquely defined, and the intended insoluble resin is obtained by empirical use. However, the most reliable insoluble resin can be obtained by using a relatively large amount of the monomer (d).

  Furthermore, in the dispersion in the present invention, a dye soluble in a hydrocarbon solvent may be added to the dispersion depending on the intended use, or the dispersion or dispersoid may be colored by chemically bonding to the dispersoid. it can.

  Examples of the polymer used in another embodiment (B) of the present invention include a monomer having a high affinity with a hydrocarbon solvent, a monomer represented by the general formula (I), and the above ( And a copolymer with the monomer (a). Moreover, as a particle component insoluble in a hydrocarbon solvent, the particle component used in the said embodiment (A) of this invention is mentioned.

  Examples of the polymer used in still another embodiment (C) of the present invention include a monomer having a high affinity with a hydrocarbon solvent, a monomer represented by the general formula (I), And a copolymer with the monomer (b). Moreover, as a particle | grain component insoluble in a hydrocarbon solvent, the particle | grain component used in the said embodiment (A) is mentioned.

  Examples of the polymer used in still another embodiment (D) of the present invention include those used in the above embodiment (B). In addition, as the particle component insoluble in the hydrocarbon solvent, a resin insoluble in the hydrocarbon solvent solvent having the monomer (b) as a component as the binder of the insoluble particle component in the above embodiment (A). What was used is mentioned. In addition, when a substance that can be chemically bonded by grafting or the like, such as carbon black or a metal oxide, is used as the solid particle, the basic group is formed by reacting the substance (b) with these substances. It may be chemically bonded.

  Examples of the polymer used in yet another embodiment (E) of the present invention include the polymers used in the above embodiment (B). In addition, as the particle component insoluble in the hydrocarbon solvent, as the binder of the insoluble particle component in the above embodiment (A), the monomer (b) and the monomer (c) are used as components. What uses resin insoluble in the hydrocarbon solvent solvent which has is mentioned. In addition, when a substance that can be chemically bonded by grafting or the like, such as carbon black or metal oxide, is used as the solid particle, the monomer (b) and the monomer (c) By reacting, a basic group and a polar group may be chemically bonded.

  Examples of the polymer used in yet another embodiment (F) of the present invention include monomers compatible with hydrocarbon solvents, monomers represented by the general formula (I), ) And a copolymer with the monomer (c). Moreover, as a particle | grain component insoluble in a hydrocarbon solvent, the particle | grain component used in said Embodiment (D) is mentioned.

  Examples of the polymer used in yet another embodiment (G) of the present invention include the copolymers used in the above embodiment (F). Moreover, as a particle component insoluble in a hydrocarbon solvent, the particle component used in said embodiment (E) is mentioned.

  Examples of the polymer used in still another embodiment (H) of the present invention include those used in the above embodiment (C). In addition, as the particle component insoluble in the hydrocarbon solvent, a resin insoluble in the hydrocarbon solvent solvent having the monomer (a) as a component is used as the binder of the insoluble particle component in the embodiment (A). The ones that have been In addition, when a substance that can be chemically bonded by grafting or the like, such as carbon black or a metal oxide, is used as the solid particles, the basic group is formed by reacting the substance (a) with these substances. It may be chemically bonded.

  Examples of the polymer used in still another embodiment (I) of the present invention include those used in the above embodiment (C). In addition, as a particle component insoluble in the hydrocarbon solvent, as the binder for the insoluble particle component in the above embodiment (A), the monomer (a) and the monomer (c) are used as components. What uses resin insoluble in the hydrocarbon solvent solvent which has is mentioned. In addition, when a substance that can be chemically bonded by grafting or the like, such as carbon black or metal oxide, is used as the solid particle, the monomer (a) and the monomer (c) By reacting, an acidic group and a polar group may be chemically bonded.

  Examples of the polymer used in yet another embodiment (J) of the present invention include monomers compatible with hydrocarbon solvents, monomers represented by the general formula (I), ) And a copolymer with the monomer (c). Moreover, as a particle | grain component insoluble in a hydrocarbon solvent, the particle | grain component used in the said embodiment (H) is mentioned.

  Examples of the polymer used in still another embodiment (K) of the present reference invention include the copolymer used in the above embodiment (J). Examples of the particle component insoluble in the hydrocarbon solvent include the particle component used in the above embodiment (I).

  In order to make the dispersion of the present invention, taking the case of the above embodiment (A) as an example, the resin components and solid particles may be mixed and dispersed in a hydrocarbon solvent. In this case, a ball mill, a sand mill, an attritor or the like may be used as the dispersing means. The mixing order is not particularly limited.

  When the hydrocarbon solvent used as the dispersion solvent of the present invention is 1000 cSt (centistokes) or less, and preferably 200 cSt or less, excellent characteristics in dispersion stability are exhibited. Although the reason for this has not been clarified, it is considered that when the viscosity of the hydrocarbon solvent increases, the molecular weight of the oil also increases, and as a result, the solubility of the resin used in the present invention or the affinity between the resin and the oil decreases. Guessed.

  In the invention of this reference, the amount of the appropriate insoluble particle component used is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. In this range of use, a very stable dispersion can be obtained even for long-term storage.

(Second dispersion)
Further, the second dispersion as a reference invention for explaining the present invention relates to a hydrocarbon solvent-based dispersion as in the above-described invention.

  In the dispersion of the present invention, the hydrocarbon solvent contains at least a hydrocarbon solvent having a viscosity of 10 mPa · s or more at room temperature, a particle component insoluble in the solvent, and a resin soluble in the solvent. By adsorbing the soluble resin to the particles insoluble in the solvent, the steric effect of the particles is exhibited and dispersion stability is obtained.

  In addition, in the dispersion of the invention of this reference, the resin that is soluble in the hydrocarbon solvent has an acidic group but does not have a basic group. The charge polarity can be controlled, and dispersion stability is increased by electrostatic repulsion.

  In addition, in the dispersion of the invention of this reference, the resin that is soluble in the hydrocarbon solvent has a basic group but does not have an acidic group. The charge polarity can be controlled, and dispersion stability is increased by electrostatic repulsion.

  Further, in the dispersion of the present invention, the resin soluble in the hydrocarbon solvent further has a nonionic polar component, so that the amount of charge generation is increased due to solvation of acid or base, and further dispersion stability is improved. Increase.

  In addition, in the dispersion of the invention of this reference, the particles have acidic groups on the surface but no basic groups, so that the particles can be negatively controlled in charge polarity and dispersed by electrostatic repulsion. Increased stability.

  In addition, in the dispersion of the invention of this reference, the particles have a basic group on the surface but do not have an acidic group, so that the particles can be positively controlled in charge polarity and dispersed by electrostatic repulsion. Increased stability.

  In addition, in the dispersion of the invention of this reference, since the particles further have a nonionic polar component on the surface, the amount of charge generation is increased by the solvation of acid or base, and the dispersion stability is further increased.

  In addition, in the dispersion of the invention of this reference, the particles have acidic groups on the surface but no basic groups, and the resin soluble in the hydrocarbon solvent has basic groups but no acidic groups. Alternatively, the particles have a basic group on the surface but no acidic group, and the resin soluble in the hydrocarbon solvent has an acidic group but no basic group. Dispersion with a long-term stability and fast responsive electrophoretic properties due to the generation of electric charge due to acid-base dissociation between the adsorbed resin and the synergistic effect of dispersion stability due to the steric effect of the adsorbed resin. Liquid can be provided.

  In the following, the configuration of the above-described reference invention will be described in more detail.

  In one embodiment (L) of the present invention, the dispersion comprises a solvent, solvent-insoluble particles, and a solvent-soluble resin.

  As the hydrocarbon solvent in the present embodiment (L), a known hydrocarbon solvent having a viscosity at room temperature of 10 mPa · s or higher, such as an alkyl naphthene hydrocarbon such as liquid paraffin, an isoparaffin hydrocarbon, a paraffin hydrocarbon, or the like is used. can do. In addition, when used in a dispersion for an image display medium such as an electrophoretic display, it is preferable to add a dye having a color different from that of a particle that is soluble in a hydrocarbon water solvent to the dispersion.

  Examples of the particles insoluble in the hydrocarbon solvent include solid particle pigments such as metal oxides as the simplest example. Further, it is also possible to use a resin that is insoluble in a hydrocarbon solvent, or a resin in which a coloring component is dispersed or mixed using the resin as a binder. As the binder resin, any known thermoplastic resin and thermosetting resin that are insoluble in the hydrocarbon solvent can be used, but in particular, non-adhesive materials can be preferably used. As a straightforward example of such a resin, styrene such as polyester resin, polystyrene, poly p-chlorostyrene, polyvinyltoluene, and a homopolymer of a substituted product thereof can be exemplified. Or the copolymer of the monomer with high affinity with the below-mentioned hydrocarbon solvent and the polyfunctional monomer which is a crosslinking agent can be used. Moreover, as a coloring component, all well-known things can be used. As the black colorant, for example, carbon black, aniline black, furnace black, lamp black and the like can be used. Examples of cyan colorants include phthalocyanine blue, methylene blue, Victoria blue, methyl violet, aniline blue, and ultramarine blue. As the magenta colorant, for example, rhodamine 6G lake, dimethylquinacridone, watching red, rose bengal, rhodamine B, alizarin lake and the like can be used. Examples of yellow colorants include chrome yellow, benzidine yellow, hansa yellow, naphthol yellow, molybdenum orange, quinoline yellow, and tartrazine. Any of these conventionally known dyes and pigments can be mixed and used. The amount that the colorant can be used is 0.1 to 300 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the binder resin.

  As the resin soluble in the hydrocarbon solvent, any of the known thermoplastic resins and thermosetting resins that are soluble in the hydrocarbon solvent can be used, but the attractive interaction with the particle surface rather than the hydrocarbon solvent. Strong ones are preferable, and the dispersion stability of the particles increases due to the steric effect of the resin adsorbed on the particles. Such resins include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, vinyl laurate, methyl Alkyl naphthenes such as (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, styrene, vinyltoluene Examples thereof include a copolymer containing as a component at least one monomer having high affinity with a hydrocarbon solvent such as hydrocarbon, isoparaffinic hydrocarbon, and paraffinic hydrocarbon.

  In order to make the dispersion of the invention of this reference, the above-mentioned components may be mixed and dispersed in a hydrocarbon solvent. In this case, a ball mill, a sand mill, an attritor or the like may be used as the dispersing means. The mixing order is not particularly limited.

  In another embodiment (M) of the present invention, although the dispersion has an acidic group as a resin soluble in the hydrocarbon solvent, it does not have a basic group or has a basic group. It has a resin that does not have acidic groups. When these resins are adsorbed on the particles in the hydrocarbon solvent, the particle surface is uniformly charged to a positive or negative polarity due to the acidic group or basic group of the solvent-soluble resin.

Specific examples of the resin soluble in the hydrocarbon solvent used in the present invention are as follows.
(A) As an example of a resin (polymer or copolymer containing a monomer having an acidic group as a constituent) which is soluble in a hydrocarbon solvent having an acidic group but not having a basic group, (meth) acrylic Acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, cinnamic acid, crotonic acid, vinyl benzoic acid, 2-methacryloxyethyl succinic acid, 2-methacryloxyethyl maleic acid, 2-methacryloxyethyl Hexahydrophthalic acid, 2-methacryloxyethyl trimellitic acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2-sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, 3-chloroamidophosphoxypropyl Methacrylate, 2-methacryloxyethyl acid phosphate, hydroxy styrene And at least one monomer having an acidic group emissions such as copolymers affinity with the hydrocarbon solvent is obtained from at least one high monomer are mentioned in the above embodiment (L).
(B) As an example of a resin having a basic group but soluble in a hydrocarbon solvent not having an acidic group (a polymer or copolymer having a monomer having a basic group as a constituent), N-methyl Aminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl acrylate, N -Phenylaminoethyl methacrylate, N, N-diphenylaminoethyl methacrylate, aminostyrene, dimethylaminostyrene, N-methylaminoethylstyrene, dimethylaminoethoxystyrene, diphenylaminoethylstyrene, N-phenylaminoethylstyrene, 2-N-piperidylethyl (meth) acrylate, 2-vinyl It is obtained from at least one monomer having a basic group such as pyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, and at least one monomer having high affinity with the hydrocarbon solvent. A copolymer is mentioned.

  In yet another embodiment (N) of the invention of this reference, the dispersion has (c) an acidic group but no basic group as a resin soluble in a hydrocarbon solvent, and is nonionic. A resin having a polar group, or (d) a resin having a basic group but no acidic group and having a nonionic polar group. When these resins are adsorbed on particles in a hydrocarbon solvent, the particle surface is uniformly charged to a positive or negative polarity due to the interaction between the acidic group or basic group of the solvent-soluble resin and the polar group. To do.

Specific examples of the resin used in the present invention are as follows.
(C) Resin having an acidic group but not a basic group and having a nonionic polar group (a copolymer having a monomer having an acidic group and a monomer having a nonionic polar group as constituents) As an example, at least one of the specific examples of the monomer having an acidic group in the above embodiment (M), 2-hydroxyethyl (meth) acrylate, and 2,3-dihydroxypropyl (meth) acrylate 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-propyl methacrylate, 2-chloroethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, (meth) acrylonitrile, isobutyl-2-cyanoacrylate, 2-cyanoethyl acrylate, ethyl-2-cyanoacrylate, methacrylate Tons, tetrahydrofurfuryl methacrylate, trifluoroethyl methacrylate, p-nitrostyrene, vinylpyrrolidone, acrylamide, methacrylamide, N, N-dimethylmethacrylamide, N, N-dibutylmethacrylamide Can be mentioned. Further, it may be a copolymer having one or more monomers having high affinity with the hydrocarbon solvent in the embodiment (M).
(D) Resin having a basic group but not an acidic group and having a nonionic polar group (a copolymer having a monomer having a basic group and a monomer having a nonionic polar group as constituents) As an example, a copolymer of at least one of the specific examples of the monomer having a basic group in the above embodiment (M) and the polar monomer may be mentioned. Further, it may be a copolymer having one or more monomers having high affinity with the hydrocarbon solvent in the embodiment (M).

  In yet another embodiment (O) of the invention of this reference, the particles have an acidic group on the surface but no basic group, or have a basic group but no acidic group. Such particles are uniformly charged to a positive or negative polarity in a hydrocarbon solvent due to their acidic or basic groups.

  The particles used in the present invention are composed of the monomer having an acidic group or the monomer having a basic group in the above embodiment (M) as the binder of the colorant in the above embodiment (L). And those using a resin that is insoluble in the hydrocarbon solvent. In addition, when a substance that can be chemically bonded by grafting or the like, such as metal oxide or carbon black, is used as the solid particle, an acidic group can be obtained by reacting these substances with the monomer having the acidic group or basic group. Alternatively, a basic group may be chemically bonded.

  In yet another embodiment (P) of the invention of this reference, the particles have nonionic polar groups on the surface and (e) acidic groups on the surface but no basic groups, or (f ) Has basic group but no acidic group. Such particles are uniformly charged to a positive or negative polarity in a hydrocarbon solvent due to the interaction of their acidic or basic groups with nonionic polar groups.

  As the particles used in the present invention, the monomer having an acidic group in the above embodiment (M) and the above embodiment (N) as the binder of the colorant in the above embodiment (L). A resin insoluble in a hydrocarbon solvent having a polar monomer as a component, or a monomer insoluble in a hydrocarbon solvent having a basic group monomer and the polar monomer as a component in the above embodiment (M) Is mentioned. In addition, when a substance that can be chemically bonded by grafting or the like, such as metal oxide or carbon black, is used as the solid particles, the monomer having the acidic group or the basic group is reacted with the polar monomer. Alternatively, an acidic group or basic group and a polar group may be chemically bonded.

  In still another embodiment (Q) of the present invention, (g) the resin has an acidic group on its surface but no basic group, and the resin soluble in a hydrocarbon solvent has a basic group. Does not have an acidic group, or (h) the particle has a basic group on the surface but does not have an acidic group, and a resin soluble in a hydrocarbon solvent has an acidic group but does not have a basic group. One of them.

  At this time, acid-base dissociation occurs between the acidic group or basic group on the particle surface and the basic group or acidic group of the resin soluble in the hydrocarbon solvent. When the resin soluble in the particle surface and / or hydrocarbon solvent has a nonionic polar group, ion generation occurs at the interface between the particle surface and the solvent via solvation, and as a result, the particles The solid particles are uniformly charged more positively or negatively, and solid particles are more stably dispersed than in the prior art by the addition of this electrostatic effect and further the steric effect. As the particles in the present embodiment, the particles in the above embodiments (O, P) can be used. In addition, as the resin soluble in the hydrocarbon solvent in the present embodiment, a resin soluble in the hydrocarbon solvent in the above embodiment (M, N) can be used.

  In the present reference invention, the amount of the appropriate insoluble particle component used is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. In this range of use, a very stable dispersion can be obtained even for long-term storage.

(Third dispersion)
The third dispersion as a reference invention for explaining the present invention relates to a silicone oil solvent-based dispersion.

  In the dispersion liquid of the invention of this reference, the silicone oil contains at least a particle component insoluble in the silicone oil and a polymer obtained by polymerizing the monomer represented by the general formula (II) as constituents. A stable dispersion can be provided.

  Further, the dispersion of the invention of the present invention contains at least a particle component insoluble in the silicone oil and a polymer obtained by polymerizing the monomer represented by the general formula (II) as constituents in the silicone oil. In this dispersion liquid, the polymer is insoluble in the silicone oil, so that a steric stabilizing action can be given to the dispersed particles, and a silicone oil dispersion liquid with improved dispersibility can be provided.

  In addition, in the dispersion of the invention of this reference, in the silicone oil, at least the particle component insoluble in the silicone oil, the co-polymerization of the monomer represented by the general formula (II) and the monomer having a polar group In the dispersion containing the coalescence, the copolymer is soluble in the silicone oil, so that it is possible to provide a dispersion system having strong interaction with the dispersed particles and excellent affinity with the silicone oil.

  In the dispersion liquid of the present invention, the silicone oil contains at least a particle component insoluble in silicone oil, a monomer represented by the general formula (II), and an acid group or basic group. By containing the copolymer of the body, the polar group interacts with the particles to give a steric effect, and a dispersion-stable silicone oil dispersion can be provided.

  In the dispersion of the present invention, the silicone oil contains at least a particle component insoluble in the silicone oil, a co-polymer of the monomer represented by the general formula (II) and the monomer having an acidic group. By containing a copolymer and a copolymer of a monomer represented by the general formula (II) and a monomer having a basic group, the dispersed particles are charged and dispersed by electrostatic repulsion. And a dispersion capable of electrophoresis can be provided.

  Further, in the dispersion of the present invention, a copolymer of a monomer represented by the general formula (II) and a monomer having an acidic group, and a monomer represented by the general formula (II) Since either one of the copolymer of the monomer having a basic group and the basic group is insoluble in silicone oil, the dispersed particles are further stabilized and electrically generated by the synergistic effect of the steric stabilizing action and the stabilizing action by electrostatic repulsion. A dispersion having excellent electrophoretic properties can be provided.

  Further, in the dispersion of the present invention, a copolymer of a monomer represented by the general formula (II) and a monomer having an acidic group, and a monomer represented by the general formula (II) And dispersion of a monomer having a basic group with one or both monomers having a polar group, thereby providing a dispersion in which the charge amount related to the charging of particles is improved can do.

(Fourth dispersion)
In the fourth dispersion according to the present invention, at least the particle component insoluble in the silicone oil, the monomer represented by the general formula (II), and the general formula (III) are contained in the silicone oil. By providing a polymer obtained by polymerizing a monomer that is a constituent requirement, it has excellent affinity with silicone oil and provides steric stabilizing action to dispersed particles, thereby providing a dispersion-stable silicone oil dispersion. be able to.

  In the dispersion of the present invention, in the silicone oil, at least a particle component insoluble in the silicone oil, a monomer represented by the general formula (II), a monomer represented by the general formula (III), And a polymer obtained by polymerizing a monomer having an acidic group as a constituent, and in the dispersion of the present invention, in the silicone oil, at least a particle component insoluble in the silicone oil, Dispersion by containing a polymer obtained by polymerizing a monomer represented by the formula (II), a monomer represented by the general formula (III), and a monomer having a basic group as a constituent requirement It is possible to provide a dispersion system that has a strong interaction with particles and an excellent affinity with silicone oil.

  In the dispersion of the present invention, the particle component insoluble in silicone oil has a basic group or an acidic group on at least the surface, thereby imparting electric charge to the dispersed particles and improving dispersibility by electrostatic repulsion. And a dispersion capable of electrophoresis can be provided.

  In the dispersion of the present invention, at least the particle component insoluble in the silicone oil has a nonionic polar group other than polyoxyethylene group. In the dispersion of the present invention, at least the general formula (II ), A monomer represented by the general formula (III), and a polymer obtained by polymerizing a monomer having an acidic group as a constituent requirement is a nonionic polar group other than a polyoxyethylene group. By having the dispersion particles, it is possible to provide a dispersion liquid that is more stable and excellent in electrophoretic characteristics due to a synergistic effect of the steric stabilization action and the stabilization action by electrostatic repulsion.

  Further, in the dispersion of the present invention, the particle component insoluble in silicone oil, the monomer represented by the general formula (II), the monomer represented by the general formula (III), and a single group having an acidic group are used. Since both of the polymers polymerized with the monomer as a constituent requirement have nonionic polar groups other than polyoxyethylene groups, a dispersion having an improved charge amount related to charging of particles can be provided.

  Moreover, in the 3rd and 4th dispersion liquid of this invention, when the viscosity of a silicone oil is 200 cSt (centistokes) or less, the silicone oil dispersion liquid excellent in the storage characteristic can be provided.

  Further, in the third dispersion liquid of the present invention and the fourth dispersion liquid of the present invention, the content of the particle component insoluble in the silicone oil is 0.1 to 20% by mass. In addition, a silicone oil dispersion having excellent storage characteristics can be provided.

  Hereinafter, the configurations of the third dispersion liquid of the present invention and the fourth dispersion liquid of the present invention will be described in more detail.

  Examples of the silicone oil used as a solvent for the third dispersion liquid and the fourth dispersion liquid include dialkyl silicone oils represented by the following general formula (IV); cyclic polydialkylsiloxane or cyclic polyalkylphenylsiloxane; alkylphenylsiloxane Etc. In addition, higher fatty acid-modified silicone oil, methyl chlorinated phenyl silicone oil, alkyl-modified silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil and the like can be used.

〔但しＲ1，Ｒ2，Ｒ3，Ｒ，Ｒ4，Ｒ5，Ｒ6，Ｒ7，Ｒ8は−ＣnＨ2n+1（ｎ＝１〜２０）を表し、これらは同一でも異なっていてもよい。ｘは０又は１以上の整数である。〕
上記一般式（ＩＶ）で表されるジアルキルシリコーンオイルが用いられた場合には、特に重合時の温度に自由に選択できる有利さがある。中でもジメチルポリシロキサンの使用が有利である。また、この一般式（ＩＶ）で表わされるシリコーンオイルは２５℃における粘度が０．０１〜１，０００，０００ｃＳｔ（センチストークス）のものが好ましい。更にまたは一般式（ＩＶ）でｘが１〜２０，０００であるものの使用が望ましい。

[However, R1, R2, R3, R, R4, R5, R6, R7, R8 represent -CnH2n + 1 (n = 1 to 20), and these may be the same or different. x is 0 or an integer of 1 or more. ]
When the dialkyl silicone oil represented by the general formula (IV) is used, there is an advantage that the temperature during polymerization can be freely selected. Of these, use of dimethylpolysiloxane is advantageous. The silicone oil represented by the general formula (IV) preferably has a viscosity at 25 ° C. of 0.01 to 1,000,000 cSt (centistokes). Furthermore, it is desirable to use those having the general formula (IV) where x is 1 to 20,000.

Further, when cyclic polydialkylsiloxane or cyclic polyalkylphenylsiloxane is used, the resulting resin has a drying property of the polymerization solvent, which is particularly advantageous for improving the coating properties of the resin and giving gloss. . When alkylphenylsiloxane (especially methylphenyl silicone oil is desirable) is used, the solubility is improved by introducing a phenyl group (5 to 50 mol%), so that the dispersion stability of the resin solution is improved. It is advantageous to raise. Specific examples of these various silicone oils are as follows.
(I) Examples of dialkyl silicone oils:
Those shown in Table 1 below can be mentioned.

（ｉｉ）環状ポリジアルキルシロキサン及び環状ポリアルキルフェニルシロキサン（フェニル基の含有量は各々５，１０，２０，５０モル％）の例：
環状ポリジメチルシロキサン、環状ポリメチルフェニルシロキサン、環状ポリジエチルシロキサン、環状ポリエチルフェニルシロキサン、環状ポリジブチルシロキサン、環状ポリブチルフェニルシロキサン、環状ポリジヘキシルシロキサン、環状ポリヘキシルフェニルシロキサン、環状ポリジラウリルシロキサン、環状ポリメチルクロロフェニルシロキサン、環状ポリジステアリルシロキサン、環状ポリメチルブロムフェニルシロキサン。
（ｉｉｉ）アルキルフェニルシリコーンオイルの例：
下記表２に示すものが挙げられる。

(Ii) Examples of cyclic polydialkylsiloxane and cyclic polyalkylphenylsiloxane (the phenyl group content is 5, 10, 20, 50 mol%, respectively):
Cyclic polydimethylsiloxane, cyclic polymethylphenylsiloxane, cyclic polydiethylsiloxane, cyclic polyethylphenylsiloxane, cyclic polydibutylsiloxane, cyclic polybutylphenylsiloxane, cyclic polydihexylsiloxane, cyclic polyhexylphenylsiloxane, cyclic polydilaurylsiloxane, cyclic Polymethylchlorophenyl siloxane, cyclic polydistearyl siloxane, cyclic polymethyl bromophenyl siloxane.
(Iii) Examples of alkylphenyl silicone oils:
The following are shown in Table 2.

これらシリコーンオイルの市販の例としては、信越化学工業（株）製のＫＦ−９６Ｌ〔０．６５，１．０，１．５，２．０センチストークス〕、ＫＦ−９６〔１０，２０，３０，５０，５００，１０００，３０００〕、ＫＦ−５６，ＫＦ−５８，ＫＦ−５４などがあげられ、また、東芝シリコーン（株）製のＴＳＦ４５１シリーズ、ＴＳＦ４５６シリーズ、ＴＳＦ４１０，４１１，４４０，４４２０，４８４，４８３，４３１，４３３シリーズ、ＴＨＦ４５０シリーズ、ＴＳＦ４０４，４０５，４０６，４５１−５Ａ，４５１−１０Ａ，４３７シリーズ、ＴＳＦ４４０，４００，４０１，４３００，４４４５，４７００，４４５０，４７０２，４７３０シリーズ、ＴＳＦ４３４，４６００シリーズ、更には東レシリコーン（株）製のＨＳ−２００などがあげられる。

Examples of commercially available silicone oils include KF-96L [0.65, 1.0, 1.5, 2.0 centistokes], KF-96 [10, 20, 30, manufactured by Shin-Etsu Chemical Co., Ltd. , 50, 500, 1000, 3000], KF-56, KF-58, KF-54, etc., and TSF451 series, TSF456 series, TSF410, 411, 440, 4420, 484 manufactured by Toshiba Silicone Co., Ltd. , 483, 431, 433 series, THF450 series, TSF404, 405, 406, 451-5A, 451-10A, 437 series, TSF440, 400, 401, 4300, 4445, 4700, 4450, 4702, 4730 series, TSF434, 4600 Series, and HS-2 manufactured by Toray Silicone Co., Ltd. 0, and the like.

  Other solvents can be mixed with the silicone oil as described above to such an extent that the properties of the silicone oil are not impaired. Examples of such solvents include aromatic hydrocarbon solvents such as toluene, xylene, benzene; ethers; esters; alcohol solvents; n-hexane, n-octane, iso-octane, iso-dodecane, and mixtures thereof. Aliphatic hydrocarbons (such as Isopar H.G.L.V manufactured by Exxon Chemical Co., Ltd.). The mixing ratio of such other solvents is about 0.1 to 500 parts by mass with respect to 100 parts by mass of the silicone oil.

  Next, the polymerizable monomer used in the present invention will be described.

First, the monomer represented by the general formula (II) has a strong affinity with silicone oil and is difficult to dissolve in silicone oil with ordinary polymers. In the case of a homopolymer, it gives a polymer that is soluble in silicone oil, and in the case of a copolymer with other monomers, it has a high affinity with silicone oil even if it is soluble or insoluble. , Can provide a stable dispersion.
Next, examples of the monomer that can be copolymerized with the monomer represented by the general formula (II) include the following.
(Iv) Examples of monomers having an acidic group:
(Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, cinnamic acid, crotonic acid, vinyl benzoic acid, 2-methacryloxyethyl succinic acid, 2-methacryloxyethyl maleic acid, 2 -Methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl trimellitic acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2-sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, 3-chloro Amidophosphoxypropyl methacrylate, 2-methacryloxyethyl acid phosphate, hydroxystyrene and the like.
(V) Examples of monomers having a basic group:
N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl Acrylate, N-phenylaminoethyl methacrylate, N, N-diphenylaminoethyl methacrylate, aminostyrene, dimethylaminostyrene, N-methylaminoethylstyrene, dimethylaminoethoxystyrene, diphenylaminoethylstyrene, N-phenylamino Ethylstyrene, vinylpyrrolidone, 2-N-piperidylethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, acrylamide, methacrylamide, N, N-dimethylmethacrylami , N, N-dibutyl methacrylamide.
(Vi) Examples of monomers having a polar group:
2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-propyl methacrylate, 2-chloroethyl (meth) acrylate, 2,3- Dibromopropyl (meth) acrylate, (meth) acrylonitrile, isobutyl-2-cyanoacrylate, 2-cyanoethyl acrylate, ethyl-2-cyanoacrylate, methacrylacetone, tetrahydrofurfuryl methacrylate, trifluoroethyl methacrylate, p-nitrostyrene, etc. Can be mentioned.
(Vii) Examples of multifunctional monomers:
Divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol tri (meth) acrylate, butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolhexane tri (meth) acrylate, bentaerythritol tetra (meth) acrylate 1,3-dibutylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, and the like.
(Viii) Examples of other monomers:
2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, vinyl laurate, lauryl methacrylamide, stearyl methacrylamide, Methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate Benzyl (meth) acrylate, phenyl (meth) acrylate, styrene, vinyl toluene, vinyl acetate and the like.
First, as a polymer having the monomer represented by the general formula (II) as a constituent, the monomer represented by the general formula (II) and the monomers (iv) to (viii) The copolymer of these is mentioned. The copolymer of the monomer of general formula (II) and the monomer having a polar group includes at least the monomer of general formula (II) and the monomer (vi) having a polar group. A copolymer is mentioned. Further, the copolymer of the monomer of the general formula (II) and the monomer having an acidic group includes at least the monomer of the general formula (II) and the monomer (iv) having an acidic group. A copolymer is mentioned. The copolymer of the monomer of the general formula (II) and the monomer having a basic group includes at least the monomer of the general formula (II) and the monomer (v) having a basic group. The copolymer containing is mentioned.
The polymer containing the monomer of the general formula (II) is insoluble in silicone oil, at least the monomer of the general formula (II) and the monomers of the above (iv) to (viii) And a copolymer. However, in this case, the ratio of using these monomers cannot be uniquely defined, and the intended insoluble resin is obtained by empirical use. This is due to the properties of silicone oil as a solvent-poor solubility. However, the most reliable insoluble resin can be obtained by using a relatively large amount of the monomer of the general formula (vii).

  In addition, when the monomer represented by the general formula (III) is included together with the monomer of the general formula (II), the monomer has a polyethylene glycol chain having a repeating unit of oxyethylene group of 25 or less, and the monomer As a constituent element, the copolymer is adsorbed on particles insoluble in a solvent, and the dispersion of the particles is stabilized by the steric effect expressed by the polyethylene glycol chain.

On the other hand, examples of the particle component insoluble in the silicone oil used in the present invention include various insoluble resins, generally known inorganic or organic pigments, metals, metal oxides, magnetic powders, waxy substances (for example, low molecular polyolefins, Waxes), chemical products (for example, agricultural chemicals), swelling agents and the like. More specifically, for example, carbon black, lamp black, ultramarine blue, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, Rogmin 6G, rake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, tri Any conventionally known dyes and pigments such as dyes and pigments such as allylmethane dyes can be used alone or in combination. Also, iron oxides such as magnetite, hematite, ferrite, metals such as iron, carbonyl iron powder, cobalt, nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium of these metals And alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof, glass beads, and the like.
Examples of the resin particles include homopolymers of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and the like; and styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyl. Toluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene -Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether Copolymer, styrene-vinylethyl Ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Examples thereof include styrene copolymers such as copolymers.

Further, depending on the purpose of use, a dye soluble in silicone oil can be added to the dispersion, or the dispersion or dispersoid can be colored by chemically bonding to the dispersoid.
In order to make the dispersion of the present invention, the above resin components and solid particles may be mixed and dispersed in a silicone oil solvent. In this case, a ball mill, a sand mill, an attritor or the like may be used as the dispersing means. The mixing order is not particularly limited.

  When the silicone oil used as the dispersion solvent of the present invention is 1000 centistokes or less, and preferably 200 centistokes or less, a characteristic excellent in dispersion stability is exhibited. The reason for this has not been clarified, but it is presumed that if the viscosity of the silicone oil increases, the molecular weight of the oil also increases, which in turn reduces the solubility of the resin used in the present invention or the affinity between the resin and the oil. Is done.

  In this invention, 0.1-20 mass% is preferable, and, as for the usage-amount of a suitable insoluble particle | grain component, 0.5-15 mass% is more preferable. In this range of use, a very stable dispersion can be obtained even for long-term storage.

The present invention will be described in more detail with reference to examples and reference examples. However, the present invention is not limited to the following examples. The parts used in the following examples and reference examples are all parts by mass.
(Reference Example 1)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 300 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar H) was taken and heated to 85 ° C. In this, 45 parts of lauryl methacrylate, 5 parts of a compound of the following structural formula,

アゾビスイソブチロニトリル１部よりなる溶液を1時間に亘つて滴下した。ついで90℃に昇温し、この温度で４時間撹拌し、反応を終了した。均一で透明な樹脂溶液が重合率98.7％で得られた。次にこの樹脂溶液100部に酸化チタン7部を加えボールミルで分散して分散液を作った。長さ４０ｃｍのガラス管を垂直に立て、この分散液を高さ３０ｃｍのところまで注液した。一ヶ月間放置後、目視判定したが、沈殿はなく非常に安定な分散液であることが分かった。
（参考例２）
参考例１と同様な反応容器に、イソパラフィン系炭化水素（エクソンケミカル、アイソパーＨ）３００部を採り、90℃に加熱した。この中にデシルメタクリレート43部、下記構造式の化合物５部、

A solution consisting of 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Then, the temperature was raised to 90 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. A uniform and transparent resin solution was obtained with a polymerization rate of 98.7%. Next, 7 parts of titanium oxide was added to 100 parts of this resin solution and dispersed with a ball mill to form a dispersion. A glass tube having a length of 40 cm was set up vertically, and this dispersion was poured to a height of 30 cm. Visual judgment was made after standing for one month, but it was found that the dispersion was very stable without precipitation.
(Reference Example 2)
In a reaction vessel similar to that of Reference Example 1, 300 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar H) was taken and heated to 90 ° C. In this, 43 parts of decyl methacrylate, 5 parts of a compound of the following structural formula,

メタクリル酸２部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして均一で透明な樹脂溶液が重合率97.4％で得られた。次にこの樹脂溶液100部にカーボンブラック1部を加えボールミルで分散して分散液を作った。参考例１と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（参考例３）
参考例１と同様な反応容器に、イソパラフィン系炭化水素（エクソンケミカル、アイソパーＧ）３００部を採り、90℃に加熱した。この中に２−エチルヘキシルメタクリレート４０部、下記構造式の化合物５部、

A solution consisting of 2 parts of methacrylic acid and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a uniform and transparent resin solution was obtained with a polymerization rate of 97.4%. Next, 1 part of carbon black was added to 100 parts of this resin solution and dispersed with a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 1, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.
(Reference Example 3)
In a reaction vessel similar to that of Reference Example 1, 300 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar G) was taken and heated to 90 ° C. In this, 40 parts of 2-ethylhexyl methacrylate, 5 parts of a compound of the following structural formula,

ジメチルアミノエチルメタクリレート５部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして均一で透明な樹脂溶液が重合率95.2％で得られた。次にこの樹脂溶液100部に酸化チタン7部を加えボールミルで分散して分散液を作った。参考例１と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（参考例４）
参考例１で用いた反応容器にイソパラフィン系炭化水素（エクソンケミカル、アイソパーＨ）300部を採り、80℃に加熱した。この中にシクロヘキシルメタクリレート２５部、ジブチルアミノエチルメタクリレート５部、エチレングリコールジメタクリレート２０部、ベンゾイルパーオキサイド１部よりなる溶液を５時間に亘つて滴下した。次いで85℃で２時間撹拌して反応終了した。濾過、洗浄処理により不溶性の樹脂が重合率92.5％で得られた。次にこの樹脂５部を参考例２で作製した樹脂溶液５０部に加えボールミルで分散して分散液を作った。参考例１と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（参考例５）
参考例１と同様な反応容器にイソパラフィン系炭化水素（エクソンケミカル、アイソパーＬ）500部を採り、80℃に加熱した。この中にヘキシルメタクリレート２０部、ジエチルアミノエチルメタクリレート５部、ヒドロキシエチルメタクリレート５部、エチレングリコールジメタクリレート２０部、及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで85℃に昇温し、この温度で４時間撹拌し、反応を終了した。濾過、洗浄処理により重合率94.7％で樹脂が得られた。次にアイソパーＨ４５部にこの樹脂５部、参考例２で作製した樹脂溶液５０部を加え超音波分散して分散液を作った。参考例１と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（参考例６）
参考例１と同様な反応容器に、イソパラフィン系炭化水素（エクソンケミカル、アイソパーＬ）３００部を採り、90℃に加熱した。この中に下記構造の化合物４４部、下記構造式の化合物４部、

A solution consisting of 5 parts of dimethylaminoethyl methacrylate and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a uniform and transparent resin solution was obtained at a polymerization rate of 95.2%. Next, 7 parts of titanium oxide was added to 100 parts of this resin solution and dispersed with a ball mill to form a dispersion. The dispersion stability was examined in the same manner as in Reference Example 1, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.
(Reference Example 4)
In a reaction vessel used in Reference Example 1, 300 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar H) was taken and heated to 80 ° C. A solution consisting of 25 parts of cyclohexyl methacrylate, 5 parts of dibutylaminoethyl methacrylate, 20 parts of ethylene glycol dimethacrylate and 1 part of benzoyl peroxide was added dropwise over 5 hours. Subsequently, the reaction was completed by stirring at 85 ° C. for 2 hours. By filtration and washing treatment, an insoluble resin was obtained with a polymerization rate of 92.5%. Next, 5 parts of this resin was added to 50 parts of the resin solution prepared in Reference Example 2 and dispersed with a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 1, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.
(Reference Example 5)
In a reaction vessel similar to that of Reference Example 1, 500 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar L) was taken and heated to 80 ° C. A solution consisting of 20 parts of hexyl methacrylate, 5 parts of diethylaminoethyl methacrylate, 5 parts of hydroxyethyl methacrylate, 20 parts of ethylene glycol dimethacrylate, and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. By filtration and washing treatment, a resin was obtained with a polymerization rate of 94.7%. Next, 5 parts of this resin and 50 parts of the resin solution prepared in Reference Example 2 were added to 45 parts of Isopar H and ultrasonically dispersed to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 1, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.
(Reference Example 6)
In a reaction vessel similar to that of Reference Example 1, 300 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar L) was taken and heated to 90 ° C. In this, 44 parts of a compound having the following structure, 4 parts of a compound having the following structural formula,

メタクリル酸１部、ビニルピロリドン１部、及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして均一で半透明な高分子ゲル分散液が重合率93.4％で得られた。次にこの高分子ゲル分散液１００部に参考例４で作製した樹脂５部、酸化チタン7部、染料（バイエル マクロレックスブルーＲＲ）0.1部を加えボールミルで分散して分散液を作った。参考例１と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（参考例７）
イソパラフィン系炭化水素（エクソンケミカル、アイソパーＬ）４５部に参考例５で作製した樹脂５部、参考例６で作製した高分子ゲル分散液５０部、を加え超音波分散して分散液を作った。この分散液を、電極間隔５ｍｍの平行に配備された真鍮電極を有するテフロン（登録商標）製容器に注ぎ、１０００Ｖの直流電圧を１分間印加した。電圧印加後、電極を取り出して観察したところ、白色粒子は陰極にのみ電着し、陽極には析出が認められなかった。このことから、粒子は全て正の電荷を帯びていることが分かる。
（参考例８）
参考例１で用いた反応容器にイソパラフィン系炭化水素（エクソンケミカル、アイソパーG）５００部を採り、80℃に加熱した。この中に２−エチルヘキシルメタクリレート２０部、エチレングリコールジメタクリレート２５部、２−ヒドロスチレンスルホン酸5部、ベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで85℃で３時間撹拌して反応終了した。濾過、洗浄処理により重合率91.2％で樹脂が得られた。アイソパーG４５部この樹脂５部、参考例３で作製した樹脂溶液５０部を加え超音波分散して分散液を作った。参考例１と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。

A solution consisting of 1 part methacrylic acid, 1 part vinylpyrrolidone and 1 part azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. In this way, a uniform and translucent polymer gel dispersion was obtained with a polymerization rate of 93.4%. Next, 5 parts of the resin prepared in Reference Example 4, 7 parts of titanium oxide, and 0.1 part of a dye (Bayer Macrolex Blue RR) were added to 100 parts of this polymer gel dispersion and dispersed with a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 1, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.
(Reference Example 7)
A dispersion was prepared by adding 5 parts of the resin prepared in Reference Example 5 and 50 parts of the polymer gel dispersion prepared in Reference Example 6 to 45 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar L) and ultrasonically dispersing it. . This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. After applying the voltage, the electrode was taken out and observed. As a result, white particles were electrodeposited only on the cathode, and no deposition was observed on the anode. From this, it can be seen that all particles have a positive charge.
(Reference Example 8)
In a reaction vessel used in Reference Example 1, 500 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar G) was taken and heated to 80 ° C. A solution consisting of 20 parts of 2-ethylhexyl methacrylate, 25 parts of ethylene glycol dimethacrylate, 5 parts of 2-hydrostyrene sulfonic acid and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, the reaction was completed by stirring at 85 ° C. for 3 hours. By filtration and washing treatment, a resin was obtained with a polymerization rate of 91.2%. 45 parts of Isopar G 5 parts of this resin and 50 parts of the resin solution prepared in Reference Example 3 were added and ultrasonically dispersed to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 1, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.

(Reference Example 9)
In a reaction vessel similar to that in Reference Example 1, 500 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar G) was taken and heated to 80 ° C. A solution comprising 20 parts of lauryl methacrylate, 20 parts of methyl methacrylate, 5 parts of lauryl methacrylamide, 5 parts of methacrylic acid and 5 parts of azobisisobutyronitrile was added dropwise over 3 hours. Subsequently, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. Thus, a resin dispersion was obtained with a polymerization rate of 91.2%. Next, 50 parts of this resin dispersion and 50 parts of the resin solution prepared in Reference Example 3 and 5 parts of copper phthalocyanine pigment were added and dispersed with a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 1, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.
(Reference Example 10)
In a reaction vessel similar to that of Reference Example 1, 300 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar G) was taken and heated to 90 ° C. In this, 37 parts of lauryl methacrylate, 5 parts of a compound of the following structural formula,

ジメチルアミノエチルメタクリレート５部、ビニルピロリドン３部、及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして均一で透明な樹脂溶液が重合率94.1％で得られた。次にこの樹脂溶液５０部に参考例８で作製した樹脂５部、カーボンブラック1部を加えボールミルで分散して分散液を作った。参考例１と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（参考例１１）
参考例９で作製した樹脂分散液５０部に参考例１０で作製した樹脂溶液５０部、Ｎ，Ｎ−ジエチルプロピオンアミド３部、酸化チタン7部、染料（バイエル マクロレックスブルーＲＲ）0.1部を加えボールミルで分散して分散液を作った。この分散液を、ＩＴＯ透明電極ガラスを電極面が間隔１ｍｍのスペーサーで向かい合うように配備されたセルに注ぎ、１０００Ｖの直流電圧を１秒間印加した。電圧印加後、陽極側から観察すると電極面は白色であった。反対の陰極側から観察すると、電極面は染料で着色した色が見られた。このことから、粒子は全て負の電荷を帯びて陽極側にのみ電着していることが分かる。
（比較例１）
イソパラフィン系炭化水素（エクソンケミカル、アイソパーＨ）１００部に酸化チタン7部、染料（バイエル マクロレックスブルーＲＲ）0.1部を加えボールミルで分散して分散液を作製し、参考例１と同様にして分散安定性を調べたが、一日の放置で上澄み部分が２０ｃｍ程現れ、非常に不安定な分散液であった。
（比較例２）
参考例１と同様な反応容器にイソパラフィン系炭化水素（エクソンケミカル、アイソパーＬ）500部を採り、80℃に加熱した。この中にデシルメタクリレート２５部、メチルメタクリレート１０部、エチレングリコールジメタクリレート１５部、及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで85℃に昇温し、この温度で４時間撹拌し、反応を終了した。濾過、洗浄処理により重合率90.9％で樹脂が得られた。この樹脂１０部をアイソパーＬ１００部、カーボンブラック１部とともにボールミルに投入し、分散液を得た。この分散液を、電極間隔５ｍｍの平行に配備された真鍮電極を有するテフロン（登録商標）製容器に注ぎ、１０００Ｖの直流電圧を１分間印加した。電圧印加後、電極を取り出して観察したところ、陰極陽極の両極に黒色粒子の電着が観測された。
（参考例１２）
撹拌機、温度計及び還流冷却器を備えた反応容器に、アイソパーＨ（エクソンケミカル社）３００部を採り、９０℃に加熱した。この中にラウリルメタクリレート４０部、メタクリル酸１０部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして、アイソパーＨに可溶な高分子を含む溶液が重合率９５．６％で得られた。アイソパーＨをエバポレーターで蒸発させた上記ポリマー５部と銅フタロシアニン２部を流動パラフィン１００部に対して加えて、超音波分散し、平均粒径０．３μｍの分散液を得た。長さ４０ｃｍのガラス管を垂直に立て、この分散液を高さ３０ｃｍのところまで注液した。

A solution consisting of 5 parts of dimethylaminoethyl methacrylate, 3 parts of vinylpyrrolidone and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a uniform and transparent resin solution was obtained with a polymerization rate of 94.1%. Next, 5 parts of the resin prepared in Reference Example 8 and 1 part of carbon black were added to 50 parts of the resin solution and dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 1, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.
(Reference Example 11)
To 50 parts of the resin dispersion prepared in Reference Example 9, add 50 parts of the resin solution prepared in Reference Example 10, 3 parts of N, N-diethylpropionamide, 7 parts of titanium oxide, and 0.1 part of a dye (Bayer Macrolex Blue RR). Dispersion was made with a ball mill. This dispersion was poured into a cell in which ITO transparent electrode glass was placed so that the electrode surfaces face each other with a spacer having a spacing of 1 mm, and a DC voltage of 1000 V was applied for 1 second. After voltage application, the electrode surface was white when observed from the anode side. When observed from the opposite cathode side, the electrode surface was colored with a dye. This shows that all particles are negatively charged and are electrodeposited only on the anode side.
(Comparative Example 1)
Disperse in the same manner as in Reference Example 1 by adding 7 parts of titanium oxide and 0.1 part of dye (Bayer Macrolex Blue RR) to 100 parts of isoparaffin hydrocarbon (Exxon Chemical, Isopar H) and dispersing with a ball mill. The stability was examined, but the supernatant portion appeared about 20 cm after standing for a day, and the dispersion was very unstable.
(Comparative Example 2)
In a reaction vessel similar to that of Reference Example 1, 500 parts of isoparaffinic hydrocarbon (Exxon Chemical, Isopar L) was taken and heated to 80 ° C. A solution consisting of 25 parts of decyl methacrylate, 10 parts of methyl methacrylate, 15 parts of ethylene glycol dimethacrylate and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. By filtration and washing treatment, a resin was obtained with a polymerization rate of 90.9%. 10 parts of this resin was put into a ball mill together with 100 parts of Isopar L and 1 part of carbon black to obtain a dispersion. This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. After applying the voltage, the electrode was taken out and observed, and black particle electrodeposition was observed on both electrodes of the cathode anode.
(Reference Example 12)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 300 parts of Isopar H (Exxon Chemical Co.) was taken and heated to 90 ° C. A solution consisting of 40 parts of lauryl methacrylate, 10 parts of methacrylic acid and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a solution containing a polymer soluble in Isopar H was obtained at a polymerization rate of 95.6%. 5 parts of the polymer obtained by evaporating Isopar H with an evaporator and 2 parts of copper phthalocyanine were added to 100 parts of liquid paraffin, and ultrasonically dispersed to obtain a dispersion having an average particle size of 0.3 μm. A glass tube having a length of 40 cm was set up vertically, and this dispersion was poured to a height of 30 cm.

Visual judgment was made after standing for one month, but it was found that the dispersion was very stable without precipitation.
(Reference Example 13)
In a reaction vessel similar to Reference Example 12, 300 parts of toluene was taken and heated to 80 ° C. A solution consisting of 40 parts of octyl methacrylate, 10 parts of diethylaminoethyl methacrylate and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Then, the temperature was raised to 90 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. A uniform and transparent resin solution was obtained with a polymerization rate of 93.6%. 5 parts of the polymer obtained by evaporating toluene with an evaporator and 7 parts of titanium oxide were added to 100 parts of isoparaffinic hydrocarbon and dispersed with a ball mill to obtain a dispersion having an average particle size of 0.2 μm. A glass tube having a length of 40 cm was set up vertically, and this dispersion was poured to a height of 30 cm.

Visual judgment was made after standing for one month, but it was found that the dispersion was very stable without precipitation.
(Reference Example 14)
In a reaction vessel similar to Reference Example 12, 300 parts of Isopar H was taken and heated to 80 ° C. A solution consisting of 35 parts of octyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, 10 parts of diethylaminoethyl methacrylate and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, the temperature was raised to 90 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. A uniform and transparent resin solution was obtained at a polymerization rate of 94.1%. 5 parts of the polymer obtained by evaporating Isopar H with an evaporator and 7 parts of titanium oxide were added to 100 parts of liquid paraffin, and dispersed with a ball mill to obtain a dispersion having an average particle size of 0.2 μm. A glass tube having a length of 40 cm was set up vertically, and this dispersion was poured to a height of 30 cm.

Visual judgment was made after standing for one month, but it was found that the dispersion was very stable without precipitation.
(Reference Example 15)
In a reaction vessel similar to Reference Example 12, 300 parts of Isopar H was taken and heated to 90 ° C. Into this, a solution comprising 25 parts of stearyl methacrylate, 10 parts of ethylene glycol dimethacrylate, 5 parts of methacrylic acid and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a polymer insoluble in Isopar H was obtained at a polymerization rate of 90.6%. 5 parts of the filtered polymer was added to 100 parts of isoparaffinic hydrocarbon and ultrasonically dispersed to obtain a dispersion having an average particle size of 0.3 μm. The dispersion stability was examined in the same manner as in Reference Example 12, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Reference Example 16)
In a reaction container similar to that of Reference Example 12, 300 parts of Isopar H was taken and heated to 85 ° C. Into this, a solution consisting of 20 parts of lauryl methacrylate, 15 parts of ethylene glycol dimethacrylate, 5 parts of dimethylaminoethyl methacrylate and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a polymer insoluble in Isopar H was obtained at a polymerization rate of 90.9%. 5 parts of the filtered polymer and 3 parts of carbon black were added to 100 parts of liquid paraffin and dispersed by a ball mill to obtain a dispersion having an average particle size of 0.2 μm. The dispersion stability was examined in the same manner as in Reference Example 12, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Reference Example 17)
In a reaction vessel similar to that of Reference Example 12, 300 parts of toluene was taken and heated to 85 ° C. Into this, a solution consisting of 20 parts of lauryl methacrylate, 10 parts of ethylene glycol dimethacrylate, 5 parts of 2-methoxyethyl methacrylate, 5 parts of methacrylic acid and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a polymer insoluble in toluene was obtained at a polymerization rate of 93.6%. 5 parts of the filtered polymer was added to 100 parts of isoparaffinic hydrocarbon and ultrasonically dispersed to obtain a dispersion having an average particle size of 0.3 μm. The dispersion stability was examined in the same manner as in Reference Example 12, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Reference Example 18)
5 parts of the polymer soluble in the hydrocarbon solvent prepared in Reference Example 12 and 5 parts of the solvent-insoluble polymer prepared in Reference Example 16 were added to 100 parts of liquid paraffin, and ultrasonically dispersed. A 2 μm dispersion was obtained. This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. After applying the voltage, the electrode was taken out and observed, and the blue particles were electrodeposited only on the cathode, and no deposition was observed on the anode. From this, it can be seen that all particles have a positive charge.
(Reference Example 19)
Add 5 parts of the polymer soluble in the hydrocarbon solvent prepared in Reference Example 14, 5 parts of the solvent-insoluble polymer prepared in Reference Example 17 and 2 parts of copper phthalocyanine to 100 parts of isoparaffinic hydrocarbon solvent, and use a ball mill. Dispersion was performed to obtain a dispersion having an average particle size of 0.3 μm. This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. When voltage was applied and the electrode was taken out and observed, the blue particles were electrodeposited only on the anode, and no deposition was observed on the cathode. From this, it can be seen that the particles are all negatively charged.
(Comparative Example 3)
A dispersion was prepared in the same manner as in Reference Example 13 except that a dispersion was prepared using only titanium oxide without adding a resin in Reference Example 13, and the dispersion stability was examined in the same manner as in Reference Example 2. Upon standing, the supernatant portion appeared about 20 cm, and it was found that the dispersion was very unstable.
(Comparative Example 4)
When a reaction was conducted in the same manner as in Reference Example 15 except that methacrylic acid was not added in Reference Example 15, a polymer insoluble in Isopar H was obtained at a polymerization rate of 91.2%. Dispersion was prepared in the same manner as in Reference Example 4 by adding 5 parts of the filtered polymer to 100 parts of isoparaffinic hydrocarbon, and the dispersion stability was examined in the same manner as in Reference Example 15. Appeared about 20 cm, and was found to be a very unstable dispersion.
(Comparative Example 5)
When voltage was applied in the same manner as in Reference Example 18 except that the dispersion liquid of Comparative Example 4 was used, particle adhesion was observed on both electrodes of the cathode anode, and migration due to the electric field of the particles was not observed.
(Reference Example 20)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 300 parts of silicone oil (SH-200; 2cs) was taken and heated to 90 ° C. In this, 40 parts of the compound of the following structural formula

及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして、シリコーンオイルに可溶な高分子を含む溶液が重合率９５．７％で得られた。
この樹脂液１００部に対して、銅フタロシアニン２部を加えて、超音波分散し、平均粒径０．３μｍの分散液を得た。長さ４０ｃｍのガラス管を垂直に立て、この分散液を高さ３０ｃｍのところまで注液した。一ヶ月間放置後、目視判定したが、沈殿はなく非常に安定な分散液であることが分かった。
（参考例２１）
参考例２０と同様な反応容器に、シリコーンオイル（ＳＨ−２００；５ｃｓ）３００部を採り、90℃に加熱した。この中に下記構造式の化合物３７部、

And a solution consisting of 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a solution containing a polymer soluble in silicone oil was obtained at a polymerization rate of 95.7%.
To 100 parts of this resin liquid, 2 parts of copper phthalocyanine was added and ultrasonically dispersed to obtain a dispersion liquid having an average particle size of 0.3 μm. A glass tube having a length of 40 cm was set up vertically, and this dispersion was poured to a height of 30 cm. Visual judgment was made after standing for one month, but it was found that the dispersion was very stable without precipitation.
(Reference Example 21)
In a reaction container similar to that of Reference Example 20, 300 parts of silicone oil (SH-200; 5cs) was taken and heated to 90 ° C. In this, 37 parts of the compound of the following structural formula,

エチレングリコールジメタクリレート３部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして粒径１〜３μｍの樹脂を含む分散液が重合率96.5％で得られた。参考例２０と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（比較例６）
参考例２０と同様な反応容器に、シリコーンオイル（ＳＨ−２００；２ｃｓ）３００部を採り、９０℃に加熱した。この中にラウリルメタクリレート２０部、２−エチルヘキシルメタクリレート２０部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして、シリコーンオイルに不溶な高分子隗を含む液が重合率８９．２％で得られた。この液をボールミルで分散し、平均粒径５〜１０μｍの分散液を得た。参考例１９と同様にして、分散安定性を調べたが、一日の放置で上澄み部分が２０ｃｍ程現れ、非常に不安定な分散液であることが分かった。
次に、これらの各樹脂塗膜を作製し、撥水性、撥油性を測定し、表３に示すような結果を得た。

A solution consisting of 3 parts of ethylene glycol dimethacrylate and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a dispersion containing a resin having a particle size of 1 to 3 μm was obtained at a polymerization rate of 96.5%. The dispersion stability was examined in the same manner as in Reference Example 20, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month.
(Comparative Example 6)
In a reaction container similar to that in Reference Example 20, 300 parts of silicone oil (SH-200; 2cs) was taken and heated to 90 ° C. A solution consisting of 20 parts of lauryl methacrylate, 20 parts of 2-ethylhexyl methacrylate and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. In this way, a liquid containing polymer soot insoluble in silicone oil was obtained at a polymerization rate of 89.2%. This liquid was dispersed with a ball mill to obtain a dispersion having an average particle diameter of 5 to 10 μm. The dispersion stability was examined in the same manner as in Reference Example 19, but the supernatant portion appeared about 20 cm after standing for a day, and it was found that the dispersion was very unstable.
Next, each of these resin coatings was prepared and measured for water repellency and oil repellency, and the results shown in Table 3 were obtained.

なお、表３の各測定法は、以下のとおりである。
撥水性：協和化学社製の接触角測定機を用いて、樹脂表面のイオン交換水に対する接触角を測定した。
撥油性：協和化学社製の接触角測定機を用いて、樹脂面のｉｓｏ−ドデカンに対する接触角を測定した。
（参考例２２）
参考例２０と同様な反応容器に、シリコーンオイル（ＳＨ−２００；１ｃｓ）３００部を採り、８５℃に加熱した。この中に下記構造式の化合物３５部、

In addition, each measuring method of Table 3 is as follows.
Water repellency: The contact angle of the resin surface with respect to ion-exchanged water was measured using a contact angle measuring machine manufactured by Kyowa Chemical Co., Ltd.
Oil repellency: The contact angle of the resin surface with respect to iso-dodecane was measured using a contact angle measuring machine manufactured by Kyowa Chemical.
(Reference Example 22)
In a reaction vessel similar to Reference Example 20, 300 parts of silicone oil (SH-200; 1 cs) was taken and heated to 85 ° C. In this, 35 parts of the compound of the following structural formula,

Ｎ−ビニルピロリドン５部及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして、シリコーンオイルに可溶な高分子を含む溶液が重合率９３．６％で得られた。

A solution consisting of 5 parts of N-vinylpyrrolidone and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a solution containing a polymer soluble in silicone oil was obtained at a polymerization rate of 93.6%.

To 100 parts of this resin liquid, 5 parts of carbon black was added and dispersed in a ball mill to obtain a dispersion liquid having an average particle size of 0.3 μm. The dispersion stability was examined in the same manner as in Reference Example 21, but it was found that the dispersion was very stable without precipitation even after standing for one month. The water repellency was 35.1 and the oil repellency was 30.0.
(Reference Example 23)
A test was performed in the same manner as in Reference Example 21, except that dimethylaminoethyl methacrylate was used instead of vinylpyrrolidone used in Reference Example 22. As a result, a uniform solution having a polymerization rate of 94.3% was obtained, and a carbon black dispersion having an average particle size of 0.2 μm was obtained. This dispersion was very stable and had water repellency of 33.0 and oil repellency of 28.7.
(Reference Example 24)
In a reaction vessel similar to Reference Example 20, 300 parts of silicone oil (SH-200; 1 cs) was taken and heated to 90 ° C. In this, 32 parts of the compound of the following structural formula,

下記構造式の化合物５部、

5 parts of a compound of the structural formula

メタクリル酸３部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして粒径２〜５μｍの樹脂を含む分散液が重合率93.5％で得られた。参考例２０と同様にして、分散安定性を調べたが、一ヶ月間放置後、上澄み部分が２ｃｍ現れただけで、安定な分散液であることが分かった。なお、撥水性３１．４、撥油性２９．０であった。
（参考例２５）
参考例２４で得た分散液５０部と参考例２２で作製した均一樹脂液５０部を撹拌混合し、分散液を作製した。参考例１９と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。なお、撥水性３０．８、撥油性２９．５であった。
この分散液を、電極間隔５ｍｍの平行に配備された真鍮電極を有するテフロン（登録商標）製容器に注ぎ、１０００Ｖの直流電圧を１分間印加した。電圧印加後、電極を取り出して観察したところ、白色粒子は陽極にのみ電着し、陰極には析出が認められなかった。このことから、粒子は全て負の電荷を帯びていることが分かる。
比較のため、参考例２４の分散液を同様にして電着を試みたが、陰極陽極の両極に白色粒子の電着が観測された。
さらに、比較のため、参考例２３の均一溶液を同様にして電着を試みたが、陰極陽極のいずれにも何らの電着は生じなかった。
（参考例２６）
参考例２０と同様な反応容器に、シリコーンオイル（ＳＨ−２００；10ｃｓ）３００部を採り、90℃に加熱した。この中に下記構造式の化合物３２部、

A solution consisting of 3 parts of methacrylic acid and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a dispersion containing a resin having a particle size of 2 to 5 μm was obtained at a polymerization rate of 93.5%. The dispersion stability was examined in the same manner as in Reference Example 20, but after standing for 1 month, only a 2 cm supernatant portion appeared, and it was found that the dispersion was stable. The water repellency was 31.4 and the oil repellency was 29.0.
(Reference Example 25)
50 parts of the dispersion obtained in Reference Example 24 and 50 parts of the uniform resin liquid prepared in Reference Example 22 were mixed with stirring to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 19, but it was found that the dispersion was very stable without precipitation even after standing for one month. The water repellency was 30.8 and the oil repellency was 29.5.
This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. When voltage was applied and the electrode was taken out and observed, white particles were electrodeposited only on the anode, and no deposition was observed on the cathode. From this, it can be seen that the particles are all negatively charged.
For comparison, electrodeposition of the dispersion liquid of Reference Example 24 was attempted in the same manner. However, electrodeposition of white particles was observed on both electrodes of the cathode anode.
Furthermore, for comparison, electrodeposition of the homogeneous solution of Reference Example 23 was attempted in the same manner, but no electrodeposition occurred on any of the cathode anode.
(Reference Example 26)
In a reaction container similar to that of Reference Example 20, 300 parts of silicone oil (SH-200; 10 cs) was taken and heated to 90 ° C. In this, 32 parts of the compound of the following structural formula,

エチレングリコールジメタクリレート４部、ヘキサヒドロフタル酸2-メタクリロイルオキシエチル４部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして粒径１〜３μｍの樹脂を含む分散液が重合率94.8％で得られた。参考例２０と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。なお、撥水性２９．４、撥油性２６．２であった。
（参考例２７）
参考例２６で得た分散液５０部と参考例２３で作製した均一樹脂液５０部を撹拌混合し、分散液を作製した。参考例２０と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。なお、撥水性３０．２、撥油性２８．０であった。

A solution consisting of 4 parts of ethylene glycol dimethacrylate, 4 parts of 2-methacryloyloxyethyl hexahydrophthalate and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a dispersion containing a resin having a particle size of 1 to 3 μm was obtained at a polymerization rate of 94.8%. The dispersion stability was examined in the same manner as in Reference Example 20, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month. The water repellency was 29.4 and the oil repellency was 26.2.
(Reference Example 27)
50 parts of the dispersion obtained in Reference Example 26 and 50 parts of the uniform resin liquid prepared in Reference Example 23 were mixed with stirring to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 20, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month. The water repellency was 30.2 and the oil repellency was 28.0.

This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. When voltage was applied and the electrode was taken out and observed, white particles were electrodeposited only on the anode, and no deposition was observed on the cathode. From this, it can be seen that the particles are all negatively charged.
For comparison, electrodeposition of the dispersion liquid of Reference Example 26 was attempted in the same manner. However, electrodeposition of white particles was observed on both electrodes of the cathode anode.
(Reference Example 28)
In a reaction vessel similar to Reference Example 20, 300 parts of silicone oil (SH-200; 20cs) was taken and heated to 85 ° C. In this, 31 parts of the compound of the following structural formula,

Ｎ−ビニルピロリドン５部、ジエチルアミノエチルメタクリレート４部及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして、シリコーンオイルに可溶な高分子を含む溶液が重合率９３．６％で得られた。
この樹脂液１００部に対して、カーボンブラック５部を加えて、ボールミル分散し、平均粒径０．２μｍの分散液を得た。参考例２０と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。なお、撥水性３２．８、撥油性２９．７であった。
（参考例２９）
参考例２０と同様な反応容器に、シリコーンオイル（ＳＨ−２００；５ｃｓ）３００部を採り、８５℃に加熱した。この中に下記構造式の化合物３７部、

A solution consisting of 5 parts of N-vinylpyrrolidone, 4 parts of diethylaminoethyl methacrylate and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a solution containing a polymer soluble in silicone oil was obtained at a polymerization rate of 93.6%.
To 100 parts of this resin liquid, 5 parts of carbon black was added and dispersed in a ball mill to obtain a dispersion liquid having an average particle size of 0.2 μm. The dispersion stability was examined in the same manner as in Reference Example 20, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month. The water repellency was 32.8 and the oil repellency was 29.7.
(Reference Example 29)
In a reaction container similar to that of Reference Example 20, 300 parts of silicone oil (SH-200; 5cs) was taken and heated to 85 ° C. In this, 37 parts of the compound of the following structural formula,

マレイン酸2-メタクリロイルオキシエチル３及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして、シリコーンオイルに可溶な高分子を含む溶液が重合率９０．４％で得られた。

A solution consisting of 2-methacryloyloxyethyl maleate 3 and 1 part azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a solution containing a polymer soluble in silicone oil was obtained at a polymerization rate of 90.4%.

  To 50 parts of this resin liquid, 45 parts of the dispersion liquid of Reference Example 28 was added and stirred well to obtain a dispersion liquid of Reference Example 10. The dispersion stability was examined in the same manner as in Reference Example 20, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month. The water repellency was 33.1 and the oil repellency was 28.3.

This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. After applying the voltage, the electrode was taken out and observed. As a result, black particles were electrodeposited only on the cathode, and no deposition was observed on the anode. From this, it can be seen that all particles have a positive charge.
For comparison, electrodeposition of the dispersion of Reference Example 28 was attempted in the same manner, but black particle electrodeposition was observed on both electrodes of the cathode anode.
(Reference Example 30)
In a reaction container similar to that of Reference Example 20, 300 parts of silicone oil (SH-200; 5cs) was taken and heated to 85 ° C. In this, 30 parts of the compound of the following structural formula,

エチレングリコールジメタクリレート３部、N-メタクリロイルモルホリン３ぶジターシャリーブチルアミノエチルメタクリレート４部及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして粒径１〜３μｍの樹脂を含む分散液が重合率90.3％で得られた。この樹脂分散液１００部に対して、フタロシアニン８部を加えて、ボールミル分散し、平均粒径０．４μｍの分散液を得た。参考例２０と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。なお、撥水性２９．１、撥油性２６．８であった。
（参考例３１）
参考例２０と同様な反応容器に、シリコーンオイル（ＳＨ−２００；１ｃｓ）３００部を採り、８５℃に加熱した。この中に下記構造式の化合物３３部、

A solution consisting of 3 parts of ethylene glycol dimethacrylate, 3 parts of N-methacryloylmorpholine, 4 parts of tertiary butylaminoethyl methacrylate and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a dispersion containing a resin having a particle size of 1 to 3 μm was obtained at a polymerization rate of 90.3%. 8 parts of phthalocyanine was added to 100 parts of this resin dispersion, followed by ball mill dispersion to obtain a dispersion having an average particle size of 0.4 μm. The dispersion stability was examined in the same manner as in Reference Example 20, but it was found that the dispersion was very stable without precipitation even after being allowed to stand for one month. The water repellency was 29.1 and the oil repellency was 26.8.
(Reference Example 31)
In a reaction vessel similar to Reference Example 20, 300 parts of silicone oil (SH-200; 1 cs) was taken and heated to 85 ° C. In this, 33 parts of the compound of the following structural formula,

２−ヒドロキシエチルメタクリレート４部、メタクリル酸３部及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして、シリコーンオイルに可溶な高分子を含む溶液が重合率９５．６％で得られた。
参考例３０の分散液５０部に、この樹脂液４０部を加えて良く撹拌し、参考例３０の分散液を得た。撥水性２８．３、撥油性２６．０であった。

A solution consisting of 4 parts of 2-hydroxyethyl methacrylate, 3 parts of methacrylic acid and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a solution containing a polymer soluble in silicone oil was obtained at a polymerization rate of 95.6%.
40 parts of this resin liquid was added to 50 parts of the dispersion liquid of Reference Example 30 and stirred well to obtain a dispersion liquid of Reference Example 30. The water repellency was 28.3 and the oil repellency was 26.0.

  The dispersion liquid of Reference Example 31 was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. After applying the voltage, the electrode was taken out and observed, and the blue particles were electrodeposited only on the cathode, and no deposition was observed on the anode. From this, it can be seen that all particles have a positive charge.

For comparison, electrodeposition of the dispersion of Reference Example 30 was attempted in the same manner, but blue particle electrodeposition was observed on both electrodes of the cathode anode.
(Comparative Example 7)
In a reaction container similar to that of Reference Example 19, 300 parts of silicone oil (SH-200; 2cs) was taken and heated to 85 ° C. In this, 28 parts of the compound of the following structural formula,

マレイン酸2-メタクリロイルオキシエチル４部、ジメチルアミノエチルメタクリレート４部、ビニルピロリドン４部及びアゾビスイソブチロニトリル１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。この結果、反応器内には、シリコーンオイルと高分子とからなると考えられるゲル状物質が生成し、これを反応容器から取り出すことはできなかった。
（比較例８）
比較例７で得たゲル状物質を３部容器からかき取り、シリコーンオイル（ＳＨ−２００；２センチストークス）１０部、カーボンブラック１部とともにボールミルに投入し、分散液を得た。この分散液を、電極間隔５ｍｍの平行に配備された真鍮電極を有するテフロン（登録商標）製容器に注ぎ、１０００Ｖの直流電圧を１分間印加した。電圧印加後、電極を取り出して観察したところ、陰極陽極の両極に黒色粒子の電着が観測された。
（実施例３２）
撹拌機、温度計及び還流冷却器を備えた反応容器に、シリコーンオイル（東レダウコーニングシリコーンSH200、2cs）300部を採り、85℃に加熱した。この中に下記構造式の化合物50部、

A solution consisting of 4 parts of 2-methacryloyloxyethyl maleate, 4 parts of dimethylaminoethyl methacrylate, 4 parts of vinylpyrrolidone and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. As a result, a gel-like substance considered to be composed of silicone oil and polymer was generated in the reactor, and this could not be taken out from the reaction vessel.
(Comparative Example 8)
The gel-like substance obtained in Comparative Example 7 was scraped from a 3 part container and charged into a ball mill together with 10 parts of silicone oil (SH-200; 2 centistokes) and 1 part of carbon black to obtain a dispersion. This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. After applying the voltage, the electrode was taken out and observed, and black particle electrodeposition was observed on both electrodes of the cathode anode.
(Example 32)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 300 parts of silicone oil (Toray Dow Corning Silicone SH200, 2cs) was taken and heated to 85 ° C. In this, 50 parts of the compound of the following structural formula,

下記構造の化合物５部、

5 parts of a compound having the structure

アゾビスイソブチロニトリル３部よりなる溶液を1.5時間に亘つて滴下した。ついで90℃に昇温し、この温度で４時間撹拌し、反応を終了した。均一で透明な樹脂溶液が重合率99.1％で得られた。次にこの樹脂溶液100部に酸化チタン7部、染料（バイエル マクロレックスブルーＲＲ）0.1部を加えボールミルで分散して分散液を作った。長さ４０ｃｍのガラス管を垂直に立て、この分散液を高さ３０ｃｍのところまで注液した。一ヶ月間放置後、目視判定したが、沈殿はなく非常に安定な分散液であることが分かった。
（実施例３３）
実施例３２と同様な反応容器に、シリコーンオイル（ＳＨ−２００；１ｃｓ）３００部を採り、90℃に加熱した。この中に下記構造式の化合物４３部、

A solution consisting of 3 parts of azobisisobutyronitrile was added dropwise over 1.5 hours. Then, the temperature was raised to 90 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. A uniform and transparent resin solution was obtained with a polymerization rate of 99.1%. Next, 7 parts of titanium oxide and 0.1 part of a dye (Bayer Macrolex Blue RR) were added to 100 parts of this resin solution and dispersed with a ball mill to prepare a dispersion. A glass tube having a length of 40 cm was set up vertically, and this dispersion was poured to a height of 30 cm. Visual judgment was made after standing for one month, but it was found that the dispersion was very stable without precipitation.
(Example 33)
In a reaction container similar to that in Example 32, 300 parts of silicone oil (SH-200; 1cs) was taken and heated to 90 ° C. In this, 43 parts of the compound of the following structural formula,

下記構造式の化合物５部、

5 parts of a compound of the structural formula

メタクリル酸２部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして均一で透明な樹脂溶液が重合率96.9％で得られた。次にこの樹脂溶液100部にカーボンブラック1部を加えボールミルで分散して分散液を作った。実施例３２と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（実施例３４）
実施例３２と同様な反応容器に、シリコーンオイル（ＳＨ−２００；１ｃｓ）３００部を採り、90℃に加熱した。この中に下記構造式の化合物４２部、

A solution consisting of 2 parts of methacrylic acid and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a uniform and transparent resin solution was obtained at a polymerization rate of 96.9%. Next, 1 part of carbon black was added to 100 parts of this resin solution and dispersed with a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Example 34)
In a reaction container similar to that in Example 32, 300 parts of silicone oil (SH-200; 1cs) was taken and heated to 90 ° C. In this, 42 parts of the compound of the following structural formula,

下記構造式の化合物３部、

3 parts of a compound of the structural formula

ジメチルアミノエチルメタクリレート５部及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして均一で透明な樹脂溶液が重合率93.3％で得られた。実施例３２と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（実施例３５）
実施例３２で用いた反応容器にシリコーンオイル（SH200、1cs）300部を採り、80℃に加熱した。この中に下記構造式の化合物１０部、

A solution consisting of 5 parts of dimethylaminoethyl methacrylate and 1 part of benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. In this way, a uniform and transparent resin solution was obtained with a polymerization rate of 93.3%. The dispersion stability was examined in the same manner as in Example 32, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Example 35)
In a reaction vessel used in Example 32, 300 parts of silicone oil (SH200, 1cs) was taken and heated to 80 ° C. In this, 10 parts of the compound of the following structural formula,

シクロヘキシルメタクリレート３５部、ジブチルアミノエチルメタクリレート５部、ベンゾイルパーオキサイド３部よりなる溶液を５時間に亘つて滴下した。次いで85℃で２時間撹拌して反応終了した。こうして乳白色の樹脂分散液が重合率92.7％で得られた。次にこの樹脂分散液５０部に実施例３２で作製した樹脂溶液５０部を加えボールミルで分散して分散液を作った。実施例３２と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（実施例３６）
実施例３２と同様な反応容器にシリコーンオイル（SH200、１cs）500部を採り、80℃に加熱した。この中に下記構造式の化合物２５部、

A solution consisting of 35 parts of cyclohexyl methacrylate, 5 parts of dibutylaminoethyl methacrylate and 3 parts of benzoyl peroxide was added dropwise over 5 hours. Subsequently, the reaction was completed by stirring at 85 ° C. for 2 hours. Thus, a milky white resin dispersion was obtained with a polymerization rate of 92.7%. Next, 50 parts of the resin dispersion was added with 50 parts of the resin solution prepared in Example 32 and dispersed with a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Example 36)
In a reaction container similar to that in Example 32, 500 parts of silicone oil (SH200, 1cs) was taken and heated to 80 ° C. In this, 25 parts of the compound of the following structural formula,

エチレングリコールジメタクリレート２０部、ジメチルアミノエチルメタクリレート５部及びアゾビスイソブチロニトリル５部よりなる溶液を３時間に亘つて滴下した。次いで85℃に昇温し、この温度で４時間撹拌し、反応を終了した。濾過、洗浄処理により重合率94.1％で樹脂が得られた。次にシリコーンオイル（SH200、１cs）４５部にこの樹脂５部、実施例３２で作製した樹脂溶液５０部を加え超音波分散して分散液を作った。参考例３１と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（実施例３７）
実施例３２と同様な反応容器に、シリコーンオイル（ＳＨ−２００；１ｃｓ）３００部を採り、90℃に加熱した。この中に下記構造式の化合物４４部、

A solution consisting of 20 parts of ethylene glycol dimethacrylate, 5 parts of dimethylaminoethyl methacrylate and 5 parts of azobisisobutyronitrile was added dropwise over 3 hours. Subsequently, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. By filtration and washing treatment, a resin was obtained with a polymerization rate of 94.1%. Next, 5 parts of this resin and 50 parts of the resin solution prepared in Example 32 were added to 45 parts of silicone oil (SH200, 1 cs) and ultrasonically dispersed to prepare a dispersion. The dispersion stability was examined in the same manner as in Reference Example 31, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Example 37)
In a reaction container similar to that in Example 32, 300 parts of silicone oil (SH-200; 1cs) was taken and heated to 90 ° C. In this, 44 parts of the compound of the following structural formula,

下記構造式の化合物４部、

4 parts of a compound of the structural formula

メタクリル酸１部、ビニルピロリドン１部、及びアゾビスイソブチロニトリル５部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして均一で半透明な高分子ゲル分散液が重合率95.4％で得られた。次にこの高分子ゲル分散液５０部に参考例４で作製した樹脂分散液５０部、酸化チタン7部、染料（バイエル マクロレックスブルーＲＲ）0.1部を加えボールミルで分散して分散液を作った。実施例３２と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（参考例３８）
シリコーンオイル（SH200、１cs）４５部に参考例５で作製した樹脂５部、実施例３６で作製した高分子ゲル分散液５０部、を加え超音波分散して分散液を作った。この分散液を、電極間隔５ｍｍの平行に配備された真鍮電極を有するテフロン（登録商標）製容器に注ぎ、１０００Ｖの直流電圧を１分間印加した。電圧印加後、電極を取り出して観察したところ、白色粒子は陰極にのみ電着し、陽極には析出が認められなかった。このことから、粒子は全て正の電荷を帯びていることが分かる。
（実施例３９）
実施例３２で用いた反応容器にシリコーンオイル（SH200、1cs）５００部を採り、80℃に加熱した。この中に下記構造式の化合物２０部、

A solution consisting of 1 part of methacrylic acid, 1 part of vinyl pyrrolidone and 5 parts of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. In this way, a uniform and translucent polymer gel dispersion was obtained with a polymerization rate of 95.4%. Next, 50 parts of the polymer gel dispersion liquid, 50 parts of the resin dispersion liquid prepared in Reference Example 4, 7 parts of titanium oxide, and 0.1 part of a dye (Bayer Macrolex Blue RR) were added and dispersed with a ball mill to prepare a dispersion liquid. . The dispersion stability was examined in the same manner as in Example 32, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Reference Example 38)
To 45 parts of silicone oil (SH200, 1 cs), 5 parts of the resin prepared in Reference Example 5 and 50 parts of the polymer gel dispersion prepared in Example 36 were added and ultrasonically dispersed to prepare a dispersion. This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. After applying the voltage, the electrode was taken out and observed. As a result, white particles were electrodeposited only on the cathode, and no deposition was observed on the anode. From this, it can be seen that all particles have a positive charge.
(Example 39)
500 parts of silicone oil (SH200, 1cs) was taken in the reaction vessel used in Example 32 and heated to 80 ° C. In this, 20 parts of the compound of the following structural formula,

エチレングリコールジメタクリレート２５部、２−ヒドロスチレンスルホン酸5部、ベンゾイルパーオキサイド３部よりなる溶液を５時間に亘つて滴下した。次いで85℃で２時間撹拌して反応終了した。濾過、洗浄処理により重合率90.3％で樹脂が得られた。次にシリコーンオイル（SH200、1cs）４５部この樹脂５部、実施例３４で作製した樹脂溶液５０部を加え超音波分散して分散液を作った。実施例３２と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（実施例４０）
実施例３２と同様な反応容器にシリコーンオイル（SH200、１cs）500部を採り、80℃に加熱した。この中に下記構造式の化合物１０部、

A solution consisting of 25 parts of ethylene glycol dimethacrylate, 5 parts of 2-hydrostyrene sulfonic acid and 3 parts of benzoyl peroxide was added dropwise over 5 hours. Subsequently, the reaction was completed by stirring at 85 ° C. for 2 hours. By filtration and washing treatment, a resin was obtained with a polymerization rate of 90.3%. Next, 45 parts of silicone oil (SH200, 1cs) 5 parts of this resin and 50 parts of the resin solution prepared in Example 34 were added and ultrasonically dispersed to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Example 40)
In a reaction container similar to that in Example 32, 500 parts of silicone oil (SH200, 1cs) was taken and heated to 80 ° C. In this, 10 parts of the compound of the following structural formula,

ラウリルメタクリレート30部、ラウリルメタクリルアミド5部、メタクリル酸5部及びアゾビスイソブチロニトリル５部よりなる溶液を３時間に亘つて滴下した。次いで85℃に昇温し、この温度で４時間撹拌し、反応を終了した。こうして樹脂分散液が重合率91.7％で得られた。次にこの樹脂分散液５０部に実施例３４で作製した樹脂溶液５０部、酸化チタン7部、染料（バイエル マクロレックスブルーＲＲ）0.1部を加えボールミルで分散して分散液を作った。実施例３２と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（実施例４１）
実施例３２と同様な反応容器に、シリコーンオイル（ＳＨ−２００；１ｃｓ）３００部を採り、90℃に加熱した。この中に下記構造式の化合物４４部、

A solution consisting of 30 parts lauryl methacrylate, 5 parts lauryl methacrylamide, 5 parts methacrylic acid and 5 parts azobisisobutyronitrile was added dropwise over 3 hours. Subsequently, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. Thus, a resin dispersion was obtained with a polymerization rate of 91.7%. Next, 50 parts of the resin dispersion, 50 parts of the resin solution prepared in Example 34, 7 parts of titanium oxide, and 0.1 part of a dye (Bayer Macrolex Blue RR) were added and dispersed with a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Example 41)
In a reaction container similar to that in Example 32, 300 parts of silicone oil (SH-200; 1cs) was taken and heated to 90 ° C. In this, 44 parts of the compound of the following structural formula,

下記構造式の化合物４部、

4 parts of a compound of the structural formula

ジメチルアミノエチルメタクリレート１部、ビニルピロリドン１部、及びベンゾイルパーオキサイド１部よりなる溶液を１時間に亘つて滴下した。次いで同温度で５時間撹拌を続け、反応を終了した。こうして均一で透明な樹脂溶液が重合率92.4％で得られた。次にこの樹脂溶液５０部に参考例８で作製した樹脂分散液５０部、カーボンブラック1部を加えボールミルで分散して分散液を作った。実施例３２と同様にして、分散安定性を調べたが、一ヶ月間放置後も沈殿はなく、非常に安定な分散液であることが分かった。
（実施例４２）
実施例４０で作製した樹脂分散液５０部、実施例４０で作製した樹脂溶液５０部、酸化チタン7部、染料（バイエル マクロレックスブルーＲＲ）0.1部を加えボールミルで分散して分散液を作った。この分散液を、電極間隔５ｍｍの平行に配備された真鍮電極を有するテフロン（登録商標）製容器に注ぎ、１０００Ｖの直流電圧を１分間印加した。電圧印加後、電極を取り出して観察したところ、白色粒子は陽極にのみ電着し、陰極には析出が認められなかった。このことから、粒子は全て負の電荷を帯びていることが分かる。
（比較例９）
シリコーンオイル（東レダウコーニングシリコーンSH200、2cs）１００部に酸化チタン7部、染料（バイエル マクロレックスブルーＲＲ）0.1部を加えボールミルで分散して分散液を作製し、参考例３１と同様にして分散安定性を調べたが、一日の放置で上澄み部分が２０ｃｍ程現れ、非常に不安定な分散液であった。
（比較例１０）
実施例３２と同様な反応容器にシリコーンオイル（SH200、１cs）500部を採り、80℃に加熱した。この中に下記構造式の化合物２５部、

A solution consisting of 1 part dimethylaminoethyl methacrylate, 1 part vinylpyrrolidone, and 1 part benzoyl peroxide was added dropwise over 1 hour. Subsequently, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a uniform and transparent resin solution was obtained with a polymerization rate of 92.4%. Next, 50 parts of the resin solution and 50 parts of the resin dispersion prepared in Reference Example 8 and 1 part of carbon black were added and dispersed with a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32, but it was found that the dispersion was very stable without precipitation even after being left for one month.
(Example 42)
50 parts of the resin dispersion prepared in Example 40, 50 parts of the resin solution prepared in Example 40, 7 parts of titanium oxide, and 0.1 part of a dye (Bayer Macrolex Blue RR) were added and dispersed with a ball mill to prepare a dispersion. . This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. When voltage was applied and the electrode was taken out and observed, white particles were electrodeposited only on the anode, and no deposition was observed on the cathode. From this, it can be seen that the particles are all negatively charged.
(Comparative Example 9)
Disperse in the same manner as in Reference Example 31 by adding 7 parts of titanium oxide and 0.1 part of dye (Bayer Macrolex Blue RR) to 100 parts of silicone oil (Toray Dow Corning Silicone SH200, 2cs) and dispersing with a ball mill. The stability was examined, but the supernatant portion appeared about 20 cm after standing for a day, and the dispersion was very unstable.
(Comparative Example 10)
In a reaction container similar to that in Example 32, 500 parts of silicone oil (SH200, 1cs) was taken and heated to 80 ° C. In this, 25 parts of the compound of the following structural formula,

エチレングリコールジメタクリレート２５部及びアゾビスイソブチロニトリル５部よりなる溶液を３時間に亘つて滴下した。次いで85℃に昇温し、この温度で４時間撹拌し、反応を終了した。濾過、洗浄処理により重合率90.5％で樹脂が得られた。この樹脂１０部をシリコーンオイル（ＳＨ−２００；２ｃｓ）１００部、カーボンブラック１部とともにボールミルに投入し、分散液を得た。この分散液を、電極間隔５ｍｍの平行に配備された真鍮電極を有するテフロン（登録商標）製容器に注ぎ、１０００Ｖの直流電圧を１分間印加した。電圧印加後、電極を取り出して観察したところ、陰極陽極の両極に黒色粒子の電着が観測された。

A solution consisting of 25 parts of ethylene glycol dimethacrylate and 5 parts of azobisisobutyronitrile was added dropwise over 3 hours. Subsequently, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. By filtration and washing treatment, a resin was obtained with a polymerization rate of 90.5%. 10 parts of this resin was charged into a ball mill together with 100 parts of silicone oil (SH-200; 2cs) and 1 part of carbon black to obtain a dispersion. This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied for 1 minute. After applying the voltage, the electrode was taken out and observed, and black particle electrodeposition was observed on both electrodes of the cathode anode.

Japanese Patent Publication No. 40-7047 JP-A-9-255728 Japanese Patent Laid-Open No. 10-30010 JP-A-6-41402 Japanese Unexamined Patent Publication No. 6-65477 JP-A-7-146660 Japanese Patent Laid-Open No. 7-292383

F. A. Waite, J. Oil Col. Chem. Assoc., 54, 342 (1971)

Claims (7)

In the silicone oil, containing at least a particle component insoluble in the silicone oil and a polymer obtained by polymerizing at least a monomer represented by the following general formula (II),

[Wherein, R represents a hydrogen atom or a methyl group, and n represents a natural number. ]
A monomer represented by the following general formula (III):

[Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, x represents an integer of 1 to 3, and y represents a natural number of 25 or less. ]
A dispersion liquid characterized by further polymerizing.   Contains a copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group or a basic group and copolymerizable with the monomer represented by the general formula (II) The dispersion according to claim 1.   A copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group and copolymerizable with the monomer represented by the general formula (II); A copolymer of a monomer represented by II) and a monomer having a basic group and copolymerizable with the monomer represented by the general formula (II). Item 4. The dispersion according to Item 1.   A copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group and copolymerizable with the monomer represented by the general formula (II), or the general formula ( The copolymer of the monomer represented by II) and the monomer having a basic group and copolymerizable with the monomer represented by the general formula (II) is insoluble in the silicone oil. The dispersion according to claim 3.   A copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group and copolymerizable with the monomer represented by the general formula (II); II) and at least any one of a copolymer of a monomer having a basic group and copolymerizable with the monomer represented by the general formula (II) is a polar group 5. The dispersion according to claim 3, wherein the dispersion is a copolymer of a monomer having a diol and a monomer that can be copolymerized with the monomer represented by the general formula (II).   The dispersion liquid according to claim 1, wherein the silicone oil has a viscosity of 200 cSt or less.   Content of the said particle component is 0.1-20 mass%, The dispersion liquid of any one of Claims 1-6 characterized by the above-mentioned.