JP2002256133A - Dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersion in which the dispersed particles have an excellent affinity for a hydrocarbon solvent or a silicone oil and are enabled to be sterically stable and which therefore has excellent dispersion stability. SOLUTION: This dispersion essentially consists of a hydrocarbon solvent, a particulate component insoluble in the solvent, and a polymer being compatible with the solvent and prepared by polymerizing at least a monomer represented by formula (I) (wherein R1 is hydrogen or methyl; R2 is hydrogen or a 1-4C alkyl; x is an integer of 1-3; and y is a natural number of 25 or smaller).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersion liquid, and more particularly, to a treatment agent for fibers, paper, plastic surfaces, metal surfaces, etc., a release agent using them, a printing ink, an ink jet ink, an adhesive, The present invention relates to a dispersion liquid useful for electrophotographic toners including dry toners and wet toners, paints, electrodeposition paints, displays, magnetic fluids, rubber roller coating materials, cosmetics, and the like.

[0002]

2. Description of the Related Art In a dispersion in which particles of a resin, a pigment, a magnetic substance and the like are dispersed in an appropriate solvent, the stability of the dispersed particles is an important issue in both a non-aqueous solvent system and an aqueous solvent system.

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

[0004] Regarding the electrostatic effect, the DLVO theory has been established, and 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 them is necessary, and some studies have been made on aqueous solvent systems in which the presence of ions is clearly defined.

On the other hand, a steric effect equivalent to the DLVO theory has not yet been established, but the following research is known in non-aqueous solvent systems (mainly petroleum solvents).

That is, FA Waite, J. Oil Col. Chem. Ass
oc., 54, 342 (1971) relates to a basic method for producing a stable non-aqueous solvent-based dispersion, which involves dispersing particles (solvent-insoluble) in a solvent in the solvent. To produce a block or graft copolymer containing a component that is compatible with the solvent and a component that is soluble in the solvent.

As a method utilizing this method, Japanese Patent Publication No.
No. 7047 describes a method for obtaining a stable polymethyl methacrylate (PMMA) dispersion by radical polymerization of methyl methacrylate (MMA) in the presence of a degraded rubber in a hydrocarbon solvent. It is not considered that the degraded rubber is adsorbed to the PMMA particles by this method, and it is considered that MMA is graft-polymerized to the degraded rubber from the fact that the PMMA particles are dispersion-stabilized. It is also believed that the insoluble portion of the graft polymer is associated with the particle surface, and the dissolved portion has a steric effect, thereby maintaining the dispersion stability of the particle.

Regarding the above, Japanese Patent Application Laid-Open No. 9-255728 and Japanese Patent Application Laid-Open No. 10-30010 can be cited as disclosures of the aqueous solvent dispersion technology.

Japanese Patent Application Laid-Open Nos. 6-41402 and 6-6-6 disclose non-aqueous solvent-based dispersion techniques.
No. 5,777,547.

Also, unlike conventional non-aqueous solvents, heat resistance,
JP-A-7-146660 and JP-A-7-292383 disclose dispersion techniques in silicone oil having various characteristics such as excellent cold resistance and chemical inertness. And the like.

[0011]

However, conventionally,
It is not known to disperse solid particles in a petroleum-based solvent, that is, a non-aqueous solvent-based dispersion such as a non-polar aprotic solvent, sufficiently and stably by charging them with ions clearly. The life of dispersions for coatings, electrophotographic liquid developers or displays has been limited.

In recent years, hydrocarbon solvents having a certain degree of viscosity have been used for dispersions in view of environmental aspects such as easy handling, low volatility and odorlessness.
In particular, it is disadvantageous in terms of fluid resistance with respect to an electrodeposition paint, an electrophotographic liquid developer or a dispersion for display, and its application is limited in terms of both dispersion stability and electrophoretic characteristics.
Therefore, a technique for dispersing and stabilizing solid particles by ionic charging even in a viscous nonpolar solvent is required.

Also, unlike a non-polar aprotic solvent represented by a conventional petroleum solvent, the silicone oil solvent does not stably dissolve and disperse the polymer. That is, it is very difficult to stabilize a dispersion using silicone oil,
It has been difficult to produce a long-term stable dispersion.

The present invention has been made in view of the above-mentioned problems, and is intended to provide a hydrocarbon solvent system having excellent affinity with a hydrocarbon solvent, imparting steric stabilization to dispersed particles, and having excellent dispersion stability. It is a first object to provide a dispersion.

Further, the present invention provides an excellent affinity for silicone oil and a steric stabilizing effect on dispersed particles,
A second object is to provide a dispersion having an improved degree of dispersion in silicone oil.

[0016]

DISCLOSURE OF THE INVENTION The dispersion of the present invention has a particle component which is at least insoluble in a hydrocarbon solvent and is compatible with the hydrocarbon solvent. ) Monomer

[0017]

Embedded image [In the formula, 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. ] Is polymerized.

This makes it possible to provide a hydrocarbon solvent-based dispersion liquid which has an excellent affinity for a hydrocarbon solvent, gives a steric stabilizing effect to the dispersed particles, and has an excellent dispersion stability.

Further, the dispersion of the present invention is characterized in that the polymer is polymerized by further containing at least one of a monomer having an acidic group and a monomer having a basic group. And

Thus, 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.

The dispersion of 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.

Thus, it is possible to provide a hydrocarbon solvent-based dispersion liquid which imparts electric charge to the dispersed particles, improves dispersibility by electrostatic repulsion, and enables electrophoresis.

Further, the dispersion of the present invention is characterized in that at least one of the surface of the particle component and at least one of the polymer has a nonionic polar group.

This makes it possible to provide a hydrocarbon solvent-based dispersion liquid which is more stable and has excellent electrophoretic properties due to the synergistic effect of the steric stabilizing action and the stabilizing action due to electrostatic repulsion on the dispersed particles.

The dispersion of the present invention comprises a hydrocarbon solvent having a viscosity of at least 10 mPa · s at room temperature,
It contains a particle component insoluble in the solvent and a resin soluble in the solvent.

As a result, it is possible to provide a dispersion system having an excellent affinity for a hydrocarbon solvent.

The dispersion of the present invention is characterized in that the resin has an acidic group or a basic group.

Thus, a dispersion having good dispersibility in a hydrocarbon solvent can be provided.

Further, the dispersion of the present invention is characterized in that at least the surface of the particle component has an acidic group or a basic group.

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

The dispersion of the present invention is characterized in that at least one of the surface 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 more excellent charge amount of particles.

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

[0034]

Embedded image [Wherein, R represents a hydrogen atom or a methyl group, and n represents a natural number. This makes it possible to provide a dispersion excellent in affinity with the silicone oil.

Further, the dispersion of the present invention has the general formula (I)
It is characterized by containing a copolymer of the monomer represented by I) and a monomer having an acidic group or a basic group.

This makes it possible to provide a dispersion system which has a strong interaction with the dispersed particles and has an excellent affinity for the silicone oil.

Further, the dispersion of the present invention has the general formula (I)
Contains a copolymer of a monomer represented by I) and a monomer having an acidic group and a copolymer of a monomer represented by the general formula (II) and a monomer having a basic group It is characterized by doing.

Thus, it is possible to provide a dispersion liquid which imparts electric charge to the dispersed particles, improves dispersibility by electrostatic repulsion, and enables electrophoresis.

Further, the dispersion of the present invention has the general formula (I)
The copolymer of the monomer represented by I) and the monomer having an acidic group or the copolymer of the monomer represented by the general formula (II) and the monomer having a basic group is the above-described copolymer. It is insoluble in silicone oil.

As a result, it is possible to provide a dispersion liquid which is more stable and has excellent electrophoretic properties due to the synergistic effect of the steric stabilizing action and the stabilizing action due to electrostatic repulsion on the dispersed particles.

Further, the dispersion of the present invention has the general formula (I)
At least one of a copolymer of a monomer represented by I) and a monomer having an acidic group and a copolymer of a monomer represented by the general formula (II) and a monomer having a basic group One of them is a copolymer with a monomer having a polar group.

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

Further, the dispersion of the present invention comprises a polymer, wherein the polymer is a monomer represented by the following general formula (III):

[0044]

Embedded image [In the formula, 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. ] Is further polymerized.

This makes it possible to provide a silicone oil dispersion which is excellent in affinity with the silicone oil and has a steric stabilizing effect on the dispersed particles, whereby the dispersion is stable.

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

Thus, it is possible to provide a dispersion liquid which imparts electric charge to the dispersed particles, improves dispersibility by electrostatic repulsion, and enables electrophoresis.

The dispersion of the present invention is characterized in that at least one of the surface of the particle component and at least one of the polymer has a nonionic polar group.

Thus, a more stable and excellent electrophoretic dispersion can be provided by the synergistic effect of the steric stabilizing action and the stabilizing action by electrostatic repulsion on the dispersed particles.

Further, the dispersion of the present invention is characterized in that the viscosity of the silicone oil is 200 cSt (centistokes) or less.

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

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

Thus, it is possible to provide a silicone oil dispersion which is inexpensive and has excellent storage characteristics.

Heretofore, in a non-aqueous solvent, particularly in a non-polar aprotic solvent dispersion, the existence of ions or charges has been unclear. This is presumably because the interaction (solvation) between ions and solvent molecules hardly occurs in this type of solvent.

Therefore, the present inventors have an acidic group,
Organic substance without basic group, with basic group,
Organic substances having no acidic group and organic substances having a nonionic polar component which are compatible with the solvent.
As a result of various experiments on the hydrocarbon solvent-based dispersion containing the component (either component of which may be present as a copolymer with the component), in the solvent and the component, acid-base ion dissociation occurs. I found that. It was also suggested that ion-dipole interaction, ie, solvation, was present. Thus, the present inventors, in the solvent,
It has been found that, when the three components are present, ions can be stably present even in a hydrocarbon solvent due to ionic dissociation between an acid and a base via solvation of polar groups in the components. This fact was similarly observed whether both components were soluble or insoluble in the solvent.

Further, the present inventors have found that when a fixed particle such as a pigment or a metal oxide is further coexisted in a system containing the three components, the acid group or the basic group of the component or It has been found that ion dissociation occurs at the interface between the surface of the solid particles and the solvent via the solvation of the components as fixed by the following.

Further, the dispersion stability of the particles, which is considered to be due to the steric effect of the polyoxyalkylene group, was confirmed. As a result, the solid particles are uniformly charged to a positive or negative polarity, and the solid particles are dispersed more stably than before by the synergistic action of the electrostatic effect and the steric effect.

The present inventors have further found that the ion amount and the charge amount can be controlled by the type and amount of each component. The present invention is based on the above findings.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, first to fourth dispersions according to embodiments of the present invention will be sequentially described. (First Dispersion) The dispersion of the present invention relates to a dispersion of a hydrocarbon solvent system.

The dispersion of the present invention contains a monomer which is compatible with the hydrocarbon solvent and a polymer obtained by polymerizing the monomer represented by the above general formula (I) as a constituent element. Excellent affinity with hydrocarbon solvents and (poly)
The dispersion stability of the dispersed particles increases due to the steric effect of the oxyalkylene group.

The dispersion of the present invention comprises a monomer which is compatible with a hydrocarbon solvent, a monomer represented by the general formula (I), and a monomer having an acidic group as constituents. By containing the polymer, the interaction between the polymer and the particles is increased, and a dispersion having excellent affinity with a hydrocarbon solvent is obtained.

The dispersion of the present invention comprises a monomer compatible with a hydrocarbon solvent, a monomer represented by the general formula (I), and a monomer having a basic group. By containing a polymer that has been polymerized as above, the interaction between the polymer and the particles by adsorption is increased, and a dispersion having excellent affinity with a hydrocarbon solvent is obtained.

In the dispersion of the present invention, a particle component insoluble in a hydrocarbon solvent has at least a basic group on its surface, so that a positive charge is imparted to the dispersed particles by acid-base dissociation, and electrostatic repulsion is achieved. Force improves dispersibility and enables electrophoresis.

In the dispersion of the present invention, since at least the particle component insoluble in the hydrocarbon solvent has a nonionic polar group other than the (poly) oxyalkylene group, a solvation effect on acid-base dissociation is exhibited. In addition, the dispersibility of the dispersed particles due to electrostatic repulsion and the electrophoretic characteristics can be improved.

In addition, in the dispersion of the present invention, at least a monomer compatible with at least a hydrocarbon solvent, represented by the general formula (I):
The polymer represented by the formula and a monomer having an acidic group as a constituent component has a nonionic polar group other than a (poly) oxyalkylene group, so that the solvation effect on acid-base dissociation is improved. It is possible to improve the dispersibility of the dispersed particles due to electrostatic repulsion and the electrophoretic properties.

Further, in the dispersion of the present invention, a particle component insoluble in a hydrocarbon solvent, a monomer compatible with the hydrocarbon solvent, a monomer represented by the general formula (I), Since both polymers obtained by polymerizing the monomer having an acidic group as a constituent requirement have a nonionic polar group other than the (poly) oxyalkylene group, it is possible to further improve the charge amount related to the charging of the particles. Becomes

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

In the dispersion of the present invention, since at least the particle component insoluble in the hydrocarbon solvent has a nonionic polar group other than the (poly) oxyalkylene group, a solvation effect on acid-base dissociation is exhibited. In addition, the dispersibility of the dispersed particles due to electrostatic repulsion and the electrophoretic characteristics can be improved.

In the dispersion of the present invention, at least a monomer compatible with at least a hydrocarbon solvent, a compound represented by the general formula (I):
The solvation effect on acid-base dissociation due to the fact that a polymer obtained by polymerizing the monomer represented by the formula and a monomer having a basic group as a constituent component has a nonionic polar group other than a (poly) oxyalkylene group And the dispersibility of the dispersed particles due to electrostatic repulsion and the electrophoretic properties can be improved.

Further, in the dispersion of the present invention, a particle component insoluble in a hydrocarbon solvent, a monomer compatible with the hydrocarbon solvent, a monomer represented by the general formula (I), Since both the polymer obtained by polymerizing the monomer having a basic group as a constituent requirement has a nonionic polar group other than the (poly) oxyalkylene group, it is possible to further improve the charge amount related to the charging of the particles. It becomes possible.

Hereinafter, the configuration of the present invention will be described in more detail.

The hydrocarbon solvent used as a dispersion medium in the present invention includes paraffinic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane and dodecane; isoparaffinic hydrocarbons such as isohexane, isooctane and isododecane; Alkyl naphthenic hydrocarbons such as liquid paraffin, benzene, toluene, xylene,
Aromatic hydrocarbons such as alkylbenzene, solvent naphtha and the like can be mentioned.

The polymer of the present invention comprises a monomer having a high affinity for a hydrocarbon solvent, an acrylic monomer having a (poly) oxyalkylene group, and, if necessary, an acidic group or a basic group. And a monomer having a polar group. Hereinafter, the polymerizable monomer in the present invention will be further described.

First, a monomer having a high affinity for a hydrocarbon solvent gives a polymer which is soluble in the hydrocarbon solvent when the polymer composed of such a monomer is a homopolymer. In the case of a copolymer with the above-mentioned monomer, even if the copolymer is soluble or insoluble, it has a high affinity for 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, and stearyl (meth) acrylate. 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, etc. It is below.

The acrylic monomer having a (poly) oxyalkylene group is a monomer represented by the above general formula (I), wherein the repeating unit of the oxyethylene group is 25.
The copolymer having the following polyethylene glycol chain and having the monomer as a component is adsorbed on particles insoluble in a solvent, and the dispersion of the particles is stabilized by the steric effect exhibited by the polyethylene glycol chain.

Next, examples of the monomer copolymerizable with the above-mentioned monomer include the following. (B) examples of the monomer having an acidic group: These are the monomeric vinyl group and -COOH group, -SO ₃ H group, _-SO 2 H
Groups, _-CH 2 NO ₂ group, -CHRNO ₂ group, -ArOH
And at least one of an —ArSH group and the like (where 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, vinylbenzoic 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
-Acrylamide-2-methylpropanesulfonic acid, 3
-Chloroamidophosphoxypropyl methacrylate, 2
-Methacryloxyethyl acid phosphate and the like. (B) Examples of monomers having a basic group: These monomers include a vinyl group, a —NH ₂ group, a —NHR group, and a —NRR ′
A group having at least one of a group, a pyridyl group and a piperidyl group (where R and R 'are an alkyl group or an 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, Examples include N-phenylaminoethylstyrene, 2-N-piperidylethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine and the like. (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-cyanoethylacrylate, ethyl-2-cyanoacrylate, methacrylacetone, vinylpyrrolidone, N-acryloylmorpholine, tetrahydrofurfuryl methacrylate, trifluoro Ethyl methacrylate, p-nitrostyrene, acrylamide, methacrylamide, N, N-dimethylmethacrylamide, N, N-dibutylmethacrylamide and the like can be mentioned. (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, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylol hexane tri (meth) acrylate, bentaerythrit Tetra (meth) acrylate,
1,3-dibutylene glycol di (meth) acrylate,
And trimethylolethanetri (meth) acrylate.

The polymer used in one embodiment (A) of the present invention is a copolymer of a monomer having a high affinity for a hydrocarbon solvent and a monomer represented by the general formula (I). Polymers.

Examples of the particle component insoluble in the hydrocarbon solvent include various insoluble resins, generally known inorganic or organic pigments, metals, metal oxides, magnetic powders, and wax-like substances (eg, low molecular weight polyolefins and waxes). , Chemical products (for example, agricultural chemicals), and swelling agents.

More specifically, for example, carbon black, lamp black, ultramarine, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, lake, calco oil blue,
Chrome yellow, quinacridone, benzidine yellow,
Any conventionally known dyes and pigments such as rose bengal and triallylmethane dyes can be used alone or in combination. In addition, iron oxides such as magnetite, hematite, ferrite, iron, carbonyl iron powder, cobalt,
Metals such as nickel or alloys of these metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and the like Mixtures, glass beads and the like can be mentioned. Also, as an example of resin particles,
Styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and its substituted homopolymer; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinyl Naphthalene 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-vinyl ethyl Ether copolymer, styrene -Vinyl methyl ketone copolymer,
Styrene-based copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer are exemplified.

Further, there may be mentioned a copolymer of a monomer having a high affinity for at least a hydrocarbon solvent and the monomer (d). However, in this case, the ratio of using these monomers cannot be unconditionally defined, and the intended insoluble resin is obtained by empirical use. However,
In order to obtain the insoluble resin most reliably, it can be achieved by using the monomer (d) in a relatively large amount.

Further, in the dispersion of the present invention, a dye soluble in a hydrocarbon solvent may be added to the dispersion or chemically bonded to the dispersoid to color the dispersion or the dispersoid depending on the purpose of use. Can also.

The polymer used in another embodiment (B) of the present invention includes a monomer having a high affinity for a hydrocarbon solvent, a monomer represented by the general formula (I), And copolymers with the monomer (a). Examples of the particle component insoluble in the hydrocarbon solvent include the particle component used in the embodiment (A) of the present invention.

The polymer used in still another embodiment (C) of the present invention includes a monomer having a high affinity for a hydrocarbon solvent, a monomer represented by the general formula (I), Copolymers with the monomer (b) are mentioned. Also,
Examples of the particle component insoluble in the hydrocarbon solvent include the particle component used in the embodiment (A).

The polymer used in still another embodiment (D) of the present invention includes the polymer used in the above embodiment (B). Further, as the particle component insoluble in the hydrocarbon solvent, as the binder of the insoluble particle component in the above embodiment (A), a resin insoluble in the hydrocarbon solvent solvent having the monomer (b) as a component is used. Used ones. 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, a basic group is formed by reacting the substance (b) with the substance. They may be chemically bonded.

The polymer used in still another embodiment (E) of the present invention includes the polymer used in the above embodiment (B). Further, as the particle component insoluble in the hydrocarbon solvent, as the binder of the insoluble particle component in the above embodiment (A), the monomer of (b) and the monomer of (c) are used as components. And a resin using a resin insoluble in a hydrocarbon solvent. 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 particles, the monomer (b) and the monomer (c) are added to these substances. To form a chemical bond between a basic group and a polar group.

The polymer used in still another embodiment (F) of the present invention includes a monomer compatible with a hydrocarbon solvent, a monomer represented by the general formula (I), And the copolymer of the monomer (a) and the monomer (c). In addition, examples of the particle component insoluble in the hydrocarbon solvent include the particle component used in the above embodiment (D).

The polymer used in still another embodiment (G) of the present invention includes the copolymer used in the above embodiment (F). In addition, examples of the particle component insoluble in the hydrocarbon solvent include the particle component used in the above embodiment (E).

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

The polymer used in still another embodiment (I) of the present invention includes the polymer used in the above embodiment (C). Further, as the particle component insoluble in the hydrocarbon solvent, as the binder of the insoluble particle component in the above-mentioned embodiment (A), the monomer of (a) and the monomer of (c) are used as components. And a resin using a resin insoluble in a hydrocarbon solvent. 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 particles, the monomer (a) and the monomer (c) may be added to these substances. May be chemically bonded to the acidic group and the polar group.

The polymer used in still another embodiment (J) of the present invention includes a monomer compatible with a hydrocarbon solvent, a monomer represented by the general formula (I), And the copolymer of the monomer (b) and the monomer (c). Further, examples of the particle component insoluble in the hydrocarbon solvent include the particle component used in the embodiment (H).

The polymer used in still another embodiment (K) of the present invention includes the copolymer used in the above embodiment (J). Further, examples of the particle component insoluble in the hydrocarbon solvent include the particle component used in the above-described embodiment (I).

To prepare the dispersion of the present invention, in the case of the above embodiment (A), the respective 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 order of mixing is not particularly limited.

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

In the present invention, the appropriate amount of the insoluble particle component is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. In use in this range, a dispersion that is very stable even for long-term storage can be obtained. (Second Dispersion) The dispersion of the present invention relates to a hydrocarbon solvent-based dispersion as in the above-described invention.

The dispersion of the present invention comprises 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. When the resin soluble in the solvent is adsorbed on the particles insoluble in the solvent, the steric effect of the particles is exhibited, and the dispersion stability is obtained.

In the dispersion of the present invention, since the resin soluble in the hydrocarbon solvent has an acidic group but no basic group, the particles adsorbed by the resin soluble in the hydrocarbon solvent are positive. , And the dispersion stability is increased by the electrostatic repulsion.

In the dispersion of the present invention, since the resin soluble in the hydrocarbon solvent has a basic group but no acidic group, particles adsorbed by the resin soluble in the hydrocarbon solvent are negative. , And the dispersion stability is increased by the electrostatic repulsion.

Further, in the dispersion of the present invention, since the resin soluble in the hydrocarbon solvent further has a nonionic polar component, the amount of charge generation is increased by solvation of an acid or a base, and the dispersion stability is further improved. The nature increases.

In the dispersion of the present invention, since the particles have an acidic group on the surface but do not have a basic group, the polarity of the particles can be negatively controlled, and the particles can be controlled by electrostatic repulsion. Increases dispersion stability.

In the dispersion of the present invention, the particles have a basic group on the surface but do not have an acidic group, so that the polarity of the particles can be controlled positively, and the electrostatic repulsion force can be applied to the particles. Increases dispersion stability.

In the dispersion of the present invention, since the particles further have a nonionic polar component on the surface, the amount of charge generation increases due to solvation of an acid or a base, and the dispersion stability further increases.

In the dispersion of the present invention, the particles have an acidic group on the surface but do not have a basic group, and the resin soluble in a hydrocarbon solvent has a basic group but does not have an acidic group. By or, alternatively, the particles have a basic group on the surface but do not have an acidic group, and the resin soluble in a hydrocarbon solvent has an acidic group but does not have a basic group. Electric charge is generated by acid-base dissociation with the resin adsorbed on the surface, and a synergistic effect of dispersion stability is obtained by the steric effect of the adsorbed resin, providing long-term stability and fast response electrophoretic characteristics. A dispersion can be provided.

Hereinafter, the structure of the present 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.

Examples of the hydrocarbon solvent in the embodiment (L) include a known hydrocarbon having a viscosity at room temperature of 10 mPa · s or more at room temperature, such as an alkylnaphthene hydrocarbon such as liquid paraffin, an isoparaffin hydrocarbon, and a paraffin hydrocarbon. Solvents can be used. When used in a dispersion for an image display medium such as an electrophoretic display, it is preferable to add a dye that is soluble in a hydrocarbon water solvent and has a color different from that of the particles to the dispersion.

As the particles insoluble in the hydrocarbon solvent, the simplest examples include solid particle pigments such as metal oxides. Alternatively, a resin insoluble in a hydrocarbon solvent alone or a resin in which a coloring component is dispersed or mixed using the resin as a binder can be used. As the binder resin, any of known thermoplastic resins and thermosetting resins which are insoluble in a hydrocarbon solvent can be used, but non-adhesive materials are particularly preferably used. As a simple example of such a resin, polyester resin, polystyrene, poly p-
Examples include styrene such as chlorostyrene and polyvinyltoluene, and homopolymers of substituted styrenes.
Alternatively, a copolymer of a monomer having a high affinity for a hydrocarbon solvent described later and a polyfunctional monomer serving as a crosslinking agent can be used. Further, as the coloring component, all known components can be used. As the black colorant, for example, carbon black, aniline black, furnace black, lamp black and the like can be used. As the cyan coloring agent, for example, phthalocyanine blue, methylene blue, Victoria blue, methyl violet, aniline blue, ultramarine blue and the like can be used. Examples of magenta colorants include Rhodamine 6G Lake,
Dimethyl quinacridone, watching red, rose bengal, rhodamine B, alizarin lake and the like can be used. As the yellow colorant, for example, chrome yellow, benzidine yellow, Hanza yellow, naphthol yellow, molybdenum orange, quinoline yellow, tartrazine and the like can be used. Any of these conventionally known dyes and pigments can be used in combination. The amount of the colorant that can be used is 0.1 to 300 parts by weight, preferably 1 to 100 parts by weight, per 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 which are soluble in the hydrocarbon solvent can be used, but the attraction between the particle surface and the hydrocarbon solvent is higher than that of the hydrocarbon solvent. Those having strong interaction are preferable. When the resin is adsorbed on the particles, the dispersion stability of the particles is increased by the steric effect. As such a resin, 2-
Ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, vinyl laurate, methyl (meth) acrylate, ethyl (meth) Acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth)
Copolymers containing, as a component, at least one monomer having a high affinity for a hydrocarbon solvent such as an alkylnaphthene-based hydrocarbon such as acrylate, styrene, and vinyltoluene, an isoparaffin-based hydrocarbon, and a paraffin-based hydrocarbon. .

To prepare the dispersion of the present invention, the above 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 order of mixing is not particularly limited.

In another embodiment (M) of the present invention, the dispersion has an acidic group as a resin soluble in the hydrocarbon solvent but has no basic group, or has a basic group. Has a resin having no acidic group. When these resins are adsorbed on the particles in the hydrocarbon solvent, the particle surfaces are uniformly charged to positive or negative polarity due to the acidic or basic groups of the solvent-soluble resin.

Specific examples of the resin soluble in the above-mentioned hydrocarbon solvent used in the present invention are as follows. (A) Examples of resins (polymers or copolymers containing a monomer having an acidic group as a component) soluble in a hydrocarbon solvent having an acidic group but not having a basic group include (meth) acrylic Acid, maleic acid, maleic anhydride, itaconic acid,
Itaconic anhydride, fumaric acid, cinnamic acid, crotonic acid, vinylbenzoic acid, 2-methacryloxyethylsuccinic acid, 2-
Methacryloxyethyl maleic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl trimellitic acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, 2-sulfoethylmethacrylate, 2-acrylamide-2-methyl At least one monomer having an acidic group such as propanesulfonic acid, 3-chloroamidophosphoxypropyl methacrylate, 2-methacryloxyethyl acid phosphate, or hydroxystyrene, and the hydrocarbon solvent in the embodiment (L). And a copolymer obtained from at least one kind of monomer having high affinity. (B) Examples of the resin (polymer or copolymer having a monomer having a basic group as a component) soluble in a hydrocarbon solvent having a basic group but not having an acidic group include 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-vinylpyridine, A copolymer obtained from at least one monomer having a basic group such as -vinylpyridine and 2-vinyl-6-methylpyridine and at least one monomer having a high affinity for the hydrocarbon solvent. Is mentioned.

In still another embodiment (N) of the present invention, (c) a resin having an acidic group but not having a basic group and having a nonionic Or (d) a resin having a basic group but not having an acidic group and having a nonionic polar group. When these resins are adsorbed on the particles in a hydrocarbon solvent, the particle surface is uniformly charged to a positive or negative polarity due to the interaction between the acidic or basic groups of the solvent-soluble resin and the polar groups. I do.

The specific examples of the resin used in the present invention are as follows. (C) a resin having an acidic group but not a basic group and having a nonionic polar group (a copolymer containing a monomer having an acidic group and a monomer having a nonionic polar group as a constituent) As examples of at least one of the specific examples of the monomer having an acidic group in the above embodiment (M), 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,
Copolymers with polar monomers such as p-nitrostyrene, vinylpyrrolidone, acrylamide, methacrylamide, N, N-dimethylmethacrylamide, and N, N-dibutylmethacrylamide. Further, the copolymer having at least one monomer having high affinity for the hydrocarbon solvent in the above embodiment (M) may be used. (D) a resin having a basic group but not an acidic group and having a nonionic polar group (a copolymer containing a monomer having a basic group and a monomer having a nonionic polar group as constituent components) Examples of ()) include copolymers of at least one of the specific examples of the monomer having a basic group in the above embodiment (M) with the polar monomer. Further, the copolymer having at least one monomer having high affinity for the hydrocarbon solvent in the above embodiment (M) may be used.

In still another embodiment (O) of the present invention, the particles have an acidic group but no basic group on the surface, 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 include, as the binder of the colorant in the above embodiment (L),
In the above embodiment (M), a resin which is insoluble in a hydrocarbon solvent having a monomer having an acidic group or a monomer having a basic group as a component may be used. 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 acid group is reacted with the monomer having an acidic group or a basic group to form an acidic group. Alternatively, a basic group may be chemically bonded.

In still another embodiment (P) of the present invention, wherein the particles have a nonionic polar group on the surface and (e) an acidic group on the surface but no basic group, or f) It has a 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 the acidic or basic groups with the nonionic polar groups.

The particles used in the present invention include, as the binder of the colorant in the above embodiment (L),
The resin having an acidic group in the above embodiment (M) and the resin insoluble in a hydrocarbon solvent having the polar monomer as a component in the above embodiment (N), or the basic resin in the above embodiment (M) Examples include those using a monomer having a group and a resin insoluble in a hydrocarbon solvent having the polar monomer as a component. Also,
When substances that can be chemically bonded by grafting or the like, such as metal oxides or carbon black, are used as solid particles, by reacting these substances with the monomer having the acidic group or basic group and a polar monomer, A group or a basic group may be chemically bonded to a polar group.

In still another embodiment (Q) of the present invention, (g) a resin in which the particles have an acidic group on the surface but do not have a basic group, and the resin soluble in a hydrocarbon solvent has a basic group. Or (h) a particle having a basic group but no acidic group on the surface, and a resin soluble in a hydrocarbon solvent having an acidic group but no basic group , Either.

At this time, acid-base dissociation occurs between the acidic or basic group on the particle surface and the basic or acidic group of the resin soluble in the hydrocarbon solvent. When the resin soluble in the particle surface and / or the 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 to a positive or negative polarity, and the solid particles are dispersed more stably than before by the sum of the electrostatic effect and the steric effect. As the particles in the present embodiment, the particles in the above-described embodiments (O, P) can be used. Further, as the resin soluble in the hydrocarbon solvent in the present embodiment, the resin soluble in the hydrocarbon solvent in the above embodiment (M, N) can be used.

In the present invention, a suitable amount of the insoluble particle component is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. In use in this range, a dispersion that is very stable even for long-term storage can be obtained. (Third Dispersion) The dispersion of the present invention relates to a silicone oil solvent-based dispersion.

In 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 the monomer represented by the general formula (II) as a constituent element. Thus, a stable dispersion can be provided.

Further, in the dispersion of the present invention, 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 a constituent component are contained in the silicone oil. When the polymer is insoluble in the silicone oil in the dispersion containing the silicone oil, a steric stabilizing effect is imparted to the dispersed particles, and a silicone oil dispersion having an improved degree of 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 monomer represented by the general formula (II) and a monomer having a polar group. In the dispersion containing the polymer,
When the copolymer is soluble in the silicone oil,
It is possible to provide a dispersion system which has a strong interaction with the dispersed particles and further has an excellent affinity for the silicone oil.

In the dispersion of the present invention, the silicone oil contains at least a particle component insoluble in the silicone oil, a monomer having the general formula (II) and a monomer having an acidic group or a basic group. By containing the monomeric copolymer, the polar group interacts with the particles to give a steric effect, whereby a silicone oil dispersion having a stable 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 monomer represented by the general formula (II) and a monomer having an acidic group. By containing a polymer and a copolymer of a monomer represented by the general formula (II) and a monomer having a basic group, a charge is imparted to the dispersed particles and the particles are dispersed by electrostatic repulsion. The present invention can provide a dispersion capable of improving electrophoresis and enabling electrophoresis.

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) One of the copolymer of the monomer and the monomer having a basic group is insoluble in silicone oil, so that the dispersed particles have a more stable and steric stabilizing effect and a synergistic effect of a stabilizing effect 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) One or both of the copolymer of the monomer having a base group and a monomer having a basic group are copolymers of a monomer having a polar group, and thus a dispersion liquid having an improved charge amount related to charging of particles is obtained. Can be provided. (Fourth Dispersion) 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), and the above-described general formula (III) ) Contains a polymer obtained by polymerizing the monomer represented by the formula (1) as a constituent requirement, and has excellent affinity with silicone oil and gives a steric stabilizing effect to dispersed particles, and is a stable dispersion of silicone oil. 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 monomer represented by the general formula (II), and a monomer represented by the general formula (III). Monomer and a polymer obtained by polymerizing a monomer having an acidic group as a constituent requirement, and in the dispersion of the present invention, the silicone oil contains at least a particle component insoluble in the silicone oil. And a monomer represented by the general formula (II),
By containing a polymer obtained by polymerizing a monomer represented by I) and a monomer having a basic group as a constituent component,
It is possible to provide a dispersion system which has a strong interaction with the dispersed particles and further has an excellent affinity for the silicone oil.

Further, in the dispersion of the present invention, a particle component insoluble in silicone oil has a basic group or an acidic group on at least its surface, thereby imparting a charge to the dispersed particles and dispersing by electrostatic repulsion. The present invention can provide a dispersion capable of improving electrophoresis and enabling electrophoresis.

In the dispersion of the present invention, at least the particle component insoluble in silicone oil has a nonionic polar group other than the polyoxyethylene group. Formula (I
A polymer obtained by polymerizing a monomer represented by I), a monomer represented by the general formula (III), and a monomer having an acidic group into a nonionic polar group other than a polyoxyethylene group By providing the dispersion liquid, it is possible to provide a dispersion liquid having a more stable and excellent electrophoretic property due to a synergistic effect of a steric stabilizing action and a stabilizing action by electrostatic repulsion on the dispersed particles.

In the dispersion of the present invention, a particle component insoluble in silicone oil, a monomer represented by the general formula (II), a monomer represented by the general formula (III), and an acidic group Both the polymer obtained by polymerizing a monomer having a non-ionic polar group other than a polyoxyethylene group as a constituent requirement can provide a dispersion liquid having an improved charge amount related to charging of particles. it can.

In the third and fourth dispersions of the present invention, since the viscosity of the silicone oil is 200 cSt (centistokes) or less, a silicone oil dispersion having excellent storage characteristics can be provided. .

In the third and fourth dispersions of the present invention, since the content of the particle component insoluble in silicone oil is 0.1 to 20% by mass, low cost and excellent storage characteristics are obtained. And a silicone oil dispersion.

Hereinafter, the constitutions of the third and fourth dispersions of the present invention will be described in more detail.

Examples of the silicone oil used as the solvent in the present invention include a dialkyl silicone oil represented by the following general formula (IV); a cyclic polydialkylsiloxane or a cyclic polyalkylphenylsiloxane; and an alkylphenylsiloxane. 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.

[0135]

Embedded image [However, R1, R2, R3, R, R4, R5, R6, R7 and 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 at the time of polymerization can be freely selected. Among them, the use of dimethylpolysiloxane is advantageous. The silicone oil represented by the general formula (IV) has a viscosity at 25 ° C. of 0.1.
01 to 1,000,000 cSt (centistokes)
Are preferred. Further, in the general formula (IV), x is 1
It is desirable to use those of ~ 20,000.

Further, when a cyclic polydialkylsiloxane or a cyclic polyalkylphenylsiloxane is used, the resulting resin has a drying property of a polymerization solvent. It is advantageous. When alkylphenylsiloxane (especially methylphenylsilicone oil is preferred) is used,
Since the solubility is improved by introducing the phenyl group (5 to 50 mol%), it is advantageous to increase the dispersion stability of the resin solution. Specific examples of these various silicone oils are as follows. (I) Examples of dialkyl silicone oils: those shown in Table 1 below.

[0137]

[Table 1] (Ii) Examples of cyclic polydialkylsiloxane and cyclic polyalkylphenylsiloxane (phenyl group content is 5, 10, 20, and 50 mol%, respectively): cyclic polydimethylsiloxane, cyclic polymethylphenylsiloxane, cyclic polydiethylsiloxane, Cyclic polyethylphenylsiloxane, cyclic polydibutylsiloxane, cyclic polybutylphenylsiloxane, cyclic polydihexylsiloxane,
Cyclic polyhexylphenylsiloxane, cyclic polydilaurylsiloxane, cyclic polymethylchlorophenylsiloxane, cyclic polydistearylsiloxane, cyclic polymethylbromophenylsiloxane. (Iii) Examples of alkylphenyl silicone oils: those shown in Table 2 below.

[0138]

[Table 2] Examples of commercially available silicone oils include KF-96L manufactured by Shin-Etsu Chemical Co., Ltd. [0.65, 1.0, 1..
5,2.0 centistokes], KF-96 [10,2
0, 30, 50, 500, 1000, 3000], KF
-56, KF-58 and KF-54, and TSF451 series manufactured by Toshiba Silicone Co., Ltd.
TSF456 series, TSF410,411,44
0,4420,484,483,431,433 series, THF450 series, TSF404,405,4
06451-A, 451-10A, 437 series, TSF440, 400, 401, 4300, 444
5,4700, 4450, 4702, 4730 series, TSF434, 4600 series, and HS-200 manufactured by Toray Silicone Co., Ltd.

Other solvents can be mixed with the above silicone oil to such an extent that the properties of the silicone oil are not impaired. Such solvents include toluene,
Aromatic hydrocarbon solvents such as xylene and benzene; ethers; esters; alcohol solvents; n-hexane, n
And aliphatic hydrocarbons such as octane, iso-octane, iso-dodecane, and mixtures thereof (for commercial products, Isopar HGLV manufactured by Exxon Chemical Co., Ltd.), and the like. The mixing ratio of such another solvent 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 has a feature that it is hardly dissolved in a silicone oil with a normal polymer.
A polymer composed of such a monomer gives a polymer soluble in silicone oil in the case of a homopolymer, and is insoluble or insoluble even in the case of a copolymer with another monomer. However, it can provide a stable dispersion having a high affinity with silicone oil. Next, as the monomer copolymerizable with the monomer represented by the general formula (II), the following are used. (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, vinylbenzoic acid, 2-methacryloxy Ethyl succinic acid, 2-methacryloxyethyl maleic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl trimellitic acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, 2-sulfoethylmethacrylate,
2-acrylamido-2-methylpropanesulfonic acid,
3-chloroamidophosphoxypropyl 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, dimethylamino Ethoxystyrene, diphenylaminoethylstyrene, N-phenylaminoethylstyrene, vinylpyrrolidone, 2-N-piperidylethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, Acrylamide, methacryl Bromide, N, N-dimethyl methacrylamide, 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-cyanoethylacrylate, ethyl-2-
Examples include cyanoacrylate, methacrylacetone, tetrahydrofurfuryl methacrylate, trifluoroethyl methacrylate, and p-nitrostyrene. (Vii) 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, tetramethylolmethanetetra (meth) acrylate, dipropylene glycol di (meth) acrylate
Examples include acrylate, trimethylolhexanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,3-dibutylene glycol di (meth) acrylate, and trimethylolethanetri (meth) acrylate. (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 can be mentioned. First, as a polymer having a monomer represented by the general formula (II) as a constituent requirement, a polymer represented by the general formula (I
Copolymers of the monomer represented by I) and the monomers (iv) to (viii) are exemplified. In addition, the general formula (I
Examples of the copolymer of the monomer (I) and the monomer having a polar group include a copolymer containing at least the monomer of the general formula (II) and the monomer (vi) having a polar group. Can be In addition, 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. And copolymers. The copolymer of the monomer of the general formula (II) and the monomer having a basic group includes at least a monomer of the general formula (II) and a monomer (v) having a basic group. And a copolymer containing The polymer containing the monomer of the general formula (II) insoluble in silicone oil includes at least the monomer of the general formula (II) and the monomer of the above (iv) to (viii) And copolymers thereof. However, in this case, the ratio of using these monomers cannot be unconditionally defined, and the intended insoluble resin is obtained by empirical use. this is,
This is due to the property of silicone oil as a solvent-poor solubility. However, in order to obtain the insoluble resin most reliably, it can be achieved by using a relatively large amount of the monomer of the general formula (vii).

When the monomer represented by the general formula (IV) is contained together with the monomer represented by the general formula (II), the repeating unit of the oxyethylene group has a polyethylene glycol chain of 25 or less. The copolymer having a monomer as a component is adsorbed on particles insoluble in a solvent, and the dispersion of particles is stabilized by a steric effect exhibited by a polyethylene glycol chain.

On the other hand, the particle components 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, wax-like substances (for example, Molecular polyolefin, waxes), chemical products (eg, pesticides), swelling agents, and the like. More specifically, for example, carbon black, lamp black, ultramarine, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow G, roguemin 6G, lake, calco oil blue,
Chrome yellow, quinacridone, benzidine yellow,
Any conventionally known dyes and pigments such as rose bengal and triallylmethane dyes can be used alone or in combination. In addition, iron oxides such as magnetite, hematite, ferrite, iron, carbonyl iron powder, cobalt,
Metals such as nickel or alloys of these metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and the like Mixtures, glass beads and the like can be mentioned. Also, as an example of resin particles,
Styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and its substituted homopolymer; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinyl Naphthalene 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-vinyl ethyl Ether copolymer, styrene -Vinyl methyl ketone copolymer,
Styrene-based copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer are exemplified.

Further, depending on the purpose of use, a dye soluble in silicone oil may be added to the dispersion or chemically bonded to the dispersoid to color the dispersion or the dispersoid. In order to prepare the dispersion of the present invention, the above-mentioned 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 order of mixing is not particularly limited.

When the silicone oil used as the dispersion solvent of the present invention is 1,000 centistokes or less, and preferably 200 centistokes or less, excellent dispersion stability is exhibited. Although the reason for this has not been elucidated, it is presumed that as the viscosity of the silicone oil increases, the molecular weight of the oil also increases, and consequently the solubility of the resin used in the present invention or the affinity between the resin and the oil decreases. Is done.

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

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

[0146]

Embedded image A solution consisting of 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Then the temperature was raised to 90 ° C,
After stirring for an hour, the reaction was completed. A uniform and transparent resin solution was obtained with a conversion of 98.7%. Next, 7 parts of titanium oxide was added to 100 parts of the resin solution and dispersed by a ball mill to prepare a dispersion. A glass tube having a length of 40 cm was set upright, and this dispersion was poured to a height of 30 cm. After standing for one month, it was visually judged, and it was found that the dispersion was very stable without precipitation. (Example 2) An isoparaffinic hydrocarbon (Exxon Chemical, Isopar H) 3 was placed in the same reaction vessel as in Example 1.
00 parts were taken and heated to 90 ° C. In this, 43 parts of decyl methacrylate, 5 parts of a compound having the following structural formula,

[0147]

Embedded image A solution consisting of 2 parts of methacrylic acid and 1 part of benzoyl peroxide was added dropwise over one hour. Then, 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 conversion of 97.4%. Next, 1 part of carbon black was added to 100 parts of the resin solution, and the mixture was dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 1. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 3) An isoparaffinic hydrocarbon (Exxon Chemical, Isopar G) 3 was placed in the same reaction vessel as in Example 1.
00 parts were taken and heated to 90 ° C. In this, 40 parts of 2-ethylhexyl methacrylate, compound 5 of the following structural formula
Department,

[0148]

Embedded image A solution consisting of 5 parts of dimethylaminoethyl methacrylate and 1 part of benzoyl peroxide was added dropwise over one hour. Then, 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 the resin solution and dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 1. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. Example 4 An isoparaffinic hydrocarbon (Exxon Chemical, Isopar H) 300 was added to the reaction vessel used in Example 1.
An aliquot was taken and heated to 80 ° C. 25 parts of cyclohexyl methacrylate, 5 parts of dibutylaminoethyl methacrylate, 20 parts of ethylene glycol dimethacrylate
And a solution consisting of 1 part of benzoyl peroxide was added dropwise over 5 hours. Then, the mixture was stirred at 85 ° C. for 2 hours to complete the reaction. Polymerization rate of insoluble resin after filtration and washing
Obtained at 92.5%. Next, 5 parts of this resin was added to 50 parts of the resin solution prepared in Example 2 and dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 1. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 5) An isoparaffinic hydrocarbon (Exxon Chemical, Isopar L) 500 was placed in the same reaction vessel as in Example 1.
An aliquot was taken and heated to 80 ° C. In this, hexyl methacrylate 20 parts, diethylaminoethyl methacrylate 5
, A solution consisting of 5 parts of hydroxyethyl methacrylate, 20 parts of ethylene glycol dimethacrylate, and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Then, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. A resin having a polymerization rate of 94.7% was obtained by filtration and washing. Next, this resin 5
And 50 parts of the resin solution prepared in Example 2, and ultrasonically dispersed to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 1. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 6) An isoparaffinic hydrocarbon (Exxon Chemical, Isopar L) 3 was placed in the same reaction vessel as in Example 1.
00 parts were 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,

[0149]

Embedded image A solution consisting of 1 part of methacrylic acid, 1 part of vinylpyrrolidone and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Then, 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 at a conversion of 93.4%. Next, this polymer gel dispersion 1
5 parts of the resin prepared in Example 4 and titanium oxide 7
Part, dye (Bayer Macrolex Blue RR) 0.1
The mixture was dispersed in a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 1. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 7) 5 parts of the resin prepared in Example 5 and 50 parts of the polymer gel dispersion prepared in Example 6 were added to 45 parts of an isoparaffinic hydrocarbon (Exxon Chemical, Isopar L), and the mixture was ultrasonically dispersed. A dispersion was made. This dispersion was poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode spacing 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, the white particles were electrodeposited only on the cathode, and no deposition was observed on the anode. This indicates that the particles are all positively charged. (Example 8) An isoparaffin-based hydrocarbon (Exxon Chemical, Isopar G) 50 was added to the reaction vessel used in Example 1.
0 parts were taken and heated to 80 ° C. In this, 20 parts of 2-ethylhexyl methacrylate, 25 parts of ethylene glycol dimethacrylate, 2-hydrostyrenesulfonic acid 5
And a solution consisting of 1 part of benzoyl peroxide was added dropwise over 1 hour. Then, the mixture was stirred at 85 ° C. for 3 hours to complete the reaction. A resin having a polymerization rate of 91.2% was obtained by filtration and washing. 45 parts of Isopar G 5 parts of this resin, Example 3
50 parts of the resin solution prepared in the above was added and ultrasonically dispersed to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 1. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable.

Example 9 A reaction vessel similar to that of Example 1 was charged with 500 parts of an isoparaffinic hydrocarbon (Exxon Chemical, Isopar G) and heated to 80 ° C. A solution consisting of 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 thereto over 3 hours. Then, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. In this way, the resin dispersion
91.2%. Next, 50 parts of the resin solution prepared in Example 3 and 50 parts of the copper phthalocyanine pigment
The mixture was dispersed in a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 1. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 10) An isoparaffinic hydrocarbon (Exxon Chemical, Isopar G) was placed in the same reaction vessel as in Example 1.
300 parts were taken and heated to 90 ° C. In this, 37 parts of lauryl methacrylate, 5 parts of a compound having the following structural formula,

[0151]

Embedded image 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. Then, 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 conversion of 94.1%. Next, 5 parts of the resin prepared in 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 Example 1. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. Example 11 50 parts of the resin dispersion prepared in Example 10, 50 parts of the resin solution prepared in Example 10, 3 parts of N, N-diethylpropionamide, 7 parts of titanium oxide, and dye (Bayer Macrolex Blue RR) ) 0.1 part was added and dispersed by a ball mill to prepare a dispersion. This dispersion was poured into a cell provided with an ITO transparent electrode glass so that the electrode surfaces faced 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. Observation from the opposite side of the cathode revealed that the electrode surface was colored with a dye. This indicates that all the particles have a negative charge and are electrodeposited only on the anode side. (Comparative Example 1) 7 parts of titanium oxide and 0.1 part of a dye (Bayer Macrolex Blue RR) were added to 100 parts of an isoparaffinic hydrocarbon (Exxon Chemical, Isopar H) and dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as described above, but the supernatant portion appeared about 20 cm after standing for one day, and the dispersion was very unstable. Comparative Example 2 An isoparaffinic hydrocarbon (Exxon Chemical, Isopar L) 500 was placed in the same reaction vessel as in Example 1.
An aliquot 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 thereto over one hour. Then, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. A resin having a polymerization rate of 90.9% was obtained by filtration and washing. 10 parts of this resin is
Parts and 1 part of carbon black were put into a ball mill to obtain a dispersion. This dispersion was poured into a Teflon container having brass electrodes arranged in parallel with an electrode spacing 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 electrodeposition of black particles was observed on both electrodes of the cathode and anode. (Example 12) In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, Isopar H (Exxon Chemical Company) 30 was added.
0 parts were 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 thereto over 1 hour. Then, 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 conversion of 95.6%. 5 parts of the polymer obtained by evaporating Isopar H by 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 diameter of 0.3 μm. A glass tube with a length of 40 cm is set up vertically,
The solution was injected up to 0 cm.

After standing for one month, the dispersion was visually judged, and it was found that the dispersion was very stable without precipitation. (Example 13) 300 parts of toluene was placed in the same reaction vessel as in Example 12, 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 thereto 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 at a conversion of 93.6%. 5 parts of the above polymer obtained by evaporating toluene with an evaporator and 7 parts of titanium oxide were added to 100 parts of isoparaffinic hydrocarbon, and the mixture was dispersed by a ball mill to obtain a dispersion having an average particle diameter of 0.2 μm. Stand up a vertical 40cm glass tube,
This dispersion was poured to a height of 30 cm.

After standing for one month, the dispersion was visually checked, and it was found that the dispersion was very stable without precipitation. Example 14 300 parts of Isopar H were placed in the same reaction vessel as in Example 12, 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 thereto 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 at a conversion of 94.1%. 5 parts of the above polymer obtained by evaporating Isopar H by an evaporator and 7 parts of titanium oxide were added to 100 parts of liquid paraffin, and dispersed by a ball mill to obtain a dispersion having an average particle diameter of 0.2 μm. A glass tube having a length of 40 cm was set upright, and this dispersion was poured to a height of 30 cm.

After standing for one month, the dispersion was visually checked, and it was found that the dispersion was very stable without precipitation. (Example 15) 300 parts of Isopar H was placed in the same reaction vessel as in Example 12, and heated to 90 ° C. In this,
A solution consisting of 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. Then, 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 an isoparaffinic hydrocarbon and ultrasonically dispersed to obtain a dispersion having an average particle diameter of 0.3 μm. The dispersion stability was examined in the same manner as in Example 12, and it was found that there was no precipitation even after standing for one month, indicating that the dispersion was very stable. (Example 16) 300 parts of Isopar H was placed in the same reaction vessel as in Example 12, and heated to 85 ° C. In 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. Then at the same temperature 5
Stirring was continued for another hour 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.
A dispersion having an average particle size of 0.2 μm was obtained. The dispersion stability was examined in the same manner as in Example 12, and it was found that there was no precipitation even after standing for one month, indicating that the dispersion was very stable. (Example 17) 300 parts of toluene was placed in a reaction vessel similar to that of Example 12, and heated to 85 ° C. 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 dropped therein over 1 hour. Then, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a polymer insoluble in toluene was obtained at a conversion of 93.6%. 5 parts of the filtered polymer was added to 100 parts of an isoparaffinic hydrocarbon and ultrasonically dispersed to obtain a dispersion having an average particle diameter of 0.3 μm. In the same manner as in Example 12,
Although the dispersion stability was examined, there was no precipitation even after standing for one month,
It turned out to be a very stable dispersion. (Example 18) 5 parts of a polymer soluble in a hydrocarbon solvent prepared in Example 12 and 5 parts of a solvent-insoluble polymer prepared in Example 16 were added to 100 parts of liquid paraffin, and ultrasonically dispersed. A dispersion having an average particle size of 0.2 μm was obtained. The dispersion was poured into a Teflon container having brass electrodes arranged in parallel with an electrode interval of 5 mm, and a DC voltage of 1000 V was applied to the container.
Min. After applying the voltage, the electrode was taken out and observed. As a result, the blue particles were electrodeposited only on the cathode, and no deposition was observed on the anode. This indicates that the particles are all positively charged. (Example 19) 5 parts of the polymer soluble in the hydrocarbon solvent prepared in Example 14, 5 parts of the solvent-insoluble polymer prepared in Example 17, and 2 parts of copper phthalocyanine were added to 100 parts of an isoparaffinic hydrocarbon solvent. And dispersed in a ball mill,
A dispersion having an average particle size of 0.3 μm was obtained. This dispersion was poured into a Teflon container having brass electrodes arranged in parallel with an electrode spacing 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,
The blue particles were electrodeposited only on the anode, and no deposition was observed on the cathode. This indicates that all the particles have a negative charge. (Comparative Example 3) A dispersion was prepared in the same manner as in Example 13 except that a dispersion was prepared using only titanium oxide without adding a resin, and the dispersion stability was examined in the same manner as in Example 2. However, the supernatant portion appeared about 20 cm after standing for one day, which proved to be a very unstable dispersion. (Comparative Example 4) A reaction was carried out in the same manner as in Example 15 except that methacrylic acid was not added, and a polymer insoluble in Isopar H was obtained at a polymerization rate of 91.2%. 5 parts of the filtered polymer was added to 100 parts of an isoparaffinic hydrocarbon to prepare a dispersion in the same manner as in Example 4, and the dispersion stability was examined in the same manner as in Example 15. Appeared about 20 cm, which proved to be a very unstable dispersion. (Comparative Example 5) Example 1 except that the dispersion of Comparative Example 4 was used.
When a voltage was applied in the same manner as in Example 8, particles adhered to both electrodes of the cathode and anode, and migration due to the electric field of the particles was not observed. (Example 20) A silicone oil (SH-200; 2c) was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser.
s) 300 parts were taken and heated to 90 ° C. In this, 40 parts of a compound of the following structural formula

[0155]

Embedded image And 1 part of benzoyl peroxide was added dropwise over 1 hour. Then, 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 conversion of 95.7%.
To 100 parts of this resin liquid, 2 parts of copper phthalocyanine was added and ultrasonically dispersed to obtain a dispersion having an average particle diameter of 0.3 μm. A glass tube having a length of 40 cm was set upright, and this dispersion was poured to a height of 30 cm. After standing for one month, it was visually judged, and it was found that the dispersion was very stable without precipitation. (Example 21) 300 parts of silicone oil (SH-200; 5cs) was placed in a reaction vessel similar to that of Example 20,
Heated to 90 ° C. In this, 37 parts of a compound of the following structural formula,

[0156]

Embedded image A solution consisting of 3 parts of ethylene glycol dimethacrylate and 1 part of benzoyl peroxide was added dropwise over one hour. Then, 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 Example 20, and it was found that there was no precipitation even after standing for one month, indicating that the dispersion was very stable. (Comparative Example 6) 300 parts of silicone oil (SH-200; 2cs) was placed in a reaction vessel similar to that of Example 20,
Heated to ° C. Lauryl methacrylate 20
, A solution consisting of 20 parts of 2-ethylhexyl methacrylate and 1 part of benzoyl peroxide was added dropwise over 1 hour. Then, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a liquid containing a polymer insoluble in silicone oil was obtained at a polymerization rate of 89.2%. This solution was dispersed by a ball mill to obtain a dispersion having an average particle size of 5 to 10 μm. The dispersion stability was examined in the same manner as in Example 19.
The supernatant portion appeared about 20 cm after standing for one day, which proved to be a very unstable dispersion. Next, each of these resin coating films was prepared, and the water repellency and oil repellency were measured. The results shown in Table 3 were obtained.

[0157]

[Table 3] In addition, each measurement method of Table 3 is as follows. Water repellency: The contact angle of the resin surface with ion-exchanged water was measured using a contact angle measuring device manufactured by Kyowa Chemical Industry Co., Ltd. Oil repellency: The contact angle of the resin surface to iso-dodecane was measured using a contact angle measuring device manufactured by Kyowa Chemical Industry Co., Ltd. (Example 22) 300 parts of silicone oil (SH-200; 1cs) was placed in the same reaction vessel as in Example 20,
Heated to 85 ° C. In this, compound 35 of the following structural formula
Department,

[0158]

Embedded image A solution consisting of 5 parts of N-vinylpyrrolidone and 1 part of azobisisobutyronitrile was added dropwise over one hour. Then, 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 the mixture was dispersed in a ball mill.
A 3 μm dispersion was obtained. The dispersion stability was examined in the same manner as in Example 21, and it was found that the dispersion was very stable without any precipitation even after standing for one month. In addition, water repellency 3
5.1, oil repellency 30.0. (Example 23) The same test as in Example 21 was performed except that dimethylaminoethyl methacrylate was used instead of vinylpyrrolidone used in 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 using the same was obtained. This dispersion is very stable, water repellent 33.0, oil repellent 2
8.7. (Example 24) 300 parts of silicone oil (SH-200; 1cs) was placed in the same reaction vessel as in Example 20,
Heated to 90 ° C. In this, 32 parts of a compound of the following structural formula,

[0160]

Embedded image 5 parts of a compound of the following structural formula,

[0161]

Embedded image A solution consisting of 3 parts of methacrylic acid and 1 part of benzoyl peroxide was added dropwise over one hour. Then, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus particle size 2
A dispersion containing 5 μm resin was obtained at a conversion of 93.5%.
The dispersion stability was examined in the same manner as in Example 20, but after standing for one month, only 2 cm of the supernatant appeared, indicating that the dispersion was stable. In addition, water repellency 31.4,
Oil repellency was 29.0. (Example 25) 50 parts of the dispersion obtained in Example 24 and 50 parts of the uniform resin liquid prepared in Example 22 were stirred and mixed to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 19. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. The water repellency was 30.8 and the oil repellency was 29.5. This dispersion is charged with an electrode spacing of 5 mm.
Was poured into a Teflon container having a brass electrode arranged in parallel with the above, 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, the white particles were electrodeposited only on the anode, and no deposition was observed on the cathode. This indicates that all the particles have a negative charge. For comparison, electrodeposition was attempted in the same manner as in the dispersion of Example 24, but electrodeposition of white particles was observed on both electrodes of the cathode and anode. Further, for comparison, electrodeposition was attempted in the same manner as in Example 23, but no electrodeposition occurred on any of the cathode and anode. (Example 26) In a reaction vessel similar to Example 20, 300 parts of silicone oil (SH-200; 10cs) was taken, and
Heated to 90 ° C. In this, 32 parts of a compound of the following structural formula,

[0162]

Embedded image 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. Then, 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%. In the same manner as in Example 20,
Although the dispersion stability was examined, there was no precipitation even after standing for one month,
It turned out to be a very stable dispersion. In addition, water repellency was 29.4 and oil repellency was 26.2. (Example 27) 50 parts of the dispersion obtained in Example 26 and 50 parts of the uniform resin liquid prepared in Example 23 were stirred and mixed to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 20, and it was found that there was no precipitation even after standing for one month, indicating that the dispersion was very stable. The water repellency was 30.2 and the oil repellency was 28.0.

This dispersion was poured into a Teflon container having brass electrodes arranged in parallel with an electrode spacing of 5 mm,
A DC voltage of 00 V was applied for one minute. After applying the voltage, the electrode was taken out and observed. As a result, the white particles were electrodeposited only on the anode, and no deposition was observed on the cathode. This indicates that all the particles have a negative charge. For comparison, electrodeposition was attempted in the same manner as in the dispersion of Example 26, but electrodeposition of white particles was observed on both electrodes of the cathode and anode. (Example 28) 300 parts of silicone oil (SH-200; 20cs) was placed in the same reaction vessel as in Example 20, and heated to 85 ° C. Compound 3 having the following structural formula
One copy,

[0164]

Embedded image 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. Then, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, the solution containing the polymer soluble in silicone oil has a conversion of 93.6.
%. 5 parts of carbon black was added to 100 parts of this resin liquid, followed by ball mill dispersion to obtain a dispersion having an average particle size of 0.2 μm. In the same manner as in Example 20,
Although the dispersion stability was examined, there was no precipitation even after standing for one month,
It turned out to be a very stable dispersion. In addition, water repellency was 32.8 and oil repellency was 29.7. (Example 29) 300 parts of silicone oil (SH-200; 5cs) was placed in the same reaction vessel as in Example 20, and
Heated to 85 ° C. Compound 37 having the following structural formula
Department,

[0165]

Embedded image A solution consisting of 2-methacryloyloxyethyl maleate 3 and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Then, 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 conversion of 90.4%.

To 50 parts of this resin liquid, 45 parts of the dispersion of Example 28 was added and stirred well to obtain the dispersion of Example 10. The dispersion stability was examined in the same manner as in Example 20, and it was found that there was no precipitation even after standing for one month, indicating that the dispersion was very stable. In addition, water repellency was 33.1 and oil repellency was 28.3.

The dispersion was poured into a Teflon container having brass electrodes arranged in parallel with an electrode spacing of 5 mm,
A DC voltage of 00 V was applied for one minute. After applying the voltage, the electrode was taken out and observed. As a result, the black particles were electrodeposited only on the cathode, and no deposition was observed on the anode. This indicates that the particles are all positively charged. For comparison, electrodeposition was attempted in the same manner as in the dispersion of Example 28, but electrodeposition of black particles was observed on both cathode and anode electrodes. (Example 30) 300 parts of silicone oil (SH-200; 5cs) was placed in the same reaction vessel as in Example 20,
Heated to 85 ° C. Compound 30 having the following structural formula
Department,

[0168]

Embedded image A solution consisting of 3 parts of ethylene glycol dimethacrylate, 3 parts of N-methacryloylmorpholine, 4 parts of di-tert-butylaminoethyl methacrylate and 1 part of azobisisobutyronitrile was added dropwise over 1 hour. Then, 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%. To 100 parts of this resin dispersion, 8 parts of phthalocyanine was added, and the mixture was dispersed in a ball mill.
m was obtained. The dispersion stability was examined in the same manner as in Example 20, and it was found that there was no precipitation even after standing for one month, indicating that the dispersion was very stable. In addition, water repellency 29.
1. The oil repellency was 26.8. (Example 31) 300 parts of silicone oil (SH-200; 1cs) was placed in the same reaction vessel as in Example 20,
Heated to 85 ° C. Compound 33 having the following structural formula
Department,

[0169]

Embedded image 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. Then, 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 of Example 30, and the mixture was thoroughly stirred to obtain a dispersion of Example 30. Water repellency was 28.3 and oil repellency was 26.0.

The dispersion of Example 31 was poured into a Teflon container having brass electrodes arranged in parallel with an electrode spacing 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, the blue particles were electrodeposited only on the cathode, and no deposition was observed on the anode. This indicates that the particles are all positively charged.

For comparison, electrodeposition was attempted in the same manner as in the dispersion of Example 30, but electrodeposition of blue particles was observed on both electrodes of the cathode and anode. (Comparative Example 7) 300 parts of silicone oil (SH-200; 2cs) was placed in the same reaction vessel as in Example 19, and
Heated to 5 ° C. 28 parts of the compound having the following structural formula

[0172]

Embedded image 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. Then, 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 a polymer was formed in the reactor, and could not be taken out of the reaction vessel. (Comparative Example 8) 3 parts of the gel-like substance obtained in Comparative Example 7 was scraped from a container and put 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. Was. This dispersion was poured into a Teflon container having brass electrodes arranged in parallel with an electrode spacing 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 electrodeposition of black particles was observed on both electrodes of the cathode and anode. Example 32 A reaction vessel equipped with a stirrer, thermometer and reflux condenser was charged with 300 parts of silicone oil (Toray Dow Corning Silicone SH200, 2cs) and heated to 85 ° C.
In this, 50 parts of a compound of the following structural formula,

[0173]

Embedded image 5 parts of a compound having the following structure,

[0174]

Embedded image 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 conversion 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 the resin solution and dispersed by a ball mill to prepare a dispersion. A glass tube having a length of 40 cm was set upright, and this dispersion was poured to a height of 30 cm. After standing for one month, it was visually judged, and it was found that the dispersion was very stable without precipitation. (Example 33) 300 parts of silicone oil (SH-200; 1cs) was placed in a reaction vessel similar to that of Example 32,
Heated to 90 ° C. In this, 43 parts of a compound of the following structural formula,

[0175]

Embedded image 5 parts of a compound of the following structural formula,

[0176]

Embedded image A solution consisting of 2 parts of methacrylic acid and 1 part of benzoyl peroxide was added dropwise over one hour. Then, 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 conversion of 96.9%. Next, 1 part of carbon black was added to 100 parts of the resin solution, and the mixture was dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 34) 300 parts of silicone oil (SH-200; 1cs) was placed in the same reaction vessel as in Example 32,
Heated to 90 ° C. In this, 42 parts of a compound of the following structural formula,

[0177]

Embedded image 3 parts of a compound of the following structural formula,

[0178]

Embedded image A solution consisting of 5 parts of dimethylaminoethyl methacrylate and 1 part of benzoyl peroxide was added dropwise over one hour. Then, 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 conversion of 93.3%. The dispersion stability was examined in the same manner as in Example 32. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 35) 300 parts of silicone oil (SH200, 1cs) was placed in the reaction vessel used in Example 32 and heated to 80 ° C. In this, 10 parts of a compound of the following structural formula,

[0179]

Embedded image 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. Then 85
The reaction was completed by stirring at 2 ° C. for 2 hours. In this way, a milky white resin dispersion was obtained at a conversion of 92.7%. Next, 50 parts of the resin solution prepared in Example 32 was added to 50 parts of the resin dispersion, and the mixture was dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 36) 500 parts of silicone oil (SH200, 1cs) were placed in the same reaction vessel as in Example 32, and heated to 80 ° C. In this, 25 parts of a compound of the following structural formula,

[0180]

Embedded image 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. Then, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. A resin having a polymerization rate of 94.1% was obtained by filtration and washing. Next, silicone oil (SH200, 1cs)
To 45 parts, 5 parts of this resin and 50 parts of the resin solution prepared in Example 32 were added and ultrasonically dispersed to prepare a dispersion. Example 3
Dispersion stability was examined in the same manner as in Example 1. No precipitation was observed even after standing for one month, and it was found that the dispersion was very stable. (Example 37) 300 parts of silicone oil (SH-200; 1cs) was placed in the same reaction vessel as in Example 32,
Heated to 90 ° C. In this, 44 parts of a compound of the following structural formula,

[0181]

Embedded image 4 parts of a compound of the following structural formula,

[0182]

Embedded image A solution consisting of 1 part of methacrylic acid, 1 part of vinylpyrrolidone and 5 parts of azobisisobutyronitrile was added dropwise over 1 hour. Then, 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 at a conversion of 95.4%. Next, this polymer gel dispersion 5
0 parts: 50 parts of the resin dispersion prepared in Example 4, 7 parts of titanium oxide, dye (Bayer Macrolex Blue RR)
0.1 part was added and dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 38) Silicone oil (SH200, 1cs) 45
5 parts of the resin prepared in Example 5 and 50 parts of the polymer gel dispersion prepared in Example 36 were added to the mixture and ultrasonically dispersed to prepare a dispersion. The dispersion was poured into a Teflon container having brass electrodes arranged in parallel with an electrode spacing of 5 mm, and
A DC voltage of 00 V was applied for one minute. After applying the voltage, the electrode was taken out and observed. As a result, the white particles were electrodeposited only on the cathode, and no deposition was observed on the anode. This indicates that the particles are all positively charged. Example 39 The reaction vessel used in Example 32 was charged with 500 parts of silicone oil (SH200, 1cs) and heated to 80 ° C. In this, 20 parts of a compound of the following structural formula,

[0183]

Embedded image A solution composed of 25 parts of ethylene glycol dimethacrylate, 5 parts of 2-hydrostyrenesulfonic acid and 3 parts of benzoyl peroxide was added dropwise over 5 hours. Then 85
The reaction was completed by stirring at 2 ° C. for 2 hours. A resin having a polymerization rate of 90.3% was obtained by filtration and washing. 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. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 40) 500 parts of silicone oil (SH200, 1cs) were placed in the same reaction vessel as in Example 32, and heated to 80 ° C. In this, 10 parts of a compound of the following structural formula,

[0184]

Embedded image A solution consisting of 30 parts of lauryl methacrylate, 5 parts of lauryl methacrylamide, 5 parts of methacrylic acid and 5 parts of azobisisobutyronitrile was added dropwise over 3 hours. Then
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 at a polymerization rate of 91.7%. Next, 50 parts of this 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 by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 41) 300 parts of silicone oil (SH-200; 1cs) was placed in the same reaction vessel as in Example 32,
Heated to 90 ° C. In this, 44 parts of a compound of the following structural formula,

[0185]

Embedded image 4 parts of a compound of the following structural formula,

[0186]

Embedded image A solution consisting of 1 part of dimethylaminoethyl methacrylate, 1 part of vinylpyrrolidone and 1 part of benzoyl peroxide was added dropwise over 1 hour. Then, 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 92.4%. Next, 50 parts of this resin solution and 50 parts of the resin dispersion prepared in Example 8 and 1 part of carbon black were added and dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 32. As a result, no precipitation was observed even after standing for one month, and the dispersion was found to be very stable. (Example 42) Resin dispersion liquid 50 prepared in Example 40
Part, 50 parts of the resin solution prepared in Example 40, titanium oxide
7 parts, dye (Bayer Macrolex Blue RR) 0.1
The mixture was dispersed in a ball mill to prepare a dispersion. This dispersion was poured into a Teflon container having brass electrodes arranged in parallel with an electrode spacing 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, the white particles were electrodeposited only on the anode, and no deposition was observed on the cathode. This indicates that all the particles have a negative charge. (Comparative Example 9) 7 parts of titanium oxide and 0.1 part of dye (Bayer Macrolex Blue RR) were added to 100 parts of silicone oil (Toray Dow Corning Silicone SH200, 2cs) and dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as described above, but the supernatant portion appeared about 20 cm after standing for one day, and the dispersion was very unstable. (Comparative Example 10) 500 parts of silicone oil (SH200, 1cs) was placed in the same reaction vessel as in Example 32, and heated to 80 ° C. In this, 25 parts of a compound of the following structural formula,

[0187]

Embedded image A solution consisting of 25 parts of ethylene glycol dimethacrylate and 5 parts of azobisisobutyronitrile was added dropwise over 3 hours. Then, the temperature was raised to 85 ° C., and the mixture was stirred at this temperature for 4 hours to complete the reaction. Polymerization rate 9 by filtration and washing treatment
Resin was obtained at 0.5%. 10 parts of this resin was put 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 container having brass electrodes arranged in parallel with an electrode spacing 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 electrodeposition of black particles was observed on both electrodes of the cathode and anode.

According to the dispersion of the present invention, at least a particle component insoluble in the hydrocarbon solvent,
It is compatible with hydrocarbon solvents and has at least the general formula (I)
By containing a polymer obtained by polymerizing the monomer represented by the formula (1), a hydrocarbon solvent-based dispersion having excellent affinity with a hydrocarbon solvent, and imparting a steric stabilizing effect to dispersed particles, and having excellent dispersion stability. A liquid can be provided. Further, according to the dispersion of the present invention, the polymer is a polymer further containing at least one of a monomer having an acidic group and a monomer having a basic group, so that the dispersion particles Can provide a hydrocarbon solvent-based dispersion system in which the interaction between the hydrocarbon solvent and the polymer is strong and the affinity with the hydrocarbon solvent is excellent. In addition, according to the dispersion of the present invention, the particle component has at least one of a basic group and an acidic group on at least the surface thereof, thereby imparting a charge to the dispersed particles, and providing an electrostatic repulsion force. It is possible to provide a hydrocarbon solvent-based dispersion liquid having improved dispersibility and capable of electrophoresis. Further, 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 steric stabilizing effect and a stabilizing effect by electrostatic repulsion. It is possible to provide a hydrocarbon solvent-based dispersion liquid that is more stable due to a synergistic effect and has excellent electrophoretic properties. In addition, according to the dispersion of the present invention, at least a hydrocarbon solvent having a viscosity at room temperature of 10 mPa · s or more, a particle component insoluble in the solvent, and a resin soluble in the solvent include a hydrocarbon. A dispersion having excellent affinity for a solvent can be provided. Further, according to the dispersion of the present invention, since the resin has one of an acidic group and a basic group, a dispersion having good dispersibility in a hydrocarbon solvent can be provided. Also,
According to the dispersion of the present invention, the particle component has one of an acidic group or a basic group, thereby imparting a charge to the dispersed particles and improving dispersibility by electrostatic repulsion,
In addition, it is possible to provide a dispersion liquid that can be electrophoresed.
Further, according to the dispersion of the present invention, since 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 improved. Can be provided. Further, according to the dispersion of the present invention, in the silicone oil,
By containing at least a particle component insoluble in silicone oil and at least a polymer obtained by polymerizing the monomer represented by the general formula (II), it is possible to provide a dispersion system having excellent affinity for silicone oil. it can. Further, according to the dispersion of the present invention, by containing a copolymer of a monomer represented by the general formula (II) and a monomer having an acidic group or a basic group, the dispersion liquid interacts with the dispersed particles. And a dispersion system having a high affinity for silicone oil. The dispersion of the present invention has the general formula (I)
It contains a copolymer of a monomer represented by I) and a monomer having an acidic group and a copolymer of a monomer represented by the general formula (II) and a monomer having a basic group. It is characterized by the following. As a result, it is possible to provide a dispersion liquid that imparts electric charge to the dispersed particles, improves dispersibility by electrostatic repulsion, and enables electrophoresis. Further, according to 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 a basic More stable and electrophoretic properties due to the synergistic effect of steric stabilization and stabilization by electrostatic repulsion on the dispersed particles due to the insolubility of any one of the copolymers with the monomer having a group in the silicone oil. A dispersion liquid excellent in the above can be provided. Further, according to 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 a basic By providing at least one of the copolymers with a monomer having a group as a copolymer with a monomer having a polar group, it is possible to provide a dispersion liquid having an improved charge amount related to the charging of particles. be able to. Further, according to the dispersion of the present invention, the polymer is obtained by further polymerizing a monomer represented by the general formula (III),
It is possible to provide a silicone oil dispersion which is excellent in affinity with silicone oil and gives a steric stabilizing effect to the dispersed particles, whereby the dispersion is stable. Further, according to the dispersion of the present invention, the particle component has a basic group or an acidic group on at least the surface, thereby imparting a charge to the dispersed particles, improving the dispersibility by electrostatic repulsion, and An electrophoretic dispersion can be provided. Further, according to the dispersion of the present invention, since at least one of the particle component and the polymer has a nonionic polar group, a synergistic effect of a steric stabilizing effect and a stabilizing effect by electrostatic repulsion is imparted to the dispersed particles. Can provide a more stable dispersion liquid having excellent electrophoretic properties. Further, according to the dispersion of the present invention, since the viscosity of the silicone oil is 200 cSt or less, a silicone oil dispersion having excellent storage characteristics can be provided. Further, according to the dispersion of the present invention, since the content of the particle component is 0.1 to 20% by mass, a silicone oil dispersion having low cost and excellent storage characteristics can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 9/08 C08K 9/08 C08L 101/02 C08L 101/02 // C08F 292/00 C08F 292/00 F term (reference) 4J002 AA031 BC032 BC042 BC052 BC062 BC071 BC072 BC081 BC082 BC101 BC112 BF021 BG011 BG041 BG051 BG061 BG071 BG101 BG121 BG131 BH001 BN181 BQ001 CP033 CP171 DA036 DA086 DE116 DL006 EA017 EA027 EA037 EU026 FA082 FA086 FB082 FB086 FB262 FB266 FD016 FD096 FD203 FD206 FD207 GB00 GH01 GJ01 GK00 GK02 GK04 4J026 AC00 BA30 BB01 DB02 DB12 DB15 FA03 GA08 4J027 AC02 AC03 AC04 AC06 AF05 BA04 BA05 BA06 BA07 BA08 BA10 BA11 BA12 BA13 BA14 BA15 BA19 BA20 BA21 CA18 CA22 CA33 CA34 CA36 CB04 CD00 CD09 CD09

Claims (18)

[Claims] In a hydrocarbon solvent, at least a particle component insoluble in the hydrocarbon solvent and a monomer which is compatible with the hydrocarbon solvent and is at least represented by the following general formula (I): [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 is an integer of 1 to 3, y is a natural number of 25 or less. And a polymer obtained by polymerizing the above. 2. The polymer according to claim 1, wherein the polymer further contains at least one of a monomer having an acidic group and a monomer having a basic group. Dispersion. 3. The dispersion according to claim 1, wherein the particle component has at least one of a basic group and an acidic group on at least the surface. 4. The dispersion according to claim 1, wherein at least one of the surface of the particle component and at least one of the polymer has a nonionic polar group. 5. A viscosity at room temperature of at least 10 mP.
A dispersion comprising: a · s or more of a hydrocarbon solvent, a particle component insoluble in the solvent, and a resin soluble in the solvent. 6. The dispersion according to claim 5, wherein the resin has an acidic group or a basic group. 7. The dispersion according to claim 5, wherein at least the surface of the particle component has an acidic group or a basic group. 8. The dispersion according to claim 5, wherein at least the surface of the resin or the particle component has a nonionic polar group. 9. A dispersion liquid comprising, in a silicone oil, at least a particle component insoluble in the silicone oil and at least a polymer obtained by polymerizing a monomer represented by the following general formula (II). Embedded image [Wherein, R represents a hydrogen atom or a methyl group, and n represents a natural number. ] 10. The dispersion according to claim 9, comprising a copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group or a basic group. 11. A copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group, and a copolymer having a monomer represented by the general formula (II) and a basic group The dispersion according to claim 9, which contains a copolymer with a monomer. 12. A copolymer of the monomer represented by the general formula (II) and a monomer having an acidic group or a monomer having a basic group and a monomer represented by the general formula (II) The dispersion according to claim 11, wherein the copolymer with the monomer is insoluble in the silicone oil. 13. A copolymer of a monomer represented by the general formula (II) and a monomer having an acidic group, and a monomer having a basic group and a monomer represented by the general formula (II). 12. A copolymer with a monomer having a polar group, wherein at least one of the copolymers with a monomer is a copolymer with a monomer having a polar group.
Or the dispersion according to 12. 14. The polymer according to claim 1, wherein the polymer is 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 is an integer of 1 to 3, y is a natural number of 25 or less. The dispersion according to any one of claims 9 to 13, wherein the dispersion is further polymerized. 15. The dispersion according to claim 14, wherein the particle component has a basic group or an acidic group on at least the surface. 16. The dispersion according to claim 14, wherein at least one of the surface of the particle component and at least one of the polymer has a nonionic polar group. 17. The silicone oil having a viscosity of 200
The dispersion according to any one of claims 9 to 16, wherein the dispersion is not more than cSt. 18. The content of the particle component is 0.1 to 2
The dispersion according to any one of claims 9 to 17, wherein the dispersion is 0% by mass.