JP2002212423A - Silicone oil dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone oil dispersion that is excellent in affinity for silicone oils, and has particles stably dispersed by furnishing a steric stabilization effect to the particles. SOLUTION: This dispersion comprises, in a silicone oil, (1) a particle component that is insoluble in the silicon oil and comprises a polymer from a specific monomer as a constituent, and (2) a polymer from a monomer having an acidic group as a constituent, the polymer being soluble in the silicone oil. It is preferable that the particle component insoluble in the silicone oil has a basic group at least on the surface. It is also preferable that the particle component has a nonionic polar group other than a (poly)oxyalkylene group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersion in which non-uniform particles are dispersed using silicone oil (silicone oil) as a dispersing solvent. The release agent used,
Printing inks, inkjet inks, adhesives, dry toners, electrophotographic toners including wet toners, paints, electrodeposition paints, displays, magnetic fluids, rubber roller coating materials,
The present invention relates to a silicone oil dispersion useful for cosmetics and the like.

[0002]

2. Description of the Related Art Silicone oil has various features different from aqueous solvents and conventional non-aqueous solvents. For example, it has excellent heat resistance and cold resistance, is chemically inert, is an odorless solvent, has a small change in viscosity with temperature, is high in viscosity, is non-volatile, has low surface tension, and has water repellency. With oil repellency, excellent release properties,
Due to its many excellent features, it is widely used as an industrial material in the fields of electrical machinery, machinery, chemical industry, etc.

In a dispersion in which particles of a resin, a pigment, a magnetic substance, etc. are dispersed in an appropriate solvent, the stability of the dispersed particles is an important issue in both non-aqueous and aqueous solvent systems. It is known that the stability of such dispersed particles can be generally obtained by an electrostatic effect or a three-dimensional effect (also called an adsorption layer effect). The DLVO theory has been established for the electrostatic effect, 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 required, and some studies have been made on aqueous solvent systems in which the presence of ions is clearly defined.

[0004] 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. Assoc.,
The work described in 54, 342 (1971) relates to a basic method for the preparation of stable non-aqueous solvent-based dispersions, in which particles dispersed in the solvent (insoluble in the solvent) are used. This is to produce a block or graft copolymer containing a compatible component and a component soluble in the solvent.

A method utilizing this method is disclosed in
Japanese Patent Application No. 0-7047 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 unlikely that the degraded rubber is adsorbed on the PMMA particles by this method.
Due to the fact that the A particles are dispersed and stabilized, the reduced rubber has MM
It is considered that A was graft-polymerized. 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.

However, unlike a non-polar aprotic solvent represented by a conventional petroleum-based 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.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention according to claims 1 and 2 is to have an excellent affinity with silicone oil and a three-dimensional dispersion of dispersed particles. An object of the present invention is to provide a silicone oil-based dispersion liquid which has a stabilizing effect and is stable.

An object of the present invention according to claims 3 and 7 is to provide a dispersion liquid which imparts electric charge to dispersed particles, improves dispersibility by electrostatic repulsion, and enables electrophoresis. is there.

An object of the present invention according to claims 4, 5 and 8, 9 is to provide a dispersed particle having a more excellent stability and electrophoretic properties due to a synergistic effect of steric stabilizing action and stabilizing action by electrostatic repulsion. Providing a liquid.

An object of the present invention according to claims 6 and 10 is to provide a dispersion liquid in which the amount of charge related to the charging of particles is improved.

[0011]

The above object is achieved by the following means. That is, the invention according to claim 1 includes, in a silicone oil, a particle component insoluble in the silicone oil, and a polymer obtained by polymerizing a monomer having an acidic group that is compatible with the silicone oil and has an acidic group. Wherein the particle component has at least the following general formula (I):

[0012]

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. ]

A silicone oil dispersion containing a polymer obtained by polymerizing a monomer represented by formula (1) as a constituent element.

According to a second aspect of the present invention, there is provided a polymer obtained by polymerizing a silicone oil-insoluble particle component and a monomer having a basic group, which is compatible with the silicone oil, as a constituent element. A dispersion containing a coalescence, wherein the particle component has at least the following general formula (I)

[0015]

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. ]

A silicone oil dispersion containing a polymer obtained by polymerizing a monomer represented by the following formula:

According to a third aspect of the present invention, there is provided the silicone oil dispersion according to the first aspect, wherein the particle component insoluble in the silicone oil has at least a basic group on the surface.

According to a fourth aspect of the present invention, there is provided the silicone oil dispersion according to the third aspect, wherein the particle component insoluble in the silicone oil has a nonionic polar group other than a (poly) oxyalkylene group. Liquid.

According to a fifth aspect of the present invention, there is provided a polymer which is compatible with silicone oil, and is obtained by polymerizing a monomer represented by the general formula (I) and a monomer having an acidic group as constituents. Both have a nonionic polar group other than a (poly) oxyalkylene group, The silicone oil dispersion of Claim 3 characterized by the above-mentioned.

According to a sixth aspect of the present invention, there is provided a particle component which is insoluble in a silicone oil, a monomer which is compatible with the silicone oil, has a monomer represented by the general formula (I), and a monomer having an acidic group. 6. The silicone oil dispersion according to claim 3, wherein both the polymer obtained by polymerizing the monomer as a constituent has a nonionic polar group other than a (poly) oxyalkylene group. .

According to a seventh aspect of the present invention, there is provided the silicone oil dispersion according to the second aspect, wherein the particle component insoluble in the silicone oil has at least an acidic group on the surface.

The invention according to claim 8 is characterized in that the particle component insoluble in silicone oil has a nonionic polar group other than a (poly) oxyalkylene group. Liquid.

According to a ninth aspect of the present invention, there is provided a polymer obtained by polymerizing a monomer represented by the general formula (I) and a monomer having a basic group, which is compatible with silicone oil. 8. Both of the unions have a nonionic polar group other than a (poly) oxyalkylene group.
The silicone oil dispersion described in the above.

According to a tenth aspect of the present invention, there is provided a particle component which is insoluble in silicone oil, and which is compatible with the silicone oil and has a monomer represented by the general formula (I) and a basic group. 10. The silicone oil dispersion according to claim 7, wherein both of the polymer obtained by polymerizing a monomer as a constituent have a nonionic polar group other than a (poly) oxyalkylene group. is there.

As described above, the presence of ions or charges was unclear in a non-aqueous solvent, especially in a non-polar aprotic solvent dispersion. This is considered to be due to the fact that interaction (solvation) hardly occurs between ions and solvent molecules in this kind of solvent.

Therefore, the present inventors have proposed (a) an organic substance having an acidic group but no basic group, (b) an organic substance having a basic group but no acidic group, and (c) the solvent And three components of an organic substance having a nonionic polar component, which are compatible with the component (where either component (a) or (b) exists as a copolymer with component (c)). You may. As a result of various experiments on silicone oil-based dispersions, it was found that components (a) and (b) caused acid-base ion dissociation in the solvent. It was also suggested that ion-dipole interaction, ie, solvation, was present.

Thus, the inventor of the present invention has found that, when the three components (a), (b) and (c) are present in the solvent, (c)
It has been found that ions can be stably present even in silicone oil by ion dissociation between an acid and a base via solvation of a polar group in a component. This fact is (a),
(B) Both components were soluble or insoluble in the solvent, and were similarly observed.

The inventor of the present invention (a),
When a fixed particle such as a pigment or a metal oxide is further coexisted in a system containing the three components (b) and (c), the acid group or the basic group of the component (a) or (b) is chemically bonded, It was fixed by adsorption or the like, and it was found that ion dissociation occurs at the interface between the surface of the solid particles and the solvent via the solvation of the component (c). In addition, the dispersion stability of the particles, which is considered to be due to the steric effect of the (poly) oxyalkylene group, was confirmed. As a result, the solid particles are uniformly charged to a positive or negative polarity, and the solid particles are more stably dispersed by the synergistic effect of the electrostatic effect and the steric effect. Further, the inventor has found that the ion amount and the charge amount can be controlled by the types and amounts of the components (a), (b) and (c). The present invention is based on the above findings.

The dispersion according to claim 1 contains a polymer which is compatible with silicone oil and is polymerized with a monomer having an acidic group as a constituent element.
The interaction between the polymer and the particles results in a dispersion having excellent affinity for the silicone oil of the particles and excellent dispersion stability due to the steric effect of the (poly) oxyalkylene groups of the particles.

The dispersion according to the second aspect contains a polymer which is compatible with the silicone oil and is polymerized with a monomer having a basic group as a constituent element, whereby the polymer and the particles are mixed. By the interaction of the particles, the dispersion liquid is excellent in the affinity with the silicone oil of the particles, and the dispersion stability is more excellent than the steric effect of the (poly) oxyalkylene group of the particles.

In the dispersion according to the third aspect, since the particle component insoluble in the silicone oil has at least a basic group on its surface, a positive charge is imparted to the dispersed particles by acid-base dissociation, and electrostatic repulsion is provided. Force improves dispersibility and enables electrophoresis.

In the dispersion according to the fourth aspect, since the particle component insoluble in the silicone oil 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 according to the fifth aspect, the polymer obtained by polymerizing a monomer compatible with the silicone oil and a monomer having an acidic group as a constituent element is not a (poly) oxyalkylene group. By having a nonionic polar group, a solvation effect on acid-base dissociation is exhibited, and it is possible to improve the dispersibility of the dispersed particles due to electrostatic repulsion and the electrophoretic properties.

In the dispersion according to the sixth aspect, a polymer obtained by polymerizing a particle component insoluble in silicone oil, a monomer compatible with the silicone oil, and a monomer having an acidic group as constituents. When both of the unions 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.

In the dispersion according to the seventh aspect, since the particle component insoluble in the silicone oil has an acidic group on at least the surface, a negative charge is imparted to the dispersed particles by acid-base dissociation, and the electrostatic repulsive force causes the dispersion. Improves dispersibility and enables electrophoresis.

In the dispersion according to the present invention, since the particle component insoluble in the silicone oil 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 according to the ninth aspect, a polymer obtained by polymerizing a monomer compatible with the silicone oil and a monomer having a basic group as a constituent component is a (poly) oxyalkylene group. By having a non-ionic polar group other than, a solvation effect on acid-base dissociation is expressed,
It is possible to improve the dispersibility of the dispersed particles due to electrostatic repulsion and the electrophoretic characteristics.

In the dispersion according to the present invention, a particle component insoluble in silicone oil, a monomer compatible with the silicone oil, and a monomer having a basic group are polymerized as constituent components. Both polymers are (poly)
By having a nonionic polar group other than the oxyalkylene group, it becomes possible to further improve the charge amount related to the charging of the particles.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, 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 (II); 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.

[0040]

Embedded image [However, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R
_9, R ₁₀ represents _{-C m H 2m + 1 (m} = 1~20), these may be the same or different. x is a natural number. ]

When the dialkyl silicone oil represented by the general formula (II) 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 (II) preferably has a viscosity at 25 ° C. of 0.01 to 1,000,000 cs (centistokes). In addition, the compounds of the general formula (I
It is desirable to use those having x of 1 to 20,000 in I).

Further, when a cyclic polydialkylsiloxane or a cyclic polyalkylphenylsiloxane is used, the resulting resin has a drying property of a polymerization solvent. Is advantageous.
When alkylphenylsiloxane (particularly, methylphenylsilicone oil is preferably used) is used, the solubility is improved by the introduction of a phenyl group (5 to 50 mol%). This is advantageous for increasing stability.

The following are specific examples of these various silicone oils. First, the following Table 1 shows examples of dialkyl silicone oils.

[0044]

[Table 1]

Examples of the cyclic polydialkylsiloxane and the cyclic polyalkylphenylsiloxane (the phenyl group content is 5, 10, 20, and 50 mol%, respectively) include cyclic polydimethylsiloxane, cyclic polymethylphenylsiloxane, and cyclic polymethylphenylsiloxane. Polydiethylsiloxane, cyclic polyethylphenylsiloxane, cyclic polydibutylsiloxane, cyclic polybutylphenylsiloxane, cyclic polydihexylsiloxane, cyclic polyhexylphenylsiloxane, cyclic polydilaurylsiloxane, cyclic polymethylchlorophenylsiloxane, cyclic polydistearylsiloxane, cyclic poly Methyl bromophenyl siloxane is mentioned.

Examples of the alkyl phenyl silicone oil include those shown in Table 2 below.

[0047]

[Table 2]

Examples of commercially available silicone oils include KF-96L [0.65, manufactured by Shin-Etsu Chemical Co., Ltd.]
1.0, 1.5, 2.0 centistokes (cs)],
KF-96 [10, 20, 30, 50, 500, 100
0,3000 (cs)], KF-56, KF-58, K
F-54, etc., and Toshiba Silicone Co., Ltd.
TSF451 series, TSF456 series, T
SF410,411,440,4420,484,48
3,431,433 series, THF450 series,
TSF404, 405, 406, 451-5A, 451
-10A, 437 series, TSF440, 400, 4
01,4300,4445,4700,4450,47
02, 4730 series, TSF434, 4600 series, and HS-200 manufactured by Toray Silicone Co., Ltd., and the like.

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

The polymer according to the present invention has a monomer having a high affinity for silicone oil, an acrylic monomer having a (poly) oxyalkylene group, and optionally having an acidic group or a basic group. It is obtained by copolymerizing a monomer, a monomer having a polar group, and the like. Hereinafter, the polymerizable monomer in the present invention will be described.

First, the monomer represented by the following general formula (III) has a strong affinity for silicone oil and has a feature that it is difficult to dissolve in silicone oil with ordinary polymers. In the case of a homopolymer, a polymer to be obtained gives a polymer soluble in silicone oil, and in the case of a copolymer with another monomer, the polymer is soluble with or insoluble in silicone oil. A stable dispersion having a high affinity can be provided.

[0052]

Embedded image [Wherein, R ₁ represents a hydrogen atom or a methyl group, and n represents a natural number. ]

Further, the monomer represented by the above general formula (I) has a (poly) alkylene glycol chain having a repeating unit of an oxyalkylene group of 25 or less, and the monomer having the monomer as a constituent element. When the polymer is present as a part of the particles insoluble in the solvent, the dispersion of the particles is stabilized by the steric effect exhibited by the (poly) alkylene glycol chains on the surface of the particles.

Next, examples of the monomer copolymerizable with the above-mentioned monomer include the following. (1) Examples of the monomer having an acidic group: These are the monomeric vinyl group and -COOH group, -SO ₃ H group, -SO ₂ H group,
-CH ₂ NO ₂ group, -CHRNO ₂ group, -ArOH group,
And those having at least one of an ArSH group and the like (R is an alkyl group, 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-methacryloxyethyl maleic acid, 2-methacryloxyethyl hexahydrophthalic acid, Vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2-sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, 3-chloroamidophosphoxypropyl methacrylate, 2-methacryloxyethyl acid phosphate, and the like. Can be

(2) Examples of monomers having a basic group: These monomers include a vinyl group, a —NH ₂ group and a —NHR
A group having at least one of a group, a -NRR '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, N- Examples include phenylaminoethylstyrene, 2-N-piperidylethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, and the like.

(3) 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,
Vinyl pyrrolidone, N-acryloyl morpholine, tetrahydrofurfuryl methacrylate, trifluoroethyl methacrylate, p-nitrostyrene, acrylamide, methacrylamide, N, N-dimethylmethacrylamide, N, N-dibutylmethacrylamide and the like.

(4) 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, trimethylol Hexane tri (meth) acrylate, ventaerythrit tetra (meth)
Acrylate, 1,3-dibutylene glycol di (meth)
Acrylate, trimethylolethane tri (meth) acrylate and the like can be mentioned.

(5) 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)
Examples include acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, styrene, vinyl toluene, and vinyl acetate.

The polymer used in the first embodiment of the present invention, which is compatible with silicone oil, includes a monomer represented by the general formula (III) having a high affinity for silicone oil. And a copolymer of the above-mentioned (1) with the monomer. Examples of the particle components insoluble in silicone oil include generally known inorganic or organic pigments, metals, metal oxides, magnetic powders, wax-like substances (eg, low molecular weight polyolefins, waxes), chemical products (eg, agricultural chemicals), and swelling. Resin-dispersed particles obtained by polymerizing particles of an agent or the like with the monomer represented by the above general formula (I) as a constituent component are dispersed in a binder resin.

Specific particles include, 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. Metals such as iron oxide such as magnetite, hematite, and ferrite, iron, carbonyl iron powder, cobalt, and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, and cadmium of these metals ,
Alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof,
Glass beads and the like can be mentioned.

Examples of the binder resin include a monomer represented by the above general formula (I) and a copolymer containing at least one of the above monomers (4) and (5) as a component. Is mentioned. Further, a copolymer containing a monomer having a high affinity for the silicone oil represented by the general formula (III) may be used. The ratio of using these monomers cannot be unambiguously defined, and the desired 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 (4) in a relatively large amount. Further, the binder resin alone may be used as particles.

Further, in the dispersion of the present invention, 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. Can also.

The polymer used in the second embodiment of the present invention, which is compatible with silicone oil, includes a monomer represented by the general formula (III) having a high affinity for silicone oil. And a copolymer having the monomer (2) as a component. Further, the particle component insoluble in silicone oil includes the first component of the present invention.
And the particle component used in the embodiment.

The polymer which is compatible with the silicone oil used in the third embodiment of the present invention includes a polymer which is compatible with the silicone oil used in the first embodiment of the present invention. Coalescence. Further, as the particle component insoluble in the silicone oil, as the binder of the insoluble particle component in the first embodiment of the present invention, at least the monomer represented by the above general formula (I) and the above (2) A resin using a resin insoluble in a silicone oil solvent having a monomer as a constituent component may be used. When substances that can be chemically bonded by grafting or the like, such as carbon black or metal oxide, are used as the solid particles, these substances may include the monomer represented by the general formula (I), (Poly) oxyalkylene group and a basic group may be chemically bonded by reacting the above monomer.

The polymer which is compatible with the silicone oil used in the fourth embodiment of the present invention includes a polymer which is compatible with the silicone oil used in the first embodiment of the present invention. Coalescence. Further, as the particle component insoluble in the silicone oil, at least a monomer represented by the general formula (I) and a monomer of the above (2) as a binder of the insoluble particle component in the first embodiment of the present invention are used. And a resin using a resin insoluble in silicone oil having the monomer (3) as a constituent component. 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, a monomer represented by the general formula (I) may be added to these substances. (Poly) oxyalkylene group, basic group, and polar group may be chemically bonded by reacting the above-mentioned monomer and the above-mentioned monomer (3).

As the polymer compatible with silicone oil used in the fifth embodiment of the present invention, a monomer represented by the general formula (III) having a high affinity for silicone oil: And a copolymer with the monomer (1) and the monomer (3). Examples of the particle component insoluble in silicone oil include the particle component used in the third embodiment of the present invention.

The polymer used in the sixth embodiment of the present invention, which is compatible with the silicone oil, includes the copolymer used in the fifth embodiment of the present invention. Examples of the particle component insoluble in the silicone oil include the particle component used in the fourth embodiment of the present invention.

The polymer which is compatible with the silicone oil used in the seventh embodiment of the present invention includes a polymer which is compatible with the silicone oil used in the second embodiment of the present invention. Coalescence. Further, as the particle component insoluble in the silicone oil, as the binder of the insoluble particle component in the second embodiment of the present invention, at least the monomer represented by the general formula (I) and the monomer (1) And a resin using a resin insoluble in a silicone oil solvent having a monomer as a constituent component. When substances that can be chemically bonded by grafting or the like, such as carbon black or metal oxide, are used as the solid particles, these substances may include the monomer represented by the general formula (I), (Poly) oxyalkylene group and acidic group may be chemically bonded by reacting the above monomer.

The polymer which is compatible with the silicone oil used in the eighth embodiment of the present invention includes a polymer which is compatible with the silicone oil used in the second embodiment of the present invention. Coalescence. Further, as the particle component insoluble in silicone oil, at least a monomer represented by the general formula (I) and a monomer of the above (1) may be used as a binder of the insoluble particle component in the second embodiment of the present invention. And a resin using a resin insoluble in a silicone oil solvent having the monomer (3) as a constituent. 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 represented by the general formula (I) may be added to these substances. The (poly) oxyalkylene group, the acidic group, and the polar group may be chemically bonded by reacting the monomer of (3) with the monomer of (3).

As the polymer compatible with silicone oil used in the ninth embodiment of the present invention, a monomer represented by the general formula (III) having a high affinity for silicone oil: And a copolymer with the monomer (2) and the monomer (3). Examples of the particle component insoluble in silicone oil include the particle component used in the seventh embodiment of the present invention.

The polymer used in the tenth embodiment of the present invention, which is compatible with the silicone oil, includes the copolymer used in the ninth embodiment of the present invention. Further, examples of the particle component insoluble in the silicone oil include the particle component used in the eighth embodiment of the present invention.

To prepare the dispersion of the present invention, the first dispersion of the present invention is used.
Taking the case of the embodiment as an example, each of the resin components described above,
And the solid particles may be mixed and dispersed in the silicone oil. 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 in the present invention is 1,000 centistokes or less, 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, an appropriate amount of the insoluble particle component is preferably 0.1 to 20% by weight.
More preferably, 0.5 to 15 weight percent is suitable. In use in this range, a dispersion that is very stable even for long-term storage can be obtained.

[0075]

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 weight.

<Example 1> 300 parts of silicone oil (Toray Dow Corning Silicone SH200.1cs) was taken and heated to 85 ° C. A solution comprising 48 parts of the compound of the following structural formula (Mn @ 1000), 2 parts of methacrylic acid, and 1 part of benzoyl peroxide was added dropwise thereto over 1 hour.

[0077]

Embedded image

Then, stirring was continued at the same temperature for 5 hours to complete the reaction. Thus, a uniform and transparent resin solution has a polymerization rate of 9
Obtained at 8.1%.

On the other hand, 300 parts of silicone oil (SH-200, 1cs) was placed in a similar reaction vessel and heated to 85 ° C. A solution comprising 30 parts of methyl methacrylate, 15 parts of decyl methacrylate, 5 parts of the compound of the following structural formula 2 (y ≒ 4), 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. An insoluble resin was obtained at a polymerization rate of 93.9% by filtration and washing.

[0080]

Embedded image

Next, 5 parts of this resin 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. 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> Silicone oil (SH-200, 1cs) 300 was placed in the same reaction vessel as in Example 1.
An aliquot was taken and heated to 90 ° C. In this, 45 parts of the compound of the above formula (Mn @ 1000), 5 parts of dimethylaminoethyl methacrylate and benzoyl peroxide 1
Part of the solution 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 97.2%.

Next, Example 1 was added to 100 parts of the resin solution.
10 parts of the insoluble resin and 5 parts of titanium oxide prepared in the above were added 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 3 The reaction vessel used in Example 1 was charged with 500 parts of silicone oil (SH-200, 1cs) and heated to 80 ° C. In this, 10 parts of the compound of the above structural formula 1 (Mn @ 10000), ethyl methacrylate 2
0 parts, dibutylaminoethyl methacrylate 5 parts, ethylene glycol dimethacrylate 15 parts, the above-mentioned structural formula 2
5 parts of compound (y ≒ 9), benzoyl peroxide 1
Part of the solution was added dropwise over 5 hours. Then 85
The reaction was completed by stirring at 2 ° C. for 2 hours. An insoluble resin was obtained at a polymerization rate of 91.8% by filtration and washing. next,
5 parts of this resin was added to 50 parts of the resin solution prepared in Example 1 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 A reaction vessel similar to that of Example 1 was charged with 500 parts of silicone oil (SH-200, 1cs) and heated to 80 ° C. 20 parts of the compound of the above structural formula 1 (Mn @ 10000), 5 parts of diethylaminoethyl methacrylate, 5 parts of hydroxyethyl methacrylate, 20 parts of ethylene glycol dimethacrylate, 5 parts of the compound of the above structural formula 2 (y @ 4), 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. Polymerization rate 9 by filtration and washing treatment
Resin was obtained at 2.9%. Next, 5 parts of this resin and 50 parts of the resin solution prepared in Example 1 were added to 45 parts of silicone oil (SH-200, 10cs), and the mixture was 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 5> Silicone oil (SH-200, 1cs) 300 was placed in the same reaction vessel as in Example 1.
An aliquot was taken and heated to 90 ° C. 47 parts of the compound of the above formula (Mn @ 1000), 1 part of methacrylic acid,
A solution consisting of 2 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. In this way, a uniform and translucent polymer gel dispersion has a conversion of 96.1.
%. Next, 5 parts of the insoluble resin prepared in Example 3 and titanium oxide 7 were added to 100 parts of the polymer gel dispersion liquid.
Part, dye (Bayer Macrolex Blue RR)
One part was added and dispersed by a ball mill to form a dispersion. The dispersion stability was examined in the same manner as in Example 1. However, no precipitation was observed even after standing for one month, indicating that the dispersion was very stable.

Example 6 Silicone oil (SH-2)
(00, 1cs) 5 parts of the insoluble resin prepared in Example 4 and 50 parts of the polymer gel dispersion prepared in Example 5 were added to 45 parts of the mixture and ultrasonically dispersed to prepare a dispersion. This dispersion is
The mixture 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 cathode, and no deposition was observed on the anode. This indicated that all the particles were positively charged.

Example 7 The reaction vessel used in Example 1 was charged with 500 parts of silicone oil (SH-200, 1cs) and heated to 80 ° C. In this, 20 parts of the compound of the above formula (Mn @ 1000), 23 parts of ethylene glycol dimethacrylate, 2 parts of methacrylic acid,
5 parts of compound (y ≒ 4), benzoyl peroxide 1
Part of the solution was added dropwise over 1 hour. Then 8
The reaction was completed by stirring at 5 ° C. for 3 hours. A resin having a polymerization rate of 93.5% was obtained by filtration and washing. 45 parts of silicone oil (SH-200, 20cs) 5 parts of this resin and 50 parts of the resin solution prepared in Example 2 were 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 8 500 parts of silicone oil (SH-200, 1cs) was placed in a reaction vessel similar to that of Example 1, and heated to 80 ° C. In this, 10 parts of the compound of the above structural formula 1 (Mn @ 5000) and methyl methacrylate 2
5 parts, lauryl methacrylamide 5 parts, methacrylic acid 5
A solution consisting of 5 parts of the compound of the formula (y ≒ 9) and 1 part of azobisisobutyronitrile was added dropwise over 3 hours. Next, 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 92.4%. Next, 50 parts of the resin dispersion prepared in Example 2 and 5 parts of a copper phthalocyanine pigment were added to 50 parts of the resin dispersion, and dispersed by a ball mill to prepare a dispersion. The dispersion stability was examined in the same manner as in Example 1.
There was no precipitation even after standing for a month, indicating that the dispersion was very stable.

<Example 9> Silicone oil (SH-200, 1cs) 500 was placed in the same reaction vessel as in Example 1.
An aliquot was taken and heated to 90 ° C. A solution comprising 42 parts of the compound of the above formula (Mn @ 1000), 5 parts of dimethylaminoethyl methacrylate, 3 parts of vinylpyrrolidone 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 uniform and transparent resin solution has a polymerization rate of 9
5.9%. Next, 5 parts of the resin prepared in Example 7 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. However, no precipitation was observed even after standing for one month, indicating that the dispersion was very stable.

Example 10 50 parts of the resin solution prepared in Example 9 were added to 50 parts of the resin dispersion prepared in Example 8
3 parts of N-diethylpropionamide, 7 parts of titanium oxide,
0.1 part of a dye (Bayer Macrolex Blue RR) was added, and the mixture was dispersed by a ball mill to prepare a dispersion. This dispersion is poured into a cell provided with an ITO transparent electrode glass so that the electrode faces face each other with a spacer having a distance of 1 mm,
A DC voltage of 1000 V was applied for 1 second. After applying voltage,
When observed from the anode side, the electrode surface was white. Observation from the opposite side of the cathode revealed that the electrode surface was colored with a dye. From this, it was found that all the particles were negatively charged and were electrodeposited only on the anode side.

Comparative Example 1 Silicone oil (SH-2)
(00, 1 cs), 100 parts of titanium oxide and 0.1 part of dye (Bayer Macrolex Blue RR) were added, 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. However, the supernatant liquid appeared about 20 cm after standing for one day, and was a very unstable dispersion.

<Comparative Example 2> 500 parts of silicone oil (SH-200, 1cs) was placed in the same reaction vessel as in Example 1, 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.
The reaction was terminated. 90.9 polymerization rate by filtration and washing
% Resin was obtained. 10 parts of this resin was put into a ball mill together with 100 parts of silicone oil (SH-200, 1cs) and 1 part of carbon black to obtain a dispersion. The dispersion is poured into a Teflon (registered trademark) container having brass electrodes arranged in parallel with an electrode spacing of 5 mm, and the solution
A DC voltage of 0 V was applied for one 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.

[0094]

As is apparent from the above description, claim 1
According to the invention according to the above, a polymer obtained by polymerizing a monomer having an acidic group as a constituent element is dissolved in the silicone oil, and the dispersed particles have a (poly) oxyalkylene group, whereby the affinity for the silicone oil is improved. It is possible to provide a silicone oil dispersion having excellent dispersibility and stable dispersion.

According to the second aspect of the present invention, a polymer obtained by polymerizing a monomer having a basic group as a constituent in silicone oil is dissolved, and the dispersed particles have a (poly) oxyalkylene group. It is possible to provide a silicone oil dispersion having excellent affinity with silicone oil and stable dispersion.

According to the third aspect of the present invention, since the particle component insoluble in the silicone oil has at least a basic group on the surface, a positive charge is imparted to the dispersed particles, and the dispersibility is enhanced by electrostatic repulsion. It is possible to provide a dispersion liquid which can be improved and can be electrophoresed.

According to the fourth aspect of the invention, since the particle component insoluble in the silicone oil has a nonionic polar group other than the (poly) oxyalkylene group, the dispersed particles have a steric stabilizing effect and an electrostatic effect. A more stable and excellent electrophoretic dispersion can be provided by the synergistic effect of the stabilizing action due to repulsion.

According to the fifth aspect of the present invention, a polymer which is compatible with silicone oil and is polymerized by using a monomer having an acidic group as a constituent is a nonionic polar polymer other than a (poly) oxyalkylene group. By having a group, it is possible to provide a dispersion liquid which is more stable and has excellent electrophoretic properties due to a synergistic effect of a steric stabilizing action and a stabilizing action by electrostatic repulsion on the dispersed particles.

According to the sixth aspect of the present invention, both the particle component insoluble in silicone oil and the polymer which is compatible with the silicone oil and is polymerized with a monomer having an acidic group as a constituent are represented by ( By having a nonionic polar group other than the poly (oxyalkylene) group, it is possible to provide a dispersion in which the charge amount related to the charging of the particles is improved.

According to the seventh aspect of the present invention, the particle component insoluble in the silicone oil has an acidic group on at least the surface, thereby imparting a negative charge to the dispersed particles and improving the dispersibility by electrostatic repulsion. And a dispersion liquid that can be electrophoresed.

According to the eighth aspect of the present invention, since the particle component insoluble in silicone oil has a nonionic polar group other than the (poly) oxyalkylene group, the dispersed particles have a steric stabilizing effect and an electrostatic effect. A more stable and excellent electrophoretic dispersion can be provided by the synergistic effect of the stabilizing action due to repulsion.

According to the ninth aspect of the present invention, a polymer which is compatible with silicone oil and is polymerized by using a monomer having a basic group as a constituent component is a nonionic polymer other than a (poly) oxyalkylene group. By having a polar group, it is possible to provide a dispersion liquid which is more stable and has excellent electrophoretic properties due to a synergistic effect of a steric stabilizing action and a stabilizing action due to electrostatic repulsion on the dispersed particles.

According to the tenth aspect of the present invention, both the particle component insoluble in silicone oil and the polymer obtained by polymerizing a monomer having a basic group, which is compatible with silicone oil and have a basic group, By having a nonionic polar group other than the (poly) oxyalkylene group, it is possible to provide a dispersion in which the charge amount related to the charging of the particles is improved.

Claims (10)

[Claims] 1. A dispersion containing, in a silicone oil, a particle component which is insoluble in the silicone oil and a polymer which is compatible with the silicone oil and is polymerized with a monomer having an acidic group as a constituent element. The particle component has at least the following general formula (I): [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. ] A silicone oil dispersion containing a polymer obtained by polymerizing the monomer represented by the formula (1) as a constituent element. 2. A dispersion containing, in a silicone oil, a particle component insoluble in the silicone oil and a polymer which is compatible with the silicone oil and is polymerized with a monomer having a basic group as a constituent element. In addition, the above-mentioned particle component has at least the following general formula (I): [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. ] A silicone oil dispersion comprising a polymer obtained by polymerizing the monomer represented by the formula (1) as a constituent element. 3. A particle component insoluble in silicone oil,
The silicone oil dispersion according to claim 1, having a basic group at least on the surface. 4. A particle component insoluble in silicone oil,
The silicone oil dispersion according to claim 3, having a nonionic polar group other than a (poly) oxyalkylene group. 5. A polymer which is compatible with silicone oil and is obtained by polymerizing a monomer represented by the general formula (I) and a monomer having an acidic group as a constituent element, The silicone oil dispersion according to claim 3, having a nonionic polar group other than an oxyalkylene group. 6. A polymer comprising a particle component insoluble in silicone oil, a monomer represented by the above general formula (I), which is compatible with the silicone oil, and a monomer having an acidic group as constituents. 6. The silicone oil dispersion according to claim 3, wherein both of the polymers have a nonionic polar group other than a (poly) oxyalkylene group. 7. A particle component insoluble in silicone oil,
The silicone oil dispersion according to claim 2, wherein the dispersion has an acidic group at least on the surface. 8. The particle component insoluble in silicone oil,
The silicone oil dispersion according to claim 7, which has a nonionic polar group other than a (poly) oxyalkylene group. 9. A polymer which is compatible with silicone oil and is obtained by polymerizing a monomer represented by the general formula (I) and a monomer having a basic group as a constituent element, 8. The silicone oil dispersion according to claim 7, wherein the silicone oil dispersion has a nonionic polar group other than an oxyalkylene group. 10. A particle component insoluble in silicone oil,
And a polymer which is compatible with the silicone oil and is polymerized by using a monomer represented by the above general formula (I) and a monomer having a basic group as a constituent element is a (poly) oxyalkylene The silicone oil dispersion according to claim 7, which has a nonionic polar group other than a group.