JPS59213428A - Nonaqueous solvent type dispersing liquid - Google Patents

Abstract

PURPOSE:To improve remarkably the stability of dispersion by incorporating a high molecular substance, contg. a monomer having groups of an acidic group organic substance, a basic group organic substance, and ester etc., into a nonpolar nonaqueous solvent. CONSTITUTION:Into a nonpolar nonaqueous solvent (e.g. pentane), a) an organic substance (e.g. formic acid) with an acidic group and without a basic group b) an organic substance (e.g. diethanolamine) with a basic group and without an acidic group, and c) a high molecular substance (e.g. octyl (metha) acrylate) contg. as a constituent a monomer C, which is compatible with said solvents and having >=1 group selected from among a group of ester, ether, amide, cyano, hydroxyl, tri-fluoromethyl, and halogen, are incorporated as essential components. In this way, solid particles in the nonpolar nonaqueous solvent are electrically charged definitely by the ions, and the stability of dispersion is improved by utilizing the synergetic action of the steric and electrostatic effects.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to coatings, particularly non-aqueous dispersions useful in electrocoating coatings, adhesives, inks, electrophotographic liquid developers, displays, magnetic fluids, and the like.

BACKGROUND OF THE INVENTION In a dispersion in which particles of resin, pigment, magnetic material, etc. are dispersed in a suitable solvent, the stability of the dispersed particles is an important issue whether in a non-aqueous solvent system or an aqueous solvent system. It is known that such stability of dispersed particles is generally obtained by the action of electrostatic effect or steric effect (also called absorption layer effect).

Regarding the electrostatic effect, the DLVO theory has been established, and in this theory, the spread of the electric double layer and the interfacial potential (so-called ξ potential) are important factors. Therefore, the presence of ions that form these is necessary, and several studies have been conducted in water solvent systems where the presence of ions is clear. On the other hand, regarding steric effects, nothing equivalent to the DLVOW theory has yet been established, but the following five studies are known for non-aqueous solvent systems (mainly petroleum-insoluble fi). Namely F, A, Waite, J, 0IICo1.
Chem, As5oa,, 54, 342 (19
The research described in 71) concerns a basic method for producing stable non-aqueous dispersions, and this method involves adding components that are compatible with the particles (insoluble in the solvent) to be dispersed in the solvent. and a component soluble in the solvent is produced. As a method utilizing this method, methyl methacrylate was
A method for obtaining a stable polymethyl methacrylate (PMMA, ) dispersion by subjecting (MMA) to a radical base is described. It is unlikely that the degraded rubber is adsorbed by the PMMA particles using this method, and the fact that the PMMA particles are dispersed stably suggests that MMA is graft polymerized to the degraded rubber. In addition, in this graft ice coalescence, the undissolved part associates with the particle ice surface, and the melted part has a steric effect.
As a result, it is believed that the dispersion stability of the particles is maintained.

However, until now, it has not been known that solid particles can be sufficiently stably dispersed in a non-aqueous solvent such as a petroleum solvent, i.e., a non-polar aprotic solvent, by specifically charging them with ions. For this reason, especially electrodeposition paints,
There is a limit to the lifespan of electrophotographic developer or display dispersion liquid.

Purpose The purpose of the present invention is to define solid particles by ions in a non-aqueous bath medium such as a non-polar aprotic solvent, that is, to eliminate the steric effects and electrostatic effects conventionally utilized in non-aqueous solvent systems. The purpose of the present invention is to provide a non-aqueous dispersion with long-term stability by utilizing the mutual effect of

composition The non-aqueous dispersion liquid of the present invention is of the following two types.

The first invention is to add a) acidic groups to 4ij in a nonpolar nonaqueous solvent.
b) an organic substance having a basic group but not having an acidic group; and C) an organic substance having a basic group but not having an acidic group; and C) an organic substance having a basic group but not having an acidic group;
It is characterized by containing as a main component a polymer substance containing as a constituent component a monomer C having at least one group selected from the group consisting of cyanide, hydroxyl, nitro, triphtetramethyl and hihalogen. , the second invention is a non-polar non-aqueous solvent containing IL) an organic substance having an acidic group but not having a basic group, and b) an organic substance having a basic group but not having an acidic group. , and the above a
At least one of component ) and component b) is compatible with the solvent and is a small group selected from the group consisting of ester, ether, amide, cyano, hydroxyl, nitro, trifluoromethyl, and halogen. It is characterized by existing as an electrolyte with monomer C having one group.

As mentioned above, in conventional non-aqueous solvents, especially in non-polar aprotic solvent dispersions, the presence of ions or charges is inevitable.
Met. This is considered to be because interactions (solvent phase) between ions and solvent molecules, that is, dipoles, are difficult to occur in a solvent with tMl. Therefore, the present inventors distributed in advance, b),
Any component of (a)lb) containing the three components of c) is C
As a result of various experiments on nonpolar, aprotic solvent-based dispersions, it was found that components a) and b) undergo dissociation of base ions in the solvent. Ta. Also, ion-dipole interaction,
It was also suggested that there is a RIJ phase. Thus, the present inventors found that when the three components ')tb) and e) are present in the solvent, the acid-
We have discovered that ions can stably exist in nonpolar aprotic solvents through ionic dissociation between bases.

This fact was similarly observed whether a) tb) both components were soluble or insoluble in the solvent. In addition, as described above, the present inventors added solid particles such as pigments and metal oxides to a system containing the three components a), b), e, and e). C) Ionic dissociation occurs at the interface between the solid particle surface and the solvent through solvation of the component when the acidic or basic group of the component is fixed by chemical bonding, adsorption, etc., and as a result, the solid particle becomes uniform. It has been found that the solid particles can be dispersed more stably than before due to the interaction between the electrostatic effect and the steric effect while being positively or negatively charged. Furthermore, the present inventors have found that the amount of ions and the amount of charge can be controlled by the types and amounts of a) I b) te e) each component.

The present invention is based on the above findings.

Examples of non-polar non-aqueous solvents used as a dispersion medium in the present invention include pentane, hexane, hezotane, octane, nonane, decane, dodecane, ligroin, and solvent naphtha (commercially available products include Isopar H, G, and L manufactured by Exxon). ,
Examples include aliphatic hydrocarbons such as Shell Sol (manufactured by Shell Oil Co., Ltd.) and aromatic hydrocarbons such as benzene, toluene, xylene, and alkylbenzene.

On the other hand, the above a) P used as a dispersoid in the present invention
b) l Specific examples of each component of e) are as follows.

a) Components (Examples of organic substances with acidic groups or without basic groups: a) -(1) Saturated aliphatic or aromatic carzene M: @acid, acetic acid, glycolic acid, octanoic acid, monochloroacetic acid ,
Dichloroacetic acid, trichloroacetic acid, cyanoacetic acid, trimethyl acetic acid, monofluoroacetic acid, monobromoacetic acid, methoxyacetic acid, methoxyacetic acid, 7-chlorohexane monocarzenic acid,
Lactic acid, nonanoic acid, pyruvic acid, hexanoic acid, hezotanic acid, zolopionic acid, butyric acid, Levulin TP・? , adipic acid, azelaic acid, oxaloacetic acid, citric acid, glutaric acid, succinic acid, oxalic acid, tartaric acid, naphthoic acid, phenylacetic acid, phenoxyacetic acid, benzenedica lune, mandelic acid, picric acid, dinitrophenol, etc. can be used alone.

a) A polymer comprising a monomer having a −+2J M group as a constituent component: In addition to a polymer obtained from at least 1 fi of the monomers in (i) below, the monomers in (a) and the following (b) and/or (
Examples include polymers with monomers c).

(a) Examples of monomers having acidic groups: (meth)acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, cinnamic acid, crotonic acid, vinylbenzoic acid, 2-methacryloxyethylsuccinic acid acid, 2-methacryloxyethylmaleic acid, 2-methacryloxyethylhexahydro7talic acid, 2-methacryloxyethyl trimellitic acid, vinyl sulfone, allylsulfonic acid 1, styrene sulfonic acid, 2-sulfoethyl methacrylate , 2-acrylamido-2-methylpronogunsulfonic acid, 3-chloroamide phosphoxyzolobyl methacrylate, 2-methacryloxyethyl acid phosphate, hydroxystyrene, and the like.

(b) Polar monomers: 2- and droxyethyl (meth)acrylate, 2,3-dihydroxyzorobyl (,,4-di)acrylate, 4-hydroxydityl (meth)acrylate, 2-hydroxy-3-propyl methacrylate, 2
-Chloroethyl (meth)acrylate, 2,3-dibromozorobyl (meth)acrylate, (meth)acrylonitrile, inbutyl-2-cyanoacrylate, 2-cyanoethyl acrylate, ethyl-2-cyanoacrylate, methacryl-7ton, tetrahydrofur Furyl methacrylate, trifluoroethyl methacrylate, p-
Nitrostyrene [listed].

(c) Polyfunctional monomers: divinylbenzene, ethylene glycol di(meth)acrylate, diethylene glycol di(
meth)acrylate, triethylene glycol tri(meth)acrylate, butanediol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, trimethylolzolonoguntri(meth)acrylate, tetramethylolmethane tri(meth)acrylate ) acrylate, tetramethylolmethanetetra(methacrylate, dipropylene glycol di(meth)acrylate, trimethylolhexane tri(meth)acrylate, pentaerythrittetra(meth)acrylate, 1,3-
Examples include dibutylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, and the like.

b) Examples of components (organic substances having basic groups but not acidic groups): b) = (Li) Organic bases: 2-amine ethanol, jetanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, Ethylenediamine, cyclohexylamine, tris(hydroxymethyl)methylay/s
Butylamine, 1,6-hex/diamine, hexylamine, diethylamine, methylamine, dimethylamine, trimethylamine, aniline, chloroaniline, dinitroaniline, dimethylaniline, nitroaniline,
Methylaniline, benzylamine, methylbenzylamine, glycine, imidazole, bipyridyl, pyridine,
Aminopyridine, dimethylpyridine, trimethylpyridine, monomethylpyridine, pyridoxine, pyrrolidine,
Examples include piperazine, piperidine, benzimidazole, purine, cysteine, etc., which can be used alone.

h)-(2) A polymer or copolymer containing a monomer having a basic group as a monomer: at least 1 (in addition to the polymer obtained from ①) of the monomers listed below) The above (b) and/or (c)
Examples include polymers with monomers of

B) Examples of monomers having basic groups 2 N-methylaminoethyl (meth)acrylate, N-ethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N.

N-diethylaminoethyl (meth)acrylate, N,
N-dizothylaminoethyl acrylate% N-phenylaminoethyl methacrylate, N,N-diphenylaminoethyl methacrylate, aminostyrene, dimethylaminostyrene, N-methylaminoethylstyrene, dimethylaminoethoxystyrene, diphenylaminoethylstyrene, N ~Phenylaminoethylstyrene, vinylpyrrolidone, 2-N-piperidylethyl (meth)acrylate, 2-vinylpyridine, 4-vinylpyridine, 2
-vinyl-〇-methylpyridine, acrylamide, methacrylamide, N,N-dimethylmethacrylamide, N,N-dibutylmethacrylamide and the like.

C) Example of component (polymer substance): For convenience, an example of monomer C will be explained.

Examples of monomer C: * 2-Ethylhexyl (meth)ac') V-), Octyl (meth)acrylate, Nonyl (meth)acrylate, Decyl (meth)acrylate*, Lauryl (meth)acrylate, Ste* Ali/I/(meth)acrylate, vinyl lauryl methacrylamide, methoxyethyl (meth)acrylate,
Ethoxyethyl(meth)acrylate, Butoxyethyl(meth)acrylate, Methyl/L/(meth)acrylate, Ethyl(meth)acrylate, Butyl(meth)acrylate, Hexyl(meth)acrylate, Cyclohexyl(meth)acrylate, Hensyl(meth)acrylate ) acrylate, phenyl (meth)acrylate, styrene, vinyltoluene, vinyl acetate and the like. All of the above monomers are soluble in aromatic hydrocarbons, but *
Those marked are also soluble in aliphatic hydrocarbons.

Therefore, it is used in the first invention. Examples of polymeric substances containing monomer C as a constituent include polymers obtained from at least one type of monomer C, but also polymers of monomer C and the monomers (0) and/or (c) above. Polymers with vinyl monomers such as ethylene, propylene, sitadiene, isoprene, etc. can also be used. others.

C) A polymer of long-chain bifunctional compounds (
Condensation polymers) such as polyesters, polyethers, polyamides, polyurethanes, polyureas, etc. can also be used.

On the other hand, as the polymer of component a) or b) and monomer C used in the second invention, the polymer of component a) and monomer C is a polymer of the monomer of the above (a) and monomer C, or a polymer of the monomer of (a) and the monomer of the above (b) and/or (c), or b) a polymer of the monomer of f12-min and monomer C) and monomer C). A polymer of or a monomer of (b)
and/or a polymer of monomer (c) and monomer C.

In the first invention and the second invention, the amounts used of each of component a), component b), and component C) (or monomer C) vary slightly depending on the purpose of use, but generally in the case of a three-component system, a
):b):c) weight ratio is 10-90:10-90:0
．． A value of about 5 to 70 is appropriate.

In addition to the above-mentioned components, solid particles insoluble in non-polar non-aqueous solvents can be added to the dispersion of the present invention. Such solid particles include various insoluble resins, pigments, metals, metal oxides, and waxy substances (e.g., low-molecular-weight polyolefins,
(wax), chemicals (e.g. pesticides), swelling agents, etc. Depending on the purpose of use, the dispersion or dispersoid may be colored by adding a dye soluble in a non-aqueous solvent to the dispersion or by chemically bonding it to the dispersoid. In addition, when using substances that can be chemically bonded by grafting, etc., such as carzen black or gold pA oxide, as solid particles, these substances should be reacted with component a) or b) and monomer C if necessary. An acidic group or a basic group may be chemically bonded.

To make the dispersion of the present invention, taking the case of the first invention as an example, each of the components a), b), and C) and, if necessary, solid particles are mixed and dispersed in a nonpolar nonaqueous solvent. good. In this case, a dill mill, sand mill, attritor, etc. may be used as the dispersion means. Note that the mixing order is not particularly limited.

Effects As described above, the dispersion of the present invention can be dissolved in a non-aqueous solvent such as a non-polar aprotic solvent by using a combination of component a), component b) and component C) (or monomer C). By clearly charging solid particles with ions, that is, by utilizing the interaction between steric effects and static electricity, dispersion stability is significantly improved, and it is particularly useful for electrodeposition paints, electrophotographic liquid developers, and displays. It is extremely useful for applications such as
Ta.

The present invention will be explained below by way of examples. Note that all parts are parts by weight.

Example 1 500 parts of Iso-ξ-G was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 99°C. This contained 80 parts of stearyl methacrylate, 85 parts of diuryl methacrylate, and 30 parts of diethylene glycol dimethacrylate.

A solution consisting of 5 parts of methacrylic acid and 13 parts of penzoyl peroxide was added dropwise over 2 hours.

Next, stirring was continued for 5 hours at the same temperature to complete the reaction. In this way, dispersion A-(1) containing resin with a particle size of 8 to io μm
was obtained with a polymerization rate of 96.5%.

On the other hand, 200 parts of Isopar G and 0 parts of Isopar H2O were placed in a similar reaction vessel and heated to 85°C. Into this was added a solution consisting of 190 parts of octyl methacrylate, 195 parts of lauryl methacrylate, 5 parts of diethylaminoethyl methacrylate, and 3 parts of azobisisobutyronitrile.
The mixture was added dropwise over 5 hours. The temperature was then raised to 90°C and stirred at this temperature for 4 hours to complete the reaction. A uniform and transparent resin solution B-(1) was obtained with a polymerization rate of 99.1%. Note that the electrical conductivity of A-(1) and B-(1) was the same as that of each solvent.

Next, 100 parts of resin dispersion A-(1) and fat solution B-(1
) and 70 parts of the mixture were mixed and pressed for 1f to prepare a non-aqueous dispersion of the present invention. The 24℃ army of this one is 3.3 x 10” S
It was found that it was charged at @cm-'.

Next, when a DC voltage was applied to the mixed dispersion liquid, all of the dispersed particles were electrodeposited on the anode and became transparent. The conductivity of this liquid (hereinafter referred to as residual liquid) was 2.2×10 S″, which was almost as low as in the case of the solvent (Isopar G) alone.

From the above-mentioned difference in conductivity, it can be seen that the dispersed particles are first charged by mixing the resin dispersion A-(1) and the resin solution B-(1).

Example 2 100 parts of Isopar 0 and 0 parts of Isopar H3O were placed in the reaction vessel used in Example 1 and heated to 90°C. This contains 200 parts of vinyl laurate, 160 parts of cetyl methacrylate, and 40 parts of 2-hydroxyzorobyl methacrylate.
A solution consisting of 50% and benzoyl peroxide was added dropwise over 3 hours. Next, the temperature was raised to 95° C., and the reaction was completed by stirring at this temperature for 3 hours. Uniform and transparent resin bath liquid B
-(2) was obtained with a polymerization rate of 97.0%. Naori-(2
) was the same as that of the solvent.

Next, 1 part of triethylamine was added to this resin solution B-(2), and this was mixed into the resin dispersion A-(1) obtained in Example 1.
A non-aqueous dispersion liquid of the present invention was prepared by mixing and stirring 100 parts of the above liquid. The conductivity of this material was 3.1×10 S·α, and it was found that it was electrically charged. Next, when a DC voltage is applied to this mixed dispersion liquid, all the dispersed particles are electrodeposited on the anode.
The liquid became clear. The electrical conductivity of this residual liquid is 2.2 X l
It was as low as in the case of O-"S a cm-" and the solvent (Isopar G) alone.

Example 3 300 parts of Iso-ξ-G and 100 parts of Isopar H were placed in the reaction vessel used in Example 1 and heated to 90°C. In this, vinyl stearate 1001i, 2-ethylhexyl methacrylate 100 parts, lauryl acrylate 5 parts
0 parts and 80 parts of 2-hydroxy-3-chlorozorobyl acrylate, 6 parts of tetrahydrofurfuryl methacrylate
A solution consisting of 0 parts of acrylic, 10 parts of acrylic, and 5 parts of benzoyl peroxide was added dropwise over 2 hours. Then, the mixture was stirred at the same temperature for 5 hours to complete the reaction. In this way, a milky white resin dispersion A-(3) was obtained with a polymerization rate of 94.8%.

On the other hand, 400 parts of Isopar H was placed in a similar reaction vessel.
Heated to 80°C. Into this was added a solution consisting of 100 parts of 2-ethylhexyl acrylate, 200 parts of cetyl methacrylate, parts of stearyl methacrylate-hso, 10 parts of vinylpyrrolidone, 10 parts of N-methylaminoethyl acrylate, and 5 parts of azobisisobutyronitrile. The mixture was added dropwise over 4 hours. Next, the temperature was raised to 85°C, and the reaction was completed by stirring at this temperature for 4 hours. In this way, a transparent and uniform resin solution B-(3) was obtained with a polymerization rate of 96.0. In addition, A-(
The conductivity of 3) and B-(3) was the same as the isoelectric constant of the solvent, respectively.

Next, resin dispersion A~(3) l O0 part and resin solution B-
(3) 100 parts were mixed and stirred to prepare a milky white non-aqueous dispersion of the present invention. The 6% rate for this is 2.7X1
It was found that the mixed dispersion was electrified at 0 S"cm. Next, when a DC voltage was applied to this mixed dispersion, only the anode became white, the liquid became transparent, and all the dispersed particles were electrodeposited. The conductivity of the residual liquid at this time was 2.2×10S
L1cIIL was as low as the solvent (Isopar G + Isopar H) alone.

Example 4 2 to 100 parts of resin dispersion A-(3) obtained in Example 3
- 2 parts of ethylhexfluamine was added and stirred well to prepare a non-aqueous dispersion of the present invention.

The conductivity of this dispersion was 26×10 5 cal, indicating that it was electrically charged. Next, when a DC voltage was applied to this dispersion liquid, only the anode became white, the liquid became transparent, and electrodeposition of all dispersed particles was observed.

The conductivity of the residual liquid at this time is 2.2X10 Bacm
and was as low as in the case of the solvent (Aitunogu-G + Isoper H) alone.

Example 5 Into the reaction vessel used in Example 1, 0 parts of Aitsunoe H3O and 200 parts of isododecane were placed and heated to 80°C. This contains 115 parts of lauryl methacrylate, 50 parts of lauryl methacrylamide, 25 parts of triethylene glycol trimethacrylate, 10 parts of di-tert-zotylaminoethyl acrylate, and 5 parts of azobisisobutyronitrile.
of the solution was added dropwise over a period of 3 hours.

Then, the temperature was raised to 85° C., and the reaction was completed by stirring at this temperature for 4 hours. In this way, resin dispersion A with a particle size of 8 to 12 μm
-(5) was obtained with a polymerization rate of 94.5%.

Meanwhile, 8.50 parts of 12-hydroxystearic acid and 50 parts of xylene were placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a dehydration device, and the mixture was heated to 190°C under reflux in a nitrogen atmosphere.

The resulting water was removed by azeotropic distillation until it reached the theoretical amount, and the reaction was completed. In this way, a polyester resin solution B-(5) having an acid value of 9.6 was obtained. Note that A-(5) and B-(
The conductivity of 5) was the same as that of each solvent.

Kayoki M9, □-(5),. .ゎ, 4 □ 8 liters of liquid (
5) and 25 parts were mixed and stirred to prepare a non-aqueous resin dispersion of the present invention. The rate of 4 of this is 2.5X10 S
ecrn showed that it was charged. Next, when a direct current voltage τ was applied to this mixed dispersion liquid, all of the dispersed particles were electrodeposited on the cathode, and the liquid became transparent. The conductivity of the residual liquid at this time is 2.4
+ isododecane + xylene) was as low as the case alone.

Example 6 1 part of butyric acid was further added to the mixed dispersion obtained in Example 5,
When stirred well, the conductivity of the dispersion is 3.7X10S.
It rose to occupancy. When a DC voltage was applied to this, all the dispersed particles were similarly electrodeposited on the cathode, and the liquid became transparent. The electrical conductivity of the residual liquid at this time was 2.4×10 Se−.

Example 7 147 parts of maleic anhydride and 102 parts of pentaerythritol were placed in the reaction vessel used for producing the resin solution in Example 5, and heated under reflux at 200°C or lower in a nitrogen atmosphere.
The produced water is removed by azeotropic distillation until it reaches the theoretical amount,
The reaction has ended. In this way, a solid polyester resin having an acid value of 38.4 was obtained.

Next, this polyester was ground, mixed with 70 parts of resin solution B-(1) obtained in Example 1 and 180 parts of Isopar G, and dispersed with a sand mill to create a non-aqueous dispersion of the present invention. . The conductivity of this material is 2.9 x 10-
It was charged at ``8 man-''.Next, when a DC voltage was applied to this dispersion, all the polyester particles were electrolyzed on the anode, and the liquid became transparent.At this time, the conductivity of the remaining liquid was 2.
．． 5 x 10” Sacm, solvent (Isopar G)
It was as low as when taken alone.

(Left below) Example 8 120 parts of octamethylene diisocyanate and 94 parts of nonamethylene diamine were subjected to an addition reaction in anhydrous anisole by a conventional method to obtain a white resin powder (polyurea) A-(8) with a basicity of 46.5. Ta.

On the other hand, 470 parts of dioxane, 100 parts of vinyl laurate, 100 parts of octyl acrylate, and 70 parts of decyl methacrylate were placed in the reaction vessel of Example 1 and heated to 70°C. A solution consisting of 5 parts of itaconic acid, 5 parts of vinylsulfonic acid, 5 parts of benzoyl peroxide, 10 parts of dioxane and 20 parts of water is added dropwise over 1.5 hours.

Next, the temperature was raised to 90°C, and the reaction was carried out for 6 hours to complete the polymerization. The obtained resin was precipitated in alcohol and then dried in vacuum. The polymerization rate was 92%. This is resin B
-(Suppose it is 81.

Next, resin powder A-(sHso part and resin B-(81
220 parts of Schersol was added to the mixture with 30 parts of Schersol and dispersed with a sand mill to prepare a non-aqueous dispersion of the present invention.

The conductivity of this material is 3.8 x 10-” S/Steel-1
And it was charged. When a DC voltage was applied to this, all the polyurea particles were electrodeposited on the cathode, and the liquid became transparent. The conductivity of the residual liquid at this time is 2.4 x 10-”S-cm
-' was as low as that of the solvent (Shelzol) alone.

Further, a non-aqueous dispersion of the present invention was prepared in the same manner except that toluene was used instead of Scherzol. The electrical conductivity of this product was 4.2 x 10-''S heat-1, and the electrical conductivity of the residual liquid was comparable to that of the solvent (toluene).Other properties were the same as above.

Example 9 420 parts of toluene and 80 parts of xylene were placed in the reaction vessel used in the example and heated to 80'C.

A solution consisting of 75 parts of styrene, 90 parts of ethoxyethyl methacrylate, 20 parts of divinylbenzene, 5 parts of acryl chloride, 1 part of aminostyrene, and 5 parts of azobisisozothitetranitrile was added dropwise into the solution over 2 hours.

Next, the temperature was raised to 85°C, and the reaction was completed by stirring at this temperature for 5 hours. In this way, resin dispersion A with a particle size of 10 to 12μ
-+9) was obtained with a polymerization rate of 94.1%.

Separately, 450 parts of dioxane, 50 parts of vinyltoluene, 75 parts of ethyl methacrylate, and 60 parts of benzyl methacrylate were placed in a similar reaction vessel and heated to 75°C.

A solution consisting of 5 MS of methoxypolyethylene dalicol methacrylate (molecular weight 468), 10 parts of 2-methacryloxyethyl acid phosphate, 3 parts of penzoyl oxide, 30 parts of dioxane and 20 parts of water was added dropwise into the solution over 1 hour. Then 90'C.

The reaction was completed by stirring at this temperature for 4 hours. The obtained resin was precipitated in alcohol and then vacuum dried. The polymerization rate was 91%. This resin B-(9
Set to 1.

Next, resin dispersion A-(91,100 parts) was added to resin B-(9 parts).
110 parts were added and mixed and stirred well to prepare a non-aqueous dispersion of the present invention. The conductivity of this thing is 3.6 x 10
It was charged at 13 a cm-'. Next, when a DC voltage was applied to this dispersion liquid, all of the dispersed particles were electrodeposited on the cathode, and the liquid became transparent. The electrical conductivity of the residual liquid at this time was 3.9 x 10-''5-cm''''1, which was as low as when the solvent (toluene + xylene) was used alone.

Example 10 0.5 part of phenyl P+i acid was added to the resin dispersion A-(9) of Example 9 and stirred well to prepare a non-aqueous dispersion of the present invention. The conductivity of this material is 4.0×10″″
It was charged at 8 s an-'. Further, the electrical conductivity of the residual liquid was 3.6 x 10-1 g S-α'''1.Other performances were the same as in Example 9.

Example 11 147 parts of maleic anhydride and 177 parts of 1,6-hexanediol were placed in the reaction vessel used in Example 1, and reacted for 30 minutes at 90°C under a nitrogen atmosphere. The obtained white solid was a polyester resin and had an acid value of 255.0.

Note that this acid value agrees well with Hafestel's theoretical acid value of 259.4.

Add 10 parts of this white solid to 5 parts of polylauryl methacrylate.
In addition, 140 parts of resin dispersion A-(9) obtained in Example 9 was added and mixed thoroughly to prepare a non-aqueous dispersion of the present invention. The conductivity of this material is 4.
5 x 10"5-an-' and when DC voltage was applied, all the dispersed particles were electrodeposited on the cathode. The conductivity of the remaining liquid at this time was 3.8 x 1o-12s-α-re It was as low as the solvent (toluene + xylene).

Example 12 250 parts of toluene and 150 parts of cyclohexane were placed in the reaction vessel used in Example 1 and heated to 90°C. In this, 50 parts of butyl acrylate, 7 parts of methyl methacrylate
0 parts, cyclohexyl methacrylate) 40 parts, 2-hydroxyethyl methacrylate 85 parts, 2,3-dizolomprobyl acrylate 50 parts, nitrostyrene 10 parts, styrene sulfonic acid 5 parts, 4-benzoyl peroxide A solution consisting of 3 parts was added dropwise over a period of 5 hours. then 9
The reaction was completed by stirring at 5° C. for 2 hours. In this way, a milky white resin dispersion A-Qa was obtained with a polymerization rate of 92.6%.

Meanwhile, 160 parts of toluene and 240 parts of xylene were placed in a reaction vessel and heated to 85°C. In this, 120 parts of octyl acrylate, 260 parts of cyclohexyl methacrylate,
A solution consisting of 20 parts of 4-vinylpyridine and 5 parts of azobisisobutyrol was added dropwise over 1 hour. Next, the mixture was stirred at the same humidity for 5 hours to complete the reaction. In this way, resin solution B-
(13 was obtained with a polymerization rate of 95.3%.

Next, 1,100 parts of resin dispersion A- (1100 parts) and 100 parts of the resin solution were thoroughly mixed and stirred to prepare a milky white non-aqueous dispersion of the present invention.The electrical conductivity of this was 3.5 x 10-"
When a DC voltage was applied to this dispersion, only the anode turned white, indicating that the resin was electrodeposited.The remaining liquid was transparent. The conductivity was 3.9 x 10-'' S-g1, which was as low as that of the solvent (toluene + cyclohexane + xylene) alone. Take 5,220 parts of Aitsunozo and heat to 90°C. This contains 72.5 parts of stearyl methacrylate, 80 parts of cetyl methacrylate, 90 parts of methoxypolyzolopylene glycol methacrylate (molecular weight 482), and 5 parts of methacrylic acid.
A solution consisting of 2.5 parts of maleic acid and 5 parts of benzoyl peroxide was added dropwise over a period of 2 hours, followed by stirring at the same temperature for 3 hours. In this way, a homogeneous and transparent resin solution A-(13) with a 1 content of 97.7 was obtained.

The conductivity of this solution was 2.2×10 S@am, the same as that of the isopar.

Next, 100 parts of resin solution A-(13), 60 parts of resin solution B-(3) of Example 3, and 15 parts of iron oxide having an average particle size of 02 μm were thoroughly mixed and stirred to obtain a non-aqueous solvent dispersion of the present invention. I made a liquid. The electrical conductivity of this material was 2.8×10 S·f. Furthermore, when a DC voltage is applied to this dispersion, 1
All dispersed particles were electrodeposited on the anode.

Example 14 Resin solution A of Example 13 - (13) N in ro and o parts
-1 part of methylbenzylamine and 3 parts of glass beads having an average particle size of 0.5 μm were added and thoroughly stirred to prepare a non-aqueous dispersion of the present invention. The conductivity of this material is Z9X10
It was S・α. Furthermore, when a DC voltage was applied to this dispersion, all of the dispersed particles were electrodeposited on the anode.

Example 15 500 parts of toluene was placed in the reaction vessel used in Example 1.
Heat to 5°C. In this, hexyl methacrylate 80
65 parts of neat 2-ethoxyethyl methacrylate, 15 parts of benzyl acrylate, 70 parts of tetraethylene glycol acrylate, 10 parts of N,N-resothylacrylamide, 10 parts of β-N-piperidylethyl methacrylate
A solution consisting of 6.9 parts and 5 parts of azobisisobutyronitrile was added over 3 hours. Then, the temperature was raised to 90°C,
The reaction was completed by stirring at this temperature for 2 hours. In this way, a uniform transparent resin solution A-(15) with a polymerization rate of 96.0% was obtained. The electrical conductivity of this solution was 17×10 S@儒, a value comparable to that of solution 1s (toluene).

Next, 1 part of hexanoic acid and 10 parts of Ni fine particles with an average particle size of 0.17 μm were added to 100 parts of this resin solution A-(15), and dispersed in a sand mill to prepare a water-based dispersion according to J of the present invention. The conductivity of this material is 17 X l 0-
IIs "cIn-'. When a DC voltage was applied to this dispersion, all of the dispersed particles were electrodeposited on the cathode.

Example 16 To 100 parts of the resin solution A-(15) of Example 15, 20 parts of the resin B-(8) of Example 8 and 70 parts of toluene were added, and further, 7 parts of Kurtson Black was added to this mixed solution, and the mixture was heated in a mail mill. to prepare an IP water solvent dispersion of the present invention. The electrical conductivity of this material (3, OX l O”S e
cm''1.If a DC voltage was applied to this dispersion, all the stripes of the dispersed particles would be electrodeposited on the cathode.

Example 17 In the reaction vessel used in Example 1, 300 parts of Ainno ξ-G and 80 parts of polylauryl methacrylate were heated to 990°C. A solution consisting of 100 parts of Isopar 0, 20 parts of polylauryl methacrylate, 50 parts of methacrylic acid (V) acid, 20 parts of itaconic acid, and 3 parts of benzoyl peroxide was added dropwise to the solution over a period of 2 hours. The reaction was then stirred at the same temperature for 4 hours (k) to complete the reaction. Thus, a milky white resin dispersion A-(1
7) was obtained with a polymerization rate of 92.0%. Next, to 100 parts of this resin dispersion A-(17) was added the resin solution B- of Example 1.
(1) 100 parts were added and thoroughly mixed and stirred to prepare a non-aqueous dispersion of the present invention. The conductivity of this material is 3. l
X 10"S-α-1. When a DC voltage was applied to this, only the anode appeared white, indicating that the resin was electrodeposited. The conductivity of the resulting transparent residual liquid was 2. .4 X
10"S-I lost a value about the same as that of the solvent (Isopar G).

Example 18 400 parts of toluene and 200 parts of xylene are placed in the reaction vessel used in Example 1 and heated to 80°C. A solution consisting of 2 parts of ethylene glycol dimethacrylate Fso, 20 parts of diethylaminostyrene and 5 parts of azobisisobutyronitrile was added dropwise into the solution over 2 hours. The temperature was then raised to 85° C. and stirred at this temperature for 5 hours to obtain a resin dispersion containing particles with a particle size of 9 to 12 μm with a polymerization rate of 90.6%.

Next, 20 parts of the polyester resin solution H-(5) of Example 5 was added to 100 parts of this dispersion, and the mixture was further dispersed in a mail mill to obtain a resin dispersion of the present invention having an average particle size of 0.5 μm. The conductivity of this liquid was 2.6X10''S-m-', and when a DC voltage was applied, the dispersed particles were electrodeposited only on the cathode.The conductivity of the resulting transparent residual liquid was 3.9X105-cm. The value was similar to that of solvents (toluene and xylene).

Example 19 In the reaction vessel used in Example 1, 450 parts of Isopar H and 350 parts of Iso'e-0 are placed and heated to 85°C. In this, 10 parts of pentaerythritol tetraacrylate, 40 parts of methyl methacrylate, 40 parts of methyl acrylate,
A solution consisting of 10 parts of acrylic acid and 5 parts of benzoyl peroxide is added dropwise over 1.5 hours. The temperature was then raised to 9°C, and the reaction was completed by stirring at this temperature for 5 hours. In this way, a resin dispersion (19) having a particle size of 8 to 12 μm was obtained with a polymerization rate of 89.0%.

Next, to this resin dispersion - (19) 100 parts Example 2
25 parts of Jugetsuji Solution B-(2) and 05 parts of tris(hydroxymethyl)methylamine were added and thoroughly dispersed with an ultrasonic disperser to prepare a non-aqueous dispersion of the product. The conductivity of this material is 2.5×10 S*c+n,
When a DC voltage was applied, all of the dispersed particles were electrodeposited on the anode, and the liquid became bright.

The conductivity of the residual liquid at this time is 2.2 x 10"8・ff1
-', which was as low as the solvent (Aituno eQ + Isoper H).

Example 20 1 part of carzen black was immersed in 3 parts of nitric acid at 50°C for 3 hours to form a carzene black. Kazen black with xyl groups introduced on its different surface was obtained. The amount of carboxyl groups in this product was determined by the sodium hydrogen carbonate method and was found to be 3.05X10-3.
Mol/,! It was 7.

Next, 100 parts of the resin solution B-(12) of Example 12 was added to 50 parts of the carin black thus treated, and dispersed with an attritor to obtain a non-aqueous dispersion of the present invention having an average particle size of 0.18 μm. I made a liquid. This carbon black dispersion was extremely stable and showed no change even after being stored at 50°C for 3 hours.Next, when a DC voltage was applied to this dispersion, all of the black dispersed particles were electrodeposited on the anode. The liquid became clear.

Example 21 Resin dispersion A-<3) and resin solution B-(3) of Example 3
7 parts of sodium copper phthalocyanine disulfonate were added to 100 parts of the mixed dispersion with the above mixture, and the mixture was thoroughly mixed and stirred to prepare a blue pigment dispersion. This dispersion was stable for at least 5 months. When a DC voltage was applied to this, all of the blue dispersed particles were electrodeposited on the anode, and the liquid became transparent.

On the other hand, in the case of a blue pigment dispersion prepared by removing resin solution B-(3) from the mixed dispersion for comparison, it was relatively well dispersed at the time of manufacture, but all the pigment settled within one week. Further, although a DC voltage was applied to the dispersion during production, no electrophoresis of the dispersed particles was observed.

Example 22 150 parts of the resin dispersion A-(5) of Example 5 and Isopar H were placed in the reaction vessel used in Example 1.

Heat to 90°C. In this, 80 methyl methacrylate
After dropping a solution consisting of 30 parts of ether methacrylate and 3 parts of benzoyl peroxide over 4 hours, 95 parts of
The temperature was raised to .degree. C. and stirred at this temperature for 1 hour to complete the reaction. In this way, a pearl-like resin dispersion A-(sj) was obtained.

Next, 37.5 parts of the resin bath liquid B-(5) of Example 5 was added to 5,550 parts of this resin dispersion A-(5,550 parts), and mixed and stirred to prepare a resin dispersion of the application example. It was extremely stable and did not cause any sedimentation or aggregation even after being stored for 6 months. When a single current voltage was applied to this dispersion, all of the dispersed particles were electrolyzed to the cathode and the liquid became transparent.

Example 23 Resin dispersion ridge Δ-(1) and resin solution B-(1) of Example 5
230 parts of Kerknob 2 fu was added to 200 parts of a mixed dispersion of carbon black with a carbon black dispersion having an average particle size of 0.20 μm.

When a DC voltage was applied to this dispersion liquid, all the black dispersed particles were electrodeposited on the anode, and the liquid became transparent.

Next, 200 parts of this carbon black dispersion was diluted with Isopar Gll to prepare a liquid developer for a transfer type electrophotographic copying machine. When copying on plain paper using this developer, the high-quality image 1 was comparable to that of commercially available developers.
A station was formed. Moreover, the durability during continuous copying is superior to this conventional product as shown in Figure 1 (1 is the developer of this example, 2 is the conventional developer), and the images obtained even after 50,000 copies were made. The concentration was almost unchanged from the initial stage of production.

In addition, Figures 2 and 4 show current one-hour curves when DC voltage is applied for the present example and the conventional developer at the early stage of copying, respectively ("t2' is the electrodeposition curve of the present example and the conventional developer, respectively. 3 and 5 respectively show the iE flow t in this example and the conventional developer after 50,000 sheets were copied.
A current one-hour curve when Li pressure is applied is shown. As can be seen from these figures, the electrical characteristics of the developer of this embodiment hardly change even during continuous copying, so that stable image quality can be obtained.

[Brief explanation of the drawing]

Figure 1 is a diagram of the relationship between image density and the number of copies made when continuous copying was performed using the developer obtained in Example 23 and a conventional developer. 3 and 5 respectively show the relationship between the current and time when DC voltage is applied to each of the above-mentioned developers after copying 50,000 copies. It is a relationship diagram. l...Developer of Example 23 2...Conventional developer 1
'...Residual liquid 2' after ¥t3I deposition of the developer of Example 23
・・・Residual liquid after T-adhesion of conventional developer 2 concave Figure 4 Flame 3 ■ Burn 5 Figure

Claims (1)

[Claims] 1. An organic substance having a) an acidic group but no basic group in a non-polar non-aqueous solvent. b) an organic substance having a basic group but not having an acidic group; and c) having bt that is compatible with the # solvent and selected from the group consisting of ester, ether, amide, cyano, hydroxyl, nitro, trifluoromethyl, and halogen. A non-aqueous dispersion liquid containing as a main component a polymer substance containing a monomer C having at least one selected group as a constituent component. 2) a non-polar non-aqueous solvent containing &) an organic substance having an M group but not a basic group; and b) an organic substance having a basic group but not an acidic group, and the above &) At least one of component and b) is compatible with the solvent and is an ester, ether, amide, cyanide, hydroxyl, nitro,
A non-aqueous dispersion liquid existing as a polymer with a monomer C having at least one group selected from the group consisting of trifluoromethyl and halogen.