JP6015809B2 - Polymerizable dispersion stabilizer, polymerizable dispersion stabilizer solution, and nanoparticle composite - Google Patents

Description

  The present invention relates to a method for producing a nanoparticle composite.

  In recent years, nano-sized fine particles have been used in various industries depending on the average particle diameter. For example, fine particles having an average particle size of several nanometers to several tens of nanometers are applied to pigments, abrasives, film fillers, paint fillers, magnetic materials, and the like. In such an industry, in order to effectively utilize the characteristics of the fine particles, it is important that the fine particles are not aggregated. For example, microcapsules are used as fine particle composites in which fine particles are coated with other materials.

  Conventionally, microcapsules are (i) chemical production methods such as (a) interfacial polymerization method (two monomers or reactants are dissolved separately in a dispersed phase and a continuous phase, A method of polymerizing monomers to form a wall film), (b) suspension polymerization method (adding a water-insoluble monomer into an aqueous medium in which a core substance is dissolved in an aqueous medium, stirring, Monomers are incorporated into micelles, and monomers are polymerized in the micelles to form a wall film), (c) in-situ polymerization method (liquid or gaseous monomer and catalyst, or two reactive substances in a continuous phase) A method of supplying a reaction from either one of the core particles to cause a reaction to form a wall film), or (ii) a physicochemical manufacturing method, for example, (a) a coacervation (phase separation) method (core material particles) Polymer solution A method of separating a dense phase and a dilute phase having a high polymer concentration to form a wall film), (b) a liquid drying method (a liquid in which a core material is dispersed in a solution of a wall film material is prepared, and For example, a method in which a dispersion is put into a liquid in which a continuous phase is not miscible to form a composite emulsion, and a wall film is formed by gradually removing a medium in which a wall film substance is dissolved.

  However, physicochemical production methods such as the coacervation method do not use chemical cross-linking, and are production methods that use dissolution / precipitation of polymer compounds, resulting in inferior heat resistance and solvent resistance. was there. In addition, the chemical production method is difficult to encapsulate in the nano-order, and particles having a particle size of 100 nm or less cannot be obtained. Since the production is mainly performed in an aqueous solvent, additional steps such as solvent replacement and drying are added. In addition, there is a problem that reaction conditions such as polycondensation reaction and polyaddition reaction become high.

In order to solve such a problem, Patent Document 1 improves the interfacial polymerization method and uses a block polymer having a hydrophobic repeating unit block and a hydrophilic repeating unit as a protective colloid in a non-aqueous medium. Then, one of the two types of reactive monomers is included in the protective colloid together with the core substance, and one of the two reactive monomers is added to the solvent in which the protective colloid is dispersed, whereby the two types of reactive monomers are added at the protective colloid interface. A method of reacting reactive monomers with each other is disclosed. According to this method, by including the reactive monomer in the protective colloid, it is possible to suppress problems such as an excessively large particle size as seen in the chemical method described above. However, the above method has a problem that the non-aqueous medium is limited to alkanes and aromatic hydrocarbons.

  Further, as a method for producing a fine particle composite other than the above, a method in which a polymer is graft-polymerized on the surface of fine particles has been proposed (Patent Documents 2 and 3). However, the above method has a problem that the core material is limited or the surface of the core material needs to be modified because the particle surface needs to have a functional group.

  Patent Documents 4 and 5 disclose, as a dispersion stabilizer, a method for producing a nanoparticle composite that can uniformly and stably disperse nanosized particles and keep the average particle size of the dispersed particles small. After adding and dispersing fine particles in a solution in which a specific polymer using an organic acid compound having a polymerizable group as a salt-forming agent is dissolved in a non-aqueous medium, the polymerizability of the organic acid compound of the polymer is A method for crosslinking groups is described.

JP-A-7-246329 JP-A-5-339516 JP-A-8-302227 JP 2010-53171 A JP 2010-53172 A

  However, the methods of Patent Documents 4 and 5 have a problem that dispersion is difficult depending on the type of particles because an organic acid compound having a polymerizable group is used as a salt forming agent for the polymer. That is, when a salt is formed with an organic acid compound, there is a problem that the polymerizable group is dissociated in a polar medium such as alcohol because the polymerizable group is on the counter anion side.

  The present invention has been made under such circumstances, and it is possible to uniformly and stably disperse nano-sized fine particles, and to keep the average particle size of the fine particles at the time of dispersion small. It aims at providing the manufacturing method of the nanoparticle composite_body | complex which increases.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a specific polymer using a halogenated hydrocarbon having a polymerizable group as a salt stabilizer as a dispersion stabilizer. Nanoparticles can be dispersed uniformly and stably by adding fine particles to the solution dissolved in the polymer and crosslinking the polymer, and the average particle size of the fine particles during dispersion can be kept small. It has been found that a composite can be obtained and that the production method can increase the types of fine particles that can be applied. The present invention has been completed based on such findings.

The polymerizable dispersion stabilizer according to the present invention is:
A polymerizable dispersion stabilizer used in a non-aqueous medium,
At least the block of the structural unit (1) represented by the following general formula (I) and the block of the structural unit (2) represented by the following general formula (II), and further the structural unit (1) It is a block copolymer in which at least a part of the amino group possessed by and a halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt.

Nanoparticle composite according to the present invention,
A nano-particle composite comprising fine particles and a polymerizable dispersion stabilizer covering the surface of the fine particles, wherein the polymerizable group of the polymerizable dispersion stabilizer is crosslinked,
The polymerizable dispersion stabilizer has at least a block of the structural unit (1) represented by the following general formula (I) and a block of the structural unit (2) represented by the following general formula (II), The structural unit (1) is a block copolymer in which at least a part of the amino group and the halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt.

(In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an alkylene group having 1 to 8 carbon atoms. , — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — Each of the divalent groups R ⁶ and R ⁷ is independently a hydrogen atom or a methyl group, and the alkyl group and alkylene group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

(In the formula (II), ^{R 4} is a hydrogen atom or a methyl group, ^{R 5} is an alkyl group, an aralkyl group having 1 to 18 carbon atoms, an aryl ^{group, - [CH (R 6)} -CH (R 7) - O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ is a monovalent group, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, ⁸ is a hydrogen atom, or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom It is an alkyl group having 1 to 5 atoms or carbon atoms, and the alkyl group, aralkyl group and aryl group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

The polymerizable dispersion stabilizer according to the present invention is
A polymerizable dispersion stabilizer used in a non-aqueous medium,
A graft copolymer containing at least a nitrogen-containing monomer represented by the following general formula (I ′) and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component The polymer chain of the macromonomer has at least one structural unit represented by the following general formula (III) or general formula (IV), and at least one amino group derived from the nitrogen-containing monomer. And a halogenated hydrocarbon having a polymerizable group is a graft copolymer in which a quaternary ammonium salt is formed .
The nanoparticle composite according to the present invention is
A nano-particle composite comprising fine particles and a polymerizable dispersion stabilizer covering the surface of the fine particles, wherein the polymerizable group of the polymerizable dispersion stabilizer is crosslinked,
The polymerizable dispersion stabilizer is a copolymerization component comprising at least a nitrogen-containing monomer represented by the following general formula (I ′) and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. The polymer chain of the macromonomer contains at least one structural unit represented by the following general formula (III) or general formula (IV), and further contains the nitrogen It is a graft copolymer in which at least a part of an amino group derived from a monomer and a halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt.

(In formula (I ′), R ¹ , R ² , R ³ and A are the same as in formula (I).)

(In Formula (III) and Formula (IV), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a cyano group, — [CH (R _{^{23) -CH (R 24) -O}} ] x -R 25, - [(CH 2) y -O] z -R 25, - [CO- (CH 2) y -O] z -R 25, -CO It is a monovalent group represented by —O—R ²⁶ or —O—CO—R ^27. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group.
R ²⁵ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ²⁸ , and R ²⁶ is alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a cyano _{^{group, - [CH (R 23)}} -CH (R 24) -O] x -R 25, - [(CH 2) y -O] z —R ²⁵ , — [CO— (CH ₂ ) _y —O] _z —R ²⁵ is a monovalent group. R ²⁷ is an alkyl group having 1 to 18 carbon atoms, and R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
m represents an integer of 1 to 5, and n and n ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

  In the polymerizable dispersion stabilizer and nanoparticle composite according to the present invention, the halogenated hydrocarbon having a polymerizable group is a halogenated aralkyl having a polymerizable group. In addition, it is preferable from the viewpoint of producing a nanoparticulate composite that can be stably dispersed and the average particle size of the fine particles during dispersion can be kept small.

  In the polymerizable dispersion stabilizer and nanoparticle composite according to the present invention, the polymerizable group of the halogenated hydrocarbon having a polymerizable group may be an ethylenically unsaturated double bond-containing group. This is preferable from the viewpoint of producing a nanoparticulate composite in which fine particles having a uniform size can be dispersed uniformly and stably and the average particle size of the fine particles can be kept small.

  The present invention also provides a polymerizable dispersion stabilizer solution comprising the polymerizable dispersion stabilizer according to the present invention and a non-aqueous medium, wherein the non-aqueous medium contains a polar medium.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the nanoparticle composite_body | complex which can disperse | distribute nanosize microparticles | fine-particles uniformly and stably, and can keep the average particle diameter of the microparticles | fine-particles at the time of dispersion | distribution small can be provided. According to the present invention, the types of fine particles that can be applied can be increased.

It is a schematic diagram which shows an example of the preferable structure of the graft copolymer preferably used in this invention.

The method for producing a nanoparticle composite of the present invention comprises a step 1: a specific structure in which a quaternary ammonium salt is formed by an amino group and a halogenated hydrocarbon having a polymerizable group as a dispersion stabilizer in a non-aqueous medium. A dispersion step of forming a nanoparticle dispersion by adding fine particles to a solution in which the polymer is dissolved or dispersed, and Step 2: a crosslinking step of crosslinking the polymer.
According to the production method of the present invention, nano-sized fine particles can be dispersed uniformly and stably, and the average particle size of the fine particles at the time of dispersion can be kept small.

Although it is unclear as an effect | action which exhibits the above effects by the manufacturing method of the said invention, it estimates as follows.
In the present invention, the dispersion stabilizer has at least a structural unit (1) represented by the general formula (I), and at least a part of the amino group of the structural unit (1) and a polymerizable group. A polymer in which a quaternary ammonium salt is formed with a halogenated hydrocarbon having a hydrogen atom is used. The quaternary ammonium salt forming site of the polymer has strong adsorptivity to fine particles, while the polymer as a whole has solubility in a non-aqueous medium.
In the production method of the present invention, it is presumed that by adding the fine particles to the polymer solution, the polymer accumulates on the surface of the fine particles and exists so as to cover the entire surface of the fine particles. . Furthermore, the polymer can be fixed to the surface of the fine particles by crosslinking the polymerizable group of the halogenated hydrocarbon having the polymerizable group contained in the polymer covering the surface of the fine particles. As a result, it is presumed that the particle size of the nanoparticle composite can be reduced and reaggregation of the particles can be effectively prevented. Therefore, according to the method for producing a nanoparticle composite of the present invention, it is presumed that nanosized particles can be uniformly and stably dispersed and the average particle size of the particles at the time of dispersion can be kept small.

Furthermore, in the present invention, by using a polymer in which a quaternary ammonium salt is formed by using a halogenated hydrocarbon having a polymerizable group, a non-salt is formed compared to the case of forming a salt with an organic acid compound having a polymerizable group. There is an advantage that the polymerizable group in the aqueous medium is difficult to dissociate. As shown in the following chemical formula (B), in the organic acid compound having a polymerizable group, since the polymerizable group is on the counter anion side, the polymerizable group can be dissociated in a polar medium such as alcohol. It was difficult to apply to fine particles that needed to disperse fine particles in combination. On the other hand, when the halogenated hydrocarbon forms a quaternary ammonium salt, the polymerizable group is directly bonded to N as shown in the following chemical formula (A). It is presumed that dissociation does not occur.
In addition, the quaternary ammonium salt formation site is less soluble in non-aqueous media and has a stronger adsorptive power on the surface of fine particles than the site where salts are formed with organic acid compounds. The site is presumed to be capable of adsorbing to fine particles whose surface is inert (for example, phthalocyanine pigments having a crystal structure in which flat molecular structures are stacked).
Thus, a polymer in which a quaternary ammonium salt is formed using a halogenated hydrocarbon having a polymerizable group has a strong adsorptive power to fine particles, and the dissociation of the polymerizable group hardly occurs in a non-aqueous medium. Therefore, it is presumed that the nanoparticle composite obtained by the production method of the present invention has improved dispersion stability as compared with the conventional method, and the number of applicable fine particles increases.

(Formula (A) shows an example in which an amino group of general formula (I) and a halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt. Formula (B) is a compound of general formula (I In the formula (A) and the formula (B), R ¹ , R ² , R ³ , and A are general ones. (Same as in formula (I).)
Hereinafter, each process of the manufacturing method of the nanoparticle composite of this invention is demonstrated.

[Step 1. Dispersion process]
Step 1 of the method for producing a nanoparticulate composite of the present invention has at least a structural unit (1) represented by the following general formula (I) as a dispersion stabilizer in a non-aqueous medium, Dispersion of nanoparticles by adding fine particles to a solution in which a polymer in which at least a part of the amino group of the structural unit (1) and a halogenated hydrocarbon having a polymerizable group formed a quaternary ammonium salt is dissolved. It is a dispersion | distribution process which forms a body.

(In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an alkylene group having 1 to 8 carbon atoms. , — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — Each of the divalent groups R ⁶ and R ⁷ is independently a hydrogen atom or a methyl group, and the alkyl group and alkylene group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

This step has at least a structural unit (1) represented by the above general formula (I) as a dispersion stabilizer, and further comprises at least a part of an amino group of the structural unit (1) and a polymerizable group. By using a polymer in which the halogenated hydrocarbon has a quaternary ammonium salt, the fine particles can be stabilized in a non-aqueous medium. As a result, the fine particles are excellent in dispersibility and stability. Can be.
Hereinafter, this step will be described in detail.

<Dispersion stabilizer>
In the present invention, as the dispersion stabilizer, at least a structural unit (1) represented by the following general formula (I) is included, and at least a part of the amino group of the structural unit (1) is polymerizable. A polymer in which a halogenated hydrocarbon having a group forms a quaternary ammonium salt is used.

(In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an alkylene group having 1 to 8 carbon atoms. , — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — Each of the divalent groups R ⁶ and R ⁷ is independently a hydrogen atom or a methyl group, and the alkyl group and alkylene group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

In the above formula (I), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable.
In the present invention, R ² and R ³ may be the same as or different from each other.

A is an alkylene group having 1 to 8 carbon atoms, * — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — **, or * — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — ** is a divalent group. Here, * represents a linking site on the ester bond side, and ** represents a linking site on the amino group side. The alkylene group having 1 to 8 carbon atoms may be linear or branched. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various kinds. Hexylene group and various octylene groups.
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2. In the present invention, if x, y, and z are within the above ranges, the dispersibility of the fine particles can be improved.
As this A, a C1-C8 alkylene group is preferable, and a methylene group and ethylene group are more preferable. If the carbon number is in the range of 1 to 8, the dispersibility of the fine particles can be kept good.

  In the polymer used in the present invention, the structural unit (1) represented by the general formula (I) is preferably contained in a proportion of 3 to 60% by mass, more preferably 5 to 50% by mass. 10 to 40% by mass is more preferable. If the content of the structural unit (1) represented by the above general formula (I) in the polymer is within the above range, the ratio of the salt forming sites formed by the amino groups in the polymer becomes appropriate, and the amount relative to the fine particles The adsorptivity becomes good, and the dispersibility and stability of the fine particles can be obtained.

(Halogenated hydrocarbon having a polymerizable group)
In the present invention, the polymerizable group used as the dispersion stabilizer is such that at least a part of the amino group of the structural unit (1) and the halogenated hydrocarbon having the polymerizable group form a quaternary ammonium salt. ing. Since at least a part of the amino group of the structural unit (1) and the halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt, fine particles can be stabilized in a non-aqueous medium. As a result, the dispersibility and stability of the fine particles can be improved.

  As the halogenated hydrocarbon having a polymerizable group that forms a quaternary ammonium salt with the amino group of the structural unit (1), any one of a chlorine atom, a bromine atom, and an iodine atom is a polymerizable group. And those in which a hydrogen atom of a hydrocarbon group having a hydrogen atom is substituted.

  The hydrocarbon group is not particularly limited, but a linear, branched, or cyclic saturated aliphatic hydrocarbon group, a linear, branched, or cyclic unsaturated aliphatic hydrocarbon group, monocyclic or polycyclic aromatic Groups and combinations thereof. When the unsaturated aliphatic hydrocarbon functions as a polymerizable group, it does not have to have a separate polymerizable group. The number of carbon atoms of the hydrocarbon group is preferably about 2 to 18, more preferably about 3 to 10. The hydrocarbon group may further have a substituent unless the effects of the present invention are impaired. Examples of the substituent include an alkoxy group.

  Of these, halogenated aralkyl or allyl halide is preferably used as the halogenated hydrocarbon, and halogenated aralkyl is particularly preferably used. Examples of the aralkyl group of the halogenated aralkyl include those having 7 to 18 carbon atoms, but are not particularly limited. Specific examples include benzyl chloride, benzyl bromide, benzyl iodide, naphthylmethyl chloride, naphthylmethyl bromide and the like. Examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. Among them, it is at least one selected from the group consisting of allyl chloride, allyl bromide, benzyl chloride and benzyl bromide and the salt formation site formed is excellent in adsorbability to fine particles. The heat resistance and alkali resistance of the dispersant can be increased.

The polymerizable group possessed by the halogenated hydrocarbon is not particularly limited. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group including a cyclic ether-containing group such as an oxirane ring and an oxetane ring. Among these, a radical polymerizable group is preferable, and an ethylenically unsaturated bond-containing group is preferable.
Examples of the ethylenically unsaturated bond-containing group include an alkenyl group having 2 to 18 carbon atoms, a (meth) acryloyl group, — [CH (R ³¹ ) —CH (R ³² ) —O] _a —R ³³ or — [ (CH ₂ ) _b —O] _c —R ³³ is a monovalent group, R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, and R ³³ has 2 to 18 carbon atoms. Alkenyl group, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH _{2 and the} like. Here, a is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2, b is an integer of 1-5, preferably an integer of 1-4, more preferably 2. Or 3. c is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2. Among them, a vinyl group, an allyl group, or — [CH (R ³¹ ) —CH (R ³² ) —O] _a —R ³³ , or — [(CH ₂ ) _b —O] _c —R ³³ , and R preferably it has ³³ is a -CO-CH = CH ₂ or _{-CO-C (CH 3) =} CH 2, in particular, a vinyl group, an allyl group, that is, (meth) acryloyl group.

  In the present invention, the halogenated hydrocarbon having a polymerizable group is, among others, chloromethylstyrene or bromomethylstyrene, which easily undergoes radical polymerization and easily stabilizes fine particles in a non-aqueous medium. And, as a result, it is particularly preferable because it is excellent in dispersibility and stability of the fine particles.

  In the present invention, after the fine particles are dispersed, the polymerizable groups possessed by the halogenated hydrocarbon having a polymerizable group can be crosslinked in the vicinity of the fine particles in a crosslinking step described later. As a result, the block copolymer is fixed around the fine particles, the fine particles are more uniformly and stably dispersed, and the average particle size of the fine particle composite at the time of dispersion can be kept small.

  Although there is no restriction | limiting in particular in content of the halogenated hydrocarbon which has the said polymeric group in the polymer used by this invention, Generally 0.05-2. With respect to the amino group contained in the said structural unit (1). About 0 molar equivalent, preferably 0.1 to 1.5 molar equivalent, more preferably 0.2 to 1.0 molar equivalent. In addition, the halogenated hydrocarbon which has a polymeric group can be used individually by 1 type or in combination of 2 or more types, and when using 2 or more types together, the total content should just be in the said range. .

In the present invention, the dispersion stabilizer has at least a structural unit (1) represented by the following general formula (I), and at least a part of the amino group of the structural unit (1), and the polymerization The polymer is not particularly limited as long as it is a polymer in which the halogenated hydrocarbon having a functional group forms a quaternary ammonium salt. Among them, the specific block copolymer described later or the specific graft copolymer described later can uniformly and stably disperse the nano-sized fine particles and keep the average particle size of the fine particles at the time of dispersion small. It is preferable from the point which can manufacture the nanoparticle composite material which can be manufactured.
Hereinafter, preferred specific block copolymers and preferred graft copolymers will be described in order.

(Block copolymer)
In the present invention, the polymer used as the dispersion stabilizer is composed of the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the following general formula (II). And a block copolymer (salt-type block copolymer) in which at least a part of the amino group of the structural unit (1) and a halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt. It is preferable that the nanoparticle composite can be produced in which the nanosized fine particles can be uniformly and stably dispersed and the average particle size of the fine particles can be kept small at the time of dispersion. .

(In the formula (II), ^{R 4} is a hydrogen atom or a methyl group, ^{R 5} is an alkyl group, an aralkyl group having 1 to 18 carbon atoms, an aryl ^{group, - [CH (R 6)} -CH (R 7) - O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ is a monovalent group, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, ⁸ is a hydrogen atom, or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom It is an alkyl group having 1 to 5 atoms or carbon atoms, and the alkyl group, aralkyl group and aryl group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

In the general formula (II), R ⁵ represents an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [ It shows the _{(CH 2) y -O] z} -R 8.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , Sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups, cyclohexane Examples include an octyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include a nitro group and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred carbon number does not include the carbon number of the substituent.

R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ^9. R ⁹ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.
In the monovalent group represented by R ⁸ , the substituent that may be included is, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a halogen atom such as F, Cl, or Br. And so on.
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group in R ⁸ are as described for R ⁵ .
In the above R ⁴ , x, y and z are as described in A above.
Moreover, R ⁴ and R ⁵ in the repeating unit (2) represented by the general formula (II) may be the same or different from each other.

In the present invention, as R ⁵ , it is preferable to use those having excellent solubility in a non-aqueous medium to be described later. Specifically, depending on the structural unit constituting the block copolymer, etc. Although different, when a medium such as ether alcohol acetate, ether, or ester is used as the non-aqueous medium, a methyl group, an ethyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group, and the like are preferable. Further, when the non-aqueous medium is a less polar one such as pentane or hexane, it is preferable to use a pentyl group, a hexyl group, a heptyl group, or the like.
Here, the reason for setting the R ⁵ in this way is that the structural unit (2) containing the R ⁵ is soluble in the non-aqueous medium, and the amino group of the structural unit (1) The salt-forming site formed by the halogenated hydrocarbon having a polymerizable group has a high adsorptivity to the fine particles, so that the dispersibility and stability of the fine particles are particularly excellent. Because you can.
Furthermore, R ⁵ is substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group as long as it does not interfere with the dispersion performance of the block copolymer. It is also good.

Regarding the molecular size of the block copolymer used in the present invention, the number of repeating units (1) is an integer of 3 to 200, preferably an integer of 3 to 50. The number of the repeating units (2) is an integer of 10 to 200, preferably an integer of 20 to 100, more preferably an integer of 20 to 70. In the present invention, when the number of the repeating units is within the above range, the soluble part and the insoluble part act effectively, and the fine particles can be excellent in dispersibility.
Furthermore, the mass average molecular weight Mw of the block copolymer is preferably in the range of 500 to 20000, more preferably in the range of 1000 to 15000, and further preferably in the range of 3000 to 12000. preferable. By being within the above range, it becomes possible to achieve both wettability and dispersion stability for the fine particles in the initial stage of dispersion in which the fine particles are uniformly dispersed.

  The mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.).

  The binding order of the block copolymer used in the present invention is not particularly limited as long as it has the repeating unit (1) and the repeating unit (2) and can stably disperse the fine particles. However, it is preferable that the repeating unit (1) is bonded to only one end of the block copolymer. That is, the repeating unit (1) and the repeating unit (2) may be bonded in the order of repeating unit (1) -repeating unit (2), or repeating unit (1) -repeating unit. (2) -repeated unit (1) may be bonded in this order, or repeating unit (1) -repeating unit (2) may be bonded repeatedly, but in the present invention, However, those bonded in the order of repeating unit (1) -repeating unit (2) are preferred. The reason is that it is excellent in adsorptivity to fine particles, and furthermore, aggregation of dispersion stabilizers using such a block copolymer can be effectively suppressed.

  In the case where two or more structural units (1) and structural units (2) are included, a block copolymer in which the structural units (1), the structural units (2 ′), and the structural units (2 ″) are combined in this order, A block copolymer bonded in the order of structural unit (1 ')-structural unit (1 ")-structural unit (2), or structural unit (1')-structural unit (1")-structural unit (2 ') -The block copolymer etc. which couple | bonded in order of the structural unit (2 ") may be sufficient.

(Production of salt type block copolymer)
In the present invention, as a method for producing a salt-type block copolymer, the structural unit (1), the structural unit (2), the amino group of the structural unit (1), and the polymerizable property are used. The method is not particularly limited as long as the method can produce a quaternary ammonium salt formed with a halogenated hydrocarbon having a group. In the present invention, for example, the structural unit (1) and the structural unit (2) are polymerized using a known polymerization means, and then dissolved or dispersed in a non-aqueous medium described later. It can manufacture by adding the halogenated hydrocarbon which has and making it react at the temperature of 30-120 degreeC.
The polymerization means is not particularly limited as long as it is a means capable of polymerizing the structural unit (1) and the structural unit (2) at a desired unit ratio to obtain a desired molecular weight. A generally used method can be employed for polymerization of the compound having, for example, anionic polymerization or living radical polymerization. In the present invention, in particular, a method in which polymerization proceeds in a living manner, such as group transfer polymerization (GTP) disclosed in “J. Am. Chem. Soc.” 105, 5706 (1983), is used. preferable. According to this method, it is easy to make the molecular weight, molecular weight distribution, and the like within a desired range, so that characteristics such as dispersibility can be made uniform.

  The salt type block copolymer may be used singly or in combination of two or more, and the content is appropriately selected according to the type of fine particles used, etc. Usually, it is in the range of 5 to 200 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the fine particles to be produced. If the content of the salt type block copolymer is within the above range, the fine particles can be uniformly dispersed.

(Graft copolymer)
In the present invention, the polymer used as the dispersion stabilizer is a nitrogen-containing monomer represented by the following general formula (I ′), a polymer chain, and a group having an ethylenically unsaturated double bond at its terminal. A graft copolymer containing a macromonomer containing quaternary ammonium salt, wherein at least part of the amino group derived from the nitrogen-containing monomer and a halogenated hydrocarbon having a polymerizable group Is a graft copolymer (sometimes referred to as a salt-type graft copolymer) that uniformly and stably disperses nano-sized fine particles and keeps the average particle size of the fine particles at the time of dispersion small. It is preferable from the point which can manufacture the nanoparticle composite material which can be manufactured.

(In formula (I ′), R ¹ , R ² , R ³ and A are the same as in formula (I).)

In the salt-type graft copolymer used as the dispersion stabilizer, the macromonomer is composed of a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. The group having an ethylenically unsaturated double bond is preferably contained only at one end of the polymer chain (hereinafter sometimes referred to as “one end”). Further, the macromonomer may be substituted with a substituent as long as it does not interfere with the dispersion performance of the graft copolymer, and examples of the substituent include a halogen atom.
Preferred examples of the group having an ethylenically unsaturated double bond include a (meth) acryloyl group, a vinyl group, and an allyl group. Among them, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable. preferable.

  The polymer chain of the macromonomer preferably has at least one structural unit represented by the following general formula (III) or general formula (IV).

(In Formula (III) and Formula (IV), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a cyano group, — [CH (R _{^{23) -CH (R 24) -O}} ] x -R 25, - [(CH 2) y -O] z -R 25, - [CO- (CH 2) y -O] z -R 25, -CO It is a monovalent group represented by —O—R ²⁶ or —O—CO—R ^27. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group.
R ²⁵ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ²⁸ , and R ²⁶ is alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a cyano _{^{group, - [CH (R 23)}} -CH (R 24) -O] x -R 25, - [(CH 2) y -O] z —R ²⁵ , — [CO— (CH ₂ ) _y —O] _z —R ²⁵ is a monovalent group. R ²⁷ is an alkyl group having 1 to 18 carbon atoms, and R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
m represents an integer of 1 to 5, and n and n ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group. R ²⁵ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ^28, which may have a substituent. It is the basis of. R ²⁸ is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, and R ²⁷ is an alkyl group having 1 to 18 carbon atoms.
In the monovalent group represented by R ²⁵ , examples of the substituent that may be included include linear, branched, or cyclic alkyl groups having 1 to 4 carbon atoms, and halogen atoms such as F, Cl, and Br. And so on.
Of the R ²² , R ²⁵ , R ²⁶ and R ²⁷ , the alkyl group having 1 to 18 carbon atoms, the aralkyl group and the aryl group are as described above for R ⁵ .
In R ²² and R ²⁶ , x, y, and z are as described in R ⁵ above.

In the present invention, as R ²² and R ²⁶ , it is preferable to use those having excellent solubility in a non-aqueous medium described later, specifically, the structural unit constituting the graft copolymer. However, when a medium such as ether alcohol acetate, ether, or ester is used as a non-aqueous medium to be described later, a methyl group, an ethyl group, an n-butyl group, a 2-ethylhexyl group, or a benzyl group is used. Etc. are preferred. Further, when the non-aqueous medium is a less polar one such as pentane or hexane, it is preferable to use a pentyl group, a hexyl group, a heptyl group, or the like.
Here, the reason for setting R ²² and R ²⁶ in this way is that the structural unit containing R ²² and R ²⁶ has solubility in the non-aqueous medium, and the amino group of the nitrogen-containing monomer. And the salt-forming sites formed by the halogenated hydrocarbons described later have high adsorptivity to the fine particles, so that the dispersibility and stability of the fine particles can be made particularly excellent. is there.

Further, R ²² and R ²⁶ are substituents such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, and a hydrogen bond-forming group as long as they do not interfere with the dispersion performance of the graft copolymer. It may be substituted by. Moreover, after synthesizing a graft copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting a graft copolymer having a carboxyl group with glycidyl (meth) acrylate, or reacting a graft copolymer having an isocyanate group with hydroxyethyl (meth) acrylate. Can do.

  Furthermore, the macromonomer used for a graft copolymer may be used individually by 1 type, but may be used in mixture of 2 or more types.

  m is an integer of 1 to 5, preferably an integer of 2 to 5, more preferably an integer of 4 or 5. The number of units n and n ′ of the constituent units of the macromonomer may be an integer of 5 to 200, and is not particularly limited, but is preferably in the range of 5 to 100.

  The mass average molecular weight Mw of the macromonomer is preferably in the range of 500 to 20000, and more preferably in the range of 1000 to 10,000. By being the said range, while being able to hold | maintain sufficient steric repulsion effect as a dispersion stabilizer, the increase in the adsorption time to the microparticles | fine-particles by a steric effect can also be suppressed.

  Such a macromonomer may be appropriately synthesized or may be a commercially available product. Examples of commercially available products include one-end methacryloylated polymethyl methacrylate oligomer (mass average molecular weight: 6000, “AA-6 (product Name) ": manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated poly-n-butyl acrylate oligomer (mass average molecular weight: 6000," AB-6 (trade name) "manufactured by Toagosei Chemical Co., Ltd.), Single-end methacryloylated polystyrene oligomer (mass average molecular weight: 6000, “AS-6 (trade name)” manufactured by Toagosei Chemical Co., Ltd.), caprolactone-modified hydroxyethyl methacrylate (“Placcel FM5 (trade name)”: Daicel Chemical ( Co., Ltd.), caprolactone-modified hydroxyethyl acrylate ("Placcel FA10L ( Name) ": manufactured by Daicel Chemical Industries Co., Ltd.), and the like.

  In order to synthesize such a macromonomer, a living polymerization method and a radical polymerization method using a chain transfer agent are well known. The radical polymerization method is easier to use because it has a greater degree of freedom in monomer selection. For example, an oligomer having a carboxyl group at one end can be obtained by radical polymerization of a monomer in the presence of a chain transfer agent having a carboxyl group such as mercaptopropionic acid. When glycidyl methacrylate is added to this oligomer, an oligomer having a methacryloyl group at one end, that is, a macromonomer is obtained.

  Further, the mass average molecular weight Mw of the graft copolymer is preferably in the range of 1000 to 100,000, more preferably in the range of 3000 to 50000, and further in the range of 5000 to 30000. preferable. By being the said range, microparticles | fine-particles can be disperse | distributed uniformly.

  The mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.).

  The graft copolymer used in the present invention has the nitrogen-containing monomer and the macromonomer as copolymer components, and the amino group and the halogenated hydrocarbon having a polymerizable group in the nitrogen-containing monomer are salts. The structure is expressed as shown in FIG. 4, for example. In FIG. 4, in the graft copolymer, a nitrogen-containing monomer unit 51 forms a main chain by a polymerization reaction, and a macromolecular monomer group (group part having an ethylenically unsaturated double bond) 52 in the polymerization reaction. Are simultaneously polymerized with the nitrogen-containing monomer, and the macromonomer forms a side chain as the polymer chain 53 while being connected to the group site having the ethylenically unsaturated double bond, and the halogenated hydrocarbon 54 having a polymerizable group. Is a salt formed with the amino group of the nitrogen-containing monomer unit 51.

(Production of salt-type graft copolymer)
In the present invention, as a method for producing a salt-type graft copolymer used as a dispersion stabilizer, a nitrogen-containing monomer, a macromonomer comprising a polymer chain and a group having an ethylenically unsaturated double bond at its terminal, Is not particularly limited as long as it is a method capable of producing a salt formed of an amino group of a nitrogen-containing monomer and a halogenated hydrocarbon having a polymerizable group. In the present invention, for example, the nitrogen-containing monomer, the macromonomer, and, if necessary, other monomers can be graft-polymerized using a known polymerization means. Next, a salt-type graft copolymer can be produced by adding a halogenated hydrocarbon having a polymerizable group to a non-aqueous medium to be described later and reacting at a temperature of 30 to 120 ° C. In the above polymerization, additives generally used for polymerization such as a polymerization initiator and a chain transfer agent may be used.

In the present invention, the dispersion stabilizer may be used alone or in combination of two or more. When two or more types are used in combination, the salt type block copolymer and the salt type are used in addition to the case where two or more types of the salt type block copolymer are used or the case where two or more types of the graft copolymer are used. A graft copolymer may be used in combination.
The content of the dispersion stabilizer in the nano fine particle dispersion is not particularly limited as long as the fine particles can be uniformly dispersed in the non-aqueous medium, and varies depending on the type of fine particles. It is preferably used in the range of 5 to 200 parts by mass, more preferably in the range of 10 to 150 parts by mass, and still more preferably in the range of 20 to 100 parts by mass with respect to parts. When the content of the dispersion stabilizer is within the above range, the fine particles can be uniformly dispersed.

<Non-aqueous medium>
The non-aqueous medium used in the present invention is not particularly limited as long as it is a medium in which the polymer is soluble. Usually, a medium having a relatively low polarity is preferably used. However, in the present invention, a medium having a relatively high polarity can be used in combination.
Specific examples of the non-aqueous medium used in the present invention include ethers such as tetrahydrofuran; alkylene glycols such as ethylene glycol and propylene glycol; dialkylene glycols such as diethylene glycol and dipropylene glycol; ethylene glycol monomethyl ether; Alkylene glycol alkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol monoethyl ether; diethylene glycol Monomethyl ether, di Diethylene glycol alkyl ethers such as tylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether, and dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether and dipropylene glycol diethyl ether Dialkylene glycol alkyl ethers such as methyl cellosolve acetate, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate Alkylene glycol alkyl ether acetates such as carbonates; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate And esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, and 3-methoxybutyl acetate; alkanes such as hexane and heptane, among others, diethylene glycols and alkylene Glycol alkyl ethers, dialkylene glycol alkyl ethers, and alkylene glycol alkyl ether acetates are preferred, particularly ethyl 3-ethoxypropionate and acetic acid-3-methoxybutyrate. And propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and ethylene glycol monobutyl ether.

In addition, the non-aqueous medium used in this step preferably has a SP value (Solubility Parameter) that is a solubility index within the range of 7 to 12, more preferably within the range of 7 to 11, What is in the range of 9-10 is still more preferable. When the SP value is within the above range, the quaternary ammonium salt formed by the amino group and the halogenated hydrocarbon having the polymerizable group in the polymer does not dissociate, and the non-aqueous medium The polymer is not completely dissolved therein. As a result, the property of selectively accumulating on the fine particle surface of the polymer, which will be described later, is not lowered.
Here, the SP value (unit: (cal / cm ³ ) ^1/2 ) is represented by the square root of the attractive force between molecules, that is, the cohesive energy density CED (cohesive energy density). Here, the definition of the CED, the amount of energy required to evaporate those 1 cm ³ (Unit: cal / cm ³⁾ is.

  The non-aqueous medium used in this step may be composed of only one type as described above, or may be a combination of two or more types. In this invention, it is preferable to use the above solvents so that it may become a ratio of 70-99 mass% with respect to the whole quantity of the nanoparticle dispersion containing the said solvent. If the amount of the non-aqueous medium is too small, the viscosity increases, the dispersibility may decrease, or the dispersion may gel in the crosslinking step described later.

<Fine particles>
The fine particles used in the present invention are not particularly limited as long as they are insoluble in the non-aqueous medium. Examples of such fine particles include inorganic / organic pigments, dyes, metal powders, monomer components for resin production, cosmetics, pharmaceuticals, microorganisms, cells, and the like.

The average particle size of the fine particles can be appropriately selected according to the use, etc., but in the range of 10 to 100 nm from the viewpoint of effectively utilizing the effect of uniformly and stably dispersing the nano-sized fine particles of the present invention. Is preferably within the range of 10 nm to 50 nm.
The average particle size of the fine particles can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle. Next, with respect to 100 or more particles, the volume (weight) of each particle was obtained by approximating it to a rectangular parallelepiped having the obtained particle size, and the volume average particle size was obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

The content of the fine particle in the nano fine particle dispersion is not particularly limited as long as it can be uniformly dispersed in the non-aqueous medium, and varies depending on the application, etc. The content is preferably in the range of 1 to 60% by mass, more preferably in the range of 1 to 30% by mass, and still more preferably in the range of 1 to 15% by mass.
When the content of the fine particles is within the above range, the fine particles can be uniformly dispersed.

<Nanoparticulate dispersion>
The nano-particle dispersion formed in Step 1 is a polymer accumulated on the surface of the fine particles by adding the fine particles to the dispersion stabilizer solution. In the present invention, since the salt forming site formed by the amino group contained in the structural unit (1) and the halogenated hydrocarbon having a polymerizable group is insoluble in the non-aqueous medium, the fine particles are dispersed. When added to the agent solution, the polymer can selectively accumulate on the surface of the fine particles. Therefore, a nano fine particle dispersion having excellent fine particle dispersibility and stability is formed.

The average particle size of the nanoparticle dispersion is preferably in the range of 10 nm to 200 nm, more preferably in the range of 10 nm to 100 nm, and still more preferably in the range of 10 nm to 50 nm. This is because the average particle size of the nanoparticle composite described later can be made small, so that the characteristics of the fine particles can be exhibited more effectively and stably.
The average particle size of the nanoparticle dispersion is a value measured by a laser scattering method. Specifically, the average particle diameter is measured by dispersing fine particles in a non-aqueous medium and capturing and calculating scattered light obtained by applying a laser beam to the dispersion.

(Method of forming nano-particle dispersion)
The nanoparticle dispersion described above can be formed by a known stirring / dispersing means. Examples of the disperser employed in stirring or dispersion include a roll mill such as a two-roll or a three-roll, a ball mill such as a ball mill or a vibration ball mill, a paint shaker, a bead mill such as a continuous disk type bead mill, or a continuous annular type bead mill. Can be mentioned. When using a bead mill, the bead diameter to be used is preferably 0.03 mm to 2.0 mm, more preferably 0.05 mm to 1.0 mm.

[Step 2. Crosslinking step]
Next, step 2 of the present invention will be described. Step 2 is a crosslinking step for crosslinking the polymer. In this step, since the polymer can be fixed on the surface of the fine particles, it is possible to form a nano fine particle composite having superior dispersibility and stability as compared with the nano fine particle dispersion.
In addition, since the polymer forming the nanoparticle dispersion is selectively accumulated on the surface of the fine particles and covers the entire surface of the fine particles, the particle size of the nanoparticle composite is reduced, and The reaggregation of the fine particles can be effectively prevented. From this, the nanoparticulate composite obtained in the present invention can be taken out from a non-aqueous medium, dried, and then redispersed in a medium according to the application.
Furthermore, in this step, the polymer is crosslinked to form a nanoparticle composite, and is not due to precipitation using the difference in solubility. Such a process is unnecessary, and productivity can be improved.

In this step, examples of the method for crosslinking the polymer include a method of crosslinking by irradiation with light in the presence of a photoinitiator or heating in the presence of a thermal initiator, depending on the type of the polymerizable group. It is selected appropriately. In this step, any method can be suitably used. For example, when the nanoparticle dispersion has low transparency, sufficient radicals can be generated by light irradiation and crosslinking cannot proceed. It is preferable to use a method of polymerizing by heating. On the other hand, when the heat resistance of the fine particles is low, it is preferable to use a method of crosslinking by light irradiation.
Moreover, the temperature conditions of 30-150 degreeC are preferable for this bridge | crosslinking process, and 30-50 degreeC is more preferable. If the temperature condition of the crosslinking step is within the above range, re-aggregation of fine particles due to heating conditions can be prevented.

(Initiator)
The initiator used in this step can be appropriately selected from various conventionally known photoinitiators and thermal initiators. Examples of the photoinitiator include benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene and other aromatic ketones, benzoin methyl ether, benzoin ethyl Benzoin ethers such as ether and benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin; 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5- Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-tri Reel imidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5 Halomethyloxadiazole compounds such as-(p-methoxystyryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4 -Bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-a Mino-6-p-methoxystyryl-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl)- Halomethyl-S-triazine compounds such as 4,6-bis-trichloromethyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2 , 2-Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzene Zoyl-4'-methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 4-benzoyl- Methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2- [(4-Methylpheny L) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-
Examples include phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  In this step, the photoinitiator is preferably used in an amount of 0.0005 to 0.1 molar equivalents relative to the polymerizable group of the halogenated hydrocarbon having a polymerizable group of the polymer. -0.05 molar equivalent is more preferred. If the amount of the photoinitiator used is within the above range, it can be sufficiently crosslinked, and the molecular weight of the crosslinked salt-type block copolymer and / or salt-type graft copolymer is not lowered, so that it is good. Strength of the nanoparticle composite can be obtained.

  Examples of the thermal initiator include organic peroxides such as alkyl peroxides, acyl peroxides, ketone peroxides, alkyl hydroperoxides, peroxy dicarbonates, sulfonyl peroxides, and inorganic peroxides. And azo compounds such as azonitrile, sulfinic acids, bisazides, and diazo compounds. Specific examples include cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, peroxodisulfate, hydrogen peroxide, potassium persulfate, ammonium persulfate, Perborate, 2,2′-azobisisobutyronitrile, 1,1′-azobis (1-cyclohexane-1-carbonitrile), dimethyl-2,2′-azoisobisbutyrate, 2,2 ′ -Azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis ( 2-amidinopropane) dicarbonate, sodium azobiscyanovalerate, 2,2′-azobis (2,4-dimethylvalerontri) ), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxy Ethyl] propionamide], 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2,2′-azobis [2-methyl-N- (2 -Hydroxyethyl) propionamide], 2,2′-azobis (2-cyanopropanol), 2,2′-azobis (2,4,4-trimethylpentane), sodium p-toluenesulfinate and the like are preferable. . Among these, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile) are sufficient even at a low temperature of about 30 to 50 ° C. It is preferable in that the effect is exhibited and re-aggregation of the fine particles due to heating conditions can be prevented. These thermal initiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  In this step, the amount of the thermal initiator used is preferably 0.0005 to 0.1 molar equivalents relative to the polymerizable group of the halogenated hydrocarbon having a polymerizable group of the polymer, and is 0.001 to 0. More preferred is 0.05 molar equivalent. If the amount of the thermal initiator used is within the above range, it can be sufficiently crosslinked, and the molecular weight of the crosslinked salt-type block copolymer and / or salt-type graft copolymer is not lowered, so that it is good. Strength of the nanoparticle composite can be obtained.

  The addition time of the photoinitiator and the thermal initiator in this step is not particularly limited as long as it is before the above-described crosslinking step, and may be before the above-described dispersion step or after the dispersion step. It can be appropriately set according to the stability of the photoinitiator and thermal initiator.

  When the concentration of the fine particles in the dispersant solution is high, this step is preferably performed while performing ultrasonic treatment. By performing ultrasonic treatment, gelation of the dispersant solution can be prevented, or even when the dispersibility of the fine particles is poor, the crosslinking proceeds rapidly, so that the average particle size of the obtained nano fine particle composite can be reduced. It can be reduced and a stable dispersion can be obtained. The ultrasonic treatment is preferably performed simultaneously with or before the addition time of the photoinitiator or the thermal initiator.

(Nanoparticle composite)
The nanoparticulate composite thus obtained is capable of uniformly and stably dispersing nanosized fine particles and keeping the average particle size of the fine particles at the time of dispersion small. The average particle diameter of the nanoparticle composite is preferably in the range of 10 nm to 200 nm, more preferably in the range of 10 nm to 100 nm, and still more preferably in the range of 10 nm to 50 nm. This is because if the average particle size of the nanoparticulate composite is within the above range, the characteristics of the fine particles can be exhibited more effectively and stably. The average particle size of the nanoparticle dispersion can be measured in the same manner as the average particle size of the nanoparticle dispersion described above.

The nanoparticulate composite obtained by the production method of the present invention can be particularly suitably used in applications that require use while maintaining the dispersibility and stability of the fine particles. For example, it can be used for printing inks, medical materials, paints, recording materials, cosmetics, semiconductor substrates, and the like, which are fields that require the use of nano-sized fine particles.
With the recent development of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. Recently, the penetration rate of home-use LCD TVs is also increasing, and the market for liquid crystal displays is expanding and the trend toward larger screens is increasing. Under such circumstances, the present invention can also be suitably applied to pigments applied to colored resin compositions used in the production of color filters having a function of causing liquid crystal display devices and organic light emitting display devices to display in color.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

(Production Example 1 Synthesis of block copolymer)
In a reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, digital thermometer, 300 parts by mass of tetrahydrofuran (THF) and 2.68 parts by mass of dimethyl ketene methyltrimethylsilyl acetal initiator are added to the addition funnel And was fully substituted with nitrogen. 0.40 part by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, benzyl methacrylate 20 A part by mass of the mixed solution was dropped over 60 minutes using an addition funnel. The temperature was kept below 40 ° C. by cooling the reaction flask with an ice bath. After 1 hour, 50 parts by mass of 2- (dimethylamino) ethyl methacrylate (abbreviation DMA) was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was purified by evaporation and vacuum drying to obtain a block copolymer. The block copolymer thus obtained was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard. Weight average molecular weight Mw: 9250, number average molecular weight Mn: 7850, molecular weight distribution Mw / Mn was 1.18. The amine value was 120 mgKOH / g.

(Production Example 2 Synthesis of Macromonomer A)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 80.0 parts by weight of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) and stirred while stirring under a nitrogen stream. Warmed to 90 ° C. 50.0 parts by weight of methyl methacrylate, 30.0 parts by weight of n-butyl methacrylate, 20.0 parts by weight of benzyl methacrylate, 4.0 parts by weight of mercaptoethanol, 30 parts by weight of PGMEA, α, α′-azobisiso A mixed solution of 1.0 part by weight of butyronitrile (abbreviation AIBN) was added dropwise over 1.5 hours, and the reaction was further continued for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., Karenz MOI (manufactured by Showa Denko KK) 8.74 parts by weight, dibutyltin dilaurate 0.125 g, p-methoxyphenol 0. 125 parts by weight and 10 parts by weight of PGMEA were added and stirred for 3 hours to obtain a 49.5% solution of Macromonomer A. When the obtained macromonomer A was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard, weight average molecular weight (Mw) 4010 The number average molecular weight (Mn) 1910 and the molecular weight distribution (Mw / Mn) were 2.10.

(Production Example 3 Synthesis of Graft Copolymer)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by weight of PGMEA and heated to 85 ° C. while stirring under a nitrogen stream. 67.34 parts by weight of macromonomer A solution of Production Example 2 (33.33 parts by weight of effective solid content), 16.67 parts by weight of 2- (dimethylamino) ethyl methacrylate (abbreviation DMA), 1.24 n-dodecyl mercaptan A mixed solution of 1 part by weight, 20.0 parts by weight of PGMEA, and 0.5 parts by weight of AIBN was added dropwise over 1.5 hours, heated and stirred for 3 hours, and then a mixed solution of 0.10 parts by weight of AIBN and 10.0 parts by weight of PGMEA Was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour to obtain a 26.0% solution of the graft copolymer. As a result of GPC measurement, the obtained graft copolymer had a weight average molecular weight (Mw) of 12420, a number average molecular weight (Mn) of 4980, and a molecular weight distribution (Mw / Mn) of 2.49. The amine value was 118 mgKOH / g.

(Production Example 4 Preparation of salt-type block copolymer solution)
In a 300 mL round bottom flask, 130.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), 30.0 parts by weight of n-butoxyethanol, 35.9 parts by mass of the block copolymer prepared in Production Example 1, As a halogenated hydrocarbon having a polymerizable group, 4.1 parts by mass of 4-chloromethylstyrene (manufactured by Acros Co., Ltd.) (0.35 molar equivalent with respect to the DMA unit of the block copolymer) was added, and the reaction temperature was 80 ° C. Was stirred for 6 hours to prepare a salt-type block copolymer solution having a solid content of 20% by mass. At this time, the amino group of the block copolymer is salt-formed by a quaternization reaction with 4-chloromethylstyrene.

(Production Example 5 Preparation of salt-type graft copolymer solution)
In a 300 mL round bottom flask, 29.2 parts by mass of PGMEA, 30.0 parts by weight of n-butoxyethanol, and 136.2 parts by mass of the graft copolymer prepared in Production Example 3 were dissolved, and halogenated carbonization having a polymerizable group. As hydrogen, 4.6 parts by mass of 4-chloromethylstyrene (manufactured by Acros Co., Ltd.) (0.40 molar equivalent based on the DMA unit of the graft copolymer) was added and stirred at a reaction temperature of 80 ° C. for 6 hours. A salt-type graft copolymer solution having a solid content of 20% by mass was prepared. At this time, the amino group of the graft copolymer is salt-formed by a quaternization reaction with 4-chloromethylstyrene.

Example 1
(Production of nano fine particle dispersion A)
30.0 parts by weight (solid content: 6.0 parts by weight) of the salt-type block copolymer solution obtained in Production Example 4, commercially available C.I. I. Pigment Yellow 150 (average primary particle size: 20 to 50 nm) 10.0 parts by weight, PGMEA 55.8 parts by weight, propylene glycol monomethyl ether (PGME) 4.2 parts by weight, 2.0 mm zirconia beads 100 parts by weight in mayonnaise bin Then, as preliminary crushing, shake with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour, and then add 100 parts by weight of the dispersion and 200 parts by weight of zirconia beads having a particle diameter of 0.1 mm into a mayonnaise bin. As a main crushing, dispersion was performed for 3 hours with a paint shaker to obtain a nanoparticle dispersion A.

(Production of nanoparticulate composite A)
In a 50 ml eggplant flask, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70: as an initiator) with respect to 30 parts by weight of the nanoparticle dispersion A obtained above. 0.010 parts by mass of Wako Pure Chemical Industries, Ltd.) was added, and the mixture was reacted at 50 ° C. for 3 hours while performing ultrasonic treatment to obtain a nanoparticulate composite dispersion A containing nanoparticulate composite A.

Example 2
In Example 1, fine particles were obtained from commercially available C.I. I. A nanoparticulate composite dispersion B containing the nanoparticulate composite B was obtained in the same manner as in Example 1 except that Pigment Blue 15: 6 (average primary particle size: 10 to 40 nm) was used.

Example 3
In Example 1, a nanoparticulate composite dispersion C containing nanoparticulate composite C was obtained in the same manner as in Example 1 except that the commercially available pigment red 209 (average primary particle size: 30 to 60 nm) was used. It was.

Example 4
Nanoparticles containing the nanoparticle composite D in the same manner as in Example 1 except that the fine particles were commercial silica fine particles (average primary particle size: 10 to 30 nm) in Example 1 and dispersed for 12 hours as the main crushing. A composite dispersion D was obtained.

Reference Examples 1-4
Dispersions containing nanoparticle dispersions A to D in Examples 1 to 4 were referred to as Reference Examples 1 to 4, respectively.

Example 5
(Production of nano fine particle dispersion E)
30.0 parts by weight of the salt-type graft copolymer solution obtained in Production Example 5 (solid content: 6.0 parts by weight), commercially available C.I. I. Pigment Yellow 150 (average primary particle size: 20 to 50 nm) 10.0 parts by weight, PGMEA 55.8 parts by weight, PGME 4.2 parts by weight, and 2.0 mm zirconia beads 100 parts by weight are put into a mayonnaise bin, Shake with a paint shaker (manufactured by Asada Tekko) for 1 hour, and then add 100 parts by weight of the dispersion and 200 parts by weight of zirconia beads having a particle size of 0.1 mm into a mayonnaise bin. For 3 hours to obtain a nanoparticle dispersion E.

(Manufacture of nano-particle composite E)
In a 50 ml eggplant flask, 0.010 parts by mass of V-70 as an initiator was added to 30 parts by weight of the nanoparticle dispersion A obtained above, and the mixture was reacted at 50 ° C. for 3 hours while performing ultrasonic treatment. As a result, a nanoparticle composite dispersion E containing the nanoparticle composite E was obtained.

Example 6
In Example 5, the fine particles were obtained from commercially available C.I. I. A nanoparticulate composite dispersion F containing the nanoparticulate composite F was obtained in the same manner as in Example 5 except that Pigment Blue 15: 6 (average primary particle size: 10 to 40 nm) was used.

Example 7
In Example 5, a nanoparticulate composite dispersion G containing the nanoparticulate composite G was obtained in the same manner as in Example 5 except that the commercially available pigment red 209 (average primary particle size: 30 to 60 nm) was used. It was.

Example 8
Nanoparticles containing the nanoparticle composite H in the same manner as in Example 5 except that in Example 5, the fine particles were commercially available silica particles (average primary particle size: 10 to 30 nm) and dispersed for 12 hours as the main crushing. A composite dispersion H was obtained.

Reference Examples 5-8
Dispersions containing nanoparticle dispersions E to H in Examples 5 to 8 were referred to as Reference Examples 5 to 8, respectively.

<Dispersion stability evaluation>
As an evaluation of the dispersion stability, the dispersions obtained in each Example and Reference Example were allowed to stand at 40 ° C. for 1 week, and the average of the nanoparticle composite and the nanoparticle dispersion in the dispersion before and after standing The particle size and shear viscosity were measured. To measure the average particle size, use “Nanotrack particle size distribution meter UPA-EX150” manufactured by Nikkiso Co., Ltd., and to measure the viscosity, use the “Rheometer MCR301” manufactured by Anton Paar, and measure the shear viscosity when the shear rate is 60 rpm. It was measured.
The results are shown in Tables 1 and 2.

[Summary of results]
In the non-aqueous medium, as a dispersion stabilizer, the structural unit (1) represented by the general formula (I) is included, and at least a part of the amino group of the structural unit (1), and a polymerizable group Examples obtained by adding fine particles to a solution in which a polymer in which a quaternary ammonium salt was formed with a halogenated hydrocarbon having a quaternary ammonium salt was added to form a nanoparticle dispersion and crosslinking the polymer 1 to 8 nanoparticle composites were found to have a smaller particle size and lower viscosity than the corresponding nanoparticle dispersions of Reference Examples 1 to 8 using the same particles and dispersant. . Furthermore, it was revealed that the nanoparticle composites of Examples 1 to 8 were excellent in dispersion stability with almost no change in particle size and viscosity even after the storage stability test.

51 Nitrogen-containing monomer unit 52 Polymerizable part of macromonomer 53 Polymer chain of macromonomer 54 Halogenated hydrocarbon having polymerizable group

Claims (9)

A polymerizable dispersion stabilizer used in a non-aqueous medium,
It has at least a block of the structural unit (1) represented by the following general formula (I) and a block of the structural unit (2) represented by the following general formula (II), and the structural unit (1) A polymerizable dispersion stabilizer, which is a block copolymer in which at least a part of an amino group and a halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt.
(In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an alkylene group having 1 to 8 carbon atoms. , — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — Each of the divalent groups R ⁶ and R ⁷ is independently a hydrogen atom or a methyl group, and the alkyl group and alkylene group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )
(In the formula (II), ^{R 4} is a hydrogen atom or a methyl group, ^{R 5} is an alkyl group, an aralkyl group having 1 to 18 carbon atoms, an aryl ^{group, - [CH (R 6)} -CH (R 7) - O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ is a monovalent group, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, ⁸ is a hydrogen atom, or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom It is an alkyl group having 1 to 5 atoms or carbon atoms, and the alkyl group, aralkyl group and aryl group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. ) A polymerizable dispersion stabilizer used in a non-aqueous medium,
A graft copolymer containing at least a nitrogen-containing monomer represented by the following general formula (I ′) and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component The polymer chain of the macromonomer has at least one structural unit represented by the following general formula (III) or general formula (IV), and at least one amino group derived from the nitrogen-containing monomer. A polymerizable dispersion stabilizer which is a graft copolymer in which a part and a halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt .
(In Formula (I ′), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an alkylene having 1 to 8 carbon atoms. A group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y The divalent group represented by —, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and the alkyl group and alkylene group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )
(In Formula (III) and Formula (IV), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a cyano group, — [CH (R _{^{23) -CH (R 24) -O}} ] x -R 25, - [(CH 2) y -O] z -R 25, - [CO- (CH 2) y -O] z -R 25, -CO It is a monovalent group represented by —O—R ²⁶ or —O—CO—R ^27. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group.
R ²⁵ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ²⁸ , and R ²⁶ is alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a cyano _{^{group, - [CH (R 23)}} -CH (R 24) -O] x -R 25, - [(CH 2) y -O] z —R ²⁵ , — [CO— (CH ₂ ) _y —O] _z —R ²⁵ is a monovalent group. R ²⁷ is an alkyl group having 1 to 18 carbon atoms, and R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
m represents an integer of 1 to 5, and n and n ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. ) The polymerizable dispersion stabilizer according to claim 1 or 2 , wherein the halogenated hydrocarbon having a polymerizable group is a halogenated aralkyl having a polymerizable group. The polymerizable dispersion stabilizer according to any one of claims 1 to 3 , wherein the polymerizable group of the halogenated hydrocarbon having a polymerizable group is an ethylenically unsaturated double bond-containing group. A polymerizable dispersion stabilizer solution comprising the polymerizable dispersion stabilizer according to any one of claims 1 to 4 and a non-aqueous medium, wherein the non-aqueous medium contains a polar medium. A nano-particle composite comprising fine particles and a polymerizable dispersion stabilizer covering the surface of the fine particles, wherein the polymerizable group of the polymerizable dispersion stabilizer is crosslinked,
The polymerizable dispersion stabilizer has at least a block of the structural unit (1) represented by the following general formula (I) and a block of the structural unit (2) represented by the following general formula (II), Further, a nanoparticulate composite, which is a block copolymer in which at least a part of the amino group of the structural unit (1) and a halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt.
(In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an alkylene group having 1 to 8 carbon atoms. , — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — Each of the divalent groups R ⁶ and R ⁷ is independently a hydrogen atom or a methyl group, and the alkyl group and alkylene group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )
(In the formula (II), ^{R 4} is a hydrogen atom or a methyl group, ^{R 5} is an alkyl group, an aralkyl group having 1 to 18 carbon atoms, an aryl ^{group, - [CH (R 6)} -CH (R 7) - O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ is a monovalent group, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, ⁸ is a hydrogen atom, or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom It is an alkyl group having 1 to 5 atoms or carbon atoms, and the alkyl group, aralkyl group and aryl group may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. ) A nano-particle composite comprising fine particles and a polymerizable dispersion stabilizer covering the surface of the fine particles, wherein the polymerizable group of the polymerizable dispersion stabilizer is crosslinked,
The polymerizable dispersion stabilizer is a copolymerization component comprising at least a nitrogen-containing monomer represented by the following general formula (I ′) and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. The polymer chain of the macromonomer contains at least one structural unit represented by the following general formula (III) or general formula (IV), and further contains the nitrogen A nanoparticle composite , which is a graft copolymer in which at least a part of an amino group derived from a monomer and a halogenated hydrocarbon having a polymerizable group form a quaternary ammonium salt .
(In Formula (I ′), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an alkylene having 1 to 8 carbon atoms. A group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y The divalent group represented by —, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and the alkyl group and alkylene group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )
(In Formula (III) and Formula (IV), R ²¹ is a hydrogen atom or a methyl group, R ²² is an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a cyano group, — [CH (R _{^{23) -CH (R 24) -O}} ] x -R 25, - [(CH 2) y -O] z -R 25, - [CO- (CH 2) y -O] z -R 25, -CO It is a monovalent group represented by —O—R ²⁶ or —O—CO—R ^27. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group.
R ²⁵ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ²⁸ , and R ²⁶ is alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a cyano _{^{group, - [CH (R 23)}} -CH (R 24) -O] x -R 25, - [(CH 2) y -O] z —R ²⁵ , — [CO— (CH ₂ ) _y —O] _z —R ²⁵ is a monovalent group. R ²⁷ is an alkyl group having 1 to 18 carbon atoms, and R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
m represents an integer of 1 to 5, and n and n ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. ) The nanoparticle composite according to claim 6 or 7 , wherein the halogenated hydrocarbon having a polymerizable group is a halogenated aralkyl having a polymerizable group. The nanoparticle composite according to any one of claims 6 to 8 , wherein the polymerizable group of the halogenated hydrocarbon having a polymerizable group is an ethylenically unsaturated double bond-containing group.