JP2011074146A - Method for producing dispersion liquid of nanoparticle composite, and resin composition containing the dispersion liquid of nanoparticle composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a dispersion liquid of a nanoparticle composite, in which a nano-sized particulate composite is uniformly dispersed in a high concentration and the dispersion stability is superior. <P>SOLUTION: The method for producing the dispersion liquid of a nanoparticle composite includes processes 1 to 4. The process 1 is a dispersion process for forming a nanoparticle dispersion by dispersing microparticles in a first solvent, using a block copolymer, as a dispersion stabilizer, in which a specified amino group contained in the copolymer and an organic acid compound having a polymerizable group form a salt. The process 2 is a dilution process for diluting the nanoparticle dispersion with a second solvent having a boiling point different from that of the first solvent. The process 3 is a composite forming process for forming the nanoparticle composite by crosslinking the block copolymer. The process 4 is a concentration process for concentrating the dispersion liquid by distilling out the first or second solvent of the nanoparticle composite. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a nanoparticle composite dispersion and a resin composition containing the nanoparticle composite dispersion.

  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 Patent Document 1, the solubility parameter difference between (A) a nitrogen-containing macromonomer (N-acylalkyleneimine), (B) a nitrogen-free macromonomer (such as PMMA), and (C) a solvent is Δsp> 1. 0.0 copolymer (2-hydroxyethyl methacrylate), the pigment is dispersed in a solvent in which the monomer (C) is dissolved, and a solvent in which the monomer (C) is not dissolved is added to dissolve the monomer (C). It is disclosed that the pigment surface is coated with a resin by precipitating the solvent to be concentrated and precipitating the (C) unit of the dispersant on the pigment surface. However, since chemical adsorption is not used and physical adsorption is used, depending on the solvent, the resin on the pigment surface may be peeled off, resulting in poor dispersibility, and the solvent resistance of the formed coating film may be reduced. There is a risk that.

In Patent Document 2, two types of reactive monomers are improved by improving the interfacial polymerization method and using a block polymer having a hydrophobic repeating unit block and a hydrophilic repeating unit in a non-aqueous medium as a protective colloid. Among them, there is a method in which one of the two reactive monomers is reacted at the interface of the protective colloid by including one in the protective colloid together with the core substance and adding one in the solvent in which the protective colloid is dispersed. It 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 Document 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.

  In addition, the present inventors added nanoparticles to a dispersion liquid in which a block copolymer formed with a salt copolymer and an acidic phosphate ester having a (meth) acryloyl group was added in a non-aqueous medium to disperse the nanoparticles. A method of obtaining a nanoparticle composite by polymerizing the (meth) acryloyl groups after forming a body is disclosed (Patent Document 4).

JP 2007-277506 A JP-A-7-246329 JP-A-8-302227 JP 2008-207093 A

  In Patent Document 4, the present inventors have found a method for producing a nanoparticle composite in which nanosized particles are uniformly and stably dispersed. However, when the concentration of the nanoparticles is increased, (meth) acryloyl groups are bonded to each other. There was a problem that gelation occurred in the polymerization step and a composite was not formed well. Therefore, further improvements have been desired for a uniform and stable dispersion containing a high concentration of nanoparticulate composite.

  The present invention has been made under such circumstances, and provides a method for producing a nanoparticle composite dispersion in which nanosized fine particle composites are uniformly dispersed at a high concentration and dispersion stability is good. It is intended to do.

  As a result of intensive studies to achieve the above object, the inventors of the present invention used two types of solvents having different boiling points as a dispersion medium for nanoparticulates, and obtained a block copolymer having a specific structure as a dispersion stabilizer. The nanoparticle is dispersed, and the nanoparticle composite is formed by reacting the polymerizable group of the block copolymer in a state where the nanoparticle is at a low concentration. It has been found that the above-mentioned problem can be solved by leaving and concentrating. The present invention has been completed based on such findings.

That is, this invention provides the manufacturing method of the nanoparticle composite dispersion which has the following process 1-process 4.
Step 1. The first solvent has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II) as a dispersion stabilizer, A block copolymer in which the amino group of the structural unit (1) and the organic acid compound having a polymerizable group represented by the following general formula (III) and / or the following general formula (IV) form a salt is used. Dispersing step of forming a nanoparticle dispersion by dispersing the particles Step 2. 2. Dilution step of adding a second solvent having a boiling point different from that of the first solvent. 3. Complex formation step of reacting a polymerizable group in the block copolymer to form a nanoparticulate complex Step 4. A concentration step of concentrating the dispersion by distilling off the first solvent or the second solvent.

［式（Ｉ）〜（ＩＶ）中、Ｒ^１は、水素原子又はメチル基、Ｒ^２及びＲ^２’は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、炭素数１〜８のアルキレン基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^３は、炭素数１〜１８のアルキル基、アラルキル基、アリール基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−Ｒ^８又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子、又はメチル基であり、Ｒ^８は、水素原子、あるいは炭素数１〜１８のアルキル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^１２で示される１価の基であり、Ｒ^１２は水素原子又は炭素数が１〜５のアルキル基である。
Ｒ^４及びＲ^４’は、それぞれ独立に水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^８、−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^８、又は−Ｏ−Ｒ^４’’で示される１価の基であり、Ｒ^４’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^８、又は−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^８で示される１価の基である。Ｒ^９及びＲ^１０は、それぞれ独立に水素原子、又はメチル基であり、Ｒ^８は水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２、又は−ＣＨ_２ＣＯＯＲ^１１で示される１価の基であり、Ｒ^１１は水素原子又は炭素数が１〜５のアルキル基である。但し、Ｒ^４及びＲ^４’のうちいずれかは、炭素数２〜１８のアルケニル基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^８、−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^８、又は−Ｏ−Ｒ^４’’で示される１価の基であり、且つ、Ｒ^４’’が、炭素数２〜１８のアルケニル基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^８、又は−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^８で示される１価の基、及び、Ｒ^８が、炭素数２〜１８のアルケニル基、−ＣＯ−ＣＨ＝ＣＨ_２、又は−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２である。
Ｒ^５は、炭素数２〜１８のアルケニル基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^８、−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^８、又は−Ｏ−Ｒ^５’で示される１価の基であり、且つ、Ｒ^５’が、炭素数２〜１８のアルケニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^８、又は−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^８で示される１価の基、及び、Ｒ^８が、炭素数２〜１８のアルケニル基、−ＣＯ−ＣＨ＝ＣＨ_２、又は−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２である。
ｘ及びａは１〜１８の整数、ｙ及びｂは１〜５の整数、ｚ及びｃは１〜１８の整数を示す。ｍ及びｎは１〜２００の整数を示す。］

[In Formulas (I) to (IV), R ¹ is a hydrogen atom or a methyl group, R ² and R ^{2 ′} are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - ₂ monovalent group represented by, ^{R 3} is 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 a monovalent group represented by — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or a monovalent group represented by _-CH 2 COOR ^{12, R 12} is a hydrogen atom or a carbon number of 1 to 5 alkyl groups.
R ⁴ and R ^{4 ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁹ ) —CH ( R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , or —O—R ^{4 ″} is a monovalent group, and R ^{4 ″} is An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , or — [(CH ₂ ) _b— O] is a monovalent group represented by _c— R ⁸ . R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, -CO-C (CH 3) = CH 2, or a monovalent group represented by _-CH 2 COOR ^{11, R 11} is a hydrogen atom or It is an alkyl group having 1 to 5 carbon atoms. However, any one of R ⁴ and R ^{4 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ or —O—R ^{4 ″} and R ^{4 ″} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , or _a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ⁸ , and R ⁸ has 2 to 18 carbon atoms An alkenyl group, —CO—CH═CH ₂ , or —CO—C (CH ₃ ) ═CH ₂ .
R ⁵ is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , or A monovalent group represented by —O—R ^{5 ′} , and R ^{5 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a — R ⁸ or a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ⁸ , and R ⁸ is an alkenyl group having 2 to 18 carbon atoms, —CO—CH═CH ₂ , or _{-CO-C (CH} 3) a = CH _2.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. ]

  In the method for producing a nanoparticulate composite dispersion according to the present invention, the concentration of the fine particles in the nanoparticulate dispersion is controlled to be 10% by mass or less by the dilution step, thereby suppressing gelation during production. This is preferable from the viewpoint of obtaining a nano-particle composite dispersion in which the fine-particle composite is uniformly dispersed with high stability.

  In the method for producing a nanoparticulate composite dispersion according to the present invention, the second solvent has a boiling point different from that of the first solvent by 30 ° C. or more. Is preferable from the viewpoint of obtaining a nanoparticulate composite dispersion in which a high concentration is uniformly dispersed with high stability.

  In the method for producing a nanoparticulate composite dispersion according to the present invention, the average particle size of the fine particles in Step 1 is preferably in the range of 10 to 100 nm. This is because, when the particle diameter of the fine particles is within a range of 10 nm to 100 nm, the particle diameter of the nanoparticle composite can be made fine. The reason why the particle size of the nanoparticle composite can be made fine is that the block copolymer can be selectively accumulated on the surface of the particles to form a stable nanoparticle dispersion. In addition, it is possible to carry out the complex forming step in that state.

  According to the present invention, there is also provided a resin composition comprising a nanoparticle composite dispersion produced by the method for producing a nanoparticle composite dispersion according to the present invention and a resin.

  According to the present invention, it is possible to provide a method for producing a nanoparticle composite dispersion in which nanosized fine particle composites are uniformly dispersed at a high concentration and the dispersion stability is good.

The method for producing the nanoparticle composite dispersion of the present invention comprises:
Step 1. The first solvent has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II) as a dispersion stabilizer, A block copolymer in which the amino group of the structural unit (1) and the organic acid compound having a polymerizable group represented by the following general formula (III) and / or the following general formula (IV) form a salt is used. A dispersion step of forming a nanoparticle dispersion by dispersing the particles;
Step 2. A dilution step of adding a second solvent having a boiling point different from that of the first solvent;
Step 3. A composite formation step of forming a nanoparticulate composite by reacting a polymerizable group in the block copolymer;
Step 4. A concentration step of concentrating the dispersion by distilling off the first solvent or the second solvent;

In the method for producing a nanoparticulate composite dispersion of the present invention, the diluting step of adding a second solvent having a boiling point different from that of the first solvent in step 2 may be performed after the dispersing step in step 1; You may perform during a dispersion | distribution process. That is, the following step 1 ′ may be used as the step including the step 1 and the step 2.
Step 1 '. A second solvent having a boiling point different from that of the first solvent is added to the first solvent, and the structural unit (1) represented by the following general formula (I) as a dispersion stabilizer and the following general formula (II) An amino group that the structural unit (1) further has, and a polymerizable group represented by the following general formula (III) and / or the following general formula (IV): A dispersion step of forming a nanoparticulate dispersion by dispersing fine particles using a block copolymer in which the organic acid compound has a salt;

According to the present invention, the dispersion step has the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II), and Use is made of a block copolymer in which the amino group of the structural unit (1) and the organic acid compound having a polymerizable group represented by the general formula (III) and / or the general formula (IV) form a salt. Therefore, the block copolymer can be selectively accumulated on the surface of the fine particles, and further exists so as to cover the entire surface of the fine particles. Nanoparticle dispersions excellent in dispersion stability can be formed.
In the complex formation step, the block copolymer is crosslinked by crosslinking the polymerizable groups of the organic acid compound having a polymerizable group represented by the general formula (III) and / or the general formula (IV). Since the polymer can be fixed on the surface of the fine particles, the re-aggregation of the fine particles can be effectively prevented, and the nano fine particle composite is more excellent in the dispersibility and stability of the fine particles than the nano fine particle dispersion. The body can be formed. Further, since the block copolymer is fixed to the surface of the fine particles by crosslinking between the polymerizable groups, unlike the physical adsorption, it has solvent resistance and improves heat resistance.

  Particularly in the present invention, after the preparation of the nanoparticle dispersion, the concentration of the nanoparticle is diluted with a second solvent having a boiling point different from that of the first solvent, or the first solvent is used during the preparation of the nanoparticle dispersion. A second solvent having a different boiling point is added and dispersed in a state where the concentration of the nanoparticles is diluted, and the polymerizable group in the block copolymer is reacted in a state where the nanoparticles are in a low concentration. It is possible to prevent the dispersion from gelling by reacting the polymerizable group in a state where the nano fine particles are in a low concentration. Furthermore, after forming a nanoparticulate composite by reacting a polymerizable group, the low boiling point solvent is distilled out of the two types of solvents, so that the dispersibility and stability are high while the nanoparticulates are at a high concentration. A dispersion of the nanoparticle composite can be obtained.

It is also possible, though difficult to adjust the concentration, to obtain a high concentration nanoparticle composite dispersion by distilling off a part of the solvent of the diluted nanoparticle composite dispersion consisting of a single solvent. However, the method of obtaining a high-concentration nanoparticle composite dispersion by distilling off the low-boiling solvent using two types of solvents as in the present invention is usually a solvent that is difficult to disperse. However, there is an advantage that a stable dispersion can be obtained by dispersing in a solvent that is easy to disperse and then replacing the solvent with a solvent that is difficult to disperse by the above-described steps.
Hereafter, each process of the manufacturing method of the nanoparticle composite dispersion liquid of this invention is demonstrated.

[Step 1. Dispersion process]
First, the dispersion | distribution process which forms the nanoparticle dispersion of the process 1 of this invention is demonstrated. In this step, the first solvent has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II) as a dispersion stabilizer. Further, the block copolymer in which the amino group of the structural unit (1) and the organic acid compound having a polymerizable group represented by the following general formula (III) and / or the following general formula (IV) form a salt. This is a step of forming a nano fine particle dispersion by dispersing fine particles using a polymer.

［式（Ｉ）〜（ＩＶ）中、Ｒ^１は、水素原子又はメチル基、Ｒ^２及びＲ^２’は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、炭素数１〜８のアルキレン基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^３は、炭素数１〜１８のアルキル基、アラルキル基、アリール基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−Ｒ^８又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子、又はメチル基であり、Ｒ^８は、水素原子、あるいは炭素数１〜１８のアルキル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^１２で示される１価の基であり、Ｒ^１２は水素原子又は炭素数が１〜５のアルキル基である。
Ｒ^４及びＲ^４’は、それぞれ独立に水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^８、−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^８、又は−Ｏ−Ｒ^４’’で示される１価の基であり、Ｒ^４’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^８、又は−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^８で示される１価の基である。Ｒ^９及びＲ^１０は、それぞれ独立に水素原子、又はメチル基であり、Ｒ^８は水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２、又は−ＣＨ_２ＣＯＯＲ^１１で示される１価の基であり、Ｒ^１１は水素原子又は炭素数が１〜５のアルキル基である。但し、Ｒ^４及びＲ^４’のうちいずれかは、炭素数２〜１８のアルケニル基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^８、−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^８、又は−Ｏ−Ｒ^４’’で示される１価の基であり、且つ、Ｒ^４’’が、炭素数２〜１８のアルケニル基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^８、又は−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^８で示される１価の基、及び、Ｒ^８が、炭素数２〜１８のアルケニル基、−ＣＯ−ＣＨ＝ＣＨ_２、又は−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２である。
Ｒ^５は、炭素数２〜１８のアルケニル基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^８、−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^８、又は−Ｏ−Ｒ^５’で示される１価の基であり、且つ、Ｒ^５’が、炭素数２〜１８のアルケニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^８、又は−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^８で示される１価の基、及び、Ｒ^８が、炭素数２〜１８のアルケニル基、−ＣＯ−ＣＨ＝ＣＨ_２、又は−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２である。
ｘ及びａは１〜１８の整数、ｙ及びｂは１〜５の整数、ｚ及びｃは１〜１８の整数を示す。ｍ及びｎは１〜２００の整数を示す。］

[In Formulas (I) to (IV), R ¹ is a hydrogen atom or a methyl group, R ² and R ^{2 ′} are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - ₂ monovalent group represented by, ^{R 3} is 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 a monovalent group represented by — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or a monovalent group represented by _-CH 2 COOR ^{12, R 12} is a hydrogen atom or a carbon number of 1 to 5 alkyl groups.
R ⁴ and R ^{4 ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁹ ) —CH ( R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , or —O—R ^{4 ″} is a monovalent group, and R ^{4 ″} is An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , or — [(CH ₂ ) _b— O] is a monovalent group represented by _c— R ⁸ . R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, -CO-C (CH 3) = CH 2, or a monovalent group represented by _-CH 2 COOR ^{11, R 11} is a hydrogen atom or It is an alkyl group having 1 to 5 carbon atoms. However, any one of R ⁴ and R ^{4 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ or —O—R ^{4 ″} and R ^{4 ″} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , or _a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ⁸ , and R ⁸ has 2 to 18 carbon atoms An alkenyl group, —CO—CH═CH ₂ , or —CO—C (CH ₃ ) ═CH ₂ .
R ⁵ is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , or A monovalent group represented by —O—R ^{5 ′} , and R ^{5 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a — R ⁸ or a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ⁸ , and R ⁸ is an alkenyl group having 2 to 18 carbon atoms, —CO—CH═CH ₂ , or _{-CO-C (CH} 3) a = CH _2.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. ]

<Dispersion stabilizer>
The dispersion stabilizer used in the dispersion step of the present invention is the specific block copolymer. Hereinafter, the block copolymer used in the present invention will be described.
(Block copolymer)
The block copolymer in the present invention has the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II), and further includes the structural unit. A salt type block copolymer in which the amino group of (1) and the organic acid compound having a polymerizable group represented by the general formula (III) and / or the general formula (IV) form a salt. .

The block copolymer comprising the salt-type block copolymer has a structural unit (1) represented by the general formula (I) and a structural unit (2) represented by the general formula (II). Is.
In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² and R ^{2 '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 ^{2 ′} 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, 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, And various hexylene groups 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 general formula (II), R ³ 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, aralkyl group, and aryl group may have a substituent.
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. The alkyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, nitro groups, and hydroxyl groups.

Examples of the aryl group that 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. 7-15 are preferable and, as for carbon number of an aralkyl group, 7-12 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 ⁶ and R ⁷ are the same as above, and 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 a monovalent group represented by —CH ₂ COOR ¹² , and R ¹² 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 ³ above.
In the above R ³ , x, y, and z are as described in A above.
Moreover, R ³ in the structural unit (2) represented by the general formula (II) may be the same or different.

In the present invention, as R ³ , it is preferable to use those having excellent solubility in the first solvent and the second solvent described later, and specifically, the block copolymer is constituted. Depending on the structural unit to be used, when the first solvent and / or the second solvent is tetrahydrofuran, toluene, etc., it is preferable to use a methyl group, an ethyl group, a benzyl group, etc. When the one solvent and / or the second solvent 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 ³ in this way is that the structural unit (2) containing R ³ has solubility in the first solvent and the second solvent, and the structural unit ( The salt-forming site formed by the amino group of 1) and the organic acid compound described later has high adsorptivity to the fine particles, so that the dispersibility and stability of the fine particles are particularly excellent. Because it can.
Further, R ³ 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.

  The ratio m / n of the number of units m of the structural unit (1) and the number of units n of the structural unit (2) used in the present invention is preferably within the range of 0.01 to 1, preferably 0.05 to More preferably, it is in the range of 0.5. If the ratio m / n is within the above range, the ratio of the salt forming site formed by the amino group of the structural unit (1) is appropriate, so that the adsorptivity to fine particles described later is improved, and the structural unit ( The solubility in the first solvent and the second solvent according to 2) is not lowered, and the dispersibility and stability of the fine particles are not lowered.

In the block copolymer used in the present invention, the number of units m of the structural unit (1) and the number of units n of the structural unit (2) may be integers of 1 to 200, respectively, and are not particularly limited. m is preferably in the range of 2-50, and more preferably in the range of 5-30. Moreover, as said n, it is preferable to exist in the range of 20-100.
Further, the weight 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, the fine particles can be uniformly dispersed.

  The weight 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 polystyrene standards for calibration curves were 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 structural unit (1) and the structural unit (2) and can stably disperse fine particles described later. Although not limited, it is preferable that the structural unit (1) is bonded to only one end of the block copolymer. That is, the structural unit (1) and the structural unit (2) may be combined in the order of the structural unit (1) -the structural unit (2), or the structural unit (1) -the structural unit. (2) -the structural unit (1) may be combined in this order, the structural unit (2) -the structural unit (1) -the structural unit (2) may be combined, The structural unit (1) -structural unit (2) may be bonded repeatedly, but in the present invention, the structural unit (1) -structural unit (2) are preferably combined in this order. The reason is that it is excellent in the adsorptivity with respect to the fine particles to be described later, and further, aggregation of the fine particle dispersions using such a block copolymer can be effectively suppressed.

(Organic acid compound)
An amino group contained in the structural unit (1) of the block copolymer having the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II); The organic acid compound that forms a salt is a compound having a structure represented by the general formula (III) and the general formula (IV).
In the present invention, by using the organic acid compound, the dispersibility and stability of fine particles described later can be improved. Furthermore, by having a salt-forming site, for example, when the nanoparticle composite dispersion liquid of the present invention is applied to a color filter resist composition, it has high solubility in an alkaline aqueous solution during alkali development. , It can be excellent in alkali developability.

In the general formula (III), R ⁴ and R ^{4 ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [ A monovalent group represented by CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , or —O—R ^{4 ″;} There, the one of R ⁴ and R ^{4 ',} is a polymerizable group.
^{Incidentally, R} 4, R ^{4 'and} R ^4''is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, which may have a substituent .

The alkyl group having 1 to 18 carbon atoms is as indicated by the ^{R 3.}
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl, allyl, propenyl, various butenyl, various hexenyl, various octenyl, various decenyl, various dodecenyl, various tetradecenyl, various hexadecenyl, various octadecenyl, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that the alkenyl group has a double bond at the terminal.

R ^{4 ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R. ⁸ or a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ⁸ .
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group in R ^{4 ″} are as described for R ³ . In addition, the alkenyl group having 2 to 18 carbon atoms in the above R ^{4 ″} is as shown in the above R ⁴ and R ^{4 ′} .

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, benzyl group, phenyl group, biphenyl group, —CHO, —CH ₂ CHO. , —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , or a monovalent group represented by —CH ₂ COOR ¹¹ , R ¹¹ is a hydrogen atom or a carbon number of 1 to 5 A linear, branched, or cyclic alkyl group.
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 in R ⁸ is as described above for R ³ . The alkenyl group having 2 to 18 carbon atoms are as above indicated by ^{R 4} and R ^{4 '.}

In addition, since the organic acid compound of the formula (III) has a polymerizable group, any one of R ⁴ and R ^{4 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH ( R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , or a monovalent group represented by —O—R ^{4 ″} , and R ^{4 ″.} Is represented by an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , or — [(CH ₂ ) _b —O] _c —R ^8. A monovalent group and R ⁸ is an alkenyl group having 2 to 18 carbon atoms, —CO—CH═CH ₂ , or —CO—C (CH ₃ ) ═CH ₂ .
In the above R ⁴ , R ^{4 ′} and R ^{4 ″} , a is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and b is an integer of 1 to 5, preferably Is an integer of 1 to 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.

In the general formula (IV), R ⁵ represents an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —. O] _c -R ⁸ or -O-R ^{5 '} , and R ^5' is an alkenyl group having 2 to 18 carbon atoms,-[CH (R ⁹ ) -CH ( _{^{R 10) -O] a -R 8}} , or _{- [(CH 2) b -O} ] 1 monovalent group represented by c -R ^8, and, ^{R 8} is an alkenyl group having 2 to 18 carbon atoms, - CO-CH = CH _2, or _{-CO-C (CH} 3) a = CH _2.
The alkenyl group having 2 to 18 carbon atoms are as above indicated by ^{R 4} and R ^{4 '.} R ⁹ and R ¹⁰ are the same as described above.
In the above R ⁵ and R ⁵ ′, a, b, and c are as described above for R ⁴ , R ^{4 ′} , and R ^{4 ″} .

The organic acid compound having a polymerizable group represented by the above general formula (III) and general formula (IV) is R ⁴ and / or R ^{4 ′} , and R ⁵ is a polymerizable group, among which a vinyl group, An allyl group or — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , —O— [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , or —O — [(CH ₂ ) _b —O] _c —R ⁸ , and R ⁸ is —CO—CH═CH ₂ or —CO—C ( CH ₃ ) ═CH ₂ is preferable, and in particular, R ⁴ and / or R ^{4 ′} and R ⁵ are each independently a vinyl group, an allyl group, a 2-methacryloyloxyethyl group, a 2-acryloyloxyethyl group. Are preferred.

In the present invention, since R ⁴ and / or R ^{4 ′} and R ⁵ in the organic acid compound have a polymerizable group, the organic acid compound has a complex forming step described later after dispersing the fine particles. The polymerizable groups can be crosslinked in the vicinity of the fine particles. 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.
In addition, the organic acid compound which has a polymeric group represented by the said general formula (III) and general formula (IV) can be used individually by 1 type or in combination of 2 or more types.

  The content of the organic acid compound in the graft copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited, and is generally represented by the general formula (I). It is about 0.05-5.0 molar equivalent with respect to the amino group contained in the structural unit derived from a nitrogen-containing monomer, More preferably, it is preferable that it is 0.2-2.0 molar equivalent. In addition, when using together 2 or more types of the said organic acid compound, content which added these should just be in the said range.

(Production of salt type block copolymer)
In the present invention, the production method of the salt-type block copolymer includes the structural unit (1), the structural unit (2), the amino group of the structural unit (1), and the general There is no particular limitation as long as it is a method capable of producing a salt formed with an organic acid compound having a polymerizable group represented by the formula (III) and / or the following general formula (IV). 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 first solvent to be described later. It can manufacture by adding the said organic acid compound in a solvent and stirring.
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, the molecular weight, the molecular weight distribution, etc. can be easily set in a desired range, so that the properties such as dispersibility of the dispersant solution can be made uniform.

  The salt-type block copolymer in the dispersion may be used alone or in combination of two or more, and the content is appropriately selected according to the type of fine particles used. However, it is usually in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the fine particles described later. If the content of the salt type block copolymer is within the above range, the fine particles can be uniformly dispersed.

<First solvent>
The first solvent used in the present invention is a solvent used for dispersing at least fine particles in the step. The first solvent used in the present invention is not particularly limited as long as the structural unit (2) of the block copolymer is soluble, but is usually a non-aqueous medium, A less polar medium is used. Specifically, 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, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene Alkylene glycol alkyl ethers such as glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol monoethyl ether; diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether Dialkylene glycol alkyl ethers such as diethylene glycol alkyl ethers such as 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 Alkylene glycol alkyl ether acetates such as ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; acetone, Ketones such as tilethylketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Esters such as ethyl acetate, ethyl acetate, butyl acetate, and 3-methoxybutyl acetate; alkanes such as hexane and heptane, among others, diethylene glycols, alkylene glycol alkyl ethers, dialkylene glycol alkyl ethers, And alkylene glycol alkyl ether acetates, particularly ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol Noethyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monomethyl ether are preferred.

In addition, the first solvent used in this step preferably has an SP value (Solubility Parameter) that is a solubility index within a range of 7 to 12, more preferably within a range of 7 to 11. And those within the range of 9 to 10 are more preferred. If the SP value is within the above range, the salt formed by the amino group and the organic acid compound in the block copolymer is not dissociated, and the block copolymer in the first solvent is not dissociated. The coalescence does not dissolve completely. As a result, the property of selectively accumulating on the fine particle surface of the block copolymer, which will be described later, is not lowered.
Here, the SP value (unit: (J / m ³ ) ^1/2 ) is represented by the square root of the attractive force between the molecules, that is, the cohesive energy density CED (Cohensive Energy Density). Here, the definition of CED is the amount of energy (unit: J / m ³ ) required to evaporate a 1 cm ³ thing.

<Fine particles>
The fine particles used in the present invention are not particularly limited as long as they are insoluble in the first solvent and the second solvent. Examples of such fine particles include inorganic / organic pigments, 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).

<Other ingredients>
When forming the nano fine particle dispersion, a dispersion assisting resin and other components may be included as long as the effects of the present invention are not hindered. The additive is appropriately selected according to the use of the nanoparticle composite, and examples thereof include a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
The dispersion auxiliary resin is a resin having a function of assisting the dispersibility of the fine particles. For example, the steric hindrance of the dispersion assisting resin may make it difficult for the fine particles to come into contact with each other and may stabilize the dispersion, or may have the effect of reducing the block copolymer as a dispersion stabilizer due to the dispersion stabilization effect. As the dispersion auxiliary resin, any resin that does not contain a reactive group such as an epoxy group or a polymerizable group can be appropriately selected and used. Examples thereof include alkali-soluble resins.

<Formation of nanoparticle dispersion>
If necessary, a second solvent to be described later is added to the first solvent, and the fine particle is dispersed using the salt-type block copolymer that is the dispersion stabilizer. Form. The second solvent to be added to the first solvent as necessary, the dispersion stabilizer, and the fine particles may be added sequentially or simultaneously, and then the fine particles may be dispersed. A dispersion solution in which the dispersion stabilizer is uniformly dissolved or dispersed in the solvent is prepared, and then a second solvent, which will be described later, is added to the dispersant solution as necessary, and fine particles are added and dispersed. It is preferable. The method for preparing the dispersant solution is not particularly limited as long as the dispersion stabilizer can be uniformly dissolved or dispersed. For example, (i) the salt form in the first solvent. Method of dispersing after adding block copolymer, (ii) Dissolving polymer obtained by polymerizing structural unit (1) and structural unit (2) (first block copolymer) in first solvent Then, a method of forming a salt-type block copolymer by adding the organic acid compound and forming a salt, and the like can be mentioned.

  The nanoparticulate dispersion formed in step 1 is one in which block copolymers are accumulated on the surface of the fine particles in at least a first solvent. In the present invention, the structural unit (2) of the block copolymer is soluble in the first solvent, and the salt-forming site formed by the amino group and the organic acid compound contained in the structural unit (1) Since it is insoluble in the first solvent, the block copolymer can be selectively accumulated on the surface of the fine particles when the fine particles are added to the dispersant solution. Therefore, a nano fine particle dispersion having excellent fine particle dispersibility and stability is formed.

  The nano fine particle dispersion can be formed by dispersing fine particles 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 0.1 mm to 1.0 mm.

The average dispersed particle size of the nanoparticles in 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 in the range of 10 nm to 50 nm. Further preferred. 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.
In addition, the average dispersion particle diameter of the nano fine particles of the nano fine particle dispersion is a value measured by a laser scattering method. Specifically, the average particle diameter is measured by capturing and calculating scattered light obtained by applying a laser beam to the nanoparticle dispersion.

  The content of the fine particles in the dispersion step in the nano fine particle dispersion is not particularly limited as long as it can be uniformly dispersed in the first solvent and the second solvent added as necessary. Although it varies depending on the use, etc., it is preferably in the range of 1 to 60% by mass, more preferably in the range of 1 to 30% by mass, and in the range of 1 to 15% by mass. Is more preferable. When the content of the fine particles is within the above range, the fine particles can be uniformly dispersed.

[Step 2. Dilution process]
This step is a step of adding a second solvent having a boiling point different from that of the first solvent, and the fine particle concentration can be diluted by this step. Since the purpose is to lower the concentration of fine particles in the nano fine particle dispersion when the polymerizable groups in the composite forming step described later are cross-linked, the dilution step should be performed before the composite forming step described later. Is preferred. If it is before the complex formation step, the dilution step may be performed after the dispersion step of forming the nanoparticle dispersion or during the dispersion step of forming the nanoparticle dispersion. Furthermore, the dilution step may be performed both during the dispersion step of forming the nanoparticle dispersion and after the dispersion step of forming the nanoparticle dispersion.

The second solvent used in the present invention is appropriately selected from solvents having a boiling point different from that of the first solvent, and one of the first solvent and the second solvent has a lower boiling point. It is used to increase the concentration of fine particles after forming the nano-particle composite by distilling off the solvent. Therefore, the second solvent must be at least a solvent that does not interfere with the dispersibility of the fine particles, and it is preferable to use a solvent suitable for dispersing the fine particles in the same manner as the first solvent.
The second solvent used in the present invention is not particularly limited as long as the structural unit (2) of the block copolymer is soluble, but is usually a non-aqueous medium, A medium with low polarity is used, and it can be appropriately selected from those mentioned in the first solvent.

  The second solvent preferably has a boiling point different from that of the first solvent by 30 ° C. or more, more preferably 50 ° C. or more. If the difference in boiling point between the first solvent and the second solvent is too small, it may be difficult to stably distill off any of the solvents.

  Whether the first solvent or the second solvent is a lower boiling solvent, the amount of the first solvent and the second solvent used depends on the concentration of the nanoparticulate composite dispersion finally obtained, etc. It is selected appropriately. For example, when it is desired to make the concentration higher than the concentration suitable for forming the dispersion, the second solvent is used as the first solvent by using a low boiling point solvent rather than the second solvent. A small amount is added from the solvent, and the first solvent is distilled off in the concentration step described later. Also, for example, in the case of a slightly higher polarity solvent, the adsorptive power becomes weaker on the surface of the fine particles at the salt forming site, so by first dispersing in a low polarity solvent, immobilizing by polymerization, and then solvent replacement, A decrease in dispersion stability due to the detachment of the dispersant in the polar solvent can be suppressed.

  The degree to which the fine particle concentration is diluted by the dilution step varies depending on the content of the polymerizable group of the block copolymer, and is preferably selected as appropriate. For example, the concentration of fine particles in the nano fine particle dispersion when performing the complex forming step described below is preferably 10% by mass or less, and more preferably 8% by mass or less. In the case of such a fine particle concentration, gelation hardly occurs when the polymerizable group is reacted, and a good nano fine particle composite can be formed.

[Step 3. Complex formation process]
In this step, since the block copolymer can be fixed to the surface of the fine particles by reacting the polymerizable group in the block copolymer, it is excellent in dispersibility and stability compared to the nano fine particle dispersion. Nanoparticle composites can be formed.

In addition, since the block copolymer that forms the nanoparticle dispersion is selectively accumulated on the surface of the fine particles and exists so as to cover the entire surface of the fine particles, the particle size of the nanoparticle composite is reduced, In addition, reaggregation of the fine particles can be effectively prevented. From this, the nanoparticulate composite obtained in the present invention can be taken out of the composite dispersion, dried, and then redispersed in a solvent according to the application.
Further, in this step, the block copolymer is crosslinked to form a nanoparticle composite, and is not due to precipitation using the difference in solubility in the solvent. It is a stable composite without the polymer on the surface of the fine particles being peeled off due to the components to be combined, and it can be expected that the solvent resistance and heat resistance are improved.

In this step, examples of the method of reacting the polymerizable group in the block copolymer include a method of crosslinking by irradiation with light in the presence of a photoinitiator or heating in the presence of a thermal initiator. 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's 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 Arylimidazole 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- 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- Nzoyl-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-Methylphenol L) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl Examples include -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 organic acid compound of the salt-type block copolymer. More preferred is 0.05 molar equivalent. 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 is not lowered, so that a good strength of the nanoparticle composite can be obtained. It is done.

  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.

  The amount of the thermal initiator used in this step is preferably 0.0005 to 0.1 molar equivalents relative to the polymerizable group of the organic acid compound of the salt-type block copolymer, and is 0.001 to 0.05. A molar equivalent is more preferred. If the amount of the thermal initiator used is within the above range, it can be sufficiently cross-linked, and the molecular weight of the cross-linked salt type block copolymer will not be lowered, so that a good strength of the nanoparticulate composite can be obtained. It is done.

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

  When the concentration of the fine particles in the dispersion is high, this step is preferably performed while performing ultrasonic treatment. By performing ultrasonic treatment, gelation of the dispersion can be prevented, or even if 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. 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.

<Nanoparticulate complex>
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 composite can be measured in the same manner as the average particle size of the nanoparticle dispersion described above.

[Step 4. Concentration process]
This step is a step of concentrating the dispersion by distilling off the first solvent or the second solvent. The amount of the first solvent or the second solvent to be distilled depends on the concentration of the nanoparticle composite dispersion to be finally obtained and the use of the first solvent or the second solvent as described above. It adjusts by selecting suitably the kind and quantity of a solvent.
Examples of the method for distilling off the first solvent or the second solvent include atmospheric distillation, vacuum distillation, and the like, but since vacuum distillation can distill off the solvent at a low temperature, deterioration of fine particles due to high-temperature heating is prevented. This is preferable.

  By passing through the concentration step, it is possible to obtain a high-concentration nanoparticulate composite dispersion that could not be obtained because gelation occurred in the composite formation step. For example, the content of the nanoparticles in the nanoparticle composite dispersion can be set to 13% by mass or more.

As described above, the nanoparticulate composite dispersion 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 negative resist compositions used in the production of color filters having the function of color-displaying liquid crystal displays and pigments applied to inkjet inks.
When a nano-particle composite dispersion with a high concentration can be obtained, for example, printing inks, pigment inks for color filters, negative resists for color filters, and paints with higher pigment concentrations than before can be obtained. Color density can be obtained, and there are advantages such as improvement in productivity and widening of the ink design range.

  The present invention also provides a resin composition comprising a nanoparticle composite dispersion produced by the method for producing a nanoparticle composite dispersion according to the present invention and a resin. The resin composition can also be used in printing inks, medical materials, paints, recording materials, cosmetics, semiconductor substrates, negative resists for color filters, etc., which are fields in which nano-sized fine particles are required. . As the resin used in the resin composition, a known resin used in its application, such as a thermoplastic resin, a thermosetting resin, and a photocurable resin, can be appropriately selected and used.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same function and effect. Are included in the technical scope.

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

(Evaluation methods)
1. Measurement of Average Particle Size A storage stability test was performed in which the nanoparticle composite dispersions obtained in each of the examples and comparative examples were allowed to stand at 40 ° C. for 1 week. The average particle size of the nano-particle composite before and after the test was measured using “Microtrac particle size distribution analyzer UPA-EX150” manufactured by Nikkiso Co., Ltd. The measurement results are shown in Table 1.
2. Measurement of Shear Viscosity For the nanoparticle composite dispersions obtained in each of the Examples and Comparative Examples, the shear viscosity at shear rates of 6 rpm and 60 rpm before and after the storage stability test was “MCR301 (model name)” manufactured by Nippon Siebel Hegner. It measured using. Further, the thixotropic index (TI value) was calculated from the shear viscosity (shear rate: 6 rpm) / shear viscosity (shear rate: 60 rpm). These measured values and calculated values are shown in Table 1. The thixotropic index (TI value) is more stable as it is closer to 1, and it becomes unstable when it is larger than 1.

Production Example 1 Production of Block Copolymer Into a 500 mL round bottom 4-neck separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, digital thermometer, 300 parts by mass of tetrahydrofuran (THF) and initiator 2.68 parts by mass of dimethyl ketene methyltrimethylsilyl acetal was added through an addition funnel, and the nitrogen substitution was sufficiently performed. 0.40 parts by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe. As a first monomer, 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, Using an addition funnel, 20 parts by mass of benzyl methacrylate was added dropwise over 60 minutes. The temperature was kept below 40 ° C. by cooling the reaction flask with an ice bath. After 1 hour, 45 parts by mass of dimethylaminoethyl methacrylate as the second monomer 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 reprecipitated in hexane, purified by filtration 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.

Production Example 2 Preparation of Dispersant Solution A In a 300 mL round bottom flask, 10 parts by mass of the block copolymer prepared in Production Example 1 was added to 48.32 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as the first solvent. Dissolve and 2.08 parts by mass of dimethacryloyloxyethyl acid phosphate (“Eye ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd.), which is a salt-forming component, with respect to the DMAEMA unit of the block copolymer Equivalent), and stirred for 2 hours at a reaction temperature of 40 ° C. to prepare a dispersant solution A containing a salt-type block copolymer A having a solid content of 20% by mass.

Production Example 3 Preparation of Dispersant Solution B In a 300 mL round bottom flask, 10 parts by mass of the block copolymer prepared in Production Example 1 is dissolved in 45.44 parts by mass of PGMEA, which is the first solvent, and is a salt-forming component. 1.36 parts by mass of dimethacryloyloxyethyl acid phosphate (“Eye ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd.) (0.3 equivalent to the DMAEMA unit of the block copolymer) was added, and the reaction temperature was 40 ° C. The dispersion solution B containing the salt-type block copolymer B having a solid content of 20% by mass was prepared by stirring for 2 hours.

Production Example 4 Preparation of Dispersant Solution C Dispersant Solution C was prepared in the same manner as in Production Example 2 except that BCA was used instead of PGMEA in Production Example 2.

Example 1
(Production of nano fine particle dispersion A)
Dispersant solution A obtained in Production Example 2 15.6 parts by mass (solid content: 3.12 parts by mass), commercially available Pigment Red 242 (average primary particle size: 50 nm) 3.9 parts by mass, first 10.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent and 30 parts by mass of 2.0 mm zirconia beads are put into a mayonnaise bottle, and shaken with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour as pre-crushing, 30 parts by mass of the dispersion and 30 parts by mass of zirconia beads having a particle diameter of 0.1 mm are placed in a mayonnaise bin, and similarly dispersed for 3 hours using a paint shaker as the main crushing, and the fine particle concentration in the dispersion is 13 parts by mass. % Nano-particle dispersion A was obtained.

(Dilution of nanoparticle dispersion A)
15 parts by mass of methyl ethyl ketone (MEK) as a second solvent was added to 15 parts by mass of the nanoparticulate dispersion A obtained above, so that the concentration of fine particles in the nanoparticulate dispersion was 6.5% by mass, and diluted nano A fine particle dispersion (A-1) was obtained.

(Production of nanoparticulate composite A)
Into a 50 ml eggplant flask, 2,2′-azobis (4-methoxy-2,4-dimethyl) as an initiator with respect to 30 parts by mass of the diluted nanoparticle dispersion (A-1) obtained above. (Valeronitrile) (V-70: manufactured by Wako Pure Chemical Industries, Ltd.) 0.016 parts by mass and reacting at 50 ° C. for 6 hours while performing ultrasonic treatment, the nanoparticulate composite containing nanoparticulate composite A Dispersion A was obtained.

(Concentration of nanoparticle composite dispersion A)
Only the MEK was distilled off by performing vacuum distillation on the nanoparticle composite dispersion A obtained above. As a result, a nanoparticulate composite dispersion liquid A ′ having a fine particle concentration of 13 mass% in the dispersion liquid was obtained.

Example 2
(Production of nano fine particle dispersion B)
4.875 parts by mass of dispersant solution B obtained in Production Example 3 (solid content: 0.975 parts by mass), 1.95 parts by mass of Pigment Green 58 (average primary particle size: 30 nm) commercially available as fine particles, first 11.10 parts by mass of PGMEA as a solvent, 12.75 parts by mass of BCA as a second solvent, and 30 parts by mass of 2.0 mm zirconia beads are placed in a mayonnaise bottle, and 1 is used as a preliminary crush by a paint shaker (manufactured by Asada Tekko). Shake with time, and then add 30 parts by mass of the dispersion and 60 parts by mass of zirconia beads having a particle size of 0.1 mm into a mayonnaise bin, and similarly disperse in a paint shaker for 2 hours as the main crushing. Nanoparticle dispersion B having a fine particle concentration of 6.5% by mass was obtained.

(Production of nano-particle composite B)
In a 50 ml eggplant flask, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70) was used as an initiator with respect to 30 parts by mass of the nanoparticle dispersion B obtained above. : Manufactured by Wako Pure Chemical Industries, Ltd.) 0.008 parts by mass was added, and the mixture was reacted at 50 ° C. for 6 hours while performing ultrasonic treatment to obtain a nanoparticulate composite dispersion B containing nanoparticulate composite B.

(Concentration of nanoparticle composite dispersion B)
Only the PGMEA was distilled off by performing vacuum distillation on the nanoparticle composite dispersion B obtained above. As a result, a nanoparticle composite dispersion B ′ having a fine particle concentration of 13% by mass in the dispersion was obtained.

Example 3
(Production of nano fine particle dispersion C)
5.85 parts by mass of dispersant solution B obtained in Production Example 3 (solid content: 1.17 parts by mass), methyl methacrylate / cyclohexyl methacrylate / benzyl methacrylate / methacrylic acid (45/35/10 / 10) 1.56 parts by mass of a copolymer (molecular weight: 8000), 3.9 parts by mass of commercially available Pigment Green 58 (average primary particle size: 30 nm) as fine particles, 18.69 parts by mass of PGMEA as a first solvent, 2 Place 30 parts by mass of 0.0 mm zirconia beads in a mayonnaise bin, shake as a preliminary crushing with a paint shaker (manufactured by Asada Tekko) for 1 hour, and then 30 parts by mass of the dispersion and zirconia beads having a particle size of 0.1 mm 60 parts by mass is put into a mayonnaise bin, and similarly disintegrated in a paint shaker for 3 hours as the main crushing, and fine particles in the dispersion Concentration was obtained nanoparticulate dispersion C of 13 wt%.

(Dilution of nanoparticle dispersion C)
15 parts by mass of BCA as a second solvent is added to 15 parts by mass of the nanoparticulate dispersion C obtained above, so that the concentration of fine particles in the nanoparticulate dispersion is 6.5% by mass, and the diluted nanoparticulate dispersion is diluted. (C-1) was obtained.

(Production of nano fine particle composite C)
In a 50 ml eggplant flask, 2,2′-azobis (4-methoxy-2,4-dimethyl) as an initiator with respect to 30 parts by mass of the diluted nanoparticle dispersion (C-1) obtained above. 0.015 parts by mass of valeronitrile) was added and reacted at 50 ° C. for 6 hours while performing ultrasonic treatment to obtain a nanoparticulate composite dispersion C containing nanoparticulate composite A.

(Concentration of nanoparticle composite dispersion C)
Only PGMEA was distilled off by performing vacuum distillation on the nanoparticle composite dispersion C obtained above. As a result, a nanoparticulate composite dispersion C ′ having a fine particle concentration of 12.8% by mass in the dispersion was obtained.

Example 4
9.68 parts by mass of butyl carbitol (BCA) as a second solvent was added to 15 parts by mass of the nanoparticle dispersion C obtained in Example 3, and the concentration of the particles in the nanoparticle dispersion was 7.9% by mass. As a result, a diluted nanoparticle dispersion (C-2) was obtained. A nanoparticle composite dispersion D was obtained in the same manner as in Example 3 using the diluted nanoparticle dispersion (C-2). PGMEA was distilled off by performing vacuum distillation on the nanoparticle composite dispersion D.
As a result, a nanoparticle composite dispersion D ′ having a fine particle concentration of 14.7% by mass in the dispersion was obtained.

Example 5
7.52 parts by mass of butyl carbitol (BCA) as a second solvent was added to 15 parts by mass of the nanoparticle dispersion C obtained in Example 3, and the concentration of the particles in the nanoparticle dispersion was 8.66% by mass. As a result, a diluted nanoparticle dispersion (C-3) was obtained. Using the diluted nanoparticle dispersion (C-3), a nanoparticle composite dispersion E was obtained in the same manner as in Example 3. PGMEA was distilled off by performing vacuum distillation on the nanoparticle composite dispersion E. As a result, a nanoparticulate composite dispersion E ′ having a fine particle concentration of 17.5% by mass in the dispersion was obtained.

The boiling points of the solvents used above are as follows.
MEK: 79.5 ° C
PGMEA: 146 ° C
BCA: 246.8 ° C

Comparative Example 1
Using the nanoparticle dispersion A obtained in Example 1 (fine particle concentration in the nanoparticle dispersion is 13% by mass) without diluting, an initiator is added in the same manner as in Example 1 to form a nanoparticle composite. The reaction to obtain the body was performed. However, gelation occurred during the reaction, and a nanoparticle composite dispersion could not be obtained (Composite A ″).

Comparative Example 2
The nanoparticle dispersion A obtained in Example 1 (the concentration of fine particles in the nanoparticle dispersion was 13% by mass) was used.

Comparative Example 3
(Production of nano-particle dispersion B ′)
Dispersant solution C obtained in Production Example 4 (9.75 parts by mass (solid content: 1.95 parts by mass)), commercially available Pigment Green 58 (average primary particle size: 30 nm) as fine particles (3.9 parts by mass), and solvent as BCA16 .35 parts by weight, 30 parts by weight of 2.0 mm zirconia beads are put into a mayonnaise bin, shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a preliminary crush, and then 30 parts by weight of the dispersion and particle size 60 parts by mass of 0.1 mm zirconia beads are put into a mayonnaise bin, and similarly dispersed for 3 hours using a paint shaker as the main crushing, and a nano fine particle dispersion B ′ having a fine particle concentration of 13% by mass in the dispersion is obtained. Obtained.

Comparative Example 4
Using the nanoparticle dispersion B ′ obtained in Comparative Example 3 (fine particle concentration in the nanoparticle dispersion is 13% by mass) without dilution, an initiator was added in the same manner as in Example 2 to add nanoparticle particles. A reaction was performed to obtain the complex. However, gelation occurred during the reaction, and a nanoparticle composite dispersion could not be obtained (Composite B ″).

Comparative Example 5
(Production of nano fine particle dispersion C ′)
Dispersant solution C 5.85 parts by mass (solid content: 1.17 parts by mass) obtained in Production Example 4, methyl methacrylate / cyclohexyl methacrylate / benzyl methacrylate / methacrylic acid (45/35/10 / 10) 1.56 parts by mass of a copolymer (molecular weight: 8000), 3.9 parts by mass of commercially available Pigment Green 58 (average primary particle size: 30 nm) as fine particles, 18.69 parts by mass of BCA as a solvent, 2.0 mm zirconia 30 parts by weight of beads are put into a mayonnaise bin, shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as preliminary crushing, and then 30 parts by weight of the dispersion and 60 parts by weight of zirconia beads having a particle size of 0.1 mm In a mayonnaise bin, and similarly disperse in a paint shaker for 3 hours as the main crushing, and the fine particle concentration in the dispersion is 3 was obtained by mass% of the nanoparticulate dispersion C '.

Comparative Example 6
Using the nanoparticulate dispersion C ′ obtained in Comparative Example 5 (fine particle concentration in the nanoparticulate dispersion is 13% by mass) without dilution, an initiator was added in the same manner as in Example 3 to form nanoparticulates. A reaction was performed to obtain the complex. However, gelation occurred during the reaction, and a nanoparticle composite dispersion could not be obtained (Composite C ″).

The following can be seen from Table 1.
The composite dispersions obtained in Examples 1 to 3 were found to have a lower viscosity, a smaller average particle size, and better dispersibility than Comparative Examples 2, 3, and 5 having the same composition. . In Comparative Examples 1, 4 and 6, it was revealed that gelation occurs when complexing is performed at a high concentration without dilution. In addition, the results of Examples 3 to 5 revealed that even when the fine particle concentration was increased, the particle size did not change and the stability over time was good.

Claims (5)

The manufacturing method of the nanoparticle composite dispersion which has the following process 1-process 4.
Step 1. The first solvent has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II) as a dispersion stabilizer, A block copolymer in which the amino group of the structural unit (1) and the organic acid compound having a polymerizable group represented by the following general formula (III) and / or the following general formula (IV) form a salt is used. Dispersing step of forming a nanoparticle dispersion by dispersing the particles Step 2. 2. Dilution step of adding a second solvent having a boiling point different from that of the first solvent. 3. Complex formation step of reacting a polymerizable group in the block copolymer to form a nanoparticulate complex Step 4. A concentration step of concentrating the dispersion by distilling off the first solvent or the second solvent.

[In Formulas (I) to (IV), R ¹ is a hydrogen atom or a methyl group, R ² and R ^{2 ′} are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - ₂ monovalent group represented by, ^{R 3} is 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 a monovalent group represented by — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or a monovalent group represented by _-CH 2 COOR ^{12, R 12} is a hydrogen atom or a carbon number of 1 to 5 alkyl groups.
R ⁴ and R ^{4 ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁹ ) —CH ( R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , or —O—R ^{4 ″} is a monovalent group, and R ^{4 ″} is An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , or — [(CH ₂ ) _b— O] is a monovalent group represented by _c— R ⁸ . R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, -CO-C (CH 3) = CH 2, or a monovalent group represented by _-CH 2 COOR ^{11, R 11} is a hydrogen atom or It is an alkyl group having 1 to 5 carbon atoms. However, any one of R ⁴ and R ^{4 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ or —O—R ^{4 ″} and R ^{4 ″} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , or _a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ⁸ , and R ⁸ has 2 to 18 carbon atoms An alkenyl group, —CO—CH═CH ₂ , or —CO—C (CH ₃ ) ═CH ₂ .
R ⁵ is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ⁸ , — [(CH ₂ ) _b —O] _c —R ⁸ , or A monovalent group represented by —O—R ^{5 ′} , and R ^{5 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a — R ⁸ or a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ⁸ , and R ⁸ is an alkenyl group having 2 to 18 carbon atoms, —CO—CH═CH ₂ , or _{-CO-C (CH} 3) a = CH _2.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. ]   The manufacturing method of the nanoparticle composite dispersion liquid of Claim 1 which makes the density | concentration of the microparticles | fine-particles in a nanoparticle dispersion 10 mass% or less by the said dilution process.   The method for producing a nanoparticle composite dispersion according to claim 1 or 2, wherein the second solvent has a boiling point different from that of the first solvent by 30 ° C or more.   The method for producing a nanoparticle composite dispersion according to any one of claims 1 to 3, wherein an average particle diameter of the fine particles in Step 1 is in a range of 10 to 100 nm.   A resin composition comprising a nanoparticle composite dispersion produced by the method for producing a nanoparticle composite dispersion according to any one of claims 1 to 4 and a resin.