JP2010053172A - Method for preparing nano-particle composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for preparing a nano-particle composite that disperses nano-sized particles uniformly and stably, and keeps a mean particle diameter of the particles small as-dispersed. <P>SOLUTION: This method for preparing the nano-particle composite includes following step 1 and step 2. The step 1 is a dispersion step that forms a nano-particle dispersion by adding the particles into a dispersant solution which contains a block copolymer dissolved in a nonaqueous medium as a dispersion stabilizer. In the step 1, the block copolymer contains a structural unit (I) and a (meth)acrylate structural unit. Furthermore, in the block copolymer, an amino group of the structural unit (I) reacts with a specific organic phosphoric acid compound having a polymerizable group to form a salt. The step 2 is a crosslinking step that crosslinks the block copolymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

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 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.

JP-A-7-246329 JP-A-5-339516 JP-A-8-302227

  The present invention has been made under such circumstances, and is capable of uniformly and stably dispersing nano-sized fine particles, and producing a nano-particle composite capable of keeping the average particle size of the fine particles at the time of dispersion small. It is intended to provide a method.

  As a result of intensive studies to achieve the above object, the present inventors have obtained fine particles in a dispersant solution in which a block copolymer having a specific structure as a dispersion stabilizer is dissolved in a non-aqueous medium. It has been found that the above-mentioned problems can be solved by adding and crosslinking the block copolymer. The present invention has been completed based on such findings.

That is, the present invention
(1) A method for producing a nanoparticle composite having the following step 1 and step 2,
Step 1. In a non-aqueous medium, the dispersion stabilizer has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II), and Fine particles are added to a dispersant solution in which a block copolymer in which the amino group of the structural unit (1) and the organic phosphate compound having a polymerizable group represented by the following general formula (III) form a salt is dissolved. 1. Dispersion step of forming a nanoparticle dispersion by adding Crosslinking step of crosslinking the block copolymer

［式（Ｉ）〜（ＩＩＩ）中、Ｒ^１は、水素原子又はメチル基、Ｒ^２及びＲ^３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^４は、炭素数１〜１８のアルキル基、ベンジル基、フェニル基、ビフェニル基、−[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、ベンジル基、フェニル基、ビフェニル基、−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^５及びＲ^５’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、ベンジル基、フェニル基、ビフェニル基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]_ａ−Ｒ^１１、又は−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^１１、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^１１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、ベンジル基、フェニル基、ビフェニル基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２、又は−ＣＨ_２ＣＯＯＲ^１３で示される１価の基であり、Ｒ^１３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^５及びＲ^５’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^１１、又は−[（ＣＨ_２）_ｂ−Ｏ]_ｃ−Ｒ^１１で示される１価の基であり、且つ、Ｒ^１１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。］
（２）前記架橋工程が、３０〜１５０℃で行われるものである上記（１）に記載のナノ微粒子複合体の製造方法、
（３）前記有機リン酸化合物の前記重合性基が、(メタ)アクリロイル基、ビニル基、又はアリル基である上記（１）又は（２）に記載のナノ微粒子複合体の製造方法、及び
（４）前記微粒子の平均粒径が、１０〜１００ｎｍの範囲内である上記（１）〜（３）のいずれかに記載のナノ微粒子複合体の製造方法、
を提供するものである。

[In the formulas (I) to (III), 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 a carbon atom having 1 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 ) The divalent group represented by _y- , R ⁴ is an alkyl group having 1 to 18 carbon atoms, benzyl group, phenyl group, biphenyl 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, and R ⁸ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, —CHO, —CH. ₂ CHO or a monovalent group represented by —CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) A monovalent group represented by —CH (R ¹⁰ ) —O] _a —R ¹¹ or — [(CH ₂ ) _b —O] _c —R ¹¹ . R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, or a phenyl group. , Biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , or —CH ₂ COOR ¹³ , R ¹³ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, one of R ⁵ and R ^{5 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ , or — [(CH _{2 B—} O] _c —R ¹¹ and R ¹¹ is an alkenyl group having 2 to 18 carbon atoms, —CO—CH═CH ₂ , or —CO—C (CH _3). ) = 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. ]
(2) The method for producing a nanoparticle composite according to (1), wherein the crosslinking step is performed at 30 to 150 ° C.
(3) The method for producing a nanoparticle composite according to (1) or (2), wherein the polymerizable group of the organophosphate compound is a (meth) acryloyl group, a vinyl group, or an allyl group; 4) The method for producing a nanoparticle composite according to any one of (1) to (3), wherein the average particle diameter of the fine particles is in the range of 10 to 100 nm,
Is to provide.

  According to the production method of the present invention, it is possible to provide a nanoparticle composite that can uniformly and stably disperse nanosized particles and keep the average particle size of the dispersed particles small.

The method for producing a nanoparticulate composite according to the present invention comprises step 1: adding fine particles to a dispersant solution in which a block copolymer having a specific structure as a dispersion stabilizer is dissolved in a non-aqueous medium, thereby adding nanoparticulates. A dispersion step for forming a dispersion, and step 2: a crosslinking step for crosslinking the block copolymer.
Hereinafter, each process of the manufacturing method of the nanoparticle composite 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. This step has, in a non-aqueous medium, a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II). A block copolymer in which the amino group of the unit (1) and an organic phosphate compound having a polymerizable group represented by the following general formula (III) form a salt (hereinafter referred to as a salt type block copolymer). Is a step of forming a nano fine particle dispersion by adding fine particles to a dispersing agent solution in which the fine particles are dispersed.

[In the formulas (I) to (III), 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 a carbon atom having 1 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 ) The divalent group represented by _y- , R ⁴ is an alkyl group having 1 to 18 carbon atoms, benzyl group, phenyl group, biphenyl 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, and R ⁸ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl 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 ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) A monovalent group represented by —CH (R ¹⁰ ) —O] _a —R ¹¹ or — [(CH ₂ ) _b —O] _c —R ¹¹ . R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, or a phenyl group. , Biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , or —CH ₂ COOR ¹³ , R ¹³ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, one of R ⁵ and R ^{5 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ , or — [(CH _{2 B—} O] _c —R ¹¹ and R ¹¹ is an alkenyl group having 2 to 18 carbon atoms, —CO—CH═CH ₂ , or —CO—C (CH _3). ) = 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 this step, the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II) are included, and the structural unit (1) The structural unit that forms a salt-forming site by being a salt-type block copolymer in which an amino group having a salt and an organophosphate compound having a polymerizable group represented by the general formula (III) form a salt The adhesion to the fine particles of (1) is strengthened, while the structural unit (2) is soluble in the non-aqueous medium, so that the fine particles in the non-aqueous medium can be stabilized. The fine particles can be excellent in dispersibility and stability.
Hereinafter, this step will be described in detail.

(1) Dispersant solution The dispersant solution used in this step is a solution in which a block copolymer is dispersed or dissolved in a non-aqueous medium. Hereafter, each structure of such a dispersing agent solution is demonstrated.

<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 phosphate compound having a polymerizable group represented by the general formula (III) 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 said general formula (I), R < ¹ > shows a hydrogen atom or a methyl group, R < ² > and R < ³ > show a hydrogen atom or a C1-C8 alkyl group each independently. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include 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, 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, 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 ⁴ represents an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ^8. or - indicates a _{[(CH 2) y -O]} z -R 8. In the case where R ⁴ is an aromatic ring, suitable substituents on the aromatic ring, for example, may have such linear or branched alkyl group having 1 to 4 carbon atoms.
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.

R ⁶ and R ⁷ are the same as described above, and R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, benzyl group, phenyl group, biphenyl group, —CHO. , —CH ₂ CHO, or —CH ₂ COOR ¹² , 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 in R ⁸ is as described for R ⁴ above.
In the above R ⁴ , x, y and z are as described in A above.
Moreover, R ⁴ in the structural unit (2) represented by the general formula (II) may be the same or different.

In the present invention, as R ⁴ , it is preferable to use those having excellent solubility in the non-aqueous medium described later, and specifically, depending on the structural unit constituting the block copolymer, etc. Although it is different, when the non-aqueous medium is tetrahydrofuran, toluene or the like, it is preferable to use a methyl group, an ethyl group, a benzyl group or the like, and the non-aqueous medium has a lower polarity such as pentane or hexane. In this case, it is preferable to use a pentyl group, hexyl group, heptyl group or the like.
Here, the reason for setting the R ⁴ in this way is that the structural unit (2) containing the R ⁴ has solubility in the non-aqueous medium, and the amino group of the structural unit (1) will be described later. This is because the salt-forming site formed by the organic phosphate compound has a high adsorptivity to the fine particles, so that the dispersibility and stability of the fine particles can be made particularly excellent.
Further, R ⁴ 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 non-aqueous medium 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 1 to 20, and more preferably in the range of 1 to 10. Moreover, as said n, it is preferable to exist in the range of 20-100.
Furthermore, 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 phosphate 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 phosphate compound that forms a salt is a compound having a structure represented by the general formula (III).
In the present invention, by using the above organic phosphoric acid compound, the dispersant solution can be made excellent in the dispersibility and stability of the fine particles described later. Furthermore, since it has a salt-forming site, for example, when the nanoparticle composite of the present invention is applied to a color filter resist composition, it has high solubility in an aqueous alkali solution during alkali development. It can be excellent in developability.

In the general formula (III), R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, or a biphenyl group. ^{, - [CH (R 9)} -CH (R 10) -O] a -R 11 or _{- [(CH 2) b -O} ] indicates _c -R ^11, or the polymerization of ^{R 5} and R ^{5 '} It is a sex group. In addition, when R ⁵ and R ^{5 ′} have an aromatic ring, they may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms. Good.
Moreover, the organic phosphoric acid compound which has a polymeric group represented by the said general formula (III) can be used individually by 1 type or in combination of 2 or more types.

The alkyl group having 1 to 18 carbon atoms is as indicated by the ^{R 4.}
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, propenyl groups, various butenyl groups, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, and various octadecenyl groups. , Cyclopentenyl group, cyclohexenyl group, cyclooctenyl group and the like.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group. R ¹¹ 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 ¹³ , R ¹³ 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 ¹¹ , 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 ¹¹ is as described above for R ⁴ .
The alkenyl group having 2 to 18 carbon atoms in R ¹¹ is as described above for R ⁵ and R ^{5 ′} .

One of R ⁵ and R ^{5 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ^11, or — [(CH _{2 B—} O] _c —R ¹¹ and R ¹¹ is an alkenyl group having 2 to 18 carbon atoms, —CO—CH═CH ₂ , or —CO—C (CH _3). ) = CH ₂ .
In R ⁵ and R ^{5 ′} , 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 1 to 4. An integer, 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.

Organic phosphoric acid compound having a polymerizable group represented by the general formula (III) are either polymerizable group of R ⁵ and R ^{5 ',} inter alia a vinyl group, an allyl group or a - [CH ( R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ , or — [(CH ₂ ) _b —O] _c —R ¹¹ , and R ¹¹ is —CO—CH═CH ₂ or —CO Those having —C (CH ₃ ) ═CH ₂ are preferred, and those having a vinyl group, an allyl group, a 2-methacryloyloxyethyl group, and a 2-acryloyloxyethyl group are particularly preferred.

In the present invention, since R ⁵ and R ^{5 ′} in the organophosphate compound have a polymerizable group, after dispersing the fine particles, in the crosslinking step described later, the polymerizable groups of the organophosphate compound are separated from each other. Can be crosslinked in the vicinity of 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.

  The content of the organic phosphate compound in the block copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited, and is generally included in the structural unit (1). About 0.05-4.0 mol% with respect to an amino group, Preferably it is 0.1-2.0 mol%, More preferably, it is 0.2-1.0 mol%. In addition, when using 2 or more types of the said organic phosphoric acid compound together, content which totaled 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 phosphate compound having a polymerizable group represented by formula (III). 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, which will be described later, and then the non-aqueous medium. It can manufacture by adding the said organic phosphoric acid compound 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), may be 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 dispersant solution 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 below. If the content of the salt type block copolymer 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 the structural unit (2) of the block copolymer is soluble, but a medium having a relatively low polarity is usually 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, and 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 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. If the SP value is within the above range, the salt formed by the amino group and the organophosphate compound in the block copolymer does not dissociate, and the block copolymer in the non-aqueous medium. 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.

  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.

(Preparation of dispersant solution)
The method for preparing the dispersant solution used in the present invention is not particularly limited as long as it can uniformly dissolve or disperse the block copolymer in the non-aqueous medium. i) a method in which the block copolymer is added to the non-aqueous medium and then dispersed; (ii) the structural unit (1) and the structural unit (2) are added to the non-aqueous medium as described above. Examples include a method of forming a block copolymer by dissolving a polymerized product and then adding the organic phosphoric acid compound to form a salt.

(2) 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, 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 particles in the dispersant solution is not particularly limited as long as it can be uniformly dispersed in the non-aqueous medium, and varies depending on the use, but is within a range of 1 to 60% by mass. It is preferable that it is within the range of 1 to 30% by mass, and more preferably within 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.

(3) Nanoparticulate dispersion The nanoparticulate dispersion formed in step 1 is obtained by adding block copolymers to the surface of the fine particles by adding the fine particles to the dispersant solution. In the present invention, the structural unit (2) of the block copolymer is soluble in the non-aqueous medium, and the salt-forming site formed by the amino group and the organic phosphate compound contained in the structural unit (1) Since it is insoluble in the non-aqueous medium, 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 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 solvent, capturing the scattered light obtained by applying a laser beam to the dispersion solvent, and calculating the scattered light.

(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 0.1 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 block copolymer. In this step, since the block copolymer can be fixed on the surface of the fine particles, a nano fine particle composite excellent in dispersibility and stability can be formed as compared with the nano fine particle dispersion.
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 nanoparticle composite obtained in the present invention can be taken out from a non-aqueous medium, dried, and then redispersed in a solvent according to the application.
Furthermore, 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. Further, a process such as drying is unnecessary, and productivity can be improved.

In this step, examples of the method of crosslinking 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 amount of the photoinitiator used is preferably 0.0005 to 0.1 mol% with respect to the polymerizable group of the organic phosphate compound of the salt-type block copolymer, 0.05 mol% is more preferable. 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-dimethylvaleronitrile), 2, '-Azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide] 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propion Amide], 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 mol% with respect to the polymerizable group of the organic phosphate compound of the salt type block copolymer, and is 0.001 to 0.00. 05 mol% is more preferable. 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 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 negative resist compositions used in the production of color filters having the function of color-displaying liquid crystal displays.

  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 that exhibits the same effects. 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 a “Microtrac particle size distribution meter” 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 a shear rate of 6 rpm and 60 rpm before and after the above 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, 250 parts by mass of tetrahydrofuran (THF) and initiator 2.18 parts by mass of dimethyl ketene methyltrimethylsilyl acetal was added through an addition funnel, followed by sufficient nitrogen substitution. 0.3 parts by mass of a 1 mol / L acetonitrile solution of catalyst tetrabutylammonium m-chlorobenzoate was injected using a syringe, and 100 parts by mass of the first monomer methyl methacrylate was added over 60 minutes using an addition funnel. And dripped. The temperature was kept below 40 ° C. by cooling the reaction flask with an ice bath. After 1 hour, 12.5 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. The composition ratio MMA / DMAEMA mass ratio of methyl methacrylate (MMA) and dimethylaminoethyl methacrylate (DMAEMA) is 8/1, weight average molecular weight Mw: 8130, number average molecular weight Mn: 9760, molecular weight distribution Mw / Mn Was 1.20.

Production Example 2 Preparation of Dispersant Solution In a 300 mL round bottom flask, 10 parts by mass of the block copolymer prepared in Production Example 1 is dissolved in 43 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), which is a salt-forming component. 0.76 parts by mass of vinylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.0 equivalent to the DMAEMA unit of the block copolymer) was added, and the mixture was stirred at a reaction temperature of 40 ° C. for 2 hours to obtain a solid content. A dispersant solution containing 20% by mass of a salt-type block copolymer was prepared.

Example 1
(Production of nano fine particle dispersion A)
9 parts by mass (solid content: 1.8 parts by mass) of the dispersant solution obtained in Production Example 2, 3 parts by mass of commercially available pigment yellow 150 (average primary particle size: 50 nm), and propylene glycol monomethyl as a non-aqueous medium Put 18 parts by mass of ether acetate and 60 parts by mass of 2.0 mm zirconia beads in a mayonnaise bottle, shake as a preliminary crushing with a paint shaker (manufactured by Asada Iron Works) for 1 hour, and then 30 parts by mass of the dispersion and granules 60 parts by mass of zirconia beads having a diameter of 0.1 mm were placed in a mayonnaise bin, and similarly disintegrated for 4 hours using a paint shaker to obtain nanoparticle dispersion A.

(Production of nanoparticulate composite A)
Into a 50 ml screw tube, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70: Jun Wako) as an initiator with respect to 20 parts by mass of the nanoparticle dispersion A obtained above. 0.016 parts by mass) (manufactured by Yakuhin Co., Ltd.) was added, and the mixture was reacted at 50 ° C. for 6 hours while performing ultrasonic treatment to obtain a nanoparticulate composite dispersion A containing nanoparticulate composite A.

Example 2
In Example 1, a nanoparticulate composite dispersion B containing nanoparticulate composite B was obtained in the same manner as in Example 1 except that the commercially available pigment red 242 (average primary particle size: 70 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 green 58 (average primary particle size: 30 nm) was used.

Comparative Examples 1-3
Dispersions containing nanoparticle dispersions A to C in Examples 1 to 3 were referred to as Comparative Examples 1 to 3, respectively.

Example 4
A mixture of the nanoparticulate composite dispersion A obtained in Example 1 and the nanoparticulate composite dispersion C obtained in Example 3 in a ratio of 3: 7 (mass ratio) was used as a nanoparticulate composite dispersion D. It was. Table 2 shows the results of the above evaluation on the obtained nanoparticulate composite dispersion D.

Comparative Example 4
Nanoparticle dispersion liquid D was prepared by mixing nanoparticle dispersion liquid A obtained in Comparative Example 1 and nanoparticle dispersion liquid C obtained in Comparative Example 3 at a ratio of 3: 7 (mass ratio). Table 2 shows the results of the above-described evaluation of the resulting nanoparticle dispersion D.

  From Table 1, Examples 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 3 and Comparative Example 3 were compared with Examples in which nanoparticle composites were formed. It was shown to be excellent in all the results before and after the storage stability test. Furthermore, in Comparative Examples 1 and 2, the fine particles were aggregated. Further, from the comparison between Example 4 and Comparative Example 4 in which colors were mixed, Example 4 in which the nanoparticle composite was formed also had a smaller average particle size and before and after the storage stability test even when colors were mixed. Both results were excellent, and in Comparative Example 4, the fine particles were aggregated.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide 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.

Claims (4)

The manufacturing method of the nanoparticle composite_body | complex which has the following process 1 and process 2. FIG.
Step 1. In a non-aqueous medium, the dispersion stabilizer has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II), and Fine particles are added to a dispersant solution in which a block copolymer in which the amino group of the structural unit (1) and the organic phosphate compound having a polymerizable group represented by the following general formula (III) form a salt is dissolved. 1. Dispersion step of forming a nanoparticle dispersion by adding step 2. Crosslinking step of crosslinking the block copolymer

[In the formulas (I) to (III), 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 a carbon atom having 1 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 ) The divalent group represented by _y- , R ⁴ is an alkyl group having 1 to 18 carbon atoms, benzyl group, phenyl group, biphenyl 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, a benzyl group, a phenyl group, a biphenyl group, —CHO, —CH. ₂ CHO or a monovalent group represented by —CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) It is a monovalent group represented by —CH (R ¹⁰ ) —O] _a —R ¹¹ or — [(CH ₂ ) _b —O] _c —R ¹¹ . R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, or a phenyl group. , Biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , or —CH ₂ COOR ¹³ , R ¹³ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, one of R ⁵ and R ^{5 ′} is an alkenyl group having 2 to 18 carbon atoms, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ , or — [(CH _{2 B—} O] _c —R ¹¹ and R ¹¹ is an alkenyl group having 2 to 18 carbon atoms, —CO—CH═CH ₂ , or —CO—C (CH _3). ) is 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 method for producing a nanoparticle composite according to claim 1, wherein the crosslinking step is performed at 30 to 150 ° C.   The method for producing a nanoparticle composite according to claim 1 or 2, wherein the polymerizable group of the organophosphate compound is a (meth) acryloyl group, a vinyl group, or an allyl group.   The method for producing a nanoparticle composite according to any one of claims 1 to 3, wherein an average particle diameter of the fine particles is within a range of 10 to 100 nm.