JP2006281099A - Method for preparing fine particle of inorganic oxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a fine particle of an inorganic oxide, which has high dispersibility in an organic solvent and high affinity with an organic polymer for forming a thin film. <P>SOLUTION: The fine particle of the inorganic oxide, which has the particle size of 5 nm to 1 μm, is prepared by subjecting a precursor of the inorganic oxide to hydrolysis and condensation reactions in a w/o type emulsion prepared by emulsifying a water phase in an oil phase and dissolving a cationic surfactant in the oil phase. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing inorganic oxide fine particles. Furthermore, the present invention relates to an inorganic oxide fine particle and an antireflection film formed using the inorganic oxide fine particle.

The optical film is used for various purposes (for example, as a polarization film, an optical compensation film, and a phase difference film) in an image display device (for example, a liquid crystal display device).
Antireflection films are used in a wide range of fields for the purpose of reducing reflectivity using the principle of optical interference. Since the antireflection film is disposed on the outermost surface of the display, high scratch resistance is required. The antireflection film is generally required to have a film thickness of 1 μm or less. In order to realize high scratch resistance at a film thickness of 1 μm or less, it is necessary to have strength of the film itself and adhesion to a layer provided below.

The method of blending fine particles to improve the scratch resistance, the strength of the cured product, and the adhesion with other materials that are in contact is not limited to the antireflection film, but other technical fields (for example, adhesives, exterior paints, Hard coats) are also widely known. In order to improve the scratch resistance and the strength of the cured product, inorganic fine particles having higher hardness than organic fine particles are preferably used. On the other hand, the antireflection film is generally composed of an organic material.
When blending inorganic fine particles in an organic material, it is necessary that the inorganic fine particles do not cause unnecessary aggregation. In general, a method is adopted in which inorganic fine particles are dispersed in a solvent having affinity for the organic material and then mixed with the organic material. In order to produce an antireflection film with stable performance, it is important to stably disperse inorganic fine particles in an organic material.

As inorganic fine particles, alkoxysilanes containing a polymerization group or hydrolysis condensates thereof have attracted attention. Specifically, production of particles by using a specific polyalkoxypolysiloxane and a polymerizable silane coupling agent in combination has been proposed (for example, see Patent Document 1). However, it is difficult to sufficiently advance the reaction between the polyalkoxypolysiloxane and the polymerizable silane coupling agent. When the reaction is insufficient, the introduction rate of the polymerizable group is lowered, and the scratch resistance and strength of the cured product are insufficient.
Moreover, the partial cohydrolysis condensate of the alkoxysilane and tetraalkoxysilane containing an organic functional group is reported (for example, refer patent document 2). However, the storage stability of the liquid was not sufficient.
As described above, according to the conventional technique, the scratch resistance and strength of the film or the storage stability of the liquid are insufficient, and further improvement has been demanded.

  On the other hand, the antireflective film is required to have a low refractive index. As a method for reducing the refractive index by mixing inorganic fine particles with an organic material, a method using hollow silica fine particles is disclosed (for example, see Patent Document 3). The hollow silica fine particles are likely to aggregate similarly to the non-hollow silica fine particles, and it has been difficult to obtain a uniform dispersion or a uniform coating surface.

The main cause of the poor efficiency of the surface modification method of the inorganic oxide fine particles is that the hydroxyl group as a reaction point hardly remains on the surface of the inorganic oxide due to the condensation reaction. Therefore, when the inorganic oxide fine particles are produced by the sol-gel reaction, cationic organic molecules are added to the reaction system, and the negatively charged reaction intermediate inorganic hydroxide and cationic organic molecules are positive. A method for producing an inorganic oxide whose outer surface is modified with an organic molecule by using electrostatic interaction with a strong charge can be considered.
Specifically, by hydrolyzing and condensing tetraethoxysilane, which is an inorganic oxide precursor, in the presence of quaternary ammonium, which is a cationic organic molecule, the organic molecule and silica are strongly affected by electrostatic interaction. It has been proposed to produce bonded composite materials (see, for example, Patent Document 4).

  By the same method, a method for producing silica fine particles to which organic molecules are bonded is disclosed (for example, see Non-Patent Documents 1 and 2). More specifically, tetraalkoxysilane is hydrolyzed and condensed in an aqueous solution in the presence of a cationic surfactant (eg, didodecyldimethylammonium bromide) to produce silica fine particles to which organic molecules are bonded. Although hollow silica fine particles can be obtained by these production methods, since the reaction is carried out in water, the cationic surfactant only binds to the inside of the hollow particles, and the outer surface of the silica fine particles is not modified. Dispersibility in organic solvents and organic materials was not improved. Further, in the aqueous solution, since the cationic surfactant of the disclosed example forms a vesicle having a particle size of several hundred nm, the particle size of the obtained particle is also several hundred nm, and the low refractive index layer of the antireflection film Could not be used.

JP-A-9-169847 Japanese Patent Laid-Open No. 9-40909 JP 2001-233611 A US Pat. No. 5,366,945 Langmuir, 9, (1993), 673-680 Adv. Mater., 12, (2000), 1286-1290

An object of the present invention is to provide a method for producing inorganic oxide fine particles having high dispersibility in an organic solvent and high affinity with an organic polymer for forming a thin film.
Another object of the present invention is to provide an antireflection film having excellent scratch resistance using a coating composition containing inorganic oxide fine particles.
Another object of the present invention is to provide an antireflection film having sufficient antireflection performance and excellent scratch resistance by imparting a hollow structure to inorganic oxide fine particles.

The object of the present invention has been achieved by the following means.
(1) By a reaction in which an inorganic oxide precursor is hydrolyzed and condensed in a W / O type emulsion in which an aqueous phase is emulsified in an oil phase and a cationic surfactant is dissolved in the oil phase. And a method for producing inorganic oxide fine particles comprising a step of producing inorganic oxide fine particles having a particle diameter of 5 nm to 1 μm.

(2) The production method according to (1), wherein the inorganic oxide is an oxide of silicon, titanium, zirconium or aluminum.
(3) The production method according to (2), wherein the precursor of the inorganic oxide is an alkoxide or carboxylate of silicon, titanium, zirconium or aluminum.
(4) The production method according to (1), wherein an acid or a base is used as a catalyst in the reaction of hydrolyzing and condensing the inorganic oxide precursor.
(5) The production method according to (1), wherein the cationic surfactant is represented by the following formula (I).

[Wherein, R ¹ and R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms; R ² and R ⁵ each independently represent 1 carbon atom. R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms; A substituted alkyl group having 1 to 20 carbon atoms; L ¹ , L ² and L ³ are each independently a single bond or an alkylene group having 1 to 5 carbon atoms, and having 6 to 20 carbon atoms; A divalent linking group selected from the group consisting of an arylene group, -O-, -S-, -CO-, -NR- and combinations thereof, wherein R is a hydrogen atom or a carbon atom number of 1 to 5 An alkyl group; X ¹ is an anion].

(6) The production method according to (1), wherein the cationic surfactant is represented by the following formula (II):
^{(II) + N (-R 11} ) (- R 12) (- R 13) (- R 14) · X 11
[Wherein, R ¹¹ and R ¹² are each independently an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group having 1 to 20 carbon atoms; and R ¹³ and R ¹⁴ are carbon atoms. Is an alkyl group having 4 to 20 carbon atoms or a substituted alkyl group having 4 to 20 carbon atoms, and the alkyl group or the alkyl portion of the substituted alkyl group has at least one branch, or the substituted alkyl group is a carbon other than the terminal. Substituted at the atom by an alkoxy group; X ¹¹ is an anion].

(7) The production method according to (1), wherein the produced inorganic oxide fine particles have a hollow structure.
(8) Inorganic oxide fine particles obtained by the production method according to any one of (1) to (7).
(9) A composition containing the inorganic oxide fine particles according to (8).
(10) An optical film comprising the composition according to (9).
(11) The optical film as described in (10), which has an antireflection function.

  As a result of the present inventors, an inorganic oxide whose outer surface is modified with organic molecules by hydrolyzing and condensing an inorganic oxide precursor using a water phase in a reverse micelle prepared from a cationic surfactant as a reaction field. It has been found that fine particles can be produced. The inorganic oxide fine particles produced as described above have high dispersibility in an organic solvent. In addition, a hollow structure can be imparted to the fine particles by reducing the amount of the inorganic oxide precursor added during the reaction.

  The inorganic oxide fine particles obtained by the production method of the present invention have improved dispersibility in an organic solvent because the outer surface is modified with a cationic surfactant added during production. Therefore, the coating composition containing the inorganic oxide fine particle dispersion produced according to the present invention is excellent in dispersion stability. An optical film formed using this coating composition has high scratch resistance. When the hollow structure inorganic oxide fine particles produced according to the present invention are used, an antireflection film having a high scratch resistance and a low refractive index can be obtained.

In the present invention, a W / O emulsion in which an aqueous phase is emulsified in an oil phase and a cationic surfactant is dissolved in the oil phase is prepared, and the inorganic oxide precursor is hydrolyzed in the emulsion. Inorganic oxide fine particles are produced by a reaction of decomposition and condensation.
In the W / O type emulsion, the oil phase (O) is a continuous phase and the water phase (W) is a discontinuous phase.
The oil phase consists of a low polarity organic solvent that is immiscible with water. The aqueous phase consists of water or an aqueous solution of optional additives.

Since the cationic surfactant is dissolved in the oil phase, in the W / O type emulsion, reverse micelles of the cationic surfactant are formed in the aqueous phase. By hydrolyzing and condensing the inorganic oxide precursor in the aqueous phase in the reverse micelle, fine inorganic oxide particles whose outer surface is coated with a cationic surfactant can be produced. In the hydrolysis and condensation reaction, it is preferable to use an acid or a base as a catalyst.
Since the inorganic hydroxide, which is a hydrolysis product of the inorganic oxide precursor, has a negative charge in water, it strongly binds to the positive charge of the cationic surfactant due to electrostatic interaction, and from the oil-water interface. The condensation reaction of the inorganic hydroxide proceeds preferentially. When the amount of the inorganic oxide precursor added is small, hollow structure particles can be obtained. When the amount of the inorganic oxide precursor added is large, particles having a non-hollow structure are obtained.

[Cationic surfactant]
The cationic surfactant is preferably a surfactant having ammonium ions as cations. The ammonium ion is preferably a quaternary ammonium ion.
The hydrophobic group of the cationic surfactant is preferably a hydrocarbon group, more preferably an aliphatic group, and most preferably an alkyl group.
The counter anion of the cationic surfactant is preferably a halide ion, aliphatic sulfonate ion, aromatic sulfonate ion, monoalkyl sulfate ion, carboxylate ion, PF ₆ ⁻ , BF ₄ ⁻ or ClO ₄ ⁻ .

  The cationic surfactant is preferably represented by the following formula (I) or (II).

In the formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, a halogen atom (F, Cl, Br, I) or an alkyl group having 1 to 20 carbon atoms.
The alkyl group preferably has a chain structure rather than a cyclic structure. The chain alkyl group may have a branch. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and most preferably 1 to 3 (methyl, ethyl, propyl, isopropyl).
R ¹ and R ⁶ are particularly preferably a hydrogen atom.

In the formula (I), R ² and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. R ² and R ⁵ are preferably each independently an alkyl group having 1 to 20 carbon atoms.
The alkyl group preferably has a chain structure rather than a cyclic structure. The chain alkyl group may have a branch. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and most preferably 1 to 3 (methyl, ethyl, propyl, isopropyl).
The alkoxy group preferably has a chain structure rather than a cyclic structure. The chain alkoxy group may have a branch. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6, and most preferably 1 to 3 (methoxy, ethoxy, propoxy, isopropoxy).

In formula (I), R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group having 1 to 20 carbon atoms. . R ³ and R ⁴ are preferably each independently an alkyl group having 3 to 10 carbon atoms or a substituted alkyl group having 3 to 10 carbon atoms. R ⁷ , R ⁸ and R ⁹ are each independently preferably an alkyl group having 1 to 3 carbon atoms or a substituted alkyl group having 1 to 3 carbon atoms.
The alkyl group preferably has a chain structure rather than a cyclic structure. The chain alkyl group may have a branch. The number of carbon atoms of the alkyl group represented by R ³ and R ⁴ is preferably 1 to 15, more preferably 2 to 12, and most preferably 3 to 10. The alkyl group represented by R ⁷ , R ⁸ and R ⁹ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 (methyl, ethyl, propyl, isopropyl). ) Is most preferred.

  The alkyl part of the substituted alkyl group is the same as the above alkyl group. Examples of the substituent of the substituted alkyl group are halogen atom, aryl group, acyl group, carboxyl, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl, substituted carbamoyl group, cyano, alkoxy group, aryloxy group, hydroxyl, acyloxy group, Alkylsulfonyloxy group, arylsulfonyloxy group, amino, substituted amino group, amide group, sulfonamido group, ureido, substituted ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, nitro group, alkylthio group, arylthio group, alkyl Including sulfonyl group, arylsulfonyl group, sulfamoyl, substituted sulfamoyl group, sulfo and heterocyclic group.

The substituted part of the substituted carbamoyl group, substituted amino group, substituted ureido group and substituted sulfamoyl group is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.
The substituent of the substituted alkyl group is preferably a halogen atom (F, Cl, Br, I), aryl group, carboxyl, hydroxyl, amino, substituted amino group and acyloxy group (eg, methacryloyloxy, acryloyloxy), carboxyl, hydroxyl More preferred are amino, substituted amino group, methacryloyloxy and acryloyloxy.

In formula (I), L ¹ , L ² and L ³ are each independently a single bond or an alkylene group having 1 to 5 carbon atoms, an arylene group having 6 to 20 carbon atoms, —O—, — It is a divalent linking group selected from the group consisting of S-, -CO-, -NR- and combinations thereof. L ¹ , L ² and L ³ are each independently ^two bonds selected from the group consisting of a single bond or an alkylene group having 1 to 5 carbon atoms, —O—, —CO—, —NR— and combinations thereof. A valent linking group is preferred. R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The alkylene group preferably has a chain structure rather than a cyclic structure. The chain alkylene group is preferably a linear alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 4, and more preferably 1 to 3. A straight-chain alkylene group having 1 to 3 carbon atoms (methylene, dimethylene, trimethylene) is particularly preferable.
The arylene group is preferably phenylene or naphthylene, and more preferably phenylene.
The alkyl group preferably has a chain structure rather than a cyclic structure. The chain alkyl group may have a branch. The alkyl group preferably has 1 to 4 carbon atoms, and most preferably 1 to 3 (methyl, ethyl, propyl, isopropyl).

  Below, the example of the bivalent coupling group which consists of a combination is shown. In the following example, left and right may be reversed. AL is an alkylene group.

L11: -CO-O-
L12: -CO-O-AL-
L13: -AL-CO-O-
L14: -AL-CO-O-AL-
L15: -CO-NR-
L16: -CO-NR-AL-
L17: -AL-CO-NR-
L18: -AL-CO-NR-AL-
L19: -NR-CO-NR-

L20: -NR-CO-NR-AL-
L21: -AL-NR-CO-NR-AL-
L22: -O-CO-NR-
L23: -O-CO-NR-AL-
L24: -AL-O-CO-NR-
L25: -AL-O-CO-NR-AL-
L26: -CO-O-CO-
L27: -CO-O-CO-AL-
L28: -AL-CO-O-CO-AL-

In the formula (I), X ¹ is an anion. Examples of anions include halide ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), aliphatic sulfonate ions, aromatic sulfonate ions, monoalkyl sulfate ions, carboxylate ions, PF ₆ ⁻ , BF ₄ ^−. , ClO ₄ ^- including the. The anion is preferably Br ⁻ , I ⁻ , p-toluenesulfonic acid ion, CH ₃ COO ⁻ , PF ₆ ⁻ , BF ₄ ⁻ or ClO ₄ ⁻ , and Br ⁻ , I ⁻ or p-toluenesulfonic acid. More preferably, it is an ion.

  Examples of the cationic surfactant represented by the formula (I) are shown below.

Table A (Part 1)
────────────────────────────────────────
Compound n p q r s R ⁸ R ¹ = R ⁶ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
A-1 0 0 1 1 1 Methyl H Ethyl Butyl Br
A-2 0 0 1 1 1 Methyl H Ethyl Butyl I
A-3 0 0 1 2 2 * 1 H Methyl * 2 Br
A-4 0 0 2 1 1 Methyl H Ethyl Butyl Br
A-5 0 0 2 2 2 Methyl H Methyl isohexyl Br
A-6 0 0 2 2 2 Ethyl H Methyl * 3 Cl
A-7 0 0 3 1 1 Methyl H Ethyl Butyl Br
A-8 0 0 3 1 1 Methyl H Methyl * 3 Br
A-9 0 0 3 2 2 * 4 H Ethoxypropyl PF ₆
A-10 0 1 2 1 1 Methyl H Ethyl Butyl Br
A-11 0 1 2 0 0 Methyl H Methyl * 5 Br
A-12 0 1 2 1 1 Propyl H Propylpropyl * 6
A-13 0 1 1 1 1 Methyl H Ethyl Butyl Br
A-14 0 1 1 2 2 Methyl H Methyl isohexyl Br
A-15 0 1 1 2 2 Ethyl H Methyl * 3 ClO ₄
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 2: 4-ethoxy-4-methylpentyl * 3: 2,2-dimethylpropyl * 4: 2-acryloyloxyethyl * 5: 4-acryloyloxybutyl * 6: 2,2, 2-trifluoroethanesulfonic acid

Table A (Part 2)
────────────────────────────────────────
Compound n p q r s R ⁸ R ¹ = R ⁶ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
A-16 1 0 1 1 1 Methyl H Ethyl Butyl Br
A-17 1 0 1 1 1 Methyl H Ethyl Butyl I
A-18 1 0 1 1 1 * 1 H Methyl * 3 I
A-19 2 0 1 1 1 Methyl H Ethyl Butyl Br
A-20 2 0 1 0 0 Methyl H ethyl pentyl acetate A-21 2 0 1 0 0 * 7 H propyl hexyl BF ₄
A-22 3 0 1 1 1 Methyl H Ethyl Butyl Br
A-23 3 0 1 1 1 Methyl H Propyl Prop Br
A-24 3 0 1 2 2 * 4 H methyl isohexyl * 8
A-25 4 0 1 1 1 Methyl H Ethyl Butyl Br
A-26 4 0 1 3 3 Methyl Br Methyl Methyl Br
A-27 4 0 1 1 1 Ethyl H Methyl * 3 * 9
A-28 5 0 1 1 1 Methyl H Ethyl Butyl Br
A-29 5 0 1 0 0 * 1 H ethyl pentyl F
A-30 5 0 1 0 0 * 4 H propyl hexyl ClO ₄
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 3: 2,2-dimethylpropyl * 4: 2-acryloyloxyethyl * 7: 2-methacryloyloxyethyl * 8: p-toluenesulfonic acid * 9: monomethylsulfuric acid

Table B (Part 1)
────────────────────────────────────────
Compound mn p q rs R ⁸ R ¹ = R ⁶ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
B-1 1 0 0 1 1 1 Methyl H Ethyl Butyl Br
B-2 2 0 0 1 2 2 Methyl H Methyl isohexyl Br
B-3 3 0 0 1 2 2 * 1 H methyl * 3 Br
B-4 4 0 0 1 1 1 Ethyl H Methyl * 3 I
B-5 5 0 0 1 0 0 Propyl H ethyl pentyl * 8
B-6 1 0 0 2 1 1 Methyl H Ethyl Butyl Br
B-7 2 0 0 2 1 1 Methyl H propyl propyl Br
B-8 3 0 0 2 2 2 Ethyl H Methyl Isohexyl Acetic acid B-9 4 0 0 2 2 2 * 1 H Methyl * 3 Cl
B-10 5 0 0 2 2 2 * 4 H methyl * 2 * 6
B-11 1 0 0 3 1 1 Methyl H Ethyl Butyl Br
B-12 2 0 0 3 1 1 Methyl H propyl propyl Br
B-13 3 0 0 3 2 2 Ethyl H Methyl isohexyl * 10
B-14 1 0 1 2 1 1 Methyl H Ethyl Butyl Br
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 2: 4-ethoxy-4-methylpentyl * 3: 2,2-dimethylpropyl * 4: 2-acryloyloxyethyl * 6: 2,2,2-trifluoroethanesulfonic acid * 8: p-toluenesulfonic acid * 10: trifluoromethanesulfonic acid

Table B (Part 2)
────────────────────────────────────────
Compound mn p q rs R ⁸ R ¹ = R ⁶ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
B-15 2 0 1 2 2 2 * 1 H methyl * 3 Br
B-16 3 0 1 2 1 1 Ethyl H Methyl * 3 BF ₄
B-17 1 0 1 1 1 1 Methyl H Ethyl Butyl Br
B-18 2 0 1 1 0 0 * 1 H ethyl pentyl Br
B-19 3 0 1 1 0 0 Ethyl H Propylhexyl * 9
B-20 1 1 0 1 1 1 Methyl H Ethyl Butyl Br
B-21 2 1 0 1 0 0 Methyl H Methyl * 5 Br
B-22 3 1 0 1 2 2 * 1 H methyl * 3 Br
B-23 4 1 0 1 1 1 Ethyl H Methyl * 3 F
B-24 5 1 0 1 2 2 Propyl H Ethoxypropyl ClO ₄
B-25 1 2 0 1 1 1 Methyl H Ethyl Butyl Br
B-26 2 2 0 1 3 3 Methyl Br Methyl Methyl Br
B-27 3 2 0 1 2 2 * 7 H methyl isohexyl PF ₆
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 3: 2,2-dimethylpropyl * 5: 4-acryloyloxybutyl * 7: 2-methacryloyloxyethyl * 9: monomethyl sulfate

Table C (Part 1)
────────────────────────────────────────
Compound mn p q rs R ⁸ R ¹ = R ⁶ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
C-1 1 0 0 1 1 1 Methyl H Ethyl Butyl Br
C-2 2 0 0 1 2 2 Methyl H Methyl isohexyl Br
C-3 3 0 0 1 2 2 * 1 H methyl * 3 F
C-4 4 0 0 1 1 1 Ethyl H Methyl * 3 ClO ₄
C-5 5 0 0 1 0 0 * 4 H ethyl pentyl I
C-6 1 0 0 2 1 1 Methyl H Ethyl Butyl Br
C-7 2 0 0 2 1 1 Methyl H propyl propyl Cl
C-8 3 0 0 2 2 2 Ethyl H Methyl * 2 Br
C-9 4 0 0 2 2 2 * 1 H methyl * 3 Cl
C-10 5 0 0 2 1 1 Propyl H methyl * 3 PF ₆
C-11 1 0 0 3 1 1 Methyl H Ethyl Butyl Br
C-12 2 0 0 3 1 1 Methyl H propyl propyl Br
C-13 3 0 0 3 2 2 Ethyl H Methyl Isohexyl Acetic acid ───────────────────────────────────── ────
(註)
* 1: 2-hydroxyethyl * 2: 4-ethoxy-4-methylpentyl * 3: 2,2-dimethylpropyl * 4: 2-acryloyloxyethyl

Table C (Part 2)
────────────────────────────────────────
Compound mn p q rs R ⁸ R ¹ = R ⁶ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
C-14 1 0 1 2 1 1 Methyl H Ethyl Butyl Br
C-15 2 0 1 2 2 2 Ethyl H Methyl * 3 Br
C-16 3 0 1 2 1 1 Propyl H methyl * 3 * 9
C-17 1 0 1 1 1 1 Methyl H Ethyl Butyl Br
C-18 2 0 1 1 3 3 Methyl Br Methyl Methyl Br
C-19 3 0 1 1 0 0 * 1 H propyl hexyl BF ₄
C-20 1 1 0 1 1 1 Methyl H Ethyl Butyl Br
C-21 2 1 0 1 2 2 Ethyl H Methyl isohexyl Br
C-22 3 1 0 1 2 2 Propyl H Ethoxypropyl * 6
C-23 1 2 0 1 1 1 Methyl H Ethyl Butyl Br
C-24 2 2 0 1 1 1 * 7 H propyl propyl * 10
C-25 3 2 0 1 0 0 Ethyl H Methyl * 5 * 8
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 3: 2,2-dimethylpropyl * 5: 4-acryloyloxybutyl * 6: 2,2,2-trifluoroethanesulfonic acid * 7: 2-methacryloyloxyethyl * 8: p -Toluenesulfonic acid * 9: Monomethyl sulfuric acid * 10: Trifluoromethanesulfonic acid

Table D (Part 1)
────────────────────────────────────────
Compound mn p q rs R ⁸ R ¹ = R ⁶ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
D-1 1 0 0 1 1 1 Methyl H Ethyl Butyl Br
D-2 1 0 0 1 1 1 Methyl H propyl propyl Br
D-3 2 0 0 1 2 2 * 1 H methyl isohexyl * 8
D-4 3 0 0 1 2 2 Propyl H methyl * 3 Br
D-5 4 0 0 1 1 1 Ethyl H Methyl * 3 ClO ₄
D-6 5 0 0 1 0 0 * 4 H ethyl pentyl * 9
D-7 1 0 0 2 1 1 Methyl H Ethyl Butyl Br
D-8 2 0 0 2 1 1 * 1 H propyl propyl Cl
D-9 3 0 0 2 2 2 Ethyl H Methyl isohexyl Br
D-10 1 0 0 3 1 1 Methyl H Ethyl Butyl Br
D-11 2 0 0 3 1 1 * 4 H propyl propyl Br
D-12 3 0 0 3 2 2 Ethyl H Ethoxypropyl Acetic acid ──────────────────────────────────── ────
(註)
* 1: 2-hydroxyethyl * 3: 2,2-dimethylpropyl * 4: 2-acryloyloxyethyl * 8: p-toluenesulfonic acid * 9: monomethyl sulfate

Table D (Part 2)
────────────────────────────────────────
Compound mn p q rs R ⁸ R ¹ = R ⁶ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
D-13 1 0 1 2 1 1 Methyl H Ethyl Butyl Br
D-14 2 0 1 2 2 2 Ethyl H Methyl * 3 Br
D-15 3 0 1 2 2 2 Propyl H methyl * 5 I
D-16 1 0 1 1 1 1 Methyl H Ethyl Butyl Br
D-17 2 0 1 1 0 0 Methyl H ethyl pentyl Br
D-18 3 0 1 1 0 0 * 1 H propyl hexyl F
D-19 1 1 0 1 1 1 Methyl H Ethyl Butyl Br
D-20 2 1 0 1 2 2 Ethyl H Methyl isohexyl * 10
D-21 3 1 0 1 3 3 * 1 Br methyl methyl PF ₆
D-22 1 2 0 1 1 1 Methyl H Ethyl Butyl Br
D-23 2 2 0 1 2 2 Methyl H Methyl * 2 * 6
D-24 3 2 0 1 2 2 Ethyl H Methyl isohexyl BF ₄
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 2: 4-ethoxy-4-methylpentyl * 3: 2,2-dimethylpropyl * 5: 4-acryloyloxybutyl * 6: 2,2,2-trifluoroethanesulfonic acid * 10: trifluoromethanesulfonic acid

Table E
────────────────────────────────────────
Compound n pr s R ⁸ R ² = R ⁵ R ³ = R ⁴ X
────────────────────────────────────────
E-1 0 1 0 0 Methyl ethyl butyl Br
E-2 0 1 0 0 Ethyl ethyl butyl * 8
E-3 0 1 0 0 Methyl propyl propyl F
E-4 0 1 1 1 * 1 Methyl isohexyl monomethyl sulfate E-5 0 1 1 1 Ethyl methyl * 3 ClO ₄
E-6 0 1 0 0 Propyl methyl * 3 Cl
E-7 1 0 0 0 Methyl ethyl butyl Br
E-8 1 0 0 0 ethyl ethyl butyl acetate E-9 1 0 0 0 * 7 propyl propyl PF ₆
E-10 1 0 1 1 * 4 Methyl isohexyl I
E-11 1 0 1 1 Propyl methyl * 3 BF ₄
E-12 1 0 0 0 Ethyl methyl * 3 * 6
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 3: 2,2-dimethylpropyl * 4: 2-acryloyloxyethyl * 6: 2,2,2-trifluoroethanesulfonic acid * 7: 2-methacryloyloxyethyl * 8: p -Toluenesulfonic acid

Table F
────────────────────────────────────────
Compound ^{m n p r s R 8 R} 2 = R 5 R 3 = R 4 X
────────────────────────────────────────
F-1 1 0 1 0 0 Methyl ethyl butyl Br
F-2 1 0 1 0 0 * 4 Propyl propyl * 8
F-3 2 0 1 1 1 * 1 Methyl isohexyl BF ₄
F-4 3 1 0 0 0 Methyl ethyl butyl Br
F-5 4 1 0 1 1 Ethyl methyl * 3 ClO ₄
F-6 5 1 0 0 0 Propyl methyl * 3 BF ₄
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 3: 2,2-dimethylpropyl * 4: 2-acryloyloxyethyl * 8: p-toluenesulfonic acid

Table G
────────────────────────────────────────
Compound ^{m n p r s R 8 R} 2 = R 5 R 3 = R 4 X
────────────────────────────────────────
G-1 1 0 1 0 0 Methyl ethyl butyl Br
G-2 1 0 1 0 0 * 7 Propyl propyl monomethyl sulfate G-3 2 0 1 1 1 Propyl methyl isohexyl I
G-4 3 1 0 0 0 Methyl ethyl butyl Br
G-5 4 1 0 1 1 Ethyl methyl * 3 Cl
G-6 5 1 0 0 0 * 1 Methyl * 3 * 8
────────────────────────────────────────
(註)
* 1: 2-hydroxyethyl * 3: 2,2-dimethylpropyl * 7: 2-methacryloyloxyethyl * 8: p-toluenesulfonic acid

Table H
────────────────────────────────────────
Compound ^{m n p r s R 8 R} 2 = R 5 R 3 = R 4 X
────────────────────────────────────────
H-1 1 0 1 0 0 Methyl ethyl butyl Br
H-2 1 0 1 0 0 Ethyl propyl propyl * 8
H-3 2 0 1 1 1 Propyl methyl isohexyl I
H-4 3 1 0 0 0 Methyl ethyl butyl Br
H-5 4 1 0 1 1 * 4 Methyl * 3 Cl
H-6 5 1 0 0 0 * 1 Methyl * 3 Acetic acid ──────────────────────────────────── ────
(註)
* 1: 2-hydroxyethyl * 3: 2,2-dimethylpropyl * 4: 2-acryloyloxyethyl * 8: p-toluenesulfonic acid

^{(II) + N (-R 11} ) (- R 12) (- R 13) (- R 14) · X 11

In the formula (II), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group having 1 to 20 carbon atoms. The definitions and examples of the alkyl group and the substituted alkyl group are the same as those in the formula (I).

In the formula (II), R ¹³ and R ¹⁴ are an alkyl group having 4 to 20 carbon atoms or a substituted alkyl group having 4 to 20 carbon atoms. The alkyl part of the alkyl group or substituted alkyl group has at least one branch, or the substituted alkyl group is substituted with an alkoxy group at a carbon atom other than the terminal. The number of carbon atoms in the alkyl group and substituted alkyl group is preferably 6 to 14, and more preferably 7 to 12. Examples of the substituent of the substituted alkyl group are the same as those in the formula (I).
A branched alkyl group having 4 to 20 carbon atoms, a substituted alkyl group having 4 to 20 carbon atoms having a branch, and 4 to 20 carbon atoms substituted with an alkoxy group at a carbon atom other than the terminal Examples of substituted alkyl groups are shown below.

R13-1: 2-ethylhexyl R13-2: 2-propylpentyl R13-3: 3,7-dimethyloctyl R13-4: 3,5,5-trimethylhexyl R13-5: 2,4,4-trimethylpentyl R13 -6: 2,6-dimethylheptyl R13-7: 2,4,4-trimethylpentyl R13-8: 7-acryloyloxy-3,7,7-trimethyloctyl R13-9: 4-butyl-4-methylpentyl R13-10: 3-ethoxyhexyl

In the formula (II), X ¹¹ is an anion. The definition and examples of anions are the same as those in formula (I).
Examples of the cationic surfactant represented by the formula (II) are shown below.

Table II (Part 1)
────────────────────────────────────────
Compound R ¹¹ R ¹² R ¹³ R ¹⁴ X ¹¹
────────────────────────────────────────
II-1 Methyl methyl R13-1 R13-1 Br
II-2 Methyl methyl R13-1 R13-2 I
II-3 Ethyl 2-hydroxyethyl R13-1 R13-3 Br
II-4 Methyl methyl R13-2 R13-2 Br
II-5 Methyl methyl R13-2 R13-1 Br
II-6 Ethyl methyl R13-2 R13-3 Cl
II-7 Methyl Methyl R13-3 R13-3 Br
II-8 Methyl methyl R13-3 R13-1 Br
II-9 Ethyl 2-acryloyloxyethyl R13-3 R13-2 PF ₆
II-10 Methyl methyl R13-4 R13-4 Br
II-11 Methyl methyl R13-4 R13-1 Br
II-12 Ethyl 2-acryloyloxyethyl R13-4 R13-2 * 6
II-13 Methyl methyl R13-5 R13-5 Br
II-14 Methyl methyl R13-5 R13-1 Br
────────────────────────────────────────
(註)
* 6: 2,2,2-trifluoroethanesulfonic acid

Table II (Part 2)
────────────────────────────────────────
Compound R ¹¹ R ¹² R ¹³ R ¹⁴ X ¹¹
────────────────────────────────────────
II-15 ethyl ethyl R13-5 R13-2 ClO ₄
II-16 Methyl methyl R13-6 R13-6 Br
II-17 Methyl methyl R13-6 R13-1 I
II-18 Ethyl 2-hydroxyethyl R13-6 R13-2 Br
II-19 Methyl Methyl R13-7 R13-7 Br
II-20 Methyl methyl R13-7 R13-1 Acetic acid
II-21 Ethyl * 7 R13-7 R13-2 BF ₄
II-22 Methyl methyl R13-8 R13-8 Br
II-23 Methyl methyl R13-8 R13-1 Br
II-24 Ethyl methyl R13-8 R13-2 * 8
II-25 Methyl methyl R13-9 R13-9 Br
II-26 Methyl methyl R13-9 R13-1 Br
II-27 ethyl ethyl R13-9 R13-2 * 9
II-28 Methyl methyl R13-10 R13-10 Br
II-29 Methyl 2-hydroxyethyl R13-10 R13-1 F
II-30 Ethyl * 4 R13-10 R13-2 * 10
────────────────────────────────────────
(註)
* 4: 2-acryloyloxyethyl * 7: 2-methacryloyloxyethyl * 8: p-toluenesulfonic acid * 9: monomethylsulfuric acid * 10: trifluoromethanesulfonic acid

  Examples of other cationic surfactants are methyl trioctyl ammonium bromide, methyl trioctyl ammonium chloride, didecyl dimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl ethyl dimethyl ammonium bromide, tridodecyl methyl ammonium chloride , Tridodecylmethylammonium iodide, myristyltrimethylammonium bromide, dimethylditetradecylammonium bromide, dicetyldimethylammonium bromide, octadecyltrimethylammonium bromide, dioctadecyldimethylammonium bromide.

[W / O type emulsion]
The W / O type emulsion is composed of a cationic surfactant, an oil phase and an aqueous phase. The aqueous phase is emulsified in the oil phase. A cationic surfactant is dissolved in the oil phase.

The oil phase is preferably composed of an organic solvent with low polarity. The low-polar organic solvent is preferably an organic solvent that does not mix with water and separates into two phases when no surfactant is present.
Examples of organic solvents include saturated hydrocarbons (eg, hexane, heptane, octane, nonane, decane, isooctane, cyclohexane), aromatic hydrocarbons (eg, benzene, toluene, xylene), halogenated hydrocarbons (eg, dichloromethane, Chloroform, carbon tetrachloride), ether (eg, diethyl ether), ester (eg, ethyl acetate). The organic solvent is preferably hexane, heptane, octane, nonane, decane, isooctane, benzene, toluene or xylene, more preferably hexane, octane, decane, isooctane or toluene.
Two or more organic solvents may be mixed and used.

The aqueous phase may be substantially pure water (eg, deionized water).
The aqueous phase can contain inorganic salts. The emulsified state can be adjusted by adding an inorganic salt. By adjusting the emulsified state, the suspended emulsion can be made into a uniform transparent emulsion. Examples of inorganic salts include alkali metal halide salts (eg, lithium fluoride, sodium fluoride, potassium fluoride, lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide, lithium iodide) , Sodium iodide, potassium iodide), alkaline earth metal halide salts (eg, magnesium chloride, calcium chloride, magnesium bromide, calcium bromide, magnesium iodide, calcium iodide), ammonium halide salts (eg, Ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide), alkali metal sulfates (eg, lithium sulfate, sodium sulfate, potassium sulfate), alkaline earth metal sulfates (eg, magnesium sulfate), and ammonium sulfate.
Inorganic salts include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, calcium iodide. Sodium sulfate, potassium sulfate and magnesium sulfate are preferable, lithium chloride, magnesium chloride, calcium chloride, lithium bromide, lithium iodide, lithium sulfate, sodium sulfate, potassium sulfate and magnesium sulfate are more preferable, and lithium sulfate and magnesium sulfate are preferable. Most preferred. Two or more inorganic salts may be used in combination.
The addition amount of the inorganic salt is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and most preferably 1 to 5 parts by mass with respect to 100 parts by mass of water.

In the W / O type emulsion, a cationic surfactant and another surfactant may be used in combination.
In the three-component composition of a cationic surfactant-organic solvent (eg, isooctane) -water, if the molar ratio of water to the cationic surfactant is too large, water droplets dispersed in the oil phase become large and uniform. Do not give a clear dispersion. The molar ratio of water to the cationic surfactant is preferably 30 or less, more preferably 20 or less, and most preferably 10 or less. The larger the molar ratio of the organic solvent to the cationic surfactant, the more stable and transparent dispersion is obtained. The molar ratio of the organic solvent to the cationic surfactant is preferably 80 or more, more preferably 100 or more, and most preferably 120 or more.

  In order to prepare a uniform transparent emulsion from a cationic surfactant, an organic solvent and water, a procedure in which the surfactant and the organic solvent are first mixed and then water is added is preferable. In order to promote emulsification, ultrasonic waves may be applied, or heating may be performed at a temperature below the boiling point of the organic solvent.

  A small amount of additives may be used in the preparation of the emulsion. Examples of additives include alcohols (eg, ethanol), carboxylic acids (eg, acetic acid), inorganic acids (eg, boronic acid, phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid), ammonia, alkali metal hydroxides (eg, Sodium hydroxide, potassium hydroxide). The additive is preferably ethanol, acetic acid or boronic acid. A preferable addition amount is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and most preferably 0.1 to 1 part by mass with respect to 100 parts by mass of water.

  Whether or not the emulsion is uniformly transparent can be evaluated by the size of the colloidal particles in the emulsion. The size of the colloidal particles in the emulsion can be measured by a light scattering method. Moreover, since the particle diameter is sufficiently smaller than the wavelength of visible light in the dispersion having a particle diameter of several nanometers to several tens of nanometers, the particle diameter can be evaluated by utilizing the low turbidity. In the W / O type emulsion according to the present invention, turbidity can be evaluated by measuring absorbance at 500 to 700 nm. When the absorbance of the emulsified dispersion in the cell having an optical path length of 1 cm is 0.002 or less, it can be determined that the intended reverse micelle having a sufficiently small particle diameter has been generated.

[Preparation of inorganic oxide fine particles]
The W / O emulsion can be used for preparing inorganic oxide fine particles. A composite inorganic oxide can also be prepared. The inorganic oxide is preferably an oxide of silicon (silica), titanium (titania), zirconium (zirconia), aluminum (alumina) or a composite thereof, more preferably silica, titania, zirconia, or a composite thereof, Silica, zirconia, or a composite thereof is most preferred.
When the W / O emulsion according to the present invention is used, spherical or nearly spherical particles can be produced. The fine particles close to a sphere are specifically shapes in which the ratio of the major axis to the minor axis is 2 or less. In the production method using the W / O type emulsion, both hollow particles and non-hollow particles can be produced.
The particles used for the low refractive index layer of the antireflection film are preferably hollow particles. In the production method using the W / O type emulsion, inorganic oxide fine particles having a particle diameter of 5 nm to 1 μm can be produced. The particles used in the low refractive index layer of the antireflective film are preferably 30% to 150% of the average particle size of the film thickness of the low refractive index layer, more preferably 35% to 80%, and 40% to 60%. Most preferred. For example, when the thickness of the low refractive index layer is 100 nm, the particle size of the inorganic oxide fine particles is preferably 30 to 150 nm, more preferably 35 to 80 nm, and most preferably 40 to 60 nm.

(Inorganic oxide precursor)
An oxide precursor is used for the preparation of the inorganic oxide fine particles. The inorganic oxide precursor is preferably an alkoxide or carboxylate of silicon, titanium, zirconium, aluminum, and alkoxysilane, titanium alkoxide, zirconium alkoxide, aluminum alkoxide titanium carboxylate (eg, titanium tetraacetylacetonate), zirconium carboxylate ( Zirconium tetraacetylacetonate) is more preferred.
Examples of alkoxysilane include tetraalkoxysilane (eg, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane), alkyltrialkoxysilane (eg, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane) Octyltriethoxysilane, decyltrimethoxysilane). Examples of titanium alkoxides include titanium tetraalkoxides (eg, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium tetra tert-butoxide), titanium dialkoxides (eg, Titanium bis (ethyl acetoacetate) diisopropoxide). Examples of zirconium alkoxides include zirconium tetraalkoxides (eg, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide, zirconium tetra tert-butoxide). Examples of aluminum alkoxide include aluminum tetraalkoxide (eg, aluminum tetraisopropoxide).

A partial condensate of an inorganic oxide precursor may be used.
Two or more kinds of inorganic oxide precursors may be used in combination. The inorganic oxide precursor is preferably tetraethoxysilane, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide, titanium tetraacetylacetonate, zirconium tetraacetylacetonate, tetraethoxysilane, titanium Tetraacetylacetonate is more preferred.
When two or more kinds of inorganic oxide precursors are used in combination, all the inorganic oxide precursors can be added simultaneously. Moreover, after adding a part of inorganic oxide precursor and advancing reaction, the remaining inorganic oxide precursor can also be added.

Depending on the amount of the inorganic oxide precursor added to the reaction system, the inorganic oxide fine particles can have a hollow structure or a non-hollow structure.
The amount of the inorganic oxide precursor when producing the spherical inorganic oxide having a hollow structure is preferably 0.01 to 1 and preferably 0.01 to 0.5 in terms of molar ratio with respect to water in the reaction system. More preferably, 0.01 to 0.25 is most preferable. In addition, the amount of the inorganic oxide precursor when producing the spherical inorganic oxide having a non-hollow structure is such that the amount of the inorganic oxide precursor is 0.1 to 2 in terms of a molar ratio with respect to water in the reaction system. Is preferable, 0.25 to 2 is more preferable, and 0.5 to 2 is most preferable.

(catalyst)
A catalyst can be added for the purpose of promoting hydrolysis and condensation of the inorganic oxide precursor. Examples of the catalyst include organic acids (eg, acetic acid), inorganic acids (eg, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid), alkali metal hydroxides (eg, sodium hydroxide), ammonia, and amines. The catalyst is preferably acetic acid, hydrochloric acid, sodium hydroxide or ammonia, more preferably hydrochloric acid or ammonia.
When using an acid as a catalyst, 0-5 are preferable, as for pH of an aqueous phase, 1-4 are more preferable, and 2-3 are the most preferable. When a base is used as a catalyst, the pH of the aqueous phase is preferably 9 to 14, more preferably 10 to 13, and most preferably 11 to 12.

(Hydrolysis / condensation process)
The process for producing inorganic oxide fine particles comprises a hydrolysis / condensation step of inorganic oxide fine particles at room temperature and a firing step under heating.
In the hydrolysis / condensation step, a cationic surfactant, water, an organic solvent, a catalyst, and an inorganic oxide precursor are mixed. If necessary, inorganic salts and additives can also be mixed. The procedure of the mixing operation is preferably the final mixing operation in which the inorganic oxide comes into contact with the catalyst. More preferably, the mixing operation in which the inorganic oxide comes into contact with water and the catalyst is the last. The specific mixing operation procedure is preferably the following (I) and (II).
(I): An aqueous solution of an inorganic salt, a catalyst and an additive, and an organic solvent dispersion of a cationic surfactant are prepared in advance, and after mixing them to prepare a W / O emulsion, an inorganic oxide precursor is prepared. Add body.
(II): An aqueous solution of an inorganic salt, a catalyst, and an additive, and an organic solvent dispersion of a cationic surfactant and an inorganic oxide precursor were prepared, mixed together, and a W / O emulsion was prepared. Prepare.
It is preferable that the mixing is always performed with stirring. In order to promote emulsification and dispersion, ultrasonic waves may be irradiated. Moreover, as long as the inorganic oxide precursor is not mixed with water or a catalyst, it may be heated at a temperature not higher than the boiling point of the organic solvent. During the mixing operation, after the mixing operation in which the inorganic oxide precursor comes into contact with water or the catalyst, the temperature of the composition is kept constant at a certain temperature within the range of 15 to 25 ° C. In the hydrolysis / condensation process, after mixing the cationic surfactant, water, organic solvent, catalyst, inorganic oxide precursor, and, if necessary, inorganic salt and additives, the temperature of the reaction composition Is kept constant at a temperature in the range of 15-25 ° C. and stirred for 1 to 7 days.

(Baking process)
In the firing step, the inorganic oxide sol or gel produced in the hydrolysis / condensation step is heat-treated at a maximum of 800 ° C. Preferred steps are the following (i) to (viii).
(I): The composition obtained in the hydrolysis / condensation step is heated in an open system at 60 to 100 ° C. for 1 to 24 hours. The solvent is distilled off and the residue is dried.
(Ii): The composition obtained in the hydrolysis / condensation step is heated in an autoclave at 60 to 150 ° C. for 1 to 24 hours. The solvent is distilled off and the residue is dried.
(Iii): The inorganic oxide obtained in the step (i) is heated at 200 to 800 ° C. for 1 to 24 hours in an electric furnace under an inert gas stream or under vacuum.
(Iv): The inorganic oxide obtained in step (ii) is heated in an electric furnace at 200 ° C. to 800 ° C. for 1 to 24 hours under an inert gas stream or in a vacuum.
(V): The inorganic oxide obtained in step (i) is dissolved in a hydrocarbon such as isooctane and heated at 200 ° C. to 800 ° C. for 1 to 24 hours in an autoclave. The solvent is distilled off and the residue is dried.
(Vi): The inorganic oxide obtained in the step (ii) is dissolved in a hydrocarbon such as isooctane and heated at 200 ° C. to 800 ° C. for 1 to 24 hours in an autoclave. The solvent is distilled off and the residue is dried.
(Vii): The inorganic oxide obtained in the step (v) is heated in an electric furnace at 200 ° C. to 800 ° C. for 1 to 24 hours under an inert gas stream or under vacuum.
(viii): The inorganic oxide obtained in the step (vi) is heated at 200 ° C. to 800 ° C. for 1 to 24 hours in an autoclave. The solvent is distilled off and the residue is dried.

(Confirmation of hollow structure)
Whether the structure of the prepared inorganic oxide fine particles is hollow or non-hollow can be determined by observation with a transmission electron microscope. Assuming that the hollow inorganic oxide shell is uniform and that the intensity of the transmission electron microscope image is proportional to the thickness of the sample in the transmission direction, the intensity is ((a ² −x ² ) ^0.5 − (b ² -x ² ) ^0.5 ) and an intensity profile is obtained.
FIG. 1 is an example of the intensity profile of hollow particles (a: outer diameter, b: inner diameter, x: radial position when the center of the fine particles is 0). When the intensity profile of the measured electron microscope image is close to the above formula, it is determined that the structure has a hollow structure.

[Low refractive index layer]
(Low refractive index binder)
The hollow fine particles of inorganic oxide can be used for the low refractive index layer of the antireflection film.
The low refractive index layer of the antireflection film preferably contains a fluorine-containing polymer as a low refractive index binder in addition to the hollow fine particles. The fluoropolymer preferably has a dynamic friction coefficient of 0.03 to 0.15 and a contact angle with water of 90 to 120 °. The fluorine-containing polymer can have a crosslinked structure. The crosslinked structure can be introduced into the fluoropolymer by heat or ionizing radiation.

  As the fluorine-containing polymer, a hydrolysis / dehydration condensate of a perfluoroalkyl group-containing silane compound (eg, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane) can be used. Further, a fluorine-containing crosslinked copolymer of a fluorine-containing monomer and a monomer for imparting crosslinking reactivity may be used.

Examples of fluorine-containing monomers include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), (meta ) A partially or fully fluorinated alkyl ester derivative of acrylic acid (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals), M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ether. Perfluoroolefin is preferred. In view of refractive index, solubility, transparency, and availability, hexafluoropropylene is particularly preferable.
Monomers for imparting crosslinking reactivity include monomers having a self-crosslinkable functional group in the molecule (eg, glycidyl (meth) acrylate, glycidyl vinyl ether) and non-crosslinkable functional groups (eg, carboxyl, hydroxy, amino, (Eg, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid). Crosslinkable reactive groups by non-crosslinkable functional groups of repeating units synthesized from monomers having noncrosslinkable functional groups by polymer reaction (for example, reaction of acrylic acid chloride on hydroxy of repeating units) (E.g., (meth) acryloyl) can be introduced.

  In addition to the fluorine-containing monomer and the monomer for imparting crosslinking reactivity, a monomer that does not contain a fluorine atom can be copolymerized from the viewpoint of solubility in a solvent and film transparency. Examples of monomers that can be used in combination include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylic acid esters ( Examples, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene, styrene derivatives (eg, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ethers (eg, methyl vinyl ether, ethyl vinyl ether, cyclohexyl) Vinyl ether), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (N-tert-butylacrylamide, N-cyclohexylacrylamide, etc.), methacryl Bromide, including acrylonitrile and derivatives thereof.

  You may introduce | transduce a crosslinked structure into a fluorine-containing polymer using a hardening | curing agent (It describes in each gazette of Unexamined-Japanese-Patent No. 10-25388 and 10-147739.).

  The fluoropolymer is preferably a random copolymer of perfluoroolefin and vinyl ether or vinyl ester. The fluorine-containing polymer preferably has a group capable of undergoing a crosslinking reaction alone. The group capable of crosslinking reaction alone is preferably a radical reactive group (eg, acryloyl, methacryloyl) and a ring-opening polymerizable group (eg, epoxy group, oxetanyl group). The repeating unit having a crosslinkable group is preferably 5 to 70 mol%, more preferably 30 to 60 mol% of the polymer.

(Film-forming binder)
The low refractive index layer preferably has a film-forming binder. The film-forming binder has a function of increasing the film strength, the stability of the coating solution, and the productivity of the coating film. The film-forming binder is preferably 10% by mass or more, more preferably 20% by mass or more and 100% by mass or less, and more preferably 30% by mass or more and 95% by mass or less, of the film-forming components excluding inorganic particles. Is most preferred.
A film-forming binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. The binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure is preferably a (co) polymer of monomers having two or more ethylenically unsaturated groups.

  Monomers having two or more ethylenically unsaturated groups are esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) ) Acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate Rate), vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid 2-acryloylethyl, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylene) Bisacrylamide) and methacrylamide are preferred. Two or more of these monomers may be used in combination.

(Polymerization initiator)
Polymerization of the monomer having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

Photo radical polymerization initiators are acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, Fluoroamine compounds and aromatic sulfoniums are preferred. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyl diphenylphosphine oxide. The radical photopolymerization initiator is also described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, Inc., published in 1991). Commercially available photocleavable photoradical polymerization initiators (for example, Irgacure 651, 184, 907 manufactured by Ciba Geigy Japan, Inc.) may be used.
0.1-15 mass parts is preferable with respect to 100 mass parts of polyfunctional monomers, and, as for the usage-amount of a photoinitiator, 1-10 mass parts is more preferable.

  In addition to the photopolymerization initiator, a photosensitizer may be used. Examples of photosensitizers include butylamine, triethylamine, tributylphosphine, Michler's ketone and thioxanthone.

The thermal radical initiator is preferably an organic or inorganic peroxide, organic azo or diazo compound.
Examples of organic peroxides include benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide. Examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of azo compounds include 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile. Examples of the diazo compound include diazoaminobenzene and p-nitrobenzenediazonium.

[Anti-reflective film]
The antireflection film having a low refractive index layer preferably has a haze value of 3 to 70%, more preferably 4 to 60%. The antireflection film preferably has an average reflectance of 450 nm to 650 nm of 3.0% or less, and more preferably 2.5% or less. When the antireflection film has a haze value and an average reflectance within the above range, good antiglare and antireflection properties can be obtained without causing deterioration of the transmitted image.

(Support)
The transparent support of the optical film (antireflection film) is preferably a polymer film. Examples of polymers constituting the polymer film include cellulose acylate (eg, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate) , Polystyrene, polyolefin, norbornene-based resin, amorphous polyolefin, commercially available polymer film (for example, TAC-TD80U and TD80UF manufactured by Fuji Photo Film Co., Ltd. for cellulose acetate film, JSR for norbornene-based resin film) ZEONEX manufactured by Nippon Zeon Co., Ltd. may be used for Arton and Amorphous Polyolefin Films manufactured by KK Films, polyethylene terephthalate films and polyethylene naphthalate films are preferred, cellulose triacetate films are more preferred, cellulose acylate films substantially free of halogenated hydrocarbons (eg, dichloromethane) are particularly preferred, and halogenated hydrocarbons are not contained. About a cellulose acylate film and its manufacturing method, it is described in Invention Association public technical bulletin (public technical number 2001-1745, published on March 15, 2001).

(Formation of a low refractive index layer)
The low refractive index layer is preferably formed by applying a coating liquid containing inorganic oxide fine particles, a low refractive index binder, a film-forming binder, and a polymerization initiator on the hard coat film. The solvent used for preparing the coating solution is preferably an organic solvent. Examples of organic solvents are amides (eg, DMF), sulfoxides (eg, DMSO), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, toluene, hexane), alkyl halides (eg, chloroform, dichloromethane), esters (Eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Two or more organic solvents may be used in combination.
The coating solution can be applied by a known method (eg, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, wire bar coating method).

(Evaluation of antireflection film)
The performance of the produced hollow inorganic oxide fine particles as a low refractive index material can be evaluated by measuring the refractive index of the film containing the fine particles. Since the hollow inorganic oxide fine particles produced according to the present invention are readily soluble in an organic solvent, the material of the film containing the fine particles is preferably an organic polymer. A thin film is prepared from an organic coating solution containing 100 parts by mass of an organic polymer and 100 to 10 parts by mass of hollow inorganic oxide fine particles, and the refractive index is measured. When the refractive index of the organic polymer thin film containing the hollow inorganic oxide fine particles is smaller than the refractive index of the organic polymer, surfactant or inorganic oxide, it can be determined that it functions as a low refractive index material.

[Example 1]
(Synthesis of Compound (A-1))
Compound (A-1) was synthesized according to Scheme 1.

A mixture of 26.6 g of aspartic acid (A-1a), 65.1 g of 2-ethyl-1-hexanol (A-1b), and 44.0 g of p-toluenesulfonic acid monohydrate was dissolved in 500 mL of toluene. Refluxed for 2 hours. Water produced by dehydration condensation was removed from the reaction system as needed by azeotropic distillation. The reaction mixture was washed with an aqueous sodium bicarbonate solution, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 65.2 g of compound (A-1c) (first stage).
A mixture of 26.7 g of compound (A-1c), 9.3 mL of iodomethane (A-1d) and 6.0 g of 60% sodium hydride was stirred in 100 mL of dimethylformamide at room temperature for 12 hours. Hexane was added to the reaction mixture, followed by washing with an aqueous sodium bicarbonate solution, and the solvent was distilled off. The residue was purified by column chromatography to obtain 11.8 g of compound (A-1e) (second stage).
A mixture of 2.0 g of compound (A-1e) and 5.3 g of bromomethane (A-1f) was stirred in 250 mL of dimethylformamide at room temperature for 2 days. The solvent and the remaining bromomethane (A-1f) were distilled off to obtain 2.5 g of 4 compounds (A-1) quantitatively (third stage).

¹ H NMR (400 MHz, CDCl ₃ )
0.86-0.94 (m, 12H), 1.20-1.40 (m, 16H), 1.54-1.70 (m, 2H), 3.19 (dd, J = 8.4) , 17.6 Hz, 1H), 3.62 (dd, J = 3.2, 17.6 Hz, 1H), 3.68 (s, 9H), 3.97-4.27 (m, 4H), 4 .80 (m, 1H)

[Example 2]
(Synthesis of Compound (A-16))
Compound (A-16) was synthesized according to Scheme 2.

A mixture of 26.0 g of itaconic acid (A-16a), 65.1 g of 2-ethyl-1-hexanol (A-1b) and 38.0 g of p-toluenesulfonic acid monohydrate was refluxed in toluene for 2 hours. . Water produced by dehydration condensation was removed from the reaction system as needed by azeotropic distillation. The reaction mixture was washed with aqueous sodium hydrogen carbonate solution, the solvent was evaporated under reduced pressure, and the residue was purified by silica column chromatography to obtain 59.3 g of compound (A-16b) (first stage).
A mixture of 7.53 mL of the compound (A-16b) and 50 mL of a 2.0 M tetrahydrofuran solution of dimethylamine (A-16c) was stirred at −5 ° C. for 4 hours. Tetrahydrofuran and remaining dimethylamine (A-16c) were distilled off, and the residue was purified by silica chromatography to obtain 7.7 g of compound (A-16d) (second stage).
A mixture of 1 g of compound (A-16d) and 2.6 g of bromomethane (A-1f) was stirred in 150 mL of dimethylformamide at room temperature for 3 days. The solvent and the remaining bromomethane (A-1f) were distilled off to obtain 1.2 g of Compound (A-16) quantitatively (third stage).

¹ H NMR (400 MHz, CDCl ₃ )
0.85-0.93 (m, 12H), 1.22-1.41 (m, 16H), 1.53-1.65 (m, 2H), 2.90 (dd, J = 5.6) , 17.6 Hz, 1H), 3.01 (dd, J = 6.2, 17.6 Hz, 1H), 3.50 (s, 9H), 3.94-4.17 (m, 6H).

[Example 3]
(Synthesis of Compound (A-19))
Compound (A-19) was synthesized according to Scheme 3.

A mixture of 25.4 g of 4-bromobutanoic acid (A-19a), 25.0 g of 2-ethyl-1-hexanol (A-1b) and 38.0 g of p-toluenesulfonic acid monohydrate was dissolved in toluene. Refluxed for 2 hours. Water produced by dehydration condensation was removed from the reaction system as needed by azeotropic distillation. The reaction mixture was washed with aqueous sodium hydrogen carbonate solution, the solvent was distilled off under reduced pressure, and the residue was purified by distillation under reduced pressure to obtain 31.1 g of compound (A-19b) (first stage).
A mixture of 27.2 g of the compound (A-19b) and 230 mL of a 2.0M tetrahydrofuran solution of dimethylamine (A-16c) was stirred at room temperature for 25 hours. Tetrahydrofuran and remaining dimethylamine (A-16c) were distilled off, and the residue was purified by silica chromatography to obtain 20.0 g of compound (A-19c) (second stage).

A mixture of 24.6 g of iodoacetic acid (A-19d), 22.0 g of 2-ethyl-1-hexanol (A-1b) and 38.0 g of p-toluenesulfonic acid monohydrate was dissolved in 500 mL of toluene. Reflux for hours. Water produced by dehydration condensation was removed from the reaction system as needed by azeotropic distillation. The reaction mixture was washed with aqueous sodium hydrogen carbonate solution, the solvent was evaporated under reduced pressure, and the residue was purified by distillation under reduced pressure to obtain 31.7 g of compound (A-19e) (third stage).
31.6 mL of a 1.58M hexane solution of butyllithium was added to a tetrahydrofuran solution of 7.8 mL of diisopropylamine at 0 ° C., and the mixture was stirred at 0 ° C. for 15 minutes. Thereafter, the mixture was cooled to −78 ° C., 12.2 g of compound (A-19c) and 9.6 mL of hexamethylphosphoramide in tetrahydrofuran were added, and the mixture was stirred at −78 ° C. for 25 minutes. While maintaining the temperature of the reaction solution at −78 ° C., a solution of 14.9 g of compound (A-19e) in tetrahydrofuran was added, and the mixture was stirred at −78 ° C. for 5 hours. Thereafter, the temperature was gradually raised to 0 ° C. over 24 hours. Hexane was added to the reaction mixture, which was then washed with dilute hydrochloric acid, and the solvent was distilled off. The residue was purified by column chromatography to obtain 2.1 g of Compound (A-19f) (Step 4).
A mixture of 1.1 g of compound (A-19f) and 2.6 g of bromomethane (A-1f) was stirred in tetrahydrofuran at room temperature for 2 days. The solvent and remaining bromomethane (A-1f) were distilled off to obtain 1.35 g of compound (A-19) quantitatively (fifth stage).

¹ H NMR (400 MHz, CDCl ₃ )
0.85-0.94 (m, 12H), 1.22-1.41 (m, 16H), 1.53-1.65 (m, 2H), 1.95-2.12 (m, 1H) ), 2.19-2.39 (m, 1H), 2.67-2.92 (m, 3H), 3.45 (s, 9H), 3.62 (dt, J = 4.5, 12) .0Hz, 1H), 3.92-4.10 (m, 5H)

[Example 4]
(Synthesis of Compound (B-1))
Compound (B-1) was synthesized according to Scheme 4.

A mixture of 23.6 g of the compound (A-1c) obtained in the first step of Scheme 1, 12.7 g of bromoacetyl bromide (B-1a) and 10.5 g of triethylamine was stirred at room temperature for 18 hours. The reaction mixture was washed with an aqueous sodium chloride solution, the solvent was distilled off under reduced pressure, and the residue was purified by silica column chromatography to obtain 18.1 g of compound (B-1b) (first stage).
A mixture of 7.0 g of compound (B-1b) and 4.0 g of trimethylamine (B-1c) is stirred in tetrahydrofuran at room temperature for 2 days. The solvent and remaining trimethylamine (B-1c) were distilled off to quantitatively obtain 7.9 g of compound (B-1) (second stage).

¹ H NMR (400 MHz, CDCl ₃ )
0.85-0.93 (m, 12H), 1.22-1.41 (m, 16H), 1.53-1.63 (m, 2H), 2.98 (d, J = 6.4 Hz) , 2H), 3.51 (s, 9H), 3.97-4.10 (m, 4H), 4.62 (d, J = 13.6 Hz, 1H), 4.88 (q, J = 6). .7 Hz, 1 H), 4.90 (d, J = 14.0 Hz, 1 H), 9.34 (d, J = 7.6 Hz, 1 H).

[Example 5]
In the same manner as in Scheme 4, compound (B-6) was synthesized.

[Example 6]
(Synthesis of Compound (II-1))
Compound (II-1) was synthesized according to Scheme 5.

A mixture of 38.6 g of 2-ethyl-1-bromohexane (II-1a) and 300 mL of a 2.0M tetrahydrofuran solution of dimethylamine (A-16c) was stirred at room temperature for 25 hours. After distilling off tetrahydrofuran and remaining dimethylamine (A-16c), the residue was dispersed in hexane and washed with an aqueous sodium hydrogen carbonate solution. After distilling off hexane, the residue was purified by silica gel column chromatography to obtain 25.8 g of compound (II-1b) (first stage).
A mixture of 15.7 g of compound (II-1b) and 38.6 g of 2-ethyl-1-bromohexane (II-1a) was stirred in 100 mL of tetrahydrofuran at room temperature for 4 days. The solvent and remaining 2-ethyl-1-bromohexane (II-1a) were distilled off to obtain 35.4 g of compound (II-1) quantitatively (second stage).

¹ H NMR (400 MHz, CDCl ₃ )
0.85-0.93 (m, 12H), 1.22-1.41 (m, 16H), 1.69 (m, 2H), 3.40 (s, 9H), 3.52 (d, (7.6Hz, 4H)

[Example 7]
(PH 3-MgSO ₄ Preparation of Aqueous Solution)
To 100 g of an aqueous solution adjusted to pH 3 with hydrochloric acid, 5.00 g of magnesium sulfate (hereinafter referred to as MgSO ₄ ) was added to prepare a pH 3-MgSO ₄ aqueous solution.

(Production of silica fine particles (II1-1))
Compound (II-1) 2.00g were dissolved in isooctane 141 mL, was added pH 3-MgSO ₄ solution 539 mg. A translucent dispersion was obtained by heating to 50 ° C.
In the production of silica fine particles (II1-1), mixing was performed so that the water content (molar ratio of water to surfactant) was 5. The temperature of the reaction solution was lowered to 20 ° C., 6.36 mL of tetraalkoxysilane (hereinafter TEOS) was added while stirring the reaction solution, and the mixture was stirred for 3 days while maintaining 20 ° C. (The molar ratio of TEOS to water was 0.00. 5). The reaction solution was heated at 65-70 ° C. for 24 hours. After the solvent was distilled off, the residue was vacuum dried. The residue was dispersed in 100 mL of isooctane and heated at 290 ° C. for 12 hours in an autoclave. The solvent was distilled off and the residue was dried.

[Example 8]
(PH 2-MgSO ₄ Preparation of Aqueous Solution)
To 100 g of an aqueous solution adjusted to pH 2 with hydrochloric acid, 5.00 g of magnesium sulfate (hereinafter referred to as MgSO ₄ ) was added to prepare a pH 2 -MgSO ₄ aqueous solution.

(Production of silica fine particles (A16-1))
After 2.00 g of the compound (A-16) was dissolved in 100 mL of isooctane, 764 mg of an aqueous pH 2-MgSO ₄ solution was added. A uniform transparent dispersion was obtained by heating to 50 ° C. In the production of silica fine particles (A16-1), mixing was performed so that the water content (molar ratio of water to surfactant) was 10. The temperature of the reaction solution was lowered to 20 ° C., while stirring the reaction solution, 4.51 mL of tetraalkoxysilane (hereinafter TEOS) was added, and the mixture was stirred for 3 days while maintaining 20 ° C. (The molar ratio of TEOS to water was 0.00. 50). The reaction solution was heated at 65 to 70 ° C. for 24 hours, the solvent was distilled off, and the residue was vacuum dried. The residue was dissolved in 100 mL of isooctane and heated at 290 ° C. for 12 hours in an autoclave. The solvent was distilled off and the residue was dried.

[Example 9]
(Production of silica fine particles (A16-2))
Instead of pH 2-MgSO ₄ solution, except for using pH 3-MgSO ₄ solution was prepared under the same conditions as the preparation of the silica fine particles (A16-1).

[Example 10]
(Production of silica fine particles (A19-1))
After dissolving 2.00 g of compound (A-19) in 97 mL of isooctane, 3.34 g of pH 2-MgSO ₄ aqueous solution was added. A uniform transparent dispersion was obtained by heating to 50 ° C. In the production of silica fine particles (B1-1), mixing was performed so that the water content was 45. The temperature of the reaction solution was lowered to 20 ° C., and 3.95 mL of tetraalkoxysilane (hereinafter TEOS) was added while stirring the reaction solution, followed by stirring for 3 days while maintaining 20 ° C. (the molar ratio of TEOS to water was 0. 0). 1). The reaction solution was heated at 65 to 70 ° C. for 24 hours, the solvent was distilled off, and the residue was vacuum dried.

[Example 11]
(Production of silica fine particles (B1-1))
After dissolving 2.00 g of compound (B-1) in 100 mL of isooctane, 703 mg of pH 2-MgSO ₄ aqueous solution was added. A uniform transparent dispersion was obtained by heating to 50 ° C. In the production of silica fine particles (B1-1), mixing was performed so that the water content was 10. The temperature of the reaction solution was lowered to 20 ° C., while stirring the reaction solution, 4.15 mL of tetraalkoxysilane (hereinafter TEOS) was added, and the mixture was stirred for 3 days while maintaining 20 ° C. (the molar ratio of TEOS to water was 0.00). 5). The reaction solution was heated at 65 to 70 ° C. for 24 hours, the solvent was distilled off, and the residue was vacuum dried. The residue was dissolved in 100 mL of isooctane and heated at 290 ° C. for 12 hours in an autoclave. The solvent was distilled off and the residue was dried.

[Example 12]
(Production of silica fine particles (B1-2))
Instead of pH 2-MgSO ₄ solution, except for using pH 3-MgSO ₄ solution was prepared under the same conditions as the preparation of the silica fine particles (B1-1).

[Example 13]
_(PH12-Li 2 SO ₄ aqueous solution preparation of)
To 100 g of an aqueous solution adjusted to pH 12 with ammonia, 5.00 g of lithium sulfate (hereinafter, Li ₂ SO ₄ ) was added to prepare a pH 12-Li ₂ SO ₄ aqueous solution.

(Production of silica fine particles (B1-3))
Instead of pH 2-MgSO ₄ solution, except for using _pH12-Li 2 SO ₄ solution was prepared under the same conditions as the preparation of the silica fine particles (B1-1).

[Examples 14 to 16]
(Production of silica fine particles (B1-4) to (B1-6))
The silica fine particles (B1-4) to (B1-4) to (B1-3) are the same as the production method of the silica fine particles (B1-1) to (B1-3) except that the TEOS addition amount is changed from 4.15 mL to 2.07 mL. B1-6) was prepared (the molar ratio of TEOS to water was 0.25).

[Example 17]
(Production of silica fine particles (B6-1))
After 2.00 g of compound (B-6) was dissolved in 90 mL of isooctane, 685 mg of an aqueous pH 2-MgSO ₄ solution was added. A uniform transparent dispersion was obtained by heating to 50 ° C. In the production of silica fine particles (B1-6), mixing was performed so that the water content was 10. The temperature of the reaction solution was lowered to 20 ° C., and 4.04 mL of TEOS was added while stirring the reaction solution, followed by stirring for 3 days while maintaining 20 ° C. (the molar ratio of TEOS to water was 0.5). The reaction solution was heated at 65 to 70 ° C. for 24 hours, the solvent was distilled off, and the residue was vacuum dried. The residue was dissolved in 100 mL of isooctane and heated at 290 ° C. for 12 hours in an autoclave. The solvent was distilled off and the residue was dried.

[Example 18]
(Production of silica fine particles (B6-2))
Instead of pH 2-MgSO ₄ solution, except for using pH 3-MgSO ₄ solution was prepared under the same conditions as the preparation of the silica fine particles (B6-1).

[Example 19]
(Production of silica fine particles (B6-3))
Instead of pH 2-MgSO ₄ solution, except for using _pH12-Li 2 SO ₄ solution was prepared under the same conditions as the preparation of the silica fine particles (B6-1).

[Examples 20 to 22]
(Production of silica fine particles (B6-4) to (B6-6))
The silica fine particles (B6-4) to (B6-4) to (B6-3) are the same as the production methods of the silica fine particles (B6-1) to (B6-3) except that the amount of TEOS added is changed from 4.04 mL to 2.02 mL. B6-6)) was prepared (the molar ratio of TEOS to water was 0.25).

[Comparative Example 1]
(Manufacture of silica fine particles (DODAB))
After 2.00 g of didodecyldimethylammonium bromide (hereinafter referred to as DODAB) was dispersed in 107 mL of isooctane, 817 mg of the aforementioned aqueous pH 3-MgSO ₄ solution was added. In the production of silica fine particles (DODAB), mixing was performed so that the water content was 10. While stirring the reaction solution, 4.82 mL of TEOS was added, and the mixture was stirred at 20 ° C. for 3 days (the molar ratio of TEOS to water was 0.5). The reaction solution was heated at 65 to 70 ° C. for 24 hours, the solvent was distilled off, and the residue was vacuum dried. The residue was dispersed in 100 mL of isooctane and heated at 290 ° C. for 12 hours in an autoclave. The solvent was distilled off and the residue was dried.

[Comparative Example 2]
(Manufacture of silica fine particles (CTAB))
After 2.00 g of cetyltrimethylammonium bromide (hereinafter referred to as CTAB) was dispersed in 136 mL of isooctane, 1.04 g of the aforementioned aqueous pH 3-MgSO ₄ was added. In the production of silica fine particles (CTAB), mixing was performed so that the water content was 10. While stirring the reaction solution, 6.12 mL of TEOS was added, and the mixture was stirred at 20 ° C. for 3 days (the molar ratio of TEOS to water was 0.5). The reaction solution was heated at 65 to 70 ° C. for 24 hours, the solvent was distilled off, and the residue was vacuum dried. The residue was dispersed in 100 mL of isooctane and heated at 290 ° C. for 12 hours in an autoclave. The solvent was distilled off and the residue was dried.

(Silica production in aqueous solution)
Inorganic solution was used to produce inorganic oxide fine particles using a cationic surfactant. The production method in an aqueous solution was referred to the description of known literature (Adv. Mater., 12, (2000), 1286-1290).

[Comparative Example 3]
(Production of silica (W-1) in aqueous solution)
After adding 800 mL of ion-exchanged water to 4.63 g of dioctadecyldimethylammonium bromide (hereinafter referred to as DODAB) which is a cationic amphiphilic molecule, an aqueous dispersion of DODAB was prepared, and then ammonia water and ion-exchanged water were added. , 1.00 L of a dispersion liquid having a DODAB concentration of 1.00 × 10 ⁻² mol / L and pH 8 was prepared. Under stirring, 13.4 mL of tetraethoxysilane was added and stirred at 20 ° C. for 7 days. During the stirring, the pH was appropriately checked. If the pH was lowered, a small amount of aqueous ammonia was added to adjust the pH to 8. After stirring, volatile components were distilled off under reduced pressure, and the residue was dried in vacuo.

[Comparative Example 4]
(Production of silica (W-2) in aqueous solution)
In the production of silica (W-1), after stirring for 7 days, the reaction solution was heated at 65 to 70 ° C. for 24 hours before the volatile component was distilled off, and then the volatile component was distilled off and the residue was vacuum-dried. .

[Comparative Examples 5 and 6]
(Production of silica (W-3) and (W-4) in aqueous solution)
In the production of silica (W-1) and (W-2), silica (W-3), (W- 4) were produced respectively.

  Table 1 shows the measurement results of the shape and size of the silica produced by the production method described above. The shape and size of the silica were observed using a scanning electron microscope S-5200 manufactured by Hitachi, Ltd.

Table 1 ─────────────────────────────────────────
Silica production conditions Product dispersibility evaluation Number pH Inorganic salt Water content TEOS / H ₂ O Shape Particle size (nm) H T M
────────────────────────────────────────
II1-1 3 MgSO ₄ 5 0.50 Non-hollow 5-20 B B B
A16-1 2 MgSO ₄ 10 0.50 Non-hollow 20-60 A A B
A16-2 3 MgSO ₄ 10 0.50 Non-hollow 20-60 A A B
A19-1 2 MgSO ₄ 45 0.10 Hollow 200-400 B B B
B1-1 2 MgSO ₄ 10 0.50 Non-hollow 20-60 A A A
B1-2 3 MgSO ₄ 10 0.50 Non-hollow 20-60 A A A
B1-3 12 Li ₂ SO ₄ 10 0.50 Non-hollow 10-80 A A A
B1-4 2 MgSO ₄ 10 0.25 Hollow 20-60 A A A
B1-5 3 MgSO ₄ 10 0.25 Hollow 20-60 A A A
B1-6 12 Li ₂ SO ₄ 10 0.25 Hollow 10-80 A A A
B6-1 2 MgSO ₄ 10 0.50 Non-hollow 20-60 A A A
B6-2 3 MgSO ₄ 10 0.50 Non-hollow 20 to 60 A A A
B6-3 12 Li ₂ SO ₄ 10 0.50 Non-hollow 10-80 A A A
B6-4 2 MgSO ₄ 10 0.25 Hollow 20-60 A A A
B6-5 3 MgSO ₄ 10 0.25 Hollow 20-60 A A A
B6-6 12 Li ₂ SO ₄ 10 0.25 Hollow 10-80 A A A
DODAB-1 3 MgSO ₄ 10 0.50 Aggregate-DD
CTAB-1 3 MgSO ₄ 10 0.50 Aggregate-DD
W-1 8---Hollow 200-400 D D D
W-2 8 − − − Aggregate − D D D
W-3 8 − − − Aggregate − D D D
W-4 8 − − − Aggregate − D D D
45 nm SiO ₂ − − − − (non-hollow) (45) D D C
12 nm SiO ₂ − − − − (non-hollow) (12) D DC
60 nm hollow SiO ₂ − − − − (hollow) (60) D DC
────────────────────────────────────────

(註)
Evaluation of dispersibility: Dispersibility in various organic solvents was evaluated in four stages of A (good) to D (poor) by the following dispersion stability evaluation method in an organic solvent.
H: Hexane T: Toluene M: Methyl ethyl ketone

(Evaluation of dispersion stability in organic solvents)
The silica produced in each example was dispersed in 10 times the mass of hexane, toluene or methyl ethyl ketone to prepare a dispersion having a solid content concentration of 9.1%. Further, commercially available silica fine particle sol (isopropyl alcohol silica sol, IPA-ST-L manufactured by Nissan Chemical Industries, Ltd., average particle size 45 nm, silica concentration 30% by mass) in 100 parts by mass, 230 parts by mass of hexane, Toluene or methyl ethyl ketone was added to prepare dispersions each having a solid concentration of 9.1% (hereinafter, 45 nm SiO ₂ dispersion). Similarly, 230 parts by mass of hexane, toluene, or methyl ethyl ketone is added to 100 parts by mass of silica fine particle sol (methanol silica sol (trade name), average particle size 12 nm, silica concentration 30%, manufactured by Nissan Chemical Industries, Ltd.) Dispersions having a solid content concentration of 9.1% (hereinafter, 12 nm SiO ₂ dispersion) were prepared. Similarly, 100 parts by mass of a hollow silica fine particle sol (isopropyl alcohol hollow silica sol, CS-60-IPA manufactured by Catalyst Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica refractive index 1.31). 120 parts by mass of hexane, toluene, or methyl ethyl ketone was added to prepare a dispersion having a solid content concentration of 9.1% (hereinafter, 60 nm hollow SiO ₂ dispersion). 10 cc of the dispersion thus prepared was collected in a test tube having a diameter of 10 mm, and foreign matters were visually observed. The degree of occurrence of foreign matters that can be visually observed was evaluated in the following four ranks.
A: Foreign matter is not recognized.
B: Foreign matter of about 50 μm is slightly observed.
C: Foreign matter of 500 μm or more is clearly observed.
D: In addition to foreign matters of 500 μm or more, clearly aggregated precipitates are observed.

As is apparent from the results shown in Table 1, when the water content is 10 or less, silica fine particles having a particle size of 100 nm or less can be produced by a production method using reverse micelles in an organic solvent, and the water content is 45 or more. Then, silica fine particles having a particle diameter of 200 nm or more could be produced. Furthermore, when the molar ratio of TEOS to water was 0.50 or more, non-hollow structure particles could be produced, and when it was 0.25 or less, hollow structure particles could be produced.
FIG. 2 is an electron micrograph of silica fine particles (A19-1). FIG. 3 is an electron micrograph of silica fine particles (B6-2). FIG. 4 is an electron micrograph of silica fine particles (B6-5).

  In order to form reverse micelles, those having high dispersibility in organic solvents such as compounds (A-16), (A-19) and (B-1) are preferred. Silica (DODAB-1) and (CTAB-1) produced from DODAB or CTAB having low dispersibility in an organic solvent were white aggregates. Moreover, in the manufacturing method in aqueous solution, although silica (W-1) was a hollow silica fine particle with a particle size of 200-400 nm, silica (W-2)-(W-4) were white aggregates. Met.

  Further, as is apparent from the results in Table 1, the silica fine particles produced according to the present invention have a good dispersibility in hexane or toluene and give a uniform transparent dispersion solution. Furthermore, the compound (B-1 ) And the compound (B-6), the silica fine particles are excellent in dispersibility in methyl ethyl ketone and give a uniform transparent dispersion solution.

[Create anti-reflection film]
(Preparation of coating solution for low refractive index layer)
2-butanone 200 parts by mass, cyclohexanone 150 parts by mass, as a low refractive index binder 30 parts by mass of the following fluoropolymer, photo radical generator (Irgacure 907) 3 parts by mass, dipentaerythritol pentaacrylate and dipentaerythritol After adding 7 parts by mass of a mixture of hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), 30 parts by mass of silica fine particles dissolved in 580 parts by mass of methyl ethyl ketone are added, and the solid content concentration of the entire coating liquid is 7 A coating solution for a low refractive index layer was prepared by diluting with methyl ethyl ketone so as to have a mass%. When the name of the silica used is (**), the name of the coating solution is (L-**). Similarly, in the above coating solution preparation method, the only difference is that 531 parts by mass of methyl ethyl ketone is used instead of 30 parts by mass of silica fine particles dissolved in 580 parts by mass of methyl ethyl ketone. L-blank) was prepared.

(Preparation of antireflection film 301)
A coating solution for a low refractive index layer was applied onto a triacetyl cellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a bar coater.
The low refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 240 W / cm ² air-cooled metal halide lamp (I graphics The irradiance was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² . The film thickness of the low refractive index layer after curing was 85 nm.

(Evaluation of antireflection film)
The obtained film was evaluated for the following items.
(1) Plane shape of coating sample Oily black ink was applied to the back of the coated sample, and the angle was changed at about 10 cm under a 500 W three-wavelength fluorescent lamp, and visually evaluated.
The unevenness in which reflected light is diffused and looks white and dull was evaluated in the following four stages.
A: Even if you look very carefully, you can't see any haze.
B: Light is diffused slightly when viewed very carefully.
C: A white portion is observed in a haze.
D: One surface has a white haze.

(2) Steel Wool Scratch Resistance (SW Strength) Evaluation Using a rubbing tester, a rubbing test was performed under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH, rubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd.) is wound around the rubbing tip (1 cm × 1 cm) of the tester that comes into contact with the sample, and the band is fixed so as not to move. .
Travel distance (one way): 13cm
Rubbing speed: 13 cm / sec Load: 500 g / cm ²
Tip contact area: 1cm x 1cm
Number of rubs: 10 round trips

An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following 6 levels.
A: Even if you look very carefully, no scratches are visible.
B: Slightly weak scratches are visible when viewed very carefully, but there is no practical problem.
C: Weak scratches are visible.
D: A moderate crack is visible.
E: There is a scratch that can be seen at first glance.
F: The single-sided film is damaged.

(3) Refractive Index Evaluation The refractive index of the formed low refractive index layer for an antireflection film was measured using a refractometer (Abbe refractometer NAR-1T, manufactured by Atago Co., Ltd.).
The results are shown in Table 2.

Table 2 ─────────────────────────────────────────
Coating liquid Fine particle number Shape Particle size (nm) Planar SW intensity Refractive index ────────────────────────────────── ──────
L-blank None-A F 1.453
L-B1-2 B1-2 Non-hollow 20-60 B A 1.452
L-B1-5 B1-5 Hollow 20-60 BB 1.387
L-B6-2 B6-2 Non-hollow 20-60 A A 1.455
L-B6-5 B6-5 Hollow 20-60 A B 1.382
L-DODAB-1 DODAB-1 aggregate-DE 1.45 (difficult to measure) L-CTAB-1 CTAB-1 aggregate-DE 1.45 (difficult to measure) L-W-1 W-1 hollow 200 to 400 D E 1.45 (measured flame) L-W-3 W- 3 aggregates - D E 1.45 (measured flame) L-45nmSiO ₂ 45nmSiO ₂ (non-hollow) (45) D F 1.438
L-12nmSiO ₂ 12nmSiO ₂ (non-hollow) (12) D F 1.438
L-60nm hollow SiO ₂ 60nm hollow SiO ₂ (hollow) (60) DF 1.400
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  As is apparent from the results shown in Table 2, the silica fine particles produced according to the present invention not only have good dispersibility in organic solvents, but also show good dispersibility in organic polymers. . Therefore, according to the present invention, a thin film having excellent coating surface properties and high scratch resistance was obtained. Furthermore, a low refractive index could be realized by using hollow fine particles.

FIG. 1 is an example of a strength profile of hollow particles. It is an electron micrograph of the hollow spherical silica fine particle (A19-1) manufactured using the reverse micelle prepared from the compound (A-19) as a template. It is an electron micrograph of the non-hollow spherical silica fine particle (B6-2) manufactured using the reverse micelle prepared from the compound (B-6) as a template. It is an electron micrograph of the hollow silica fine particle (B6-5) manufactured using the reverse micelle prepared from the compound (B-6) as a template.

Claims (11)

  In the W / O emulsion in which the aqueous phase is emulsified in the oil phase and the cationic surfactant is dissolved in the oil phase, the particle size is reduced by the reaction of hydrolyzing and condensing the inorganic oxide precursor. A method for producing inorganic oxide fine particles comprising a step of producing inorganic oxide fine particles having a thickness of 5 nm to 1 μm.   The production method according to claim 1, wherein the inorganic oxide is an oxide of silicon, titanium, zirconium, or aluminum.   The method according to claim 2, wherein the inorganic oxide precursor is an alkoxide or carboxylate of silicon, titanium, zirconium or aluminum.   The manufacturing method of Claim 1 which uses an acid or a base as a catalyst in reaction which hydrolyzes and condenses an inorganic oxide precursor. The production method according to claim 1, wherein the cationic surfactant is represented by the following formula (I):

[Wherein, R ¹ and R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms; R ² and R ⁵ each independently represent 1 carbon atom; R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms; A substituted alkyl group having 1 to 20 carbon atoms; L ¹ , L ² and L ³ are each independently a single bond or an alkylene group having 1 to 5 carbon atoms, and having 6 to 20 carbon atoms; A divalent linking group selected from the group consisting of an arylene group, -O-, -S-, -CO-, -NR- and combinations thereof, wherein R is a hydrogen atom or a carbon atom number of 1 to 5 An alkyl group; X ¹ is an anion]. The production method according to claim 1, wherein the cationic surfactant is represented by the following formula (II):
^{(II) + N (-R 11} ) (- R 12) (- R 13) (- R 14) · X 11
[Wherein R ¹¹ and R ¹² are each independently an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group having 1 to 20 carbon atoms; and R ¹³ and R ¹⁴ are carbon atoms. Is an alkyl group having 4 to 20 carbon atoms or a substituted alkyl group having 4 to 20 carbon atoms, and the alkyl group or the alkyl portion of the substituted alkyl group has at least one branch, or the substituted alkyl group is a carbon other than the terminal. Substituted at the atom by an alkoxy group; X ¹¹ is an anion].   The production method according to claim 1, wherein the produced inorganic oxide fine particles have a hollow structure.   Inorganic oxide microparticles | fine-particles obtained with the manufacturing method as described in any one of Claims 1-7.   A composition containing the inorganic oxide fine particles according to claim 8.   An optical film comprising the composition according to claim 9.   The optical film according to claim 10, which has an antireflection function.

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