JP2007262163A - Fine pigment particles, liquid dispersion and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide fine pigment particles as a near-infrared ray-absorbing material that satisfies both invisibility that performs important roles as an optoelectronics-related product such as a near-infrared ray-absorbing filter and other properties, a liquid dispersion and its manufacturing method. <P>SOLUTION: The fine pigment particles comprises fine particles of vanadyl-2,3-naphthalocyanine having an average particle size of at most 0.5 μm. The fine particles are manufactured via a liquid dispersion which is obtained by dispersing a mixture of a solvent and vanadyl-2,3-naphthalocyanine using at least one surfactant selected from among cationic surfactants, anionic surfactants and nonionic surfactants thereby converting vanadyl-2,3-naphthalocyanine into fine particles having an average particle size of at most 0.5 μm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to pigment fine particles, a liquid dispersion containing the same, and a method for producing the same, and more specifically, a near infrared absorption filter, a near infrared absorption coloring composition, a liquid crystal display element, an optical card, an optical recording medium, The present invention relates to pigment fine particles, liquid dispersions of near-infrared absorbing materials that achieve both invisibility and near-infrared absorbing properties that play an important role in optoelectronics such as protective glasses, and a method for producing the same.

Near-infrared absorbing dyes that do not substantially absorb visible light but absorb infrared rays are used in various optoelectronic products such as near-infrared absorbing filters. These are required to be invisible, that is, they are not colored when viewed with the naked eye, that is, have no absorption in the visible range. For this purpose, it is essential that the absorption is not visible in the visible region, and that the absorption in the near infrared region is as strong as possible. For this, a method of designing the structure so as to suppress the associative property so that the original absorption can be expressed (for example, Patent Document 1), and by increasing the absorption wavelength, the short-wave side tail of the absorption peak is improved and invisibility is increased. However, further improvements have been desired.
JP-A-2-29685 Japanese Patent Laid-Open No. 11-152413 Japanese Patent Laid-Open No. 11-152414 Japanese Patent Laid-Open No. 11-152415

  The object of the present invention is to achieve both invisibility and near-infrared absorption characteristics that play an important role in optoelectronics such as near-infrared absorption filters, near-infrared absorption coloring compositions, liquid crystal display elements, optical cards, optical recording media, and protective glasses. An object of the present invention is to provide a pigment fine particle, a liquid dispersion and a method for producing the same of a near-infrared absorbing material.

  As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following means.

(1) Fine particles of vanadyl-2,3-naphthalocyanine having an average particle size of 0.5 μm or less.
(2) A liquid dispersion comprising the fine particles according to (1).
(3) The liquid dispersion according to (2), wherein the dispersion component contains water.
(4) The liquid dispersion contains at least one selected from a cationic surfactant, an anionic surfactant or a nonionic surfactant, as described in (2) or (3) Liquid dispersion.
(5) The liquid dispersion according to any one of (2) to (4), wherein the liquid dispersion is obtained by bead dispersion.
(6) A solvent and a vanadyl-2,3-naphthalocyanine mixture are dispersed with at least one surfactant selected from a cationic surfactant, an anionic surfactant, or a nonionic surfactant, and vanadyl- A method for producing a liquid dispersion, characterized in that the average particle size of 2,3-naphthalocyanine is fine particles of 0.5 μm or less.
(7) The method for producing a liquid dispersion according to (6), wherein the dispersion is dispersed by bead dispersion.
(8) A method for producing a liquid dispersion, wherein a solution obtained by dissolving vanadyl-2,3-naphthalocyanine in an easily soluble solvent is added to the hardly soluble solvent.

  The near infrared absorption filter, near infrared absorption coloring composition, liquid crystal display element, optical card, optical recording medium, protective glasses, etc. It is possible to provide a pigment fine particle, a liquid dispersion of an infrared absorbing material, and a production method thereof.

Hereinafter, embodiments of the present invention will be described in detail.
The vanadyl-2,3-naphthalocyanine fine particles of the present invention have an average particle size of 0.5 μm or less, preferably 0.4 μm or less, preferably 0.35 μm or less. When the average particle size of the vanadyl-2,3-naphthalocyanine fine particles exceeds 0.5 μm, absorption characteristics in the near infrared region are not observed.

The vanadyl-2,3-naphthalocyanine in the present invention can be produced, for example, by the method described in JP-A-10-158533. The purity of vanadyl-2,3-naphthalocyanine as a dispersion raw material in the present invention is preferably 90% or more, but preferably 95% or more.
In order to obtain fine particles of vanadyl-2,3-naphthalocyanine of 0.5 μm or less in the present invention, 1) bead dispersion (bead mill dispersion), roll mill dispersion, ultrasonic dispersion, etc. are methods for making fine particles by mechanical dispersion. Yes, described in “Pigment Dispersion Technology Surface Treatment and Use of Dispersing Agents and Evaluation of Dispersibility” (Edited by Technical Information Association), among them, bead dispersion is preferable.
2) As a method using the difference in solubility, a reaction mixture in which vanadyl-2,3-naphthalocyanine is dissolved is added as it is to a poor solvent (for example, water, methanol) to precipitate crystals, or isolated once. There is a method (for example, an acid paste method) in which a crystal of vanadyl-2,3-naphthalocyanine is dissolved in an easily soluble solvent (for example, sulfuric acid) and then added to a hardly soluble solvent (for example, water) to precipitate the crystal. .

  In bead dispersion, a mixture of a solvent and vanadyl-2,3-naphthalocyanine is dispersed with at least one surfactant selected from a cationic surfactant, an anionic surfactant, or a nonionic surfactant.

  The solvent used for dispersion in the present invention is not particularly limited. For example, water, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone) , Sulfone solvents (eg, sulfolane), sulfoxide solvents (eg, dimethyl sulfoxide), ether solvents (eg, dioxane, cyclopentyl methyl ether), ketone solvents (eg, acetone, methyl ethyl ketone), hydrocarbon solvents (eg, toluene, xylene) , Halogen solvents (eg, tetrachloroethane, chlorobenzene), alcohol solvents (eg, methanol, ethanol, isopropanol, 1-butanol, ethylene glycol), pyridine solvents (eg, pyridine, γ-picoline, 2,6-lutidine) alone Some Used in mixing. Preferred are water, amide solvents, sulfone solvents, sulfoxide solvents, ether solvents, ketone solvents, alcohol solvents, and more preferred are water, ether solvents, ketone solvents, alcohol solvents. More preferred are water, methanol, ethanol and methyl ethyl ketone, and most preferred is a case of water alone. In addition to adding these solvents at the time of dispersion, they can be added after dispersion or removed by distillation.

  The mass ratio of vanadyl-2,3-naphthalocyanine to the solvent when dispersing is preferably 3 to 500 solvent, more preferably 8 to 200 solvent with respect to vanadyl-2,3-naphthalocyanine 1. More preferably, it is a solvent 15-100, Most preferably, it is a solvent 20-50.

    In the present invention, a mixture of a solvent and vanadyl-2,3-naphthalocyanine is dispersed with a surfactant. Surfactants include alkylene oxide, glycerin, glycidol, nonionic surfactants such as alkylphenol ethylene oxide adducts, cyclic amines, ester amides, quaternary ammonium salts, hydantoin derivatives, heterocycles, phosphonium or Cationic surfactants such as sulfoniums, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, and sulfate ester groups, amino acids, aminosulfonic acids, amino alcohol sulfuric acid or phosphate esters, alkylbetaine type Amphoteric surfactants such as can also be used. These surfactants are described in detail in “Surfactant Handbook” (published by Sangyo Tosho Co., Ltd.). These are not necessarily pure and may contain impurities such as isomers, unreacted products, side reaction products, decomposition products, oxides, etc. in addition to the main components. These impurities are preferably 30% by mass or less, more preferably 10% by mass or less. These additives can be used alone or in combination of two or more.

  Of the additives, nonionic surfactants, anionic surfactants or cationic surfactants are preferred, nonionic surfactants or anionic surfactants are more preferred, and anionic surfactants are more preferred. An organic sulfonic acid metal salt having 40 or less carbon atoms, more preferably an organic sulfonic acid metal salt having 30 or less carbon atoms, and most preferably sodium or 25% of organic sulfonic acid having 25 or less carbon atoms. Potassium salt.

In addition to the surfactant described above, additives can be added to the dispersion of the present invention as necessary.
Additives include silicone oil, silicone with polar group, fatty acid-modified silicone, fluorine-containing silicone, fluorine-containing alcohol, fluorine-containing ester, polyolefin, polyglycol, polyphenyl ether, phenylphosphonic acid, benzylphosphonic acid group, phenethylphosphonic acid , Α-methylbenzylphosphonic acid, 1-methyl-1-phenethylphosphonic acid, diphenylmethylphosphonic acid, biphenylphosphonic acid, benzylphenylphosphonic acid, α-cumylphosphonic acid, toluylphosphonic acid, xylylphosphonic acid, ethylphenylphosphonic acid, Aromatic ring-containing organics such as cumenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, heptylphenylphosphonic acid, octylphenylphosphonic acid, nonylphenylphosphonic acid Phosphonic acid and its alkali metal salts, octylphosphonic acid, 2-ethylhexylphosphonic acid, isooctylphosphonic acid, (iso) nonylphosphonic acid, (iso) decylphosphonic acid, (iso) undecylphosphonic acid, (iso) dodecylphosphonic Acids, alkylphosphonic acids such as (iso) hexadecylphosphonic acid, (iso) octadecylphosphonic acid, (iso) eicosylphosphonic acid and alkali metal salts thereof, phenyl phosphate, benzyl phosphate, phenethyl phosphate, α-methylbenzyl phosphate, 1-methyl-1-phenethyl phosphate, diphenylmethyl phosphate, biphenyl phosphate, benzyl phenyl phosphate, α-cumyl phosphate, toluyl phosphate, xylyl phosphate, ethyl phenyl phosphate, cumenyl phosphate, propyl phenyl phosphate, butyl phenyl phosphate, heptyl phenyl phosphate, Phosphoric acid Aromatic phosphates such as octylphenyl, nonylphenyl phosphate and alkali metal salts thereof, octyl phosphate,

2-ethylhexyl phosphate, isooctyl phosphate, (iso) nonyl phosphate, (iso) decyl phosphate, (iso) undecyl phosphate, (iso) dodecyl phosphate, (iso) hexadecyl phosphate, (iso) octadecyl phosphate, (iso) eicosyl phosphate, etc. Alkyl phosphates and their alkali metal salts, alkyl sulfonic acid esters and their alkali metal salts, fluorine-containing alkyl sulfates and their alkali metal salts, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, butyl stearate, Monobasic fatty acids that may contain or be branched, such as oleic acid, linoleic acid, linolenic acid, elaidic acid, erucic acid, acid, etc., or branched, and their metal salts, or stearic acid Butyl, octyl stearate, stearic acid Unsaturated bonds having 10 to 24 carbon atoms, such as sodium, isooctyl stearate, octyl myristate, butyl laurate, butoxyethyl stearate, anhydrosorbitan monostearate, anhydrosorbitan distearate, anhydrosorbitan tristearate A monobasic fatty acid that may be branched or branched, a 1 to 6-valent alcohol that may be branched or include an unsaturated bond having 2 to 22 carbon atoms, or an unsaturated bond that has 12 to 22 carbon atoms Mono-fatty acid ester, difatty acid ester or polyvalent fatty acid ester, any one of alkoxy alcohol which may be branched or monoalkyl ether of alkylene oxide polymer, C2-C22 fatty acid amide, C8- 22 aliphatic amines can be used. In addition to the above hydrocarbon groups, alkyl groups, aryl groups, and aralkyl groups substituted with nitro groups and groups other than hydrocarbon groups such as halogen-containing hydrocarbons such as F, Cl, Br, CF ₃ , CCl ₃ , and CBr ₃ It may be one with

  The amount of the dispersing agent such as the surfactant described above is preferably 2% by mass or less, more preferably 0.01 to 15% by mass in the mixture containing the solvent and vanadyl-2,3-naphthalocyanine and the like. More preferably, it is 0.05-12 mass%, More preferably, it is 0.1-10 mass%, More preferably, it is 1-8 mass%.

  For the dispersion media, conventionally used glass beads, metal beads, alumina beads, titania beads, zirconia beads, etc. can be used, preferably ceramic beads such as zirconia beads, titania beads, most preferably. Are zirconia beads.

  As the diameter of the dispersion medium is reduced, the unevenness of the surface can be reduced, and is preferably 2.0 mm or less, more preferably 1.5 mm or less, further preferably 1.0 mm or less, and most preferably. Is 0.05 to 0.5 mm.

  The mass ratio of vanadyl-2,3-naphthalocyanine to the dispersion medium during dispersion is preferably 1 to 1,000, more preferably 5 for the dispersion medium with respect to vanadyl-2,3-naphthalocyanine 1. It is -200, More preferably, it is 10-150, More preferably, it is 15-100, Most preferably, it is 20-50.

  Dispersers used in the dispersion process include Ashizawa Finetech Co., Ltd. agitator mill LMJ, LMZ or ultra-fine crusher AMC, Asada Tekko Co., Ltd. Pure Mill, Nano Mill or Picomill, Kotobuki Giken Kogyo Co., Ltd. Super Apex mills, SC mills manufactured by Mitsui Mining Co., Ltd., etc. can be used.

  The step of adding a dispersant such as the above-described surfactant is preferably added in the dispersion step or after the dispersion, and the method of adding in the dispersion step is most preferable. The term “after dispersion” refers to the step after the breakdown of the particles and the separation from the media.

  In the dispersion step, it varies depending on the type of beads, the diameter of the beads, the sand mill, etc., but the dispersion time is preferably 500 to 6000 rpm, 1000 to 4000 rpm in the sand mill, and preferably 3 minutes to 12 hours, more preferably 15 minutes to 3 hours. is there.

  The dispersion viscosity of the dispersion is preferably 10 to 100000 [mPa · S], more preferably 30 to 30000 [mPa · S], and still more preferably 50 to 10000 [mPa · S]. is there.

In the present invention, a method using the difference in solubility of vanadyl-2,3-naphthalocyanine can be used in addition to the above-described method using bead dispersion.
For example, a method in which a reaction mixture in which vanadyl-2,3-naphthalocyanine is dissolved is added as it is to a poor solvent (for example, water, methanol) to precipitate crystals, or once isolated vanadyl-2,3-naphthalocyanine There is a method (for example, acid paste method) in which the crystal is dissolved in an easily soluble solvent and then added to the hardly soluble solvent to precipitate the crystal.

Here, the easily soluble solvent means a solvent in which 2 g or more of vanadyl-2,3-naphthalocyanine is dissolved when vanadyl-2,3-naphthalocyanine is added to 100 g of the solvent at 25 ° C.
As an example of such a solvent, sulfuric acid is preferable. Further, the hardly soluble solvent is a solvent in which when vanadyl-2,3-naphthalocyanine is added to 100 g of the solvent, vanadyl-2,3-naphthalocyanine does not dissolve at 0.5 g, and the solution starts to become opaque. Say.
Examples of such a solvent include, for example, water, ethyl acetate, hexane and the like. Among these, water is preferable from the viewpoint of miscibility with an easily soluble solvent.

  Various known methods can be used to measure the particle size of vanadyl-2,3-naphthalocyanine produced by the method of the present invention, and an optical method such as light scattering is preferred.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Hereinafter, “part” means “part by mass”.

Example 1
: Preparation of vanadyl-2,3-naphthalocyanine fine particles Crude vanadyl-2,3-naphthalocyanine 3 parts Water 20 parts Sodium dodecylbenzenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.09 parts 0.3 mmΦ zirconia beads 100 parts The raw material was processed at 3000 rpm for 1 hour in the batch ratio sand mill. When an aqueous dispersion of beads and vanadyl-2,3-naphthalocyanine was separated and the particle size distribution was measured, the average particle size was 0.31 μm, and the viscosity was measured with an E-type viscometer to find 950 [mPa · S]. Moreover, when this sample was apply | coated to the glass plate and the near-infrared absorption was measured, the favorable absorption characteristic was acquired. Invisibility was evaluated by a value obtained by dividing an absorption value at 400 nm, which is a visible absorption region, by λmax in a near infrared absorption region (800 to 1100 nm).
The viscosity was measured at 25 ° C. using a Toki Sangyo E-type viscometer RE-80R. For the particle size distribution of the dispersion, a laser diffraction / scattering type particle size distribution analyzer LA-920A manufactured by HORIBA, Ltd. was used. The IR absorption test was evaluated by applying it to a glass plate by the following operation and measuring the transmitted light. Hitachi spectrophotometer U-4100 was used for the measurement.

(Production of glass plate for evaluation)
A sample obtained by adding 100 ml of chloroform to 10 g of polystyrene and 0.1 g of vanadyl-2,3-naphthalocyanine (dry weight) and stirring and dispersing at 40 ° C. is applied to a glass plate and dried at room temperature. Was made.

(Example 2)
The same procedure as in Example 1 was performed except that the media of Example 1 was changed from 100 parts of 0.3 mmΦ zirconia beads to 150 parts of 0.5 mmΦ zirconia beads.
When the particle size distribution was measured, the average particle size was 0.41 μm, and when the viscosity was measured with an E-type viscometer, it was 240 [mPa · S]. Moreover, when this sample was apply | coated to the glass plate and the near-infrared absorption was measured, the favorable absorption characteristic was acquired.

(Example 3)
The same procedure as in Example 1 was performed except that the surfactant in Example 1 was changed from 0.09 part of sodium dodecylbenzenesulfonate to 0.3 part of DINSNa (sodium diisopropylnaphthalenesulfonate).
When the particle size distribution was measured, the average particle size was 0.27 μm, and when the viscosity was measured with an E-type viscometer, it was 500 [mPa · S]. Moreover, when this sample was apply | coated to the glass plate and the near-infrared absorption was measured, the favorable absorption characteristic was acquired.

Example 4
The surfactant of Example 1 was changed from 0.09 part of sodium dodecylbenzenesulfonate to 0.09 part of PEG-OP (polyethylene glycol mono-4-octylphenyl ether), and the media was changed from 100 parts of 0.3 mmΦ zirconia beads. The same procedure as in Example 1 was performed except that the content was changed to 150 parts of 0.5 mmΦ zirconia beads.
When the particle size distribution was measured, the average particle size was 0.47 μm, and when the viscosity was measured with an E-type viscometer, it was 120 [mPa · S]. Moreover, when this sample was apply | coated to the glass plate and the near-infrared absorption was measured, the favorable absorption characteristic was acquired.

(Example 5)
The surfactant of Example 1 was changed from 0.09 part of sodium dodecylbenzenesulfonate to 0.15 part of PEG-OP (polyethylene glycol mono-4-octylphenyl ether), and the media was changed from 100 parts of 0.3 mmΦ zirconia beads. The same procedure as in Example 1 was performed except that 90 parts of 0.3 mmφ titania beads were used.
When the particle size distribution was measured, the average particle size was 0.30 μm, and when the viscosity was measured with an E-type viscometer, it was 7000 [mPa · S]. Moreover, when this sample was apply | coated to the glass plate and the near-infrared absorption was measured, the favorable absorption characteristic was acquired.

(Example 6)
The same procedure as in Example 1 was carried out except that the surfactant of Example 1 was changed from 0.09 part of sodium dodecylbenzenesulfonate to 0.3 part of MODA-Cl (dimethyldioctadodecylammonium chloride).
When the particle size distribution was measured, the average particle size was 0.28 μm, and when the viscosity was measured with an E-type viscometer, it was 1100 [mPa · S]. Moreover, when this sample was apply | coated to the glass plate and the near-infrared absorption was measured, the favorable absorption characteristic was acquired.

(Example 7)
By dissolving crude vanadyl-2,3-naphthalocyanine (1 part) in concentrated sulfuric acid (10 parts), which is a readily soluble solvent, and pouring it into water (20 parts), a poorly soluble solvent, to precipitate crystals, A refined vanadyl-2,3-naphthalocyanine crystal having an average particle size of 0.30 μm was obtained. When this sample was applied to a glass plate and near-infrared absorption was measured, good absorption characteristics were obtained.

Comparative Example 1
Crude vanadyl-2,3-naphthalocyanine was ground in a mortar, and the particle size distribution of the obtained powder was measured. The average particle size was 1.05 μm. This sample was applied to a glass plate, and near-infrared absorption was measured, but good absorption characteristics were not obtained.

Comparative Example 2
The same operation as in Example 1 was performed except that the sand mill treatment time in Example 1 was reduced from 1 hour to 5 minutes. By this operation, vanadyl-2,3-naphthalocyanine having an average particle diameter of 0.54 μm was obtained. When the viscosity was measured with an E-type viscometer, it was 140 [mPa · S]. This sample was applied to a glass plate, and near-infrared absorption was measured, but good absorption characteristics were not obtained.

  These results are summarized in Table 1 below.

IR absorption test value (invisibility) =
(Absorption value at 400 nm) / (Absorption value at λmax of 800-1100 nm)
(Abbreviation of surfactant)
* DBSNa: sodium normal dodecyl benzene sulfonate * DINSNa: sodium diisopropyl naphthalene sulfonate * PEG-OP: polyethylene glycol mono-4-octyl phenyl ether * MODA-Cl: dimethyl dioctadodecyl ammonium chloride

Claims (8)

  Fine particles of vanadyl-2,3-naphthalocyanine having an average particle size of 0.5 μm or less.   A liquid dispersion comprising the fine particles according to claim 1.   The liquid dispersion according to claim 2, wherein water is contained in the components of the dispersion.   4. The liquid dispersion according to claim 2, wherein the liquid dispersion contains at least one selected from a cationic surfactant, an anionic surfactant, and a nonionic surfactant.   The liquid dispersion according to claim 2, wherein the liquid dispersion is obtained by bead dispersion.   A solvent and a vanadyl-2,3-naphthalocyanine mixture are dispersed with at least one surfactant selected from a cationic surfactant, an anionic surfactant, or a nonionic surfactant, and vanadyl-2,3 A method for producing a liquid dispersion, wherein the average particle diameter of naphthalocyanine is fine particles having a size of 0.5 μm or less.   The method for producing a liquid dispersion according to claim 6, wherein the dispersion is dispersed by bead dispersion.   The manufacturing method of the liquid dispersion characterized by adding the solution which melt | dissolved vanadyl-2,3-naphthalocyanine in the easily soluble solvent to a hardly soluble solvent.