KR20150020576A - Fine inorganic compound particle dispersed composition and fine inorganic compound particle dispersed cured product - Google Patents

Abstract

There can be provided an inorganic fine particle dispersion composition and a cured product which can exhibit excellent dispersibility and dispersion stability of inorganic metal compound fine particles and also have excellent surface smoothness after being cured into a film. The inorganic compound fine particle dispersion composition according to the present invention comprises (A) inorganic fine particle, (B) polymerizable compound and, if necessary, (C) solvent, wherein (A) (A-1) a fine particle sol of a metal oxide or a fine particle sol of a (A-2) metal or a semimetal nitride is used as the inorganic fine particle. By curing the dispersion composition, a cured product related to the present invention is obtained.

Description

TECHNICAL FIELD [0001] The present invention relates to a fine particle dispersed inorganic compound fine particle dispersion composition and a fine particle dispersed inorganic particle fine particle dispersible curable composition,

The present invention relates to a composition in which inorganic fine particles are dispersed and a cured product thereof, and more particularly to a composition and a cured product of the composition, wherein the fine inorganic particles are metal oxide or fine particles of metal or semimetal nitride.

In recent years, as one of the utilization forms of various inorganic materials, there can be enumerated dispersed materials which are dispersed as fine particles in an aqueous dispersion medium or a non-aqueous dispersion medium. This dispersion is in a state in which the fine particles are dispersed in a liquid dispersion medium, which is a " fine-size solid " in which the inorganic material is fine particles. Therefore, in the production of various products using inorganic materials, it is possible to efficiently improve processing characteristics, product characteristics, material properties and the like, and to contribute to quality stabilization or improvement in yield at the time of production.

On the other hand, there are cases where fine particles in a dispersion medium can not be stably dispersed in the dispersion medium due to, for example, changing the material, making the particle size more minute, controlling the particle shape, or the like. In this case, there is a possibility that the fine particles are aggregated in the dispersion medium in a short time, and the aggregation causes the decrease in the productivity of the dispersion, the deterioration of the processing characteristics, the lowering of the handling property and the lowering of the yield, There is a possibility that the properties of the final product produced may be lowered, the quality may be lowered, and the material properties of the dispersion quality (inorganic material) may be lowered.

Hitherto, in the field of a dispersion containing fine particles of an inorganic material, various techniques for suppressing aggregation of fine particles as a dispersion medium and improving stabilization of the dispersion state have been proposed.

For example, Patent Document 1 discloses a surface treatment agent for metal oxide particles, which uses a metal oxide as a fine particle of an inorganic material and surface treatment of the metal oxide particle to improve dispersibility, and a hard coat layer And a hard coat film obtained by using the same. This hard coat film is particularly preferable for an image display apparatus.

As the metal oxide fine particles used in Patent Document 1, for example, titania particles, zirconia particles, or alumina particles are exemplified. These particles are known to improve the refractive index by being added to an optical material, and a material obtained by compounding these fine particles and a resin material (ionizing radiation curable compound) can be used as a coating agent for a display screen of an image display device, It is possible to improve the optical performance, and furthermore, the heat radiation performance can be improved depending on the field of use.

In order to improve the dispersibility of these particles and to improve the transparency and scratch resistance of the hard coat film to be formed, Patent Document 1 discloses a resin composition containing a carboxylic acid group and at least four ethylenically unsaturated groups per molecule And a coating agent comprising a metal oxide particle surface-treated with the surface-treating agent and an ionizing radiation-curable compound.

As a technique for improving the dispersibility of the dispersed fine particles, there has been proposed a technique of using a dispersing agent as well as a technique of surface treating the fine particles as described above. For example, the applicant of the present application discloses a dispersion composition using a dispersant having a specific structure in order to improve dispersibility of nano-sized zirconium oxide particles in Patent Document 2.

Japanese Patent Application Laid-Open No. 2010-275483 Japanese Laid-Open Patent Publication No. 2012-007144

Here, all of the above-mentioned conventional techniques are limited to a specific use or a case where specific inorganic fine particles are used. Specifically, the technique disclosed in Patent Document 1 is substantially limited to the hard coat film field of an image display apparatus, and the inorganic compound fine particles are substantially limited to titania particles, zirconia particles, or alumina particles. The technique disclosed in Patent Document 2 is not particularly limited in its application, but the inorganic metal compound fine particles are limited to zirconium oxide particles (zirconia particles).

In the case of forming a film with the coating agent disclosed in Patent Document 1, the surface smoothness and storage stability of the film may not be sufficient although the conditions may vary depending on the conditions.

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve such problems, and it is an object of the present invention to provide an inorganic fine particle which is excellent in dispersibility and dispersion stability of inorganic fine metal particles as dispersoids and has excellent surface smoothness And a cured product obtained by curing the inorganic compound fine particle dispersion composition.

The inorganic compound fine particle dispersion composition according to the present invention is a dispersion medium containing inorganic fine particles (A) and (B) a polymerizable compound, wherein the inorganic fine particle (A) (A-1) a particulate sol of a metal oxide or a particulate sol of a (A-2) metal or a semimetal nitride is used as the inorganic fine particle (A).

According to the above-described constitution, by using fine particulate sol as the inorganic fine particle (A) instead of using a powder such as metal or semimetal oxide, it is possible to obtain a fine dispersion of fine inorganic compound particles (A) having excellent dispersibility and storage stability And the surface smoothness after curing into a film, for example, is also excellent. In addition, since it is not necessary to use a dedicated mechanism or device for dispersing the dispersoid, it is possible to easily produce the inorganic fine particle dispersion composition.

In the inorganic fine particle dispersion composition having the above-described constitution, the fine particulate sol of the metal oxide (A-1) is at least one of a fine particulate sol composed of one kind of metal oxide and a complex oxide fine particol composed of a complex oxide .

In the inorganic fine particle dispersion composition having the above-mentioned constitution, the fine particle sol of the metal oxide (A-1) or the fine metal sol of the (A-2) metal or semimetal nitride is preferably at least one selected from the group consisting of Group 4, Or a particulate sol containing a metal element or a semimetal element belonging to at least one of Group 14 of the Periodic Table of Elements.

In the inorganic fine particle dispersion composition having the above-mentioned constitution, the (B) polymerizable compound may be a compound having a carboxyl group and an ethylenic unsaturated group in the molecule.

(C) a solvent in the range of 0.001 to 4.0 times the total weight of the inorganic fine particles (A) and the polymerizable compound (B) in the inorganic fine particle dispersion composition having the above- .

Further, the present invention also includes a cured dispersion of an inorganic fine particle obtained by curing the inorganic fine particle dispersion composition having the above-described constitution.

According to the present invention, it is possible to make the above-described constitution excellent in dispersibility and dispersibility of the dispersed inorganic metal compound microparticles, and also have excellent surface smoothness after being cured in the form of a film. It is possible to provide an inorganic compound fine particle dispersion composition and a cured product thereof.

Hereinafter, preferred embodiments of the present invention will be described. The inorganic fine particle dispersion composition according to the present invention is a fine inorganic particle particle dispersion composition containing at least (A) inorganic fine particles and (B) a polymerizable compound and the inorganic fine particles (A) (A-1) a fine particulate sol of a metal oxide or a fine particulate sol of a (A-2) metal or a semimetal nitride is used as the inorganic fine particulate. The inorganic compound fine particle dispersion cured product according to the present invention is obtained by curing the inorganic fine particle dispersion composition having the above constitution.

In the following description, for convenience of explanation, the inorganic compound fine particle dispersion composition is simply referred to as a " dispersion composition ", and the inorganic compound fine particle dispersion cured product is also simply referred to as " cured product ".

[(A) fine inorganic particles]

The inorganic fine particle (A) used as the "component A" in the present invention is either a fine particle sol of a metal oxide (A-1), a fine particle sol of a metal or semimetal nitride (A-2), or both.

The specific kind of the fine particle sol of the metal oxide (A-1) in the inorganic fine particle (A) is not limited, and may be a simple oxide fine particle sol composed of one kind of metal oxide or a composite oxide fine particle sol composed of a complex oxide, Or both. Likewise, the specific kind of the particulate sol of the (A-2) metal or semimetal nitride is not particularly limited and may be a particulate sol of one or more types of metal or semi-metal nitride. Here, the semimetal in the present invention refers to six elements of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb) and tellurium (Te).

Here, in the present invention, the specific kind of the metal or semi-metal forming the fine particle sol is not particularly limited as described above, but is preferably at least one of Group 4, Group 13 and Group 14 of the periodic table A metal element or a semimetal element belonging to the metal element. Examples of the metal element of Group 4 of the periodic table include titanium (Ti), zirconium (Zr) and hafnium (Hf), and metals or semimetal elements of Group 13 of the periodic table include boron (B) (Si), germanium (Ge), tin (Sn), and lead (Pb) may be used as the metal or semi-metal element of group 14 of the periodic table. ).

In the present invention, the metal forming the fine particle sol may contain a metal or a semi-metal element other than Group 4, Group 13 and Group 14 of the periodic table. Typically, a metal of a second group such as barium (Ba), strontium (Sr), calcium (Ca), and magnesium (Mg), or a metal of a first group such as potassium (K) Element, and the like, but are not particularly limited.

The inorganic compound specifically used as the fine particle sol in the present invention is not particularly limited as long as it is an oxide or a nitride of a metal or a semimetal capable of becoming liquid. Representative examples of the compound include monooxides such as titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), magnesium oxide (magnesia), and silicon oxide (silica); potassium titanate, barium titanate, strontium titanate, A composite oxide such as calcium nitride, magnesium titanate, lead titanate, aluminum titanate, lithium titanate, lead zirconate titanate (PZT) and indium tin oxide (ITO) Nitride; and the like. These inorganic compounds are not limited to oxides or nitrides, and may be used singly or as a mixture of two or more of them as the fine particle sol.

In the present embodiment, at least one metal or semi-metal of the group consisting of titanium oxide, aluminum oxide, zirconium oxide, barium titanate, zinc titanate zirconate, indium tin oxide and boron nitride, A particulate sol composed of a metal oxide can be preferably used. Needless to say, it is needless to say that various kinds of inorganic compounds can be used as the fine particle sol according to the use, the use conditions, the manufacturing conditions, and the like of the dispersion composition or the cured product according to the present invention.

The particle diameter of the fine particle sol as the inorganic fine particle (A) is not particularly limited. For example, the average particle diameter is preferably in the range of 1 to 500 nm, more preferably in the range of 2 to 100 nm, more preferably in the range of 4 to 20 nm, More preferably in the range of 50 nm. In the present invention, the average particle diameter refers to a particle diameter of 50% accumulated from the small diameter side in the particle diameter measured by the microtrack type particle size distribution measurement method.

The method for producing the fine particle sol (A) as the fine inorganic particles is not particularly limited, and the fine or metallic metal particles produced by a known wet synthesis method (or dry synthesis method) may be mixed with a known solvent Or the like, and then preparing a suspension to make it liquefy, or the like. In the present invention, commercially available fine particle sol may be used as (A) inorganic compound fine particles as described later.

[(B) Polymerizable compound]

The (B) polymerizable compound used as the " component B " in the present invention is not particularly limited as long as it is a known compound having polymerizability and capable of being polymerized and cured under predetermined conditions.

Representative compounds usable as the polymerizable compound (B) include compounds having an ethylenic unsaturated group in the molecule (ethylenic compound), a compound having an epoxy group at the terminal (epoxy compound), a compound having an amino group, a carboxyl group or a derivative thereof A compound having a hydroxyl group, and the like. These compounds are classified on the basis of functional groups contributing to polymerizability contained in the molecule, but a plurality of types of functional groups may be contained in the structure of one compound. For example, the ethylenic compound may contain an amino group or a carboxyl group in addition to the ethylenic unsaturated group. Further, only one functional group of the same kind may be contained in one compound (monofunctional), or two or more (multifunctional) may be used. These compounds may be used singly or in combination.

The kind of the polymer (resin) obtained by polymerizing (B) the polymerizable compound is not particularly limited, and can be appropriately selected depending on the use of the dispersion composition or the cured product according to the present invention, use conditions, production conditions and the like. Polymerization conditions of the polymerizable compound (B) are not particularly limited. Depending on the type of the compound (B) to be used as the polymerizable compound, polymerization by heating, polymerization by irradiation of radiation or the like, Curing). Similarly, the molecular weight of the polymer is not particularly limited, and can be appropriately set according to various conditions similar to those described above.

Representative (B) polymerizable compounds exemplified in the present embodiment include compounds having a carboxyl group and an ethylenic unsaturated group in the molecule. More specifically, as the ethylenic unsaturated group, a (meth) acrylic compound having a (meth) acryl group and a carboxyl group can be exemplified.

In the examples described later, a carboxylic acid-containing monofunctional acrylate or a carboxylic acid-containing polyfunctional acrylate is used. A resin obtained by polymerizing a (meth) acrylic compound is a (meth) acrylic resin excellent in optical performance. In this case, the dispersion composition and the cured product according to the present invention can be preferably used for optical system applications.

Another example of the compound having a carboxyl group and an ethylenic unsaturated group in the molecule includes a compound obtained by esterifying a polycarboxylic acid or an acid anhydride thereof with a compound having a hydroxyl group and an ethylenic unsaturated group. Examples of usable polycarboxylic acids include maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, oxalic acid, trimellitic acid, and citric acid. Examples of the acid anhydride which can be used include maleic anhydride, phthalic anhydride, succinic anhydride, trimellitic anhydride and the like. Examples of the compound having a hydroxyl group and an ethylenic unsaturated group that can be used include hydroxyethyl acrylate, dipentaerythritol acrylate, pentaerythritol acrylate, and compounds obtained by adding alkylene oxide thereto KAYARAD DPEA-12 or trade name: KAYARAD RP-1040 (all manufactured by Nippon Yakusho Co., Ltd., KAYARAD is a registered trademark)), and the like.

As described above, the polymerizable compound (B) may be used alone or in combination of two or more thereof. For example, a compound having a carboxyl group and an ethylenic unsaturated group in the molecule as described above May also be used as the polymerizable compound (B). A compound having a carboxyl group and an ethylenic unsaturated group in the molecule and a compound having no carboxyl group in the molecule and having an ethylenic unsaturated group may be used together as the polymerizable compound (B).

In the dispersion composition according to the present invention, the content of the inorganic fine particles (A) and the polymerizable compound (B) is not particularly limited, but the content of the polymerizable compound (B) , A compound having at least a carboxyl group and an ethylenically unsaturated group in the molecule is contained in an amount of 1 to 90% by weight, based on 100% by weight of the total weight of the inorganic fine particles (A) and the polymerizable compound (B) , Preferably within the range of 3 to 80 wt%, and more preferably within the range of 4 to 80 wt%.

[(C) Solvent and (D) Other Components]

In the present invention, in addition to the above-mentioned fine particle sol as the inorganic fine particles (A) and the polymerizable compound (B) described above, the (C) solvent may be further used as the " C component ". As the solvent (C), known solvents may be appropriately selected and used depending on the kind of the inorganic fine particles (A) or the polymerizable compound (B), the physical properties, the use conditions and the like.

Examples of the solvent (C) usable as the solvent in the present invention include, but are not particularly limited to, at least one organic solvent selected from the group consisting of hydrocarbons, esters, ketones and alcohols. These organic solvents may be used singly or in combination of two or more. In the examples described below, for example, 3-methoxybutanol, which is one kind of alkoxylated alcohol (alkoxide alcohol), or propylene glycol monomethyl ether acetate (PMA), which is one kind of glycol ester, is used as the solvent (C) have.

Needless to say, depending on the kind of the polymerizable compound (B), water (C) can be used as a solvent. When water (C) is used as the solvent, a polar organic solvent that can be mixed with water may be used in combination.

In the present invention, other components (D) may be contained in addition to the above-mentioned components (A) to (C). (D) Other components include surfactants, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, leveling agents, antifoaming agents, and various additives known in the field of dispersion compositions. Representative examples include surfactants . By adding a surfactant, the dispersibility and dispersion stability of the fine particle sol in the dispersion composition can be further improved.

The specific kind of the surfactant usable in the present invention is not particularly limited, and the kind of the fine particle sol ((A) inorganic fine particles), (B) the polymerizable compound and (C) Accordingly, a known surfactant can be selected and used preferably.

[Dispersion Composition and Cured Product]

The dispersion composition according to the present invention is a dispersion composition containing (D) a particulate sol as the above-mentioned (A) inorganic fine particles, (B) a polymerizable compound and (C) a solvent and, And the content of each of the components (A) to (D) can be suitably set in accordance with various conditions such as the kind of each component, the physical properties thereof, and the use of the dispersion composition.

(A) the fine particulate sol as the fine inorganic compound particles is contained in an amount of 10 to 90 wt% in terms of solid content, and the weight ratio of the fine particulate sol (A) %, Preferably in the range of 30 to 80 wt%, and more preferably in the range of 40 to 80 wt%. Therefore, the amount of the polymerizable compound (B) should be within a range of 10 to 90% by weight, preferably within a range of 20 to 70% by weight, and more preferably within a range of 20 to 60% by weight.

The solvent (C) may be blended in the range of 0.001 to 4.0 times (0.1 to 400% by weight) with respect to the total weight (100% by weight) of the inorganic fine particles and the polymerizable compound (A) , And 0.1 to 3.0 times (10 to 300% by weight). The other components (D) may be added within a range capable of exhibiting a desired function by the addition of the component (for example, in the case of a surfactant, the dispersion stability of the fine particle sol may be exerted By volume).

The method (preparation method) of the dispersion composition according to the present invention is not particularly limited, and the components (A) to (C) and, if necessary, (D) , And stirring is continued until (A) the inorganic fine particles and (B) the polymerizable compound are sufficiently dispersed in the (C) solvent.

Herein, when the "sol-gel solvent" (not the (C) solvent) remains in the fine particle sol (A) as the inorganic fine particles, the sol-gel solvent may be removed if necessary. For example, by comparing the boiling point (or evaporation point) of the solvent (C), which is an essential component of the dispersion composition, with the boiling point (or evaporation point) of the sol-gel solvent, It may be heated while mixing.

As described above, the dispersion composition according to the present invention can disperse the fine particle sol (A) as the inorganic fine particles in a satisfactory manner only by mixing the components (A) to (C) in a predetermined weight and stirring. Particularly, as shown in Examples and Comparative Examples to be described later, in the case of using fine particulate sol as compared with the case of using (A) fine particulate oxide of general metal or semi-metal as fine particulate inorganic compound, In addition, even when stored for one month, precipitation or flocculation of the fine particulate sol, which is a dispersion medium, is not confirmed, and excellent storage stability can be obtained.

In addition, since the dispersion composition according to the present invention is excellent in dispersibility, when applied to various applications, improvements in the performance, properties, and functions of the applied materials can be expected. For example, a cured product according to the present invention can be obtained by curing under known conditions according to the kind of the polymerizable compound (B), etc. However, when the cured product is formed as a film (layer) on a desired substrate , Excellent surface smoothness can be realized. Therefore, the cured product according to the present invention can be preferably used as a film or a coating layer.

Of course, the use of the dispersion composition and the cured product according to the present invention is not limited to a film such as a film or a coating layer, but may be suitably used for various molded products or industrial chemicals depending on the kind of the fine particle sol (A) .

Further, for example, as described above, it is preferable that the inorganic fine particles (A) are fine particulate sols of metallic elements or semi-metallic elements belonging to at least any one of Group 4, Group 13 and Group 14 described above B) If the polymerizable compound is the above-mentioned (meth) acrylic compound, the dispersion composition and the cured product according to the present invention can be expected to improve optical performance because (A) the inorganic fine particles are excellent in dispersibility. Therefore, the dispersion composition and the cured product having the above-described constitution can be preferably used in the fields of optical materials such as a lens material, a sealing material, and an antireflection film. As exemplified in Examples and Comparative Examples to be described later, the cured product obtained from the dispersion composition having the above-mentioned constitution is not only excellent in surface smoothness in the form of a film, but also has excellent properties such as a refractive index, transparency, Optical performance is also excellent.

Example

The present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited thereto. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. The evaluation of the dispersion composition and the cured product in the following examples and comparative examples was carried out as follows.

(Evaluation method of dispersion composition)

[Hayes]

The haze of the obtained dispersion composition was measured and evaluated in accordance with JIS K 7136 using a haze computer (model: HGM-2DP) manufactured by Suga Test Instruments Co., Ltd.

[Average particle diameter]

The average particle size of the fine particles dispersed in the obtained dispersion composition was measured and evaluated using Nanotrack (registered trademark) manufactured by Microtrac Incorporated. At this time, the particle diameter of cumulative 50% was taken as the average particle diameter from the small diameter side.

[Dispersion stability]

The dispersion composition thus obtained was kept still at 25 캜 for one month. Thereafter, whether or not any sedimentation was observed in the dispersion composition was visually confirmed. The time when sedimentation was not observed was evaluated as " ", and the time when sedimentation was observed was evaluated as " x ".

(Evaluation method of cured product)

[Refractive index]

The obtained film-like cured product (cured film) was evaluated by measuring the refractive index at a wavelength of 633 nm using a prism coupler (product name) manufactured by Metricon Corporation.

[Hayes]

The haze of the cured film obtained was measured and evaluated in accordance with JIS K 7136 using a Hitachi computer (model: HGM-2DP) manufactured by Suga Test Instruments Co., Ltd.

[Exterior]

The appearance of the obtained cured film was visually confirmed, and when no turbidity, fogging, or unevenness was observed, it was evaluated as "? &Quot;, and when the turbidity, cloudiness, or unevenness was observed was evaluated as " C ".

[Surface smoothness]

Surface smoothness (Ra), surface smoothness (Pa), and maximum height (Ry) of the obtained cured film were measured by using Surf test (registered trademark, type SJ-400) manufactured by Mitsutoyo Corporation.

(Example 1)

(A) a zirconium oxide sol (trade name: OZ-S30M, average particle size of 10 to 30 nm, methanol solution having a solid content of 30%) manufactured by Nissan Chemical Industries, Ltd. as a fine particle sol of the inorganic compound fine particles, (B) Carboxylic acid-containing polyfunctional acrylate (trade name: M-520) manufactured by Synthetic Co., Ltd., and (C) 3-methoxybutanol as a solvent.

70 parts by weight of the zirconium oxide sol in terms of solid content, 30 parts by weight of the carboxylic acid-containing polyfunctional acrylate, and 100 parts by weight of 3-methoxybutanol were mixed and blended, (Methanol) was distilled off to prepare a dispersion composition according to the present invention.

To the obtained dispersion composition, a photopolymerization initiator (trade name: Irgacure 184, BASF Japan Ltd.) was added in an amount of 3% by weight based on the total solid content. Using a bar coater, polyethylene terephthalate PET) film, and the solvent was volatilized in a heating oven under the condition of 80 占 폚 for 10 minutes and irradiated with a high-pressure mercury lamp at 500 mJ / cm2 (oxygen concentration: 0.3% or less) for curing. Thus, a film having a thickness of 20 mu m, which is a cured product according to the present invention, was formed.

The obtained dispersion composition and the cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Example 2)

(Trade name: WZ220, average particle diameter 30 nm, solid content 22% aqueous solution) manufactured by Sumitomo Osaka Cement Co., Ltd. as the fine particle sol of the inorganic fine particle (A) A dispersion composition and a cured product according to the present invention were obtained in the same manner as in Example 1 except that a carboxylic acid-containing polyfunctional acrylate (trade name: M-510) was used. The dispersion composition and the cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Example 3)

(A) a zirconium oxide sol (trade name: SZR-M, average particle size of 5 nm, a methanol solution having a solid content of 30%) manufactured by Sakai Chemical Industry Co., Ltd. was used as the fine particle sol of the inorganic compound fine particles, (B) The same procedure as in Example 1 was carried out except that a carboxylic acid-containing monofunctional acrylate (trade name: CB-01) manufactured by Nakamura Chemical Industries Co., Ltd. was used and propylene glycol monomethyl ether acetate (PMA) To obtain a dispersion composition and a cured product according to the present invention. The dispersion composition and the cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Example 4)

(Trade name: SRD-02M, average particle size of 15 nm, methanol solution having a solid content of 15%) manufactured by Sakai Chemical Industry Co., Ltd. as the fine particle sol of the inorganic fine particles (A), (B) (Trade name: M-520), and (C) 3-methoxybutanol as a solvent were used.

50 parts by weight of the titanium oxide sol in terms of solid matter, 50 parts by weight of the carboxylic acid-containing polyfunctional acrylate, and 100 parts by weight of 3-methoxybutanol were mixed and mixed, (Methanol) was distilled off to prepare a dispersion composition according to the present invention.

Using the obtained dispersion composition, a cured product according to the present invention was obtained in the same manner as in Example 1 above. The dispersion composition and the cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Example 5)

(Trade name: SZR-M) manufactured by Sakai Chemical Industry Co., Ltd. was used as the fine particle sol of the inorganic fine particle (A) as the fine particle sol of the inorganic fine particle, and (B) A carboxylic acid-containing monofunctional acrylate (trade name: A-SA) was used, and (C) a solvent was not used.

50 parts by weight of the zirconium oxide sol in terms of solid content and 50 parts by weight of the carboxylic acid-containing monofunctional acrylate were mixed and mixed, and the solvent (methanol) was distilled off using this disperser, A related dispersion composition was prepared.

The obtained dispersion composition was coated on a PET film and cured under the same conditions as in Example 1 to form a film having a thickness of 20 mu m as a cured product according to the present invention. The dispersion composition and the cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Comparative Example 1)

Except that the inorganic zirconium powder (trade name: PCS60) manufactured by Nippon Kogaku Co., Ltd. was used as the fine inorganic particles (A) and the amount of 3-methoxybutanol (C) as the solvent was 200 parts by weight, The same components as in Example 1 were used in the same amount. These components were mixed and dispersed using a paint shaker to prepare a comparative dispersion composition.

The dispersion composition thus obtained was coated in the same manner as in Example 1 to form a film as a comparative hardened product. The obtained comparative dispersion composition and comparative cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Comparative Example 2)

A comparative dispersion composition and a comparative cured product were obtained in the same manner as in Comparative Example 1, except that (A) zirconium oxide powder (trade name: PCS150) manufactured by Nippon Electric Industrial Co., Ltd. was used as the inorganic fine particles. The dispersion composition and the cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Comparative Example 3)

Comparative Example 1 was repeated except that the zirconium oxide (Zirconium (IV) oxide-8% yttria stabilized, nanopawder) of Aldrich (registered trademark) reagent was used as the fine inorganic particles (A) A dispersion composition and a comparative cured product were obtained. The dispersion composition and the cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Comparative Example 4)

(A) Inorganic fine particles are prepared by using not only a particulate sol but a zirconium oxide powder (trade name: PCS60) manufactured by Nippon Electric Industrial Co., Ltd., using methyl isobutyl ketone as a solvent (C) , A comparative dispersion composition was obtained.

The comparative dispersion composition thus obtained was coated in the same manner as in Example 1, and a film as a comparative hardened product was formed. The obtained comparative dispersion composition and comparative cured product were evaluated as described above. The results of the dispersion composition are shown in Table 1, and the results of the cured product are shown in Table 2.

(Comparative Example 5)

(Trade name: PCS60) manufactured by Nippon Electric Industrial Co., Ltd. (trade name: PCS60) was used instead of the fine particle sol as the inorganic fine particle (A), and as the polymerizable compound (B), a carboxylic acid-containing monofunctional Acrylate (trade name: A-SA) was used, and (C) solvent was not used.

50 parts by weight of the zirconium oxide sol in terms of solid content and 50 parts by weight of the carboxylic acid-containing monofunctional acrylate were mixed and dispersed using a paint shaker. However, since this was a gel-like material having no fluidity, It was impossible to evaluate.

As shown in Table 1, the dispersion composition according to the present invention had low haze and excellent dispersion stability as compared with the comparative dispersion composition using powder instead of fine particle sol. The average particle diameter of the dispersion medium ((A) inorganic fine particles) is equal to or less than the average particle diameter of the fine particle sol before preparation in the dispersion composition according to the present invention, Was equal to or less than the average particle diameter.

As shown in Table 2, the cured product of the present invention had a refractive index almost equal to or higher than that of the comparative cured product, had a low haze, and had an excellent appearance. Particularly, regarding the haze, the dispersion composition according to the present invention was in a level close to that of Comparative Example 2 in Examples 2 and 4, though the numerical value was lower than all of the comparative dispersion compositions. On the other hand, in the cured products, the haze was clearly lower than that in Comparative Example 2 in all of Examples 1 to 5.

With respect to the surface smoothness, the cured product according to the present invention was found to be sufficiently smaller than the comparative cured product in any of surface roughness (Ra), surface smoothness (Pa) and maximum height (Ry).

As is clear from the comparison between Example 5 and Comparative Example 5 which does not contain a solvent (C), when a dispersion composition is prepared using a powder other than the particulate sol, (C) when a solvent is not used, There is a possibility that a dispersion composition may not be obtained. On the other hand, in the present invention, as is apparent from the results of Example 5, (C) a dispersion composition having a good flowability even without a solvent can be obtained.

Further, as apparent from the comparison between Examples 1 to 4 containing the solvent (C) and Example 5 containing no solvent (C), by adding the solvent (C) within the above-mentioned range, It is possible to obtain a dispersion composition having good fluidity without inhibiting the physical properties of water. Depending on the composition, the physical properties of the dispersion composition or the physical properties of the cured product may be improved (see, for example, the results of the cured products of Examples 3 and 5 using the same kind of zirconium oxide sol).

From the above results, it can be seen that the dispersion composition according to the present invention not only has excellent storage stability but also (B) a (meth) acrylic compound as the polymerizable compound, . It is also understood that, when the cured product is in the form of a film, the surface smoothness is also excellent.

The excellent optical performance of the cured product can also be an index showing the excellent dispersibility of the inorganic fine particles (A). That is, since it is considered that excellent optical performance can be exhibited by being well dispersed as compared with the case where the zirconium oxide sol or titanium oxide sol is powder, the dispersion composition and the cured product according to the present invention can be used in fields It is expected that the performance, characteristics, and functions of the applied material can be improved.

In addition, compared with the comparative dispersion composition, a dispersion composition can be easily obtained without using a device (apparatus) for dispersion such as a paint shaker. Therefore, according to the present invention, a dispersion composition can be easily produced.

It should be noted that the present invention is not limited to the description of the above embodiments and can be modified in various ways within the scope of the claims and can be obtained by appropriately combining the technical means disclosed in the different embodiments And the like are also included in the technical scope of the present invention.

Industrial availability

INDUSTRIAL APPLICABILITY The present invention can be widely and preferably used in the field of dispersing metal or semi-metal fine particles as a dispersion medium in a dispersion medium (a field of dispersion).

Claims (6)

A fine inorganic particle dispersion composition containing (A) an inorganic fine particle and (B) a polymerizable compound, wherein (A) the inorganic fine particle is in a dispersed state,
Characterized in that a fine particle sol of a metal oxide (A-1) or a fine particle sol of a metal or a semi-metal nitride (A-2) is used as the inorganic fine particle (A). The method according to claim 1,
Wherein the fine particulate sol of the metal oxide (A-1) is at least one of a fine particulate sol composed of one kind of metal oxide and a complex oxide fine particle sol composed of a complex oxide. 3. The method of claim 2,
The particulate sol of the metal oxide (A-1) or the particulate sol of the (A-2) metal or semimetal nitride may be at least one selected from the group consisting of a metal element belonging to at least one of Groups 4, 13, Wherein the inorganic fine particle dispersion is a fine particle sol containing an element. 4. The method according to any one of claims 1 to 3,
Wherein the polymerizable compound (B) is a compound having a carboxyl group and an ethylenic unsaturated group in the molecule. 5. The method according to any one of claims 1 to 4,
(C) a solvent within a range of 0.001 to 4.0 times the total weight of the inorganic fine particles (A) and the polymerizable compound (B).  An inorganic compound fine particle-dispersed cured product obtained by curing the inorganic fine particle-dispersed composition according to any one of claims 1 to 5.