TW201408363A - Fine inorganic compound particle dispersed composition and fine inorganic compound particle dispersed cured product - Google Patents

Abstract

Provided are: a fine inorganic compound particle dispersed composition which is capable of having excellent dispersibility of fine inorganic compound particles and excellent storage stability of the dispersion state, while achieving excellent surface smoothness after being cured in a film form; and a cured product. A fine inorganic compound particle dispersed composition of the present invention contains (A) fine inorganic compound particles, (B) a polymerizable compound, and if necessary, (C) a solvent. The fine inorganic compound particles (A) are in a dispersed state, and (A-1) a sol of fine particles of a metal oxide or (A-2) a sol of fine particles of a metal or semimetal nitride is used as the fine inorganic compound particles (A). A cured product of the present invention can be obtained by curing this fine inorganic compound particle dispersed composition.

Description

Inorganic compound fine particle dispersion composition and inorganic compound fine particle dispersion cured product

The present invention relates to a composition of a fine particle of an inorganic compound in a dispersed state and a cured product thereof, and more particularly to a composition of a fine particle of a metal compound oxide or a metal or metalloid nitride and a cured product thereof.

In recent years, as one of the utilization forms of various inorganic materials, a dispersion which is dispersed as fine particles in an aqueous dispersion medium or a non-aqueous dispersion medium can be exemplified. In this dispersion, the inorganic material is such a "micro-sized solid" of fine particles which are dispersed in a liquid, that is, a dispersion medium. Therefore, in terms of manufacturing various products using inorganic materials, it is possible to efficiently improve processing characteristics, product characteristics, material properties, etc., and contribute to quality stabilization or improvement in yield during production.

On the other hand, regarding the dispersoid, that is, the fine particles, by changing the material, miniaturizing the particle size, controlling the particle shape, and the like, the fine particles are stabilized in the dispersion medium and may become undispersible. At this point, the particles are There is a possibility that the dispersion medium will agglomerate in a short period of time, and this aggregation may be caused by a decrease in productivity of the dispersion, a decrease in processing characteristics, a decrease in workability, a decrease in yield, and the like, and may be caused by the use of the dispersion. The characteristics of the final product produced are degraded, the quality is degraded, and the material properties of the dispersoid (inorganic material) are degraded.

Therefore, various techniques have been proposed in the field of dispersions containing fine particles of inorganic materials, which are to suppress the dispersibility, that is, the aggregation of fine particles, and to improve the stability of the dispersed state.

For example, Patent Document 1 discloses a surface treatment agent for metal oxide particles, a coating agent for forming a hard coat layer obtained by using the surface treatment agent for metal oxide particles, and a coating layer for forming a hard coat layer. A hard coat film obtained by coating a metal oxide oxide as a fine particle of an inorganic material for the surface treatment agent, and subjecting the metal oxide particle to surface treatment, thereby improving dispersibility . This hard coat film is preferably used as an image display device.

As the metal oxide fine particles used in Patent Document 1, for example, titanium oxide particles, zirconium oxide particles, or alumina particles can be exemplified. It is known that these particles are added to an optical material to increase the refractive index, and these particles are composited with a resin material or the like (ionizing radiation-curable compound), and are used as a coating agent for a display screen of an image display device. Or in various optical transmissions The mirror material is used to improve the optical performance, and further, it is also possible to improve the heat release property depending on the field of use.

Then, Patent Document 1 discloses a surface treatment agent which improves the dispersibility of these particles and has a carboxyl group in the molecule in order to improve the transparency and scratch resistance of the formed hard coat film. And a polymerizable compound having 4 or more ethylenically unsaturated groups per molecule; and a coating agent comprising metal oxide particles surface-treated with the surface treatment agent and ionizing radiation hardening Type (ionizing radiation curable) compound.

Further, as a technique for improving the dispersibility of the fine particles, that is, the dispersibility of the fine particles, not only the technique of surface-treating the fine particles as described above but also a technique using a dispersing agent has been proposed. For example, the applicant of the present application disclosed in Patent Document 2 a dispersion composition using a dispersant having a specific structure in order to improve the dispersibility of zirconia particles having a nanometer size.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-275483

Patent Document 2: Japanese Laid-Open Patent Publication No. 2012-007144

Here, any of the above-described conventional techniques is limited to use for a substantially specific use or specific inorganic compound fine particles. Specifically, the technique disclosed in Patent Document 1 is substantially limited to the field of a hard coat film of an image display device, and the inorganic compound fine particles are also substantially limited to titanium oxide particles, zirconium oxide particles, or aluminum oxide. particle. Further, in the technique disclosed in Patent Document 2, the use is not particularly limited, but the inorganic compound fine particles are limited to zirconia particles.

Further, when a film is formed by using the coating agent disclosed in Patent Document 1, the surface smoothness, storage stability, and the like of the film may not be sufficient depending on conditions.

The present invention has been made to solve such a problem, and an object thereof is to provide an inorganic compound fine particle-dispersed composition and a cured product obtained by hardening the inorganic compound fine particle-dispersed composition, and the inorganic compound fine particle-dispersed composition can be dispersed The dispersibility of the inorganic metal compound fine particles and the storage stability in the dispersed state are excellent, and the surface smoothness after being cured into a film shape is also excellent.

The inorganic compound fine particle dispersion composition of the present invention contains (A) inorganic compound fine particles and (B) polymerizable compound in order to solve the aforementioned problems. The (A) inorganic compound fine particles are in a dispersed state, and as the (A) inorganic compound fine particles, (A-1) metal oxide fine particle sol or (A-2) metal or metalloid-like fine particle is used. The composition of the sol.

According to the above configuration, as the (A) inorganic compound fine particles, by using a fine particle sol instead of using a powder such as a metal or a metal oxide, the dispersibility is also the storage stability of the dispersibility and dispersion state of the (A) inorganic metal compound fine particles. It is excellent in the properties, and further, for example, it is excellent in surface smoothness after being cured into a film shape. Further, since it is not necessary to use a special-purpose device or machine for dispersing the dispersoid, the inorganic metal compound fine particle-dispersed composition can be easily produced.

Further, in the fine dispersion composition of the inorganic metal compound fine particles having the above configuration, the fine particle sol of the metal oxide (A-1) may be a single oxide fine particle sol composed of one type of metal oxide, and may be compounded. At least one of the composite oxide fine particle sols composed of an oxide.

Further, in the fine dispersion composition of the inorganic metal compound fine particles having the above configuration, the fine particle sol of the (A-1) metal oxide or the fine particle sol of the (A-2) metal or metalloid nitride may be included in the cycle. A fine particle sol of at least one of a metal element or a metalloid element of Groups 4, 13, and 14.

Further, in the inorganic metal compound fine particle dispersion composition having the above configuration, the (B) polymerizable compound may be a compound having a carboxyl group and an ethylenically unsaturated group in the molecule.

Further, in the fine dispersion composition of the inorganic metal compound fine particles having the above-described configuration, the total weight of the (A) metal oxide fine particles and the (B) polymerizable compound may be contained in the range of 0.001 to 4.0 times (C). ) Solvent.

Furthermore, the present invention also includes an inorganic metal compound fine particle dispersion-cured material obtained by curing the inorganic metal compound fine particle dispersion composition having the above-described structure.

Hereinafter, preferred embodiments of the present invention will be described. The inorganic compound fine particle-dispersed composition of the present invention contains at least (A) inorganic compound fine particles and (B) a polymerizable compound, and the (A) inorganic compound fine particles are in a dispersed state, and (A) inorganic compound fine particles are used (A- 1) A fine particle sol of a metal oxide or a fine particle sol of (A-2) a metal or a metalloid-like nitride. Further, the inorganic compound fine particle-dispersed product of the present invention is obtained by curing the inorganic compound fine particle-dispersed composition having the above-described configuration.

In the following description, for the sake of convenience, the inorganic compound fine particle dispersed composition may be simply referred to as "dispersed composition", and the inorganic compound fine particle dispersed and cured product may be simply referred to as "cured material".

[(A) Inorganic compound microparticles]

The (A) inorganic compound fine particles used as the "component A" in the present invention are (A-1) metal oxide fine particle sol, or (A-2) metal or metalloid-like fine particle sol, or Both.

(A) Among the inorganic compound fine particles, the specific type of the fine particle sol of the (A-1) metal oxide is not limited, and may be a single oxide fine particle composed of one type of metal oxide, or may be a composite The composite oxide fine particle sol composed of an oxide may be both. Similarly, the specific type of the fine particle sol of the metal (A-2) metal or metalloid nitride is not particularly limited, and may be one type or more of metal or a metal nitride-like fine particle sol. Here, the metal of the present invention is specified as six elements of boron (B), germanium (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

Here, the specific kind of the metal or metalloid in which the fine particles are formed in the present invention is not particularly limited as described above, but as a preferred example, it may be exemplified by Group 4, Group 13, and 14 of the periodic table. Any of a group of metal elements or metalloid elements. As a metal element of Group 4 of the periodic table, titanium can be exemplified (Ti), zirconium (Zr), and hafnium (Hf), as a metal element of the 13th group of the periodic table or a metalloid element, examples of boron (B), aluminum (Al), gallium (Ga), and indium (In As the metal element of the group 14 of the periodic table or a metalloid element, cerium (Si), germanium (Ge), tin (Sn), and lead (Pb) can be exemplified.

Further, the metal forming the fine particles in the present invention may contain a metal element or a metalloid element other than Group 4, Group 13, and Group 14 of the periodic table. Typically, a metal element of Group 2 such as barium (Ba), strontium (Sr), calcium (Ca), or magnesium (Mg), or a group 1 of potassium (K) or lithium (Li) may be exemplified. Metal elements and the like are not particularly limited.

The inorganic compound to be specifically used in the microparticle sol of the present invention is not particularly limited as long as it is a metal or metalloid oxide or nitride which may be solified. As an example of a typical compound, a single oxide such as titanium oxide (titanium dioxide), alumina, zirconia, magnesia, cerium oxide (cerium oxide), or the like; potassium titanate, Composite oxide of barium titanate, barium titanate, calcium titanate, magnesium titanate, lead titanate, aluminum titanate, lithium titanate, lead zirconate titanate (PZT), indium tin oxide (ITO), etc.; A nitride such as boron, aluminum nitride, tantalum nitride, gallium nitride, titanium nitride or lithium nitride. These inorganic compounds are not limited to oxides or nitrides, and may be used alone or in combination of two or more kinds as the fine particle sol.

In the present embodiment, in the group of the inorganic compounds, a group consisting of titanium oxide, aluminum oxide, zirconium oxide, barium titanate, lead zirconium titanate, indium tin oxide, and boron nitride can be suitably used. A fine particle sol consisting of at least one metal or metalloid oxide. Of course, depending on the use, use conditions, production conditions, and the like of the dispersion composition or the cured product of the present invention, it is of course possible to use various types of inorganic compounds as the fine particle sol.

Here, the particle diameter of the fine particle sol as the (A) inorganic compound fine particles is not particularly limited. Typically, it may be fine particles of less than 1 μm, more specifically, for example, preferably, the average particle diameter is in the range of 1 to 500 nm, more preferably in the range of 2 to 100 nm, and even more preferably 4 to 50 nm. Within the scope. In addition, the average particle diameter of the present invention means a particle diameter which is 50% accumulated from the small diameter side among the particle diameters measured by a micro track type particle size distribution measuring method.

Further, the method for producing the fine particle sol of the (A) inorganic compound fine particles is not particularly limited, and a metal or metalloid fine particle produced by a conventional wet synthesis method (or dry synthesis method) can be used. A conventional solvent (for convenience, referred to as "solvent for sol") is prepared by a conventional method such as preparing a suspension and sol-forming. Further, in the present invention, a commercially available fine particle sol can be used as the (A) inorganic compound fine particles as described later.

[(B) Polymerizable Compound]

In the present invention, the (B) polymerizable compound used as the "component B" is polymerizable and polymerized and cured according to specific conditions. The specific kind of the compound is not particularly limited.

A typical compound which can be used as the (B) polymerizable compound is exemplified by a compound having an ethylenically unsaturated group in the molecule (ethylene compound), a compound having an epoxy group at the terminal (epoxy compound), and having an amino group. A compound having a carboxyl group or a group derived therefrom, a compound having a hydroxyl group, or the like. These compounds are classified based on a functional group contained in a molecule and contributing to polymerizability, but a structure of a compound may also include a plurality of types of functional groups. For example, the vinyl compound may contain an amino group or a carboxyl group in addition to the ethylenically unsaturated group. Further, in one compound, there may be only one (monofunctional) functional group of the same kind, or two or more (polyfunctional). Further, these compounds may be used alone or in combination of plural types.

(B) The type of the polymer (resin) obtained by the polymerization of the polymerizable compound is not particularly limited, and can be appropriately selected in accordance with the use, the use conditions, the production conditions, and the like of the dispersion composition or the cured product of the present invention. In addition, the polymerization conditions of the (B) polymerizable compound are not particularly limited, and examples of the type of the compound used as the (B) polymerizable compound include polymerization by heating, polymerization by irradiation of radiation, and the like. Polymerization (hardening) or the like using a hardener. 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.

As a typical (B) polymerizable compound exemplified in the embodiment, a compound having a carboxyl group and an ethylenically unsaturated group in the molecule can be exemplified. As a more specific example, a (meth)acryl-based compound having a (meth)acryl group as an ethylenically unsaturated group and having a carboxyl group can be exemplified.

In the examples described later, a monofunctional acrylate containing a carboxylic acid or a polyfunctional acrylate containing a carboxylic acid is used. The resin obtained by polymerizing a (meth)acryl-based compound is a (meth)acryl-based resin excellent in optical properties. In this case, the dispersion composition and the curing agent of the present invention can be suitably used for optical applications.

Further, as another example of the compound having a carboxyl group and an ethylenically unsaturated group in the molecule, a polycarboxylic acid or an anhydride thereof, a compound containing a hydroxyl group and an ethylenically unsaturated group, and a hydroxyl group and an ethylene group can be exemplified. A compound obtained by esterification of a compound of a unsaturated group. As the polycarboxylic acid which can be used, for example, maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, oxalic acid, trimellitic acid, citric acid, etc. can be exemplified. . Further, examples of the acid anhydride which can be used include, for example, maleic anhydride, phthalic anhydride, succinic anhydride, and trimellitic anhydride. Further, as the compound having a carboxyl group and an ethylenically unsaturated group which can be used, for example, hydroxyethyl acrylate, dipentaerythritol acrylate, pentaerythritol acrylate, and a compound obtained by adding an alkylene oxide to the compound (for example, , trade name: KAYARAD DPEA-12 or trade name: KAYARAD RP-1040 (any one is Japanese Made by Pharmaceutical Co., Ltd., KAYARAD is a registered trademark)).

In addition, as the above-mentioned (B) polymerizable compound, it is possible to use only two types, and it is also possible to use two or more types as appropriate. For example, it is possible to have only a carboxyl group and an ethylenic unsaturated group in the molecule as described above. The compound which is used as the (B) polymerizable compound may also be a compound having a carboxyl group and an ethylenically unsaturated group in the molecule, and a compound having no carboxyl group in the molecule but having an ethylenically unsaturated group. B) Polymeric compounds are used in combination.

In the dispersion composition of the present invention, the content of the (A) inorganic compound fine particles and (B) the polymerizable compound is not particularly limited, and particularly, as the (B) polymerizable compound, at least a carboxyl group and an ethyl group are used in the molecule. In the case of the unsaturated group compound, when the total weight of the (A) inorganic compound fine particles and the (B) polymerizable compound is regarded as 100% by weight, the compound having at least a carboxyl group and an ethylenically unsaturated group in the molecule may be In the range of 1 to 90% by weight, preferably in the range of 3 to 80% by weight, more preferably in the range of 4 to 80% by weight.

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

In the present invention, the (C) solvent can be used as the "C component" in addition to the fine particle sol which is the fine particle of the inorganic compound (A) and the (B) polymerizable compound. As the solvent (C), the type (A) of the inorganic compound fine particles or (B) the polymerizable compound, the physical properties, and the use strip A member or the like can be appropriately selected and used as a solvent.

The solvent (C) in the present invention is not particularly limited as a solvent which can be used, but typically, at least 1 selected from the group consisting of hydrocarbons, esters, ketones, and alcohols is exemplified. An organic solvent. These organic solvents may be used alone or in combination of two or more. In the examples described later, for example, one type of 3-methoxybutanol of alkoxylated alcohol or one type of propylene glycol monomethyl ether acetate (PMA) of a glycol ester is used as ( C) Solvent to use.

Further, depending on the type of the (B) polymerizable compound, it is of course possible to use water as the solvent (C). Further, when water is used as the solvent (C), a polar organic solvent which can be mixed with water may be used in combination.

Further, in the present invention, in addition to the components (A) to (C) described above, (D) other components may be contained. Examples of the other component (D) include a surfactant, an antioxidant, an ultraviolet absorber, a photostabilizer, an antistatic agent, a homogenizer, an antifoaming agent, and the like, and various additives conventionally known in the field of dispersion compositions, but As a representative, a surfactant can be exemplified. By adding a surfactant, the dispersibility of the fine particle sol in the dispersion composition and the stability of the dispersed state can be further improved.

Further, the specific kind of the surfactant which can be used in the present invention is not particularly limited, and corresponds to the type of the fine particle sol ((A) inorganic compound fine particles), (B) polymerizable compound, and (C) solvent used, Conditions such as physical properties can be suitably selected by using a conventional surfactant.

[Dispersed composition and hardened matter]

The dispersion composition of the present invention is a composition containing the fine particle sol as the fine particles of the inorganic compound (A), (B) a polymerizable compound, (C) a solvent, and, if necessary, a surfactant (D). The content of each component of (A) to (D) can be set to an appropriate range depending on the conditions of the type of each component, the physical properties, and the use of the dispersion composition.

When the total weight of the (A) inorganic compound fine particles and the (B) polymerizable compound is 100% by weight, the fine particle sol of the (A) inorganic compound fine particles can be converted into solid content in a typical composition. In the range of 10 to 90% by weight, preferably in the range of 30 to 80% by weight, more preferably 40 to 80% by weight. Therefore, the (B) polymerizable compound may be in the range of 10 to 90% by weight, preferably 20 to 70% by weight, more preferably 20 to 60% by weight.

Further, the solvent (C) is 0.001 to 4.0 times the total weight (100% by weight) of the (A) inorganic compound fine particles and (B) the polymerizable compound. It can be blended in the range of (0.1 to 400% by weight), preferably in the range of 0.1 to 3.0 times (10 to 300% by weight). Further, (D) other components may be added within a range in which a desired function is exhibited by the addition of the component (for example, when a surfactant is added, dispersibility and dispersion stability of the microparticle sol can be added. The amount of the degree can be).

Further, the production method (modulation method) of the dispersion composition of the present invention is not particularly limited, and the components (A) to (C) and, if necessary, the other components (D) are blended in a composition within the above range. The stirring is carried out until (A) the inorganic compound fine particles and (B) the polymerizable compound are sufficiently dispersed in the (C) solvent.

When the "sol solvent" (non-(C) solvent) remains in the fine particle sol of the (A) inorganic compound fine particles, the solvent for the sol can be removed as necessary. For example, after comparing the boiling point (or vaporization point) of the solvent of the essential component (C) of the dispersion composition and the boiling point (or vaporization point) of the solvent for the sol, the temperature conditions for evaporating only the solvent for the sol are set, and the respective conditions are mixed. The ingredients can be heated.

In the dispersion composition of the present invention, only the components (A) to (C) are blended and stirred with a predetermined weight, and the fine particle sol as the fine particles of the inorganic compound (A) can be favorably dispersed. Especially as in the following examples and ratios As shown in the comparative example, as the (A) inorganic compound fine particles, when using a fine metal or metalloid oxide fine particle, when the fine particle sol is used, not only the dispersion composition can be produced very simply, but also preserved. During the course of the month, the dispersoid, that is, the sedimentation or agglomeration of the microparticle sol, was not confirmed, and excellent preservation stability was obtained.

Moreover, since the dispersion composition of the present invention is excellent in dispersibility and is suitable for various applications, improvement in performance, characteristics, and function of the object to be applied can be expected. For example, it can be cured according to the type of the (B) polymerizable compound by a known condition, and can be a cured product of the present invention. However, when the cured product is formed as a mold (layer) on a desired substrate, Excellent surface smoothness is achieved. Therefore, the cured product of the present invention can be suitably used as a film, a coating layer or the like.

In particular, the use of the dispersion composition and the cured product of the present invention is not limited to a film such as a film or a coating layer, and may be suitably used in various types depending on the type of the particulate sol which is the fine particle of the inorganic compound (A). A molded product, an industrial chemical, or the like.

Further, for example, as described above, (A) the inorganic compound fine particles are fine particle sols belonging to at least one metal element or metalloid element of Group 4, Group 13, and Group 14 of the periodic table, and (B) a polymerizable compound. If the above (A The acryl-based compound, the dispersion composition and the cured product of the present invention are excellent in dispersibility of the (A) inorganic compound fine particles, and improvement in optical properties can be expected. Therefore, the dispersion composition and the cured product having the above-described configuration can be suitably used in the field of optical materials such as a lens material, a sealing material, and an antireflection film. As exemplified in the examples and comparative examples described later, the cured product obtained from the dispersion composition having the above-described composition is excellent not only in surface smoothness but also in refractive index, transparency, or The optical properties such as appearance are also excellent.

In other words, the present invention provides an inorganic compound fine particle-dispersed composition and a cured product obtained by curing the inorganic compound fine particle-dispersed composition, and the inorganic compound fine particle-dispersed composition can be dispersed. The inorganic metal compound fine particles are excellent in storage stability in the dispersibility and dispersion state of the inorganic metal compound fine particles, and are excellent in surface smoothness after being cured into a film form.

[Examples]

The present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited thereto. Various changes, modifications, and alterations may be made without departing from the scope of the invention. Moreover, 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 dispersed composition) [haze]

The Hag Computer (type: HGM-2DP) of Suga Test Machine Co., Ltd. was used, and the haze of the obtained dispersion composition was measured according to JIS K7136 of Japan.

〔The average particle size〕

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

[dispersion stability]

The obtained dispersion composition was allowed to stand at 25 ° C for 1 month. Thereafter, it was confirmed by visual observation whether or not any precipitate was observed in the dispersed composition, and it was considered that "○" was observed when the precipitate was observed, and "x" was evaluated when the precipitate was not observed.

(Method for evaluating hardened materials) [refractive index]

The obtained film-shaped cured product (cured film) was measured using a 稜鏡 coupler (product name) manufactured by Metricon Corporation (Metricon Corporation). The refractive index was evaluated at a wavelength of 633 nm.

[haze]

The Haze computer (type: HGM-2DP) of Suga Test Machine Co., Ltd. was used to measure the haze of the obtained cured film according to JIS K7136, Japan.

〔Exterior〕

The appearance of the obtained cured film was visually confirmed, and when it was not observed that turbidity, fogging, spots, etc., it was regarded as "○", and when it was observed that turbidity, fogging, spots, and the like were regarded as "x", it was evaluated.

[surface smoothness]

The surface smoothness was evaluated by measuring the surface roughness Ra, the surface smoothness Pa, and the maximum height Ry of the obtained cured film using a surface roughness meter (registered trademark, model SJ-400) manufactured by Mitutoyo Corporation.

(Example 1)

As the fine particle sol of the inorganic compound fine particles (A), a zirconia sol (trade name: OZ-S30M, a methanol solution having an average particle diameter of 10 to 30 nm and a solid content of 30%) manufactured by Nissan Chemical Industry Co., Ltd. was used as B) A polymerizable compound containing a carboxylic acid produced by Toagosei Co., Ltd. A monofunctional acrylate (trade name: M-520), and (C) a solvent, 3-methoxybutanol was used.

The zirconia sol is prepared by mixing and mixing 70 parts by weight of the solid component, 30 parts by weight of the carboxylic acid-containing monofunctional acrylate, and 100 parts by weight of the 3-methoxybutanol, and using a solvent for the sol in an evaporation gas. (Methanol) was distilled off to prepare a dispersion composition of the invention.

In the obtained dispersion composition, a photopolymerization initiator (trade name (registered trademark) irgacure 184, BASF Japan Co., Ltd.) was added in such a manner that the total solid content was 3 wt%, and a bar coating was used. The cloth is coated on a substrate, that is, a polyethylene terephthalate (PET) film, and the solvent is volatilized in a heating and drying oven at 80 ° C for 10 minutes, and accumulated under a high pressure water lamp. 500 mj/cm ² (oxygen concentration 0.3% or less) was irradiated and hardened. Thereby, a film having a film thickness of 20 μm is formed as the cured product of the present invention.

The obtained dispersion composition and 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)

As the fine particle sol of the (A) inorganic compound fine particles, a zirconia sol (trade name: WZ220, average particle diameter: 30 nm, solid content 22% solution) manufactured by Sumitomo Osaka Cement Co., Ltd. was used as the (B) polymerizable compound. The dispersion composition and the cured product of the invention were obtained in the same manner as in the above Example 1 except that a carboxylic acid-containing polyfunctional acrylate (trade name: M-510) manufactured by Toagosei Co., Ltd. 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)

As the fine particle sol of the inorganic compound fine particles (A), a zirconia sol (trade name: SZR-M, a methanol solution having an average particle diameter of 5 nm and a solid content of 30%) manufactured by Suga Chemical Industry Co., Ltd. was used as the (B) polymerization. For the compound, a carboxylic acid-containing polyfunctional acrylate (trade name: CB-01) manufactured by Shin-Nakamura Chemical Co., Ltd. was used, and as the solvent (C), propylene glycol monomethyl ether acetate (PMA) was used. Other than the above, the dispersion composition and the cured product of the invention were obtained in the same manner as in the above-described first embodiment. 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)

As the particulate sol of the fine particles of the inorganic compound (A), a titanium oxide sol (trade name: SRD-02M, a methanol solution having an average particle diameter of 15 nm and a solid content of 15%) was used as the (B) polymerization. a compound containing a carboxylic acid-containing polyfunctional compound manufactured by Toagosei Co., Ltd. Acrylate (trade name: M-520), and (C) solvent, 3-methoxybutanol was used.

The titanium oxide sol is prepared by mixing 50 parts by weight of the solid component, 50 parts by weight of the carboxylic acid-containing monofunctional acrylate, and 100 parts by weight of the 3-methoxybutanol, and using the sol for evaporation. The solvent (methanol) was distilled off to prepare a dispersion composition of the invention.

Using the obtained dispersion composition, the cured product of the present invention was obtained in the same manner as in the above Example 1. 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)

As the fine particle sol of the (A) inorganic compound fine particles, a zirconia sol (trade name: SZR-M) manufactured by Suga Chemical Industry Co., Ltd. was used as the polymerizable compound, and New Nakamura Chemical was used as the (B) polymerizable compound. The carboxylic acid-containing polyfunctional acrylate (trade name: A-SA) manufactured by Industrial Co., Ltd. does not use the (C) solvent.

The zirconia sol is blended and mixed with 50 parts by weight of the solid component and 50 parts by weight of the carboxylic acid-containing monofunctional acrylate. The sol was distilled off with a solvent (methanol) to prepare a dispersion composition of the invention.

The obtained dispersion composition was coated on a PET film under the same conditions as in the above-mentioned Example 1, and cured to form a film having a film thickness of 20 μm, which is a cured product of 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)

As the (A) inorganic compound fine particles, a zirconia powder (trade name: PCS60) manufactured by Nippon Denshi Co., Ltd., and (C) a solvent of 3-methoxybutanol were used without using a fine particle sol. The amount of the same component as that of the above-mentioned Example 1 was the same as the amount of 200 parts by weight. Thus, the components were mixed and mixed using a paint shaker to prepare a comparative dispersion composition.

The obtained dispersion composition was set and coated in the same manner as in Example 1 to form a film, that is, a cured product. The obtained dispersed composition and the 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 the above Example 1 except that the zirconia powder (trade name: PCS150) manufactured by Nippon Denshoku Co., Ltd. was used as the (A) inorganic compound fine particles. The dispersion composition and the comparative cured product of this comparison 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)

The (A) inorganic compound fine particles were set in the same manner as in Example 1 except that the zirconia powder of the Aldrich (registered trademark) drug (drug name: Zirconium (IV) oxide-8% yittria stabilized, nanopawder) was used. Comparative dispersed compositions and comparative hardened materials. The dispersion composition and the comparative cured product of this comparison 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)

As the (A) inorganic compound fine particles, zirconia powder (trade name: PCS60) manufactured by Nippon Denshi Co., Ltd. was used instead of the fine particle sol, and methyl isobutyl ketone was used as the solvent (C). The sample was set in the same manner as in Example 1 of Patent Document 1, and a comparative dispersion composition was obtained.

The obtained dispersion composition was set and coated in the same manner as in Example 1 to form a film, that is, a cured product. About the dispersion of the comparison obtained The composition and the 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)

As the (A) inorganic compound fine particles, zirconia powder (trade name: PCS60) manufactured by Nippon Denshi Co., Ltd. is used instead of the fine particle sol, and (B) a polymerizable compound is used, and the new Nakamura Chemical Industry Co., Ltd. is used. A polyfunctional acrylate containing a carboxylic acid (trade name: A-SA) was produced, and the solvent (C) was not used.

The zirconia sol is prepared by mixing and mixing 50 parts by weight of the solid component and 50 parts by weight of the carboxylic acid-containing monofunctional acrylate, and dispersing the mixture using a paint shaker, but forming a gel-like substance having no fluidity. Can't evaluate.

As shown in Table 1, the powder composition of the present invention was compared with the dispersion composition using powder instead of the microparticle sol, and either of them had a low haze and was excellent in dispersion stability. Further, the average particle diameter of the dispersoid ((A) inorganic compound fine particles) is equal to or smaller than the average particle diameter of the fine particle sol before preparation in the dispersion composition of the present invention. The dispersed composition is also an average particle diameter equal to or lower than that of the dispersed composition.

Further, as shown in Table 2, the cured product of the present invention has a refractive index which is substantially equal to or higher than that of the comparative cured product, and is a finished product which has a low haze and an excellent appearance. In particular, regarding the haze, the dispersion composition of the present invention has a lower total value than the comparative dispersion composition, but in the second and fourth embodiments, it is close to the comparative example 2. On the other hand, in Examples 1 to 5, the haze of the cured product was known, and it was apparent that it was a smaller level than Comparative Example 2.

Further, regarding the surface smoothness, the cured product of the present invention has a very small value compared to the comparative cured product in any of the surface roughness Ra, the surface smoothness Pa, and the maximum height Ry.

Further, from the comparison of Example 5 and Comparative Example 5 containing no (C) solvent, it is apparent that when a powder is used instead of a fine particle sol to produce a dispersion composition, it may not be obtained without using the solvent (C). A dispersed composition of fluidity. On the other hand, in the present invention, from the results of Example 5, it is apparent that a dispersion composition having good fluidity can be obtained without (C) a solvent.

Further, from the comparison of Examples 1 to 4 containing (C) solvent and Example 5 containing no (C) solvent, it is apparent that the addition of (C) solvent within the above range does not impair the dispersion composition. The physical properties of the substance or the cured product can provide a dispersed composition having good fluidity. Also, depending on the composition, you can seek The physical properties of the dispersion composition or the physical properties of the cured product are improved (for example, the results of the cured products of Examples 3 and 5 using the same kind of zirconia).

From the above results, it is understood that the dispersion composition of the present invention not only has excellent storage stability, but also can be used as a (B) polymerizable compound when a (meth)acryl-based compound is used, particularly when it is a cured product. Excellent optical performance. Further, it was found that when the cured product is a film, the surface smoothness is also excellent.

In addition, the excellent optical properties of the cured product can also be an indicator showing the excellent dispersibility of the (A) inorganic compound fine particles. In other words, when the zirconia sol or the titanium oxide sol is used as a powder, it is considered to exhibit excellent optical properties by being well dispersed. Therefore, the dispersion composition and the cured product of the present invention are applicable to fields other than the optical field. It is also expected to improve the performance, features, functions, etc. of the applicable materials.

Further, the dispersion composition can be easily obtained without using a dispersing device such as a paint shaker as compared with the comparative dispersion. Therefore, according to the present invention, the dispersion composition can be easily produced.

Further, the present invention is not limited to the description of the above embodiments, and various modifications can be made within the scope of the claims, and the technical means disclosed in the different embodiments or the plural variations are suitable. The examples and the like obtained by the combination are all included in the technical scope of the present invention.

[Industry use possibility]

The present invention can be widely used as a dispersant in a dispersant in the field of dispersing fine particles of a metal or a metalloid (in the field of dispersion).

The present invention has been described in detail and with reference to the specific embodiments of the present invention. Easy to know.

The present application is based on the Japanese Patent Application No. 2012-169131, filed on Jul. 31, 2012, which is hereby incorporated by reference.

Claims (9)

An inorganic compound fine particle-dispersed composition comprising (A) inorganic compound fine particles and (B) a polymerizable compound, wherein the (A) inorganic compound fine particles are dispersed, and the (A) inorganic compound fine particles are used ( A-1) a fine particle sol of a metal oxide or a fine particle sol of (A-2) a metal or a metalloid-like nitride. The fine particle dispersion composition of the inorganic compound according to claim 1, wherein the fine particle sol of the (A-1) metal oxide is a single oxide fine particle sol composed of one type of metal oxide, and is oxidized by the composite At least one of the composite oxide fine particle sols composed of the objects. The inorganic compound fine particle dispersion composition according to claim 2, wherein the fine particle sol of the (A-1) metal oxide or the fine particle sol of the (A-2) metal or metalloid nitride is contained in the periodic table. At least one metal element or metalloid-like fine particle sol of Group 4, Group 13, and Group 14. The inorganic compound fine particle-dispersed composition according to claim 1, wherein the (B) polymerizable compound is a compound having a carboxyl group and an ethylenically unsaturated group in the molecule. The inorganic compound fine particle-dispersed composition according to claim 2, wherein the (B) polymerizable compound is a compound having a carboxyl group and an ethylenically unsaturated group in the molecule. The inorganic compound fine particle dispersion composition according to claim 3, wherein The (B) polymerizable compound is a compound having a carboxyl group and an ethylenically unsaturated group in the molecule. The inorganic compound fine particle-dispersed composition according to any one of Claims 1 to 6, wherein the total weight of the (A) inorganic compound fine particles and (B) the polymerizable compound is in the range of 0.001 to 4.0 times. Containing (C) solvent. An inorganic compound fine particle dispersion-cured material obtained by curing the inorganic compound fine particle dispersion composition according to any one of Claims 1 to 6. An inorganic compound fine particle dispersion-cured product obtained by curing the inorganic compound fine particle dispersion composition according to claim 7.