JP4474938B2 - Inorganic compound resin dispersion, molded pellets and molded products - Google Patents

Description

  The present invention relates to an inorganic compound resin dispersion. More specifically, the present invention relates to a thermoplastic resin molded article having good dispersibility, transparency, specific wavelength shielding properties, mechanical properties and appearance.

The metal oxide has a function of shielding a specific wavelength. In addition, by controlling the particle size, it is expected to be used for applications that require transparency. For example, when the particle size is 0.1 μm or less, the scattering of visible light is suppressed and the film has a transparency function.
However, the metal oxide has a very strong cohesive strength. In particular, particles having a particle size of 0.1 μm or less easily aggregate because they have a large surface energy. Therefore, when they are kneaded into a resin or the like, the dispersion state is very poor, and the above functions cannot be fully exerted. . Furthermore, since the surface activity of the particles becomes very large, it has become a major factor for promoting resin degradation.

In order to solve the above problems, there is a technique for obtaining a desired weather resistance by maintaining the dispersibility by surface-treating a titanate coupling agent to a fine inorganic compound having a particle size of 0.06 μm or less (Patent Document 1). .
In addition, a technique (Patent Document 2) for improving dispersibility in a resin by using organopolysiloxane and titanium oxide amorphous for the titanium oxide ultrafine particles, or trialkoxysilanes bonded to the titanium oxide ultrafine particles in the resin. A distributed technique is also disclosed (Patent Document 3).

Furthermore, a method of obtaining a resin composition in which semiconductor ultrafine particles are dispersed while suppressing particle formation and aggregation by reacting the surface-modified semiconductor ultrafine particles with a resin has been reported (Patent Document 4).
However, even if the resin composition technology disclosed in these publications is used, it has been difficult to obtain a resin composition or a molded product having high dispersibility, transparency and excellent physical properties.

  Therefore, the use of organic compounds has become the mainstream for the above-mentioned uses having specific wavelength shielding and transparency. Among organic compounds, benzotriazole compounds can be mentioned as the most typical ones. The benzotriazole-based compound exhibits an immediate shielding effect due to its absorption action, but its use may be limited due to problems such as durability and safety.

JP-A-7-003070 JP 2001-2417 A JP-A-5-221640 JP 11-43556 A

  In order to solve the above problems, an object of the present invention is to provide an inorganic compound resin dispersion excellent in dispersibility and transparency and suppressing deterioration in physical properties and excellent in shielding property at a specific wavelength, and a molded article. .

The first invention of the present invention is a metal oxide (A) having a primary particle size of 0.1 μm or less and sulfuric acid having a primary particle size of 0.1 μm or less and a refractive index of 1.45 to 1.64. Inorganic containing metal salt (B), reactive silicone (C) selected from carboxy-modified polysiloxane, alcohol-modified polysiloxane and amino-modified polysiloxane, and thermoplastic resin (D) having an Abbe number of 20 or more Compound resin dispersion.

  2nd invention is an inorganic compound resin dispersion as described in 1st invention whose metal oxide (A) is 0.01 to 50 weight%.

  3rd invention is an inorganic compound resin dispersion as described in 1st or 2nd invention which is 0.01-100 weight part of metal sulfate (B) with respect to 100 weight part of metal oxides (A). is there.

  4th invention is an inorganic compound in any one of 1st-3rd invention whose metal oxide (A) is 1 or more types chosen from the group of a zinc oxide, a titanium oxide, a cerium oxide, iron oxide, and a zirconium oxide. It is a resin dispersion.

5th invention is inorganic compound resin dispersion | distribution in any one of 1st-4th invention whose metal sulfate (B) is 1 or more types chosen from the group of barium sulfate, magnesium sulfate, calcium sulfate, and potassium sulfate. Is the body.

A sixth invention is the inorganic compound resin dispersion according to any one of the first to fifth inventions, wherein the viscosity of the reactive silicone (C) is in the range of 10 to 1000 mm ² / s.

7th invention is a shaping | molding pellet obtained by melt-kneading the inorganic compound resin dispersion in any one of 1st- 6th invention.

The eighth invention is a molded article obtained using the inorganic compound resin dispersion described in any of the first to sixth inventions.

The ninth invention is a molded article obtained by using the molded pellets described in the seventh invention.

  The inorganic compound resin dispersion of the present invention comprises a metal oxide (A) having a primary particle size of 0.1 μm or less, a metal sulfate salt (B) having a primary particle size of 0.1 μm or less, a reactive silicone ( C) and the thermoplastic resin (D), so that the transparency and mechanical properties of the thermoplastic resin (D) are not deteriorated, and the reactive silicone (C) covers the surface of the metal oxide (A). By doing so, a stable dispersion of the inorganic compound is obtained, and the shielding property at a specific wavelength is excellent.

  Since the inorganic compound resin dispersion of the present invention contains 0.01 to 50% by weight of the metal oxide (A), the dispersibility of the inorganic compound and the shielding property at a specific wavelength are further improved.

  Moreover, since it is 0.01-100 weight part of metal sulfate (B) with respect to 100 weight part of metal oxides (A), since it is an inorganic compound resin dispersion of Claim 1 or 2, transparency, dispersibility Is superior and does not impair the physical properties of the resin.

  Further, since the metal oxide (A) is at least one selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, iron oxide and zirconium oxide, it is more preferable in terms of transparency.

  Since the inorganic compound resin dispersion according to the present invention has a refractive index of 1.45 to 1.64 of the metal sulfate salt (B), the transparency of the inorganic dispersion can be improved without impairing the transparency.

  Further, since the metal sulfate metal salt (B) is at least one selected from the group of barium sulfate, magnesium sulfate, calcium sulfate and potassium sulfate, it is more preferable.

In the inorganic compound resin dispersion of the present invention, the viscosity of the reactive silicone (C) is in the range of 10 to 1000 mm ² / s, so that the dispersibility is good and flash or the like that impairs the appearance of the molded product does not occur.

  In addition, since the Abbe number of the thermoplastic resin (D) is 20 or more, a molded product that does not impair quality such as chromatic aberration and transparency can be obtained.

  Since the molded pellet of the present invention is obtained by melt-kneading the inorganic compound resin dispersion, the reactive silicone (C) reacts with the thermoplastic resin (D) and crosslinks to suppress resin deterioration, The physical properties can be maintained.

  Since the molded article of the present invention is obtained using the inorganic compound dispersion or molded pellet, it has properties such as dispersibility, transparency, specific wavelength shielding properties, mechanical properties, and good appearance.

<Metal oxide (A)>
The primary particle size of the metal oxide (A) used in the present invention is 0.1 μm or less from the viewpoint of exerting the intended function in the present invention. 0.001-0.05 micrometer is preferable and 0.005-0.04 micrometer is more preferable.
Specific examples of the metal oxide (A) include inorganic metal oxides such as zinc oxide, titanium oxide, cerium oxide, iron oxide, and zirconium oxide. Zinc oxide is particularly preferable in terms of transparency and low colorability.

  The metal oxide (A) may be subjected to a surface treatment. Specific examples include inorganic treatment such as silica and alumina or organic treatment such as siloxane, silane and polyol. Moreover, since an absorption wavelength changes with kinds of metal oxide (A), what differs in the kind and particle size of the said metal oxide (A) can also be mixed and used according to the objective.

<Sulfuric acid metal salt (B)>
The metal sulfate metal salt (B) used in the present invention has a role as a transparentizing aid for the metal oxide (A).
The primary particle diameter of the metal sulfate (B) is 0.1 μm or less from the viewpoint of exerting the intended function in the present invention. 0.001-0.05 micrometer is preferable.
The metal sulfate (B) preferably has a refractive index of 1.45 to 1.64 from the viewpoint of transparency. Further, barium sulfate (refractive index 1.636), magnesium sulfate (refractive index 1.455), calcium sulfate (refractive index 1.526), and potassium sulfate (refractive index 1.495) are more preferable, and barium sulfate is particularly preferable. .

<Reactive silicone (C)>
The reactive silicone (C) used in the present invention improves the dispersibility by covering the surface of the metal oxide (A) or crosslinks the resin to suppress a decrease in physical properties of the resin.
The reactive silicone (C) is a silicone modified with a functional group (organopolysiloxane having a functional group). Specific examples thereof include methylhydrogen polysiloxane, carboxy-modified polysiloxane, alcohol-modified polysiloxane, and epoxy. Examples thereof include modified polysiloxane, amino-modified polysiloxane, methacryl-modified polysiloxane, mercapto-modified polysiloxane, and phenol-modified polysiloxane.

It is preferable to select an optimal reactive silicone (C) for each resin. In addition to one functional group modification, a reactive silicone (C) modified with two or more different functional groups can also be used. Further, different types of reactive silicones (C) can be used in combination for (A) surface coating and (D) for maintaining physical properties.
Examples of the functional group of these reactive silicones (C) include those attached to the main chain, side chain, both ends, or both side chains and both ends in the molecule, and any of them can be preferably used.

As the viscosity of the reactive silicone (C), those having a measured value at 25 ° C. of 10 to 1000 mm ² / s with a spindle-type rotational viscometer are preferable from the viewpoint that they can be uniformly mixed. Viscosity in some cases 10 mm 2 / unreacted silicone during molding ^s is less than causes flash gasification molded article. Moreover, when a viscosity exceeds 1000 mm < ² > / s, the uniform coating | cover on the metal oxide (A) surface will become difficult, and there exists a tendency for the improvement of a dispersibility to be unpreferable.

<Thermoplastic resin (D)>
The thermoplastic resin (D) used in the present invention is preferably a resin having an Abbe number of 20 or more as an index of transparency. More preferably, it is 30 or more.
The Abbe number here is the reciprocal of the dispersion obtained from the refractive index of Brown Forfer's c-line, d-line, and F-line. The higher the Abbe number, the smaller the chromatic aberration and the more useful as an optical material for lens applications. It is said.

Specific examples include the following.
Aromatic polycarbonate resin: produced by reaction of one or more bisphenols which may contain trivalent or higher polyhydric phenols as a copolymerization component with carbonate esters such as bisalkyl carbonate, bisaryl carbonate and phosgene. Polymer.
Styrenic resin: polystyrene resin, poly (α-methylstyrene), styrene-acrylonitrile copolymer (SAN), styrene-methyl methacrylate copolymer, and the like.
Acrylic resin: polymethyl methacrylate (PMMA), polycyclohexyl methacrylate (PCHM), polymethyl acrylate, methyl methacrylate-cyclohexyl methacrylate copolymer, and the like.
Amorphous polyolefin resins: cycloolefin polymers obtained by hydrogenating double bonds of double bonds of ring-opening metathesis polymers of norbornenes, ethylene / norbornene hydrocarbon copolymers, polytetracyclododecene Etc.
Aromatic polyester resin: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.

  The form of the thermoplastic resin (D) is not particularly defined, but a powder form is preferable in consideration of dispersibility of the metal oxide (A) and the like.

<Inorganic compound resin dispersion>
The inorganic compound resin dispersion of the present invention is obtained by dispersing the components (A) to (D). Preferred examples of the method of mixing each component include adding (B) and (D) to the mixture of (A) and (C), and adding (B) and (C) to the mixture of (A), (B), and (C). D) is added, or (A) to (D) are mixed at the same time.
These can be mixed and dispersed with an attritor, ball mill, sand mill, Henschel mixer, super mixer, jet mill, Q-type mixer, mechano-fusion, etc. to obtain an arbitrary shape such as powder or granule. The dispersion of the inorganic compound on the surface of the thermoplastic resin (D) is obtained by the shearing force generated by the flow, rotation, and collision of the dispersion medium. At this time, the reactive silicone (C) has an action of improving dispersibility by covering the surface of the metal oxide (A).

  The content of the metal oxide (A) in the resin dispersion of the present invention is preferably 0.01 to 50% by weight, more preferably 0.1 to 20% by weight. 0.1 to 10% by weight is particularly preferred. If it is less than 0.01% by weight, the effect of selective light transmittance of the metal oxide (A) may not be exhibited, and if it exceeds 50% by weight, dispersibility may be hindered.

  The content of the metal sulfate salt (B) in the resin dispersion of the present invention is preferably 0.01 to 100 parts by weight, particularly preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the metal oxide (A). . If the amount is less than 0.01 part by weight, the effect on the transparency of the metal sulfate salt (B) may not be exhibited. If the amount exceeds 100 parts by weight, the dispersibility may be impaired, or the thermoplastic resin (D) may deteriorate. It may become a factor to promote.

<Molded pellets>
The molded pellets of the present invention are obtained by melt-kneading the inorganic compound resin dispersion of the present invention and extruding the pellets, granules, beads, and the like. By taking a form such as a pellet, it becomes easy to handle the thermoplastic resin molded product. The reactive silicone (C) has an action of cross-linking the resin during melt-kneading to suppress deterioration of the physical properties of the resin.
The molded pellet of the present invention may be a master batch. The master batch has a relatively high inorganic compound concentration, and is used after being diluted with a molding resin in the production of a molded product. Further, the molded pellet of the present invention may be a compound. The compound has a relatively low inorganic compound concentration compared to the masterbatch and the same composition as the molded product, and is used as it is in the production of the molded product.

<Molded product>
The molded product of the present invention may be a product obtained by directly melting and mixing the resin dispersion and the thermoplastic resin (D). The reactive silicone (C) has an action of cross-linking the resin and suppressing deterioration of the physical properties of the resin during melt mixing.
In addition, a master batch pellet obtained by melt extrusion of a resin dispersion having a relatively high inorganic compound concentration and a molding resin may be mixed and molded, or a resin dispersion having a relatively low inorganic compound concentration And the thermoplastic resin (D) may be melt-mixed to form a compound, and the compound may be molded as it is.

  The molding method may be obtained by any method such as extrusion molding, injection molding and blow molding. Since the molded product of the present invention is thin and excellent in transparency, and further excellent in impact resistance, it is suitable for internal parts and housings of OA equipment and home appliances. As such a use, for example, as a sheet for a liquid crystal display, it can be used for various optical films and sheets such as a deflection film, a retardation film, a light guide plate for backlight, a light diffusion sheet, and a light collecting sheet.

<Other ingredients>
Moreover, various additives can be used for the inorganic compound resin dispersion, molded pellets, and molded products of the present invention within a range that does not impair the effects of the present invention, depending on the purpose.
The general dispersant is not particularly limited as long as it has good compatibility with the thermoplastic resin (D) and does not affect the thermoplastic resin (D).
For example, stearic acid, zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene bisamide, low molecular weight polyester, low molecular weight polyamide, low molecular weight polycarbonate, montanic acid ester, styrene-maleic anhydride copolymer resin, styrene -Acrylic acid copolymer resins, α-olefin / maleic anhydride copolymer resins, oxidized waxes, glycerin waxes, polystyrene waxes, polyethylene waxes, polypropylene waxes and derivatives thereof, waxes made of acid-modified products and hydroxyl-modified products, etc. Can be mentioned. Any of these can be used alone or in combination.
Here, the low molecular weight refers to a thing of 1000 Pa · s or less under 220 ° C. condition and 10 kg load with a capillary viscometer defined in JIS K 7199.

  In addition, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, metal flake, metal Fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, aramid particle, aramid fiber, polyarylate fiber, graphite, conductive carbon black, various whiskers, etc.), organic alkali metal Flame retardants other than salts and organic alkaline earth metal salts (halogen, phosphate ester, metal salt, red phosphorus, metal hydrate, etc.), heat stabilizer, ultraviolet absorber, light stabilizer, mold release Agent, lubricant, sliding agent (PTFE particles, etc.), light diffusing agent (a) Lil cross-linked particles, silicone cross-linked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, Examples thereof include impact modifiers typified by graft rubber, infrared absorbers, and photochromic agents.

  The present invention will be described in more detail below, but the present invention is not limited to these examples without departing from the technical idea of the present invention. In the following, “parts by weight” is simply referred to as “parts”, and “% by weight” is simply referred to as “%”.

1. Preparation of inorganic compound resin dispersion and molded pellet (Example 1)
Zinc oxide (A) having a primary particle size of 0.03 μm, barium sulfate (B) having a primary particle size of 0.03 μm, carboxy-modified polysiloxane (viscosity: 125 mm ² / s, manufactured by Toray Dow Corning, both (Terminal modification type) (C) and powdery polycarbonate resin (Abbe number: 30) (D), (A) / (B) / (C) / (D) = 5% / 0.5% / The inorganic compound resin dispersion was obtained by blending at a ratio of 2% / 92.5% and dispersing with a Q-type mixer (Mitsui Mining Co., Ltd.) at a peripheral speed of 100 m / sec for 5 minutes.
Thereafter, melt extrusion was performed with a 30 mm twin screw extruder to obtain molded pellets.

(Example 2)
A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that (C) was changed to alcohol-modified polysiloxane (viscosity: 55 mm ² / s, manufactured by Toray Dow Corning, both terminal modified type).

(Example 3)
A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that (A) was changed to cerium oxide having a primary particle size of 0.03 μm.

Example 4
A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that (A) was changed to titanium oxide having a primary particle size of 0.03 μm.

(Example 5)
A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that (A) was changed to iron oxide having a primary particle size of 0.03 μm.

(Example 6)
A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that (A) was changed to zirconium oxide having a primary particle size of 0.03 μm.

(Example 7)
A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that (D) was changed to polyethylene terephthalate (Abbe number: 24).

(Example 8)
A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that (D) was changed to polystyrene (Abbe number: 31).

Example 9
(C) was changed to amino-modified polysiloxane (viscosity: 13 mm ² / s, manufactured by Toray Dow Corning Co., Ltd., both terminal-modified type), and (D) was an amorphous polyolefin resin having a methyl ester group as a side difference ( A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that the Abbe number was changed to 57).

(Comparative Example 1)
A dispersion and molded pellets were obtained under the same conditions as in Example 1 except that (A ′) was replaced with (A ′) instead of zinc oxide having a primary particle size of 0.5 μm.

(Comparative Example 2)
(A) Zinc oxide having a primary particle size of 0.03 μm and (D) powdered polycarbonate resin (Abbe number: 30) in a ratio of (A) / (C) = 5% / 95% Then, a dispersion and molded pellets were obtained under the same conditions as in Example 1.

(Comparative Example 3)
Instead of (C ′), (C ′) is changed to non-reactive dimethylpolysiloxane (viscosity: 100 mm ² / s, manufactured by Toray Dow Corning), and (B) is not added to (A) / ( C ′) / (D) = 5% / 2% / 93%, and a dispersion and molded pellets were obtained under the same conditions as in Example 1.

(Comparative Example 4)
(A) zinc oxide having a primary particle size of 0.03 μm, (C) carboxy-modified polysiloxane (viscosity: 125 mm ² / s, manufactured by Toray Dow Corning, both terminal-modified types), and (D) Powdered polycarbonate resin (Abbe number: 30) was blended at a ratio of (A) / (C) / (D) = 5% / 2% / 93%, and the dispersion and molding were performed under the same conditions as in Example 1. Pellets were obtained.

(Comparative Example 5)
Zinc oxide having a primary particle size of 0.03 μm as (A), barium sulfate having a primary particle size of 0.03 μm as (B), and a powdery polycarbonate resin (Abbe number: 30) as (D), (A) / (B) / (D) = 5% / 0.5% / 94.5% were blended, and a dispersion and molded pellets were obtained under the same conditions as in Example 1.

2. Fabrication of molded article Using the molded pellets obtained in Examples and Comparative Examples and the thermoplastic resin used in the fabrication of each molded pellet, the final metal oxide ((A) or (A ')) The mixture was blended so that the concentration was 0.3%, and an injection plate and Izod test piece having a thickness of 1 mm were obtained by an injection molding machine.

3. Evaluation method (evaluation of dispersibility of metal oxide)
Transmission electron microscope (TEM): An H-9000UHR transmission electron microscope (acceleration voltage 300 kV) manufactured by Hitachi, Ltd. was used to observe a 1 mm-thick injection plate.
○: Maximum particle mass is less than 0.05 μm.
Δ: The maximum particle mass is 0.05 μm or more and less than 0.1 μm.
X: There exists an aggregate of 0.1 μm or more.

(Evaluation of transparency)
The HAZE of a 1 mm-thick injection plate was measured with HAZE-GARD PLUS manufactured by Big Chemie Japan. A value of 10 or less was judged to have transparency.

(Evaluation of specific wavelength shielding)
The average of the light transmittance at a wavelength of 350 nm in a 1 mm-thick injection plate was determined using UV-265FW manufactured by Shimadzu Corporation. An average means the arithmetic average value of the transmittance | permeability in arbitrary 10 places of a molded article. The reason for measuring the specific wavelength of 350 nm is that it is possible to effectively shield the wavelength at which the photodecomposition of the resin becomes significant due to the basic absorption of the metal oxide (A).

(Evaluation of mechanical properties)
The physical property retention of Izod impact strength (ASTM D256) of the Izod test pieces of Examples and Comparative Examples was determined. The retention rate is the retention rate of each impact strength value when the Izod impact strength value of the thermoplastic resin alone is 100%.
○: Retention rate of 96% or more Δ: Retention rate of 90 to less than 96% ×: Retention rate of less than 90%

(Evaluation of molded product appearance)
The surface of each 10-mm-thick injection plate was visually observed, and the surface roughness (flash) of the molded product due to volatile components was evaluated as follows.
○: No flash was observed.
Δ: A flash was observed on one or more sheets.
X: Flash was observed in all.

The inorganic compound resin dispersion, molded pellets and molded products of the present invention are useful as optical materials because they are excellent in transparency, mechanical properties and shielding properties at specific wavelengths.

Claims (9)

A metal oxide (A) having a primary particle size of 0.1 μm or less , a metal sulfate (B) having a refractive index of 1.45 to 1.64 having a primary particle size of 0.1 μm or less, and carboxy-modified An inorganic compound resin dispersion comprising a reactive silicone (C) selected from polysiloxane, alcohol-modified polysiloxane and amino-modified polysiloxane, and a thermoplastic resin (D) having an Abbe number of 20 or more .   The inorganic compound resin dispersion according to claim 1, wherein the metal oxide (A) is 0.01 to 50% by weight.   The inorganic compound resin dispersion according to claim 1 or 2, wherein the amount of the metal sulfate (B) is 0.01 to 100 parts by weight with respect to 100 parts by weight of the metal oxide (A).   The inorganic compound resin dispersion according to any one of claims 1 to 3, wherein the metal oxide (A) is at least one selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, iron oxide, and zirconium oxide. The inorganic compound resin dispersion according to any one of claims 1 to 4, wherein the metal sulfate salt (B) is at least one selected from the group consisting of barium sulfate, magnesium sulfate, calcium sulfate, and potassium sulfate. Reactive silicone (C) has a viscosity of 10 to 1000 mm ² The inorganic compound resin dispersion according to claim 1, which is in the range of / s. Molded pellets obtained by melt-kneading the inorganic compound resin dispersion according to any one of claims 1 to 6. A molded article obtained by using the inorganic compound resin dispersion according to claim 1. A molded product obtained by using the molded pellet according to claim 7.