TW200837103A - Silicone particles with high luminance and excellent light resistance, method for preparing the same, and light diffusion plate using the same - Google Patents

Abstract

One aspect of the invention relates to silicone particles whose surfaces are imparted with a hydroxyl group in a predetermined concentration through surface treatment. The silicone particles according to the present invention may have excellent luminance and light resistance and improved workability and compatibility with resin by controlling the water contents on the surfaces of the silicone particles.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycrystalline oxygen particle having high luminance and excellent light resistance, a method for producing the same, and a light diffusion sheet using the same. The invention particularly relates to a polythene oxide particle having excellent brightness and light resistance, and bonding a predetermined concentration of hydroxyl groups on the surface of the particle by surface treatment to improve the usability and compatibility with the resin. And the present invention relates to a light diffusing sheet using the polysiloxane particles. [Prior Art]

Poly-stones (for example, polysilsesquioxan Q particles and silica particles) are generally excellent in compatibility with polymer resins and organic materials, and are therefore often used in paints, plastics, and rubbers. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, It has many properties such as low optical refractive index, good fluidity and compatibility with resins. Polyorganopyquid siloxane particles are used as diffusers for lampshades, signs, LCD backlights and light diffusers, or additives for light guides. The preparation of the polyfluorene oxide particles is carried out by a sol. gel method using a methyltrialkoxydecane monomer (which is composed of a hydrolysis reaction and a condensation reaction mechanism), such as an early Japanese patent. No. 54-72300, 63-077940, 1〇_〇45914, 2〇〇〇-186148, and similar patents. However, there is a difference in the rate of question when polychlorinated particles 5 200837103 is used as a light diffusing agent. The light diffusibility is good, and the luminance of the polyoxynene particles is lowered. [Because (4) and the refraction of the resin, but because of the deterioration of the light transmittance, ... to solve the above problem, Japanese Early Patent No. 2006-10819, 1-172801, 1-269902, 1〇_8Cai B and 颛like special ^

It is not necessary to control the proportion and composition of the resin composition to increase the brightness thereof. However, there is a need for a new method for controlling the optical properties of the diffusing agent itself by controlling the ratio and composition of the above-mentioned controlling resin composition. "Thinness and Resistance" Therefore, the inventors of the present invention have developed a polysecond oxygen particle having excellent luminance lightness, and by surface treatment, a predetermined concentration of a warp group is bonded to a polyorganic surface to enhance the resin. And the development of a polyfluorene oxide particle. [Inventive] The present invention is directed to providing a polycrystalline oxygen particle having excellent luminance and light resistance. A further object of the present invention is to provide a method for preparing agglomerated particles having excellent luminance and light resistance by subjecting the surface of the particles to 2 〇 = treatment. Light-cut oxygen particles for improved usability and compatibility of resins 0 200837103 Light: Γ 再 — 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的And the advantages will be known from the following description and application of the patent: i, polyoxynized particles, the surface of which has a hydroxyl group index of about 0.7 to 1.0 (〇Η. The preparation is carried out by surface treatment of polyorganopyquid oxynized powder particles to control the concentration of hydroxyl groups on the surface of the particles, so that the particles have a hydroxyl group index of about 0.77 to 1.0. 10 15 In the present invention In one embodiment, the poly-xylene particles are prepared by picking a latex from a polyorganopyquidoxane (10) to form powdered polysiloxane particles; and drying or sintering the powdered poly The oxygen-containing particles are used to control the concentration of the hydroxyl groups on the surface of the powdery polysiloxane particles. The polysiloxane particles prepared by the above method can be used as a diffusing agent, and can be used together with a thermoplastic resin in the manufacture of a light-diffusing sheet because of the polyoxyl The particles have excellent luminescence and light resistance and have excellent workability and compatibility with other resins. [Embodiment] The polyfluorene oxide particles of the present invention have the following formula having a formula of about 〇·7 to 1·〇. Hydroxyl index: hydroxyl group index = [absorption position at (3350~3400~3450 cnr1)] / [absorption peak at (2920~2970~3020 cm-1)] 7 200837103 where [absorption position at (33 50~3400~ 3450 cm-b] : S i-OH absorption peak, and [absorption position at (2920~2970~3020 cnT1)]: Si-CH3 absorption peak. The side-containing base index is equal to the Si-ΟΗ absorption peak value (infrared spectrum range 3350~3400~3450 cm· 1) Divided by the value of the Si-CH3 absorption peak value (infrared spectrum range 2920~2970~3020 cm_1). By ir (infrared) light 5 Jinyi analysis of the base absorption on the surface of the polysulfide oxide particles After the concentration, the hydroxyl group index can be obtained according to the above formula. This measurement method can measure and analyze the most 10 15

20 25 The desired hydroxyl concentration range, and the hydroxyl group index of the present invention is preferably between about 0.7 and 1 Torr. When the hydroxyl group index of S exceeds about 丨·〇, since the large amount of hydroxyl groups on the surface of the polyoxygen oxide particles increases the affinity of the polysiloxane particles with water, the twins of the polysiloxane particles and the resin deteriorate. Moreover, since the gas is generated during the injection and extrusion process, the warp index exceeding about 1 Å causes a significant decrease in usability. Further, when the warp-containing index is less than about G·?, the luminance of the polyparticles is lowered. Λ The milk essence can effectively adjust the hydroxyl-containing index of Shixi oxygen particles, which can be changed to m: 1 1 The optical properties of the base to the right/right body, thus providing the characteristics of Lewis/Br〇nsted acid In the machine (4) oxygen burning between the surface of the oxygen particles. ...the structure of polyorganic sesquitertes is usually expressed as muscle ~, ΪΓ / has a quilt. The polyorgano (tetra)oxygen of the present invention has the same as the following: The repeating unit of the formula 1 is as follows: [Formula 1] RSi〇i.5-x (〇Η) 8 200837103 wherein R is 1 to 6 carbon atoms An alkyl group (alkyl with (10) p), a vinyl group having 6 carbon atoms, an aryl group having 6 to 2 carbon atoms, or 6 to 2 An alkyl-substituted aromatic hydroxy group of a carbon atom, and 〇<X < X. 5 In a representative example of the invention, R is methyl, ethyl or phenyl. In industrial terms, R is preferably a methyl group. In style! In the middle, the range is 〇<χ<ι·5. The absorption concentration of the hydroxyl group on the surface of the polysiloxane particles is analyzed by IR, so that the hydroxyl group-containing index can be obtained according to the above formula. The polyfluorene oxide particles of the present invention are used to surface-treat the polyorganopyquioxalate powder particles to control the hydroxyl group concentration on the surface of the particles, so that the hydroxyl group index obtained by the above formula is about 〇.7 Between 1 。. The surface treatment can be heat treatment, chemical treatment, or the like. Preferably, the particles are heat-treated at a temperature between 200 and 400 ° C, more preferably between 200 and 300 ° C. 15 These polyorganosilsesquioxane powder particles can be prepared by a sol-gel method using an alkyl 〇rganosilane as a monomer, as disclosed in Japanese Laid-Open Patent Publication No. 54-72300, 63- Techniques disclosed in 077,940, 1 〇-45914, 2000-186148, and similar patents. However, the method of preparing the particles is not limited to a particular method. In one embodiment of the present invention, a method of preparing the poly-xonium oxide particles includes the steps of: drying a polyorganosilsesquioxane latex to obtain powdered polysiloxane particles, and drying or sintering the powdered poly The oxygen absorbing particles are used to control the concentration of the hydroxyl groups on the surface of the powdery polysiloxane particles such that the powdery polyoxynene particles have a hydroxyl group index of between about 至7 and 1 Torr. 200837103 The preparation of the ruthenium polysesquioxane latex is carried out by using a sol-gel method of an organic alkoxylate, but is not limited thereto. The above-mentioned polyorganosilsesquioxane latex was dried at a temperature between 8 Torr and 2 cc using a direct spray dryer to obtain white powder 5 terminal polysecond oxygen particles. In one embodiment of the present invention, the above polyorganopyoid sesquioxane # can be recovered into a white powdery polyoxoparticle, which is a centrifuge, a filter press, a vibrating screen or the like. The apparatus dehydrates the polyorganopyquioxane gum to prepare a sludge, and then washes the dehydrated sludge 10 to remove impurities, followed by a spin flash dryer, a vacuum dryer, or The temperature between the similar devices K8 〇 s20 〇 t: dries the mud from which the impurities have been removed. The obtained powdery polysiloxane particles have a water content of about 5% or less, preferably 3% or less, and can be formed into a polysulfide of the present invention after the second drying or sintering step 15 particle. The hydroxyl concentration of the polyoxynium particles is controlled via a drying or sintering step and the drying or sintering step is carried out between 2 Torr and 4 Torr. This drying or sintering step is carried out for about 3 minutes to 3 hours, preferably for about an hour. In one embodiment of the invention, the calciner is dried at a temperature between 2 Torr and 400 C by means of a calciner such as a kiln rotary dryer or a convecti〇n 〇ven. And sintering the powdery polyfluorene oxide particles for about 3 minutes to 3 hours, so that the inclusion base index of the poly-stone particles is controlled to be between about 77. 200837103 The surface treated polyadipenoid particles have an average particle diameter of about 0.1 to 20 μm. In another aspect, the present invention provides a light-diffusing sheet using the above-mentioned polyorganosilsesquioxane particles as a light diffusing agent. This light diffusing sheet can have excellent brightness and light resistance. In the present invention, the light diffusing sheet is particularly suitable as a diffusing sheet for an LCD TV. In one embodiment of the invention, the light diffusing sheet comprises from about 0.1 to 10 parts by weight of the polyoxynene particles and about 100 parts by weight of the thermoplastic resin. 10 This light diffusing sheet can be prepared by a method well known to those skilled in the art of the present invention. The thermoplastic resin may be vinyl chloride resins, styrenic resins, styrene-acrylonitrile based resins, C:) #酉曼才封Acryl 15 resins, acryl-styrene based resins, polyester resins, ABS resins, polycarbonate resins, or mixtures thereof . When the polyorganosilsesquioxane particles of the present invention are added to a thermoplastic resin, the polyorganosilsesquioxane particles lower the light transmittance of the thermoplastic resin. Therefore, the diffusing plate for LCD-TV using the polyorganossesquioxane particles can have excellent luminance and light resistance. The invention may be further understood by reference to the following examples, which are intended to illustrate the invention and not to limit the scope of the invention. Example 25 Example 1 200837103 420 g of methyltrinieth〇xysilane was dispersed in 2580 ml of distilled water, and the solution was stirred for 1 hour. Next, ammonia water was added to the mixture to adjust the pH to hydrazine, and the adjusted solution was stirred for 1 hour. Next, the stirred solution was allowed to stand at room temperature for 2 hours to form a polyoxyl latex. Next, the synthetic latex was filtered and washed with a centrifuge to obtain a white fine particle slurry of about 200 §. First, the internal temperature was 16 (the external temperature of the TC was 8 (the rc rotary flash dryer was used to dry the polymethoxy L-semi-stone slurry to obtain white poly-stone powder. #200.〇 The white 10 water sec. oxygen was allowed to be twice dried with a vacuum dryer for 2 hours to provide an effective and concentration-adjusted surface based on the poly-stone powder. Finally, a poly-organic ratio having a hydroxyl group index of 〇88 was obtained. Semi-oxygenated particles. Example 2 15 20 37 〇g"-based methoxy sulphite and methyl sulphate (methyhdch 丨 (10) silane) were added to 258 _ ion-exchanged water for 1 hour. Ammonia water is added to the dropped solution to adjust the pH to I. The adjusted pH value is allowed to stand for 4 hours to carry out the reaction. After filtering and washing the obtained product, it is dried by a spray dryer to obtain fine §, under the same conditions as in Example 1, the white powder was dried by a rotary flash dryer to obtain a white (tetra) oxygen powder. The white (tetra) oxygen powder was twice dried in a kiln-like rotary dried mash. 40 minutes to provide; and the wave is adjusted based on poly% oxygen powder Finally, a poly-organopyloxane particle having a base index of 0.93. B 12 25 200837103 Example 3 370 g of 3-mercaptopropyltrimethoxysilane was dispersed in 2580 ml of steamed water, Further, 50 g of 3-aminopropylmethoxysilane was dispersed in the solution. Then, the solution was allowed to stand at room temperature for 6 hours, and then stirred and washed by a centrifuge. The solution was used to obtain 200 g of a polymethoxysilsesquioxane particle slurry. The polysulfide slurry was poured into a rotary flash dryer and dried at 160 ° C to obtain a white polyoxyn powder. 10 The polyfluorene powder particles are placed in a kiln rotary dryer and dried at 300 ° C for 40 minutes for a secondary drying process for surface treatment of the polyfluorene powder particles to make the surface of the polyoxygen oxide powder effective. And a controlled hydroxyl group. Finally, a polyorganosilsesquioxane particle having a hydroxyl group index of 0.80 was obtained. 15 Example 4 370 g of 3-mercaptopropyltrimethoxysilane was classified. Disperse in 2580 ml of distilled water, and then add 50 g of 3-aminopropylmethoxysilane to this dispersion solution. Then, the solution 20 was allowed to stand at room temperature for 6 hours. The resulting solution was further stirred and washed with a centrifuge to obtain 200 g of a polymethoxysilsesquioxane particle slurry. This polysulfide slurry was poured into a rotary flash dryer and dried at 160 ° C to obtain a white polyoxynium powder. The polyfluorene powder particles are placed in a kiln-like rotary drier and dried at 300 ° C for 2 hours and 25 hours to carry out a secondary drying process for surface treatment of the polyfluorinated powder particles 13 200837103 to make the polythene The oxygen powder surface has an effective and controlled hydroxyl group. Finally, a polysecond oxygen particle having a base index of 〇·71 is applied. Comparative Example 1 5 42 g of methyltdmethoxysilane was dispersed in 2580 ml of distilled water, and the solution was stirred for several hours. Next, ammonia water was added to the solution to adjust the pH to 1 Torr, and the pH-adjusted solution was stirred for 1 hour. Next, the stirred solution was allowed to stand at room temperature for 2 hours to synthesize a polyaluminum latex. Next, the synthetic milk 10 was filtered and washed with a centrifuge to obtain about 2 g of a white fine particle slurry. The polymethoxysilsesquioxane slurry was dried at a temperature of 200 C using a rotary flash dryer to obtain a white polysulfide powder. Comparative Example 2 15 ^ 42 〇g of methyltrimethoxysilane was dispersed in 2580 ml of distilled water, and the solution was stirred for a few hours. Next, ammonia water was added to the solution to adjust the pH to 10, and the pH-adjusted bath was stirred for 1 hour. Next, the stirred solution was allowed to stand at room temperature for 2 hours to synthesize a poly-xyloxy latex. Next, the synthetic milk 20 was filtered and washed with a centrifuge to obtain about 20 angstroms of white fine particle sludge. The slurry was dried with a vacuum dryer at a temperature of 6 ° C for 2 hours. Finally, polyorganosil sesquioxanes particles having a hydroxyl group index of 〇·60 were obtained. In the above examples and comparative examples, the number of the particles of the surface-treated (changing the temperature and time conditions) was compared, and different poly-stone particles were prepared according to the basis index of the particle surface 25. In order to prepare the poly-stone oxygen 14 200837103 particles into the master batch for injection molding the diffusion plate, the particles can be prepared by a screw extruder with a pore diameter of φ=45 mm, and the poly-xonium particles are aggregated. The styrene tree was mixed with EXL_5136 (R〇hm & Haas, usa) in a ratio of 1:100:1. Then, a plate type sample (simple diffusion plate) having a thickness of 1.5 πππ can be obtained at a casting temperature of 21 〇 5 °C in a 1 〇 0z syringe. The optimum amount of hydroxyl groups, i.e., the hydroxyl group-containing index, can be obtained by measuring the luminance of a plate-like sample prepared. The table shows the warp-containing index and the 10-degree luminance calculated by the above-described superbase-based index relationship after the polysiloxane particles subjected to the drying and surface treatment processes in each of the examples and the comparative examples were subjected to signal analysis. The physical properties of the particles obtained through the above process can be evaluated by the following methods. The results are shown in Table 1. (1) Analysis of the warp-containing index: The number of the base groups of each other was compared by analyzing the surface of the polyoxynitride particles by IR analysis 'the hydroxyl group index 15 obtained from the above-mentioned hydroxyl group-containing index relationship. (2) Luminance: The luminance of the five diffuser-like mouths prepared through the extrusion and injection process can be continuously measured using Luminometer NL-1 (Nippon, Japan). The measurement of the luminance on the diffuser plate is repeated three times, using the average. Values are compared to each other. 20 Table 1 Hydroxyl index brightness relative absorbance Example 1 0.88 2503 2 0.93 2891 15 200837103 3 T 0.80 ~------ 2596 --- -- - 0.71 2499 Comparative example 1 1.41 Can not squeeze 2 0.60 ~___ 2400 ---------- It can be confirmed from Table 1 that the luminance decreases as the number of warp groups decreases. Therefore, instead of the appropriate concentration of the warp group (that is, the best contains the base of the base is necessary, rather than unlimited number of hydroxyl groups (concentration). The ratio of k is shown in Figure 1 'When the surface of the rock particles There are a large number of warp groups', that is, when X absorption increases, the affinity between the poly-stone particles and water increases, so that the compatibility of the money and fat is lowered. And, since the water is generated during the injection and extrusion 2 The gas 'is reduced in workability, making the diffusion plate injection molding difficult, and the sample cannot be produced. Therefore, as shown in Table 1, Examples 1 to 4 having a hydroxyl group index of between 〇7 and 1〇 show The present invention has been described above on the basis of specific examples, and it is to be understood by those skilled in the art that the present invention can be variously modified without departing from the spirit of the invention and the scope of the appended claims. And modification. [Simple description of the diagram] [Explanation of main component symbols] 16

Claims (1)

200837103 X. Patent application scope: 1 · The type I stone oxygen particle 'has its surface treated with about 〇. 7 to 1 〇 as shown in the following formula: OH index: hydroxyl index = [absorption Position at (335〇~34〇〇~345〇cm-% / 5 [absorption peak located at (2920~2970~3020 cm·1)] where [absorption position at (3350~3400~3450 cm·1)] ·· Si-0H absorption peak, and [absorption position at (2920~2970~3020 cm·1)] ·· Si-CH3 absorption peak. 2. The polysiloxane particle according to claim 1, wherein 10 The polysiloxane particles have a repeating unit represented by the following formula 1: [Formula 1] RSi〇i.5-x (OH) x Wherein R is an alkyl group having from 1 to 6 carbon atoms (alkyl group p), a vinyl group having from 2 to 6 slave atoms, and an aromatic hydroxyl group having 6 to 2 carbon atoms ( An aryl group), or an alkyl-substituted aromatic hydroxy group having 6 to 2 carbon atoms, and 〇< χ <丨.5. 3. The polyfluorene oxide particle of claim 2, wherein R is a fluorenyl group. 4. The polysiloxane particles according to claim 1, wherein the polyoxynium particles have an average particle diameter of about 0.1 to 2 μm. 5) A method for preparing I oxime oxygen particles, comprising surface treating polyorganopyloxane (P〇ly0rgan〇silsesqui〇xane) powder particles to control the concentration of hydroxyl groups on the surface of the particles to obtain含·7 to 1〇 has the hydroxyl group index as shown in the following formula: 17 200837103 Containing warp index = [absorption position at (3350~3400~3450 cm-l)] / [absorption peak at (2920~2970~3020 cm) -1)] where [absorption position is (3350~3400~3450 cm-1)]: Si-OH absorption peak, and 5 [absorption position at (2920~2970~3020 cm-1)] : Si-CH3 absorption peak . 6. The method of claim 5, wherein the surface treatment is a heat treatment at a temperature between 200 and 400 °C. 7 - A method for preparing polyoxo oxygen particles, comprising: drying a polyorganosilsesquioxane latex to obtain a powdery polyxonium oxide 10; and drying or sintering the powdered polysiloxane particles Controlling the concentration of the hydroxyl group on the surface of the powdery polyfluorene oxide particles so that the powdery polyfluorene oxide particles have a hydroxyl group index represented by the following formula of about 0.7 to 1··············· 3350~3400~3450 cm-1)] / 15 [Absorption peak located at (2920 to 2970 to 3020 cm-1)] where [absorption position at (3350~3400~3450 cm-1)]: Si-OH absorption peak, And [absorption position at (2920~2970~3020 cm-1)]: Si-CH3 absorption peak. 8. The method according to claim 7, wherein the preparation of the polyfluorene sesquioxane latex is carried out by using an organoalkoxysilane via a sol-gel (s〇1- Prepared by gel method. 9. The method of claim 7, wherein the drying or sintering step is carried out at about 200 to 400 ° C for about 3 minutes to 3 hours. A light-diffusing sheet according to any one of claims 1 to 4, which is a light diffusing agent. 11. The light-diffusing sheet of claim 10, wherein the light-diffusing sheet comprises from about 0.1 to 10 parts by weight of the polyoxynene particles and about 100 parts by weight of a thermoplastic resin. 12. The light-diffusing sheet of claim 11, wherein the thermoplastic resin is vinyl chloride resins, styrenic resins, styrene-acrylonitrile-based resins (styrene- Acrylonitrile based resins),acrylic 10 resins, acryl-styrene based resins, polyester resins, ABS resins, polycarbonate Resins) or a mixture thereof. 13. The light diffusing sheet of claim 10, wherein the light diffusing sheet is used for an LCD-TV. 19 200837103 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: