JPS646011B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to plastic particles that have been modified in various surface properties such as hydrophilicity and colorability. [Prior art and its problems] Needless to say, plastics have been used in various products in the past. However, while it has various advantages such as moldability, cost, and chemical resistance, it also has various disadvantages such as hydrophilicity and strength. In other words, if plastics could be given properties similar to those of metals, their usefulness would be extremely high. In response to this, there are three possible countermeasures: Searching for new materials for plastic itself Mixing foreign substances into plastic Surface treatment of plastic All of these methods have already been adopted, but even if the most favorable one is obtained for the target product, it may be difficult to use for other products. In addition, it is extremely difficult to find new materials, and it is not always possible to uniformly disperse the foreign matter mixture, and when it is commercialized, it may be partially strong or weak, etc. In addition, the surface properties of plastics are generally inert, which limits processing methods, resulting in a significant increase in costs. As a result of various studies in view of the above-mentioned points, the present inventors have determined that among the methods described above, the method based on the method described above is superior in terms of applicability and After extensive research into processing, they discovered that fine plastic particles with inorganic fine powder adhered only to their surfaces were optimal. [Means for Solving the Problems] Therefore, the present inventors conducted intensive research with the basic goal of being able to modify the surface of micronized plastic, control the reactivity, etc. into functional microparticles with a wide range of uses. As a result, the present invention has finally been completed, and the gist of the present invention is to provide fine plastic particles having inorganic fine powder adhered only to the surface thereof. Now, the type of inorganic substance fine powder that can be used in the present invention is not particularly limited, but silica fine powder is particularly preferable in consideration of imparting hydrophilicity, adhesion to the plastic surface, powdering effect, etc. Therefore, the case of using fine silica powder will be discussed below. Fine silica powder having a particle size of 1 to 100 μm is good from the viewpoint of pulverizing plastics and improving surface polarity. The amount of fine silica powder to be used should be sufficient to coat the surface of the plastic and make it granular.Generally, it is good to use 10 to 200 parts by weight of fine silica powder per 100 parts by weight of plastic. After the oxidation, it is preferable to remove the excess silica fine powder by sizing it. In order to adjust surface properties, color, etc., an appropriate amount of fine silica powder is added to fine powders of various bentonites, aluminum oxide, carbon black, calcium carbide, talc, kaolin, various pigments, magnesium carbonate, titanium oxide, zinc oxide, single metals, etc. Of course, it is also possible to use these alone or in combination without using the silica fine powder. It is also possible to treat the surface of the plastic fine particles in the present invention with a silane coupling agent, a titanate coupling agent, etc., and further to modify the surface to have completely different properties. This can be done by dry blending the coupling agent and plastic particles for 0.5 to 5 minutes in a commonly used stirring device, or
Alternatively, the plastic particles may be applied to a coupling agent solution, or the plastic particles may be brought into contact with a saturated gas flow of the coupling agent. Examples of coupling agents include vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl-trimethoxysilane, β-(3, Silane coupling agents such as 4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethyldimethoxysilane, triethylchlorosilane, isopropyltriiso Titanium coupling agents such as stearoyl titanate, isopropyloctanoyl titanate, isopropyl dimethacrylate, isostearoyl titanate, isopropyl tri(dioctyl phosphate), titanate, etc. can be used. The amount of these coupling agents to be used is appropriately selected depending on the type of plastic particles and the purpose of use, but it is generally preferred to use 0.1 to 5 parts by weight per 100 parts by weight of plastic particles. The plastic fine particles obtained in this way are used as raw materials for various moldings and compacts, and are also used as functional fine particles such as powder for sintering, reinforcing materials, catalyst carriers, water-based and oil-based pigments, modifiers, and adsorbents. It can be used in a wide range of applications such as powder hot melt adhesives, etc. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 250 parts by weight of fine silica powder (average particle size 12 mμ, surface area 200 m ² /g) was stirred in a stirring device with a rotary blade and a capacity of about 5. (manufactured by Mitsui Polychemical Co., Ltd.) was added in 5 portions by adding 100 parts by weight at a time and stirring at a rotational speed of 13,000 rpm for 20 seconds. After adding the entire amount, the mixture was further stirred at 15,000 rpm for 1 minute. After stirring, the mixture was allowed to cool for 30 minutes. Next, excess silica fine powder was removed using a jet separator (manufactured by Nippon Neumatic Industries), and white fine particles (polyethylene fine particles) were found throughout the 100-mesh wire mesh.
535 parts by weight were obtained. When these polyethylene fine particles were spread on the surface of water, they were extremely wettable. On the other hand, 200 parts by weight of the polyethylene fine particles thus obtained were placed in a stirring device with an internal capacity of about 1, and while stirring at about 500 rpm, 1 part by weight of trimethylchlorosilane dissolved in 30 c.c. of carbon tetrachloride. was added dropwise over a period of about 5 minutes. After 10 minutes of post-stirring, the mixture was air-dried to obtain silane-treated polyethylene fine particles. When placed on the surface of water, this material repelled water and was extremely difficult to get wet. Example 2 ^A blue pigment (PV
20 parts by weight of Fast Blue B2G (manufactured by Hoechst) was added and stirred intermittently for 30 seconds to form a pale blue colored silica powder bed. This includes 180 parts by weight of PVC paste resin, 120 parts by weight of dioctyl phthalate, and Cd.Ba.
Add 306 parts by weight of a well-mixed paste consisting of 6 parts by weight of Zn stabilizer in 3 to 6 times, stirring at 13000 rpm for about 20 seconds each time, and after adding the entire amount. 1 more at 13000r.pm
After stirring for a minute, transfer to an enamel vat and place in the oven.
Heated at 180°C for 30 minutes. After cooling, excess fine silica powder was removed by passing through a jet separator to obtain 374 parts by weight of pale blue powder (soft polyvinyl chloride fine particles) that passed through a 200-mesh wire mesh.
When this powder was sprinkled with water, it developed an extremely bright blue color. On the other hand, 200 parts by weight of the soft polyvinyl chloride fine particles thus obtained were placed in a stirring device with an internal capacity of about 1,000 rpm, and while stirring at about 1000 rpm, titanate coupling agent KR-TTS (Kenrich
4 parts by weight (manufactured by Petrochemicals, Inc.) were added dropwise and stirred for 3 minutes at 3000 rpm to obtain 201 parts by weight of pale blue powder. This powder easily repelled when water was poured on it, and although it only slightly strengthened the blue color and did not show as bright a blue color as the untreated powder described above, when ethanol was poured on it, it showed a bright blue color. ^Example 3 [3,4-epoxy-6-methyl 400 parts by weight of cyclohexyl, methyl carboxylate (UNOX201) and phthalic anhydride
Mixed liquid consisting of 160 parts by weight and 30 parts by weight of nonylphenol] Add 590 parts by weight in 4 parts, stirring at 13,000 rpm for about 20 seconds each time, and add the entire amount at 13,000 rpm. 1 more in .pm
After stirring for a minute, transfer to an enamel vat and place in the oven.
Heated at 130°C for 1 hour. After cooling, excess fine silica powder was removed by passing through a jet separator to obtain 731 parts by weight of a white powdered epoxy resin cured product (epoxy resin fine particles) that passed through a 200-mesh wire mesh. When these epoxy resin particles were spread on the water surface, they were extremely wettable. The surface conditions of the plastic particles obtained in Examples 1 to 3 were investigated below. About plastic fine particles and polyethylene fine particles obtained in Example 1 Polyethylene fine particles obtained in Example 1
After taking approximately 0.5 g of the 535 parts by weight and accurately weighing this value, add 20% hydrofluoric acid in an amount 50 times the weight of the polyethylene fine particles, stir for 30 seconds, and filter. The obtained filtrate was analyzed using an atomic absorption spectrophotometer. Furthermore, after filtration, the remaining polyethylene fine particles were washed with water and then incinerated in a crucible. The same amount of 20% hydrofluoric acid as above was added to the residue, stirred for 10 minutes, filtered, and the filtrate was measured using an atomic absorption spectrophotometer. Analyzed by. Meanwhile, polyethylene (high pressure polyethylene Mitsui Polychemical Co., Ltd.)
15 parts by weight of fine silica powder (average particle size 12 mμ, surface area 200 m ² /g) were added little by little, and thoroughly kneaded to obtain 515 parts by weight of polyethylene containing silica. Ta. 500 parts by weight of this silica-containing polyethylene was treated in the same manner as in Example 1 to obtain 535 parts by weight of white fine particles (polyethylene fine particles) that were passed through a 100-mesh wire mesh. After taking about 0.5g of this white fine particle and accurately weighing this value,
To this was added 20% hydrofluoric acid in an amount 50 times the weight of the polyethylene fine particles, and analysis was carried out using an atomic absorption spectrophotometer in the same manner as above. Table 1 below shows the results of analysis using an atomic absorption spectrophotometer. The unit indicates the ratio of fine silica powder to the total amount of fine polyethylene particles obtained.

【table】

[Table] As a result, 1.25% Si was detected in the filtrate after incineration of polyethylene fine particles mixed with silica powder. It was found that the fine silica powder contained in the polyethylene particles obtained in Example 1 was not eluted, and the fine silica powder was fixed only to the surface of the polyethylene. About the soft polyvinyl chloride particles obtained in Example 2: Take about 0.5 g of the 374 parts by weight of the soft polyvinyl chloride particles obtained in Example 2, weigh this value accurately, and add this Add 20% hydrofluoric acid 50 times the weight of the soft polyvinyl chloride fine particles,
After stirring for 30 seconds, the mixture was filtered and the resulting filtrate was analyzed using an atomic absorption spectrophotometer. Furthermore, after filtration, the remaining soft polyvinyl chloride fine particles are washed with water and then incinerated in a crucible. The same amount of 20% hydrofluoric acid as above is added to the residue, stirred for 10 minutes, filtered, and the filtrate is Analyzed by spectrophotometer. On the other hand, in a silica powder bed obtained in the same manner as in Example 2, 180 parts by weight of vinyl chloride paste resin, 120 parts by weight of dioctyl phthalate, 6 parts by weight of Cd.Ba.Zn stabilizer, fine silica powder (average particle size 7mμ, surface area 380
m ² /g) a well-mixed paste consisting of 10 parts by weight
316 parts by weight was added in 3 to 6 portions in the same manner as in Example 2 to obtain 385 parts by weight of a pale blue powder (soft polyvinyl chloride fine particles) that was passed through a 200-mesh wire mesh. Approximately 0.5g of this soft polyvinyl chloride fine particle
After accurately weighing this value, add a weight that is 50 times the weight of this soft polyvinyl chloride fine particle.
20% hydrofluoric acid was added, and analysis was performed using an atomic absorption spectrophotometer in the same manner as above. Table 2 below shows the results of analysis using an atomic absorption spectrophotometer. The unit indicates the ratio of fine silica powder to the total amount of soft polyvinyl chloride fine particles obtained.

[Table] As a result, the soft polyvinyl chloride fine particles mixed with silica powder contain 1.20% Si in the filtrate after incineration.
Since it has been detected, by adding 20% hydrofluoric acid and stirring for 30 seconds, the fine silica powder kneaded into the soft polyvinyl chloride will not be eluted, and the soft polychloride obtained in Example 2 will be dissolved. It was found that the silica fine particles of the vinyl particles adhered only to the surface of the soft polyvinyl chloride. Regarding plastic fine particles and epoxy resin fine particles obtained in Example 3 Epoxy resin fine particles obtained in Example 3
After taking approximately 0.5 g of the 731 parts by weight and weighing this value accurately, add 20% hydrofluoric acid in an amount 50 times the weight of the epoxy resin fine particles, stir for 30 seconds, and filter. The resulting filtrate was analyzed using an atomic absorption spectrophotometer. Furthermore, after filtration, the remaining epoxy resin particles were washed with water and then incinerated in a crucible. The same amount of 20% hydrofluoric acid as above was added to the residue, stirred for 10 minutes, filtered, and the filtrate was analyzed by atomic absorption spectrometry. It was analyzed by a meter. On the other hand, in 300 parts by weight of fine silica powder, [400 parts by weight of 3,4-epoxy-6-methylcyclohexyl, methyl carboxylate (UNOX201), 160 parts by weight of phthalic anhydride, 30 parts by weight of nonylphenol,
Mixed liquid consisting of 10 parts by weight of fine silica powder] 600 parts by weight was added in 4 parts, and the same procedure as in Example 3 was carried out.
745 parts by weight of a white powdered epoxy resin cured product (epoxy resin fine particles) was obtained through a 200-mesh wire mesh.
After taking about 0.5 g of these epoxy resin particles and accurately weighing this value, add 20% hydrofluoric acid, which is 50 times the weight of the epoxy resin particles, and proceed in the same manner as above. Analyzed by spectrophotometer. Table 3 below shows the analysis results using an atomic absorption spectrophotometer. The unit indicates the ratio of fine silica powder to the total amount of fine epoxy resin particles obtained.

[Table] As a result, 0.61% Si was detected in the filtrate of the epoxy resin fine particles mixed with silica powder after incineration, so by adding 20% hydrofluoric acid and stirring for 30 seconds, It was found that the silica fine powder kneaded into the epoxy resin fine particles obtained in Example 3 was not eluted, and the silica fine powder was fixed only on the surface of the epoxy resin. [Effects of the Invention] As described in detail above, according to the plastic particles of the present invention, various properties such as hydrophilicity and colorability on the surface can be appropriately modified, thereby improving the quality of the material. As a result, it can provide excellent plastic particles that can be used in a wide variety of applications.

Claims (1)

[Claims] 1. Fine plastic particles having inorganic fine powder adhered only to their surfaces. 2. Plastic fine particles according to claim 1, wherein the inorganic substance fine powder contains silica as a main component. 3. Plastic fine particles according to claims 1 and 2, characterized in that they have been treated with a coupling agent.