JPS6311051B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of mixing an inorganic powder and an organic compound or a mixture thereof (hereinafter simply referred to as an organic compound). Traditionally, plastics, rubber, paints, inks,
During the production of adhesives, etc., technology has been developed to improve the physical and chemical properties of organic compounds by adding various inorganic substances to them, or to impart properties that are not originally present or are poor in the organic compounds. , has been applied in a variety of fields, but in recent years, as the fields of application have further expanded, improvements have been required in terms of improved processing conditions, resource conservation, and energy conservation. When adding inorganic substances to organic compounds, compounds called so-called coupling agents are used. Typical examples include organic silane-based, organic chromic acid-based, and organic titanium-based compounds. materials, handling, environmental hygiene,
There are advantages and disadvantages in terms of price, etc., and further improvements are desired. The purpose of the present invention is to provide an organic compound of inorganic powder or granule that has extremely good dispersibility and allows the addition amount to be increased without increasing the viscosity of the blended mixture. The objective is to provide a method for mixing. The method of mixing the inorganic powder and the organic compound of the present invention is expressed by the formula [], (In formula [], R ₁ and R ₂ each represent a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and m and n represent 0 or an integer of 1 to 3.) This method is characterized by mixing an inorganic powder and an organic compound in the presence of a phosphorus compound. According to the method of the present invention, when adding inorganic powder to an organic compound, the dispersibility is extremely good, and the amount added can be increased without increasing the viscosity of the blended mixture. Not only the effects can be obtained, but also the effects such as resource saving and energy saving by shortening the processing time and lowering the processing temperature, improving and stabilizing product quality, and improving environmental hygiene can be obtained. The organic phosphorus compound of the formula [] (hereinafter abbreviated as HCA) used in the present invention is disclosed in Japanese Patent Publication No. 48-41009,
This compound is described in publications such as No. 49-45397 and No. 50-17979, and has an excellent effect on stabilizing organic compounds. Therefore, the blended composition obtained by the method of the present invention also exhibits extremely good stability despite the blending of various kinds and large amounts of inorganic additives. In addition, it dissolves easily in ordinary organic solvents, has good compatibility with various resins, has high heat resistance, has almost no skin irritation or toxicity, and is not flammable, making it extremely advantageous in terms of work and environmental hygiene. be. Inorganic substances targeted by the present invention include additives for plastics, rubber, paints, inks, adhesives, etc., such as extenders, fillers, flame retardants, reinforcing agents,
Examples include coloring agents, abrasives, friction resistance agents, magnetizing agents, and the like. Specifically, oxides (including spinel compounds, hydrates, etc.) of zinc, aluminum, antimony, chromium, silicon, zirconium, tungsten, titanium, iron, copper, lead, manganese, etc., aluminum, zinc, copper hydroxide, calcium, etc.
Carbonates such as barium and lead, basic carbonates, sulfates, calcium, barium, strontium, zirconium, chromates such as lead, copper and iron, manganates such as barium and potassium, borates such as copper,
Phosphates such as manganese, iron, nickel, cobalt, chromium, and lead, aluminates such as cobalt and chromium, zincates such as cobalt and copper, stannate, tungstates such as calcium and barium, magnesium, Examples include titanates such as lead, zinc, and cobalt, sulfides such as calcium, zinc, cadmium, mercury, and antimony, silica, diatomaceous earth, mica, clay, talc, asbestos, rock wool, and glass. The shape of these inorganic substances is not particularly limited as long as it is in the form of powder or granules, and may be in the form of whiskers, fibers, or flakes as well as normal powder and granule shapes. Target organic compounds include synthetic polymers such as polyolefins, polyvinyl chloride, polystyrenes, AS resins, ABS resins, polyamides, polyurethanes, polyesters, polyethers, polycarbonates, and polyvinyl acetate. classes, polyvinyl alcohols, epoxy resins,
Phenol resins, silicone resins, natural resins, rubber, cellulose derivatives, natural and synthetic drying oils, synthetic polymer oligomers and prepolymers, plasticizers, organic low-molecular compounds such as aliphatic, aromatic, and ester-based Examples include organic solvents. In the present invention, surface-treating the inorganic substance with HCA in advance makes mixing effective. This is particularly effective when the blending ratio of the inorganic substance is large, its particle size is small, or its oil absorption is large. Surface treatment of inorganic substances with HCA can be carried out by commonly employed methods. For example, an inorganic substance and HCA may be mixed in powder form or in a slurry form with an appropriate medium added in a mixer such as a ball mill, and the medium may be removed if necessary, or a solution of HCA may be sprayed and adsorbed onto the surface of an inorganic substance. If necessary, remove the solvent, add the inorganic substance to the solution containing HCA,
A method is adopted in which the slurry is thoroughly stirred and then the solvent is removed. The amount of HCA added is 0.1 of the amount of inorganic substances to be blended.
~5% (by weight, same hereinafter), preferably 0.2~1%. Next, examples of the present invention will be described. Examples 1 to 10 Various inorganic substances (powder) are suspended in methylene chloride in the form of a slurry, and 9,10-dihydro-9 phosphor-10-oxaphenanthrene-9 is added to this in an amount equivalent to 0.5% of the inorganic substance. - oxide (hereinafter referred to as H-HCA)
After stirring for 1 hour, the solvent was removed under reduced pressure and heating in a rotary evaporator to obtain a surface-treated product. On the other hand, for comparison, a comparative product was obtained by processing in the same manner as above except that H-HCA was not added. Each inorganic substance obtained in this way was added to liquid paraffin (22c.ps, 25℃) in various proportions.
After stirring for 10 minutes, the viscosity (cps/25°C) was measured using a B-type viscometer (rotor No. 4, 60 rpm). The results are shown in Table 1. The blending ratio in Table 1 is 100 parts of liquid paraffin (weight, same below)
This is the part of added inorganic material per unit.

[Table] Instead of H-HCA in Examples 1 to 10, H
-Similar results were obtained using HCA in which the 1-position was substituted with a cyclohexyl group, the 3-position was substituted with an α-methylbenzyl group, or the 1,3-position was di-substituted with a chlorine atom. was gotten. Examples 11-12 Table 2 shows the results of measuring the viscosity of the mixture in the same manner as in Example 1 except that ethyl acetate or xylene was used instead of liquid paraffin as the organic compound.

[Table] Example 13 Surface treatment with H-HCA equivalent to 0.5% (Example 1
Calcium carbonate (heavy) treated in the same way as
When mixed with the same amount of dioctyl phthalate, the viscosity was 150 c.ps (25°C).
On the other hand, a calcium carbonate mixture treated in the same manner except that H-HCA was not added had a yield of 5500 c.ps. Example 14 The viscosity was similarly measured for a mixture of 100 parts of calcium carbonate (heavy) as an inorganic substance and 100 parts of bisphenol A diglycidyl ether (trade name: Epicote 828, manufactured by Yuka Cielpoxy Co., Ltd.) as an organic compound. (However, rotor No. 4, 10 rpm) The result was 105 p.s. in the case of H-HCA 0.5% treatment and 140 p.s. in the case of the comparative example. Example 15 Talc was surface-treated with H-HCA in an amount equivalent to 0.5% (treated in the same manner as in Example 1), and 67 parts (Example 15-1) or 82 parts (Example 15) were added to 100 parts of polypropylene. -2) are added and mixed, each with MFI
(Melt flow index) (g/10 minutes, 230℃)
was measured. For comparison and reference, 67 parts of talc treated in the same manner except that H-HCA was not added (Comparative Example 15), and H- without talc mixed.
Measurements were also carried out for those to which only 0.25% HCA (based on polypropylene) was added (Reference Example-1) and only for polypropylene itself (Reference Example 2). The results are shown in Table 3.

[Table] Example 16 Calcium carbonate (heavy) was surface-treated with H-HCA in an amount equivalent to 0.5% of calcium carbonate, and 43 parts (Example 16-1) and 67 parts were prepared for 100 parts of HDPE (high-density polyethylene). (Example 16-2) and 100 parts (Example 16-3) were added and mixed, respectively at MFI (g/10 minutes, 230°C).
was measured. In addition, the same comparative and reference tests as in Example 16 were conducted. The result is the fourth
Shown in the table.

【table】

Claims (1)

[Claims] 1. The surface of the inorganic powder or granular material is prepared in advance by the formula [] (In formula [], R ₁ and R ₂ each represent a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and m and n represent 0 or an integer of 1 to 3.) A method for mixing inorganic powder and an organic compound, which comprises treating with a phosphorus compound and then mixing with an organic compound or a mixture thereof.