JP2003026856A - Powdery hybrid material for blending with synthetic resin and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powdery hybrid material for blending with a synthetic resin, excellent in a dispersing property on blending with the synthetic resin, and capable of improving mechanical properties and a coloring property of the synthetic resin molded article. SOLUTION: This powdery hybrid material for blending with a synthetic resin is obtained by mixing titanium dioxide with calcium carbonate and a fatty acid or its salts with a dry type high speed agitator. The mean particle diameter of the titanium dioxide, is preferably 0.1-1 μm, and the mean particle diameter of the calcium carbonate is preferably 0.05-5 μm. The circumferential speed of rotary blades of the agitator is preferably >=20 m/s.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hybrid powder for blending synthetic resin, and more specifically, it has excellent dispersibility when blended with a synthetic resin, and mechanical strength and coloring of the obtained synthetic resin molded product. TECHNICAL FIELD The present invention relates to a hybrid powder for compounding a synthetic resin capable of improving the property.

[0002]

2. Description of the Related Art There are various quality requirements for fillers used in the plastics field. Among them, dispersibility, light discoloration resistance, etc. are particularly important, and various studies have been made to improve them, and titanium dioxide, calcium carbonate, etc. surface-treated with organic silane, organic silicone, etc. have already been commercialized. ing.

[0003]

However, when the above-mentioned filler is blended with a synthetic resin such as polyolefin, the resulting synthetic resin molded article has mechanical strength such as impact strength, tensile strength, bending strength, and colorability. However, there is a problem in that it cannot be sufficiently improved.

The present invention solves the above-mentioned problems of the conventional fillers for compounding synthetic resins, and has excellent dispersibility when compounding synthetic resins such as polyolefins, and a machine for synthetic resin moldings obtained. An object of the present invention is to provide a filler for compounding a synthetic resin, which can improve dynamic strength and colorability.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that titanium dioxide, calcium carbonate and fatty acids or salts thereof are mixed by dry high speed stirring. When the hybrid powder is mixed with synthetic resin such as polyolefin,
The inventors have found that they have excellent dispersibility and can improve the mechanical strength such as impact strength, tensile strength, bending strength, and colorability of a synthetic resin molded product, and have completed the present invention.

That is, in the hybrid powder for blending a synthetic resin of the present invention, titanium dioxide and calcium carbonate serve as base materials, and fatty acids or salts thereof improve the affinity of the base material for the synthetic resin. Since these ingredients are mixed uniformly by dry high speed stirring, the agglomeration of titanium dioxide and calcium carbonate unlike the case of mixing by normal dry (dry) mixing does not occur, and excellent mechanical properties based on titanium dioxide The properties, hiding power, and excellent dispersibility based on calcium carbonate are suitably exhibited, and when blended in a synthetic resin, the dispersibility is excellent, and the mechanical strength and colorability of the resulting synthetic resin molded product are improved. Can be made.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the titanium dioxide used as one of the base materials of the hybrid powder of the present invention, what is called a pigment grade size is suitable, and its average particle size is 0.
1 to 1 μm is preferable, and 0.18 to 0.3 μm is particularly preferable.
m is preferable. The crystal form of this titanium dioxide may be either anatase type or rutile type, but the rutile type is preferable in consideration of improvement of whiteness of the film. In addition, in this invention, the average particle diameter of titanium dioxide is a transmission electron microscope [JEM-12 made by JEOL Ltd.].
30 (trade name)] is obtained by statistically processing the image taken.

As the titanium dioxide, the surface of the titanium dioxide is A for the purpose of improving its dispersibility, light discoloration resistance and the like.
The surface-treated with an inorganic surface-treating agent composed of a hydrous oxide or oxide such as 1, Si, Zr, Zn, or Sn may be used, or after the surface-treating with the above-mentioned inorganic surface-treating agent, Those surface-treated with an organic surface-treating agent such as organic silane, organic silicone, and metallic soap may be used.

The calcium carbonate used as the other base material of the hybrid powder of the present invention may be either heavy calcium carbonate or light calcium carbonate.
The surface of the calcium carbonate may be surface-treated with a fatty acid or the like, but the calcium carbonate preferably has an average particle diameter of 0.05 to 5 μm, and particularly 0.5 to 3 μm. Is preferable, and it is preferable to use one having a maximum particle diameter of 10 μm or less. In the present invention, the average particle size of the calcium carbonate is determined by measuring a specific surface area measuring device [Yuasa Ionics Multisorb 1
2 (trade name)], and the specific surface area was measured and calculated from the value.

Regarding the fatty acid or its salt, first,
As the fatty acid, for example, capric acid, lauric acid, mistyric acid, stearic acid, coconut oil fatty acid, beef tallow fatty acid,
7 carbon atoms such as oleic acid, linoleic acid and linolenic acid
One or more higher fatty acids are preferable, and as the salts of fatty acids, for example, alkali metal salts, ammonia salts, organic amine salts of the above fatty acids are preferable.

The mixing ratio of titanium dioxide and calcium carbonate, which forms the base material of the hybrid powder for blending synthetic resin of the present invention, is not particularly limited, but the weight ratio is 25:75 to 75:25. , Especially 40:60 to 60: 4
A range of 0 is preferred. That is, when the mixing ratio of titanium dioxide is less than the above range, the mechanical strength and colorability of the obtained synthetic resin molded product tend to decrease, and
When the mixing ratio of titanium dioxide is more than the above range, the dispersibility when blended with the synthetic resin tends to decrease.

The mixing ratio of the fatty acid or its salt is preferably 0.1 to 10 parts by weight per 100 parts by weight of titanium dioxide and calcium carbonate. When the mixing ratio of the fatty acid or its salt is less or more than the above range, the affinity of the obtained hybrid powder for the synthetic resin is lowered, and the aggregation of the powder in the obtained synthetic resin molded product becomes remarkable. And tends to reduce its mechanical strength.

The above-mentioned titanium dioxide, calcium carbonate and fatty acid or salts thereof are mixed by dry high speed stirring to obtain the hybrid powder of the present invention. As a mixer used for the dry high speed stirring, for example, a Henschel mixer is used. Are preferred. The peripheral speed of the rotary blades of the mixer is preferably 20 m / s or more, and particularly 25 m / s.
s or more is preferable. That is, when the peripheral speed of the rotary blade is low, a hybrid powder having the effect of the present invention cannot be obtained, and there is a possibility that the powder becomes a normal powder that does not have such an effect. Further, when performing the high speed stirring and mixing, a surface modifier such as silicon oil may be added in addition to the titanium dioxide, calcium carbonate, fatty acid or salts thereof.

[0014]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only those examples.

Example 1 Titanium dioxide having an average particle size of 0.25 μm [J manufactured by Teika Co., Ltd.
R-600A (trade name)] 25 parts by weight and average particle size 1.
Titanium dioxide, heavy calcium carbonate at a ratio of 1.5 parts by weight of stearic acid to a total of 100 parts by weight of 0 μm heavy calcium carbonate [Escalon # 2200 (trade name) manufactured by Sankyo Seiko Co., Ltd.] 75 parts by weight. And stearic acid were put into a Henschel mixer type dry mixer [FM10B (trade name) manufactured by Mitsui Miike Chemical Industry Co., Ltd.], and the peripheral speed of the rotary blade was 40.
After high speed stirring at m / s and uniform mixing and pulverization to confirm that the powder temperature was 60 ° C. or higher, which is the melting point of stearic acid, stirring was continued for 5 minutes to obtain a hybrid powder. .

After mixing 20 parts by weight of the obtained hybrid powder and 80 parts by weight of polypropylene [BC03B (trade name) manufactured by Nippon Polychem Co., Ltd.] with a twin-screw extruder [TEX30α (trade name manufactured by Nippon Steel Works)]. Then, it was molded with an injection molding machine to prepare a test piece for measuring Izod impact strength, a test piece for measuring tensile strength, a test piece for measuring bending strength and a test piece for evaluating dispersibility. A masterbatch 1 containing 0.1 part by weight of carbon black based on 100 parts by weight of the mixture of the hybrid powder and polypropylene.
After adding parts by weight and mixing with a twin-screw extruder, a gray test piece for evaluation of coloring degree was prepared with an injection molding machine to have a thickness of 2 mm. The titanium dioxide, ground calcium carbonate, stearic acid, etc. used in the following Examples and Comparative Examples are the same as those used in Example 1.

Example 2 Dry high speed stirring was carried out in the same manner as in Example 1 except that stearic acid was 1.9 parts by weight with respect to 100 parts by weight of 40 parts by weight of titanium dioxide and 60 parts by weight of ground calcium carbonate. Were uniformly mixed and pulverized to obtain a hybrid powder. Then, the obtained hybrid powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

Example 3 Dry high speed stirring was carried out in the same manner as in Example 1 except that 2.1 parts by weight of stearic acid was added to 100 parts by weight of 50 parts by weight of titanium dioxide and 50 parts by weight of calcium carbonate. Were uniformly mixed and pulverized to obtain a hybrid powder. Then, the obtained hybrid powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

Example 4 Dry high speed stirring was carried out in the same manner as in Example 1 except that the total amount of stearic acid was 2.4 parts by weight based on 100 parts by weight of titanium dioxide 40 parts by weight and heavy calcium carbonate 60 parts by weight. Were uniformly mixed and pulverized to obtain a hybrid powder. Then, the obtained hybrid powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

Example 5 Dry high speed stirring was carried out in the same manner as in Example 1 except that the total amount of stearic acid was 2.7 parts by weight based on 100 parts by weight of titanium dioxide 75 parts by weight and ground calcium carbonate 25 parts by weight. Were uniformly mixed and pulverized to obtain a hybrid powder. Then, the obtained hybrid powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

Comparative Example 1 Stearic acid (1.5 parts by weight) was added to 100 parts by weight of titanium dioxide (25 parts by weight) and ground calcium carbonate (75 parts by weight). The mixture was shaken without mixing to obtain a mixed powder. Then, the obtained mixed powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

Comparative Example 2 Mixing was carried out in the same manner as Comparative Example 1 except that stearic acid was 1.9 parts by weight based on 100 parts by weight of 40 parts by weight of titanium dioxide and 60 parts by weight of ground calcium carbonate. A mixed powder was obtained. Then, the obtained mixed powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

Comparative Example 3 Mixing was carried out in the same manner as in Comparative Example 1 except that stearic acid was 2.1 parts by weight with respect to 100 parts by weight of titanium dioxide 50 parts by weight and heavy calcium carbonate 50 parts by weight. A mixed powder was obtained. Then, the obtained mixed powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

COMPARATIVE EXAMPLE 4 Mixing was carried out in the same manner as in Comparative Example 1 except that stearic acid was added to 2.4 parts by weight based on 100 parts by weight of 40 parts by weight of titanium dioxide and 60 parts by weight of ground calcium carbonate. A mixed powder was obtained. Then, the obtained mixed powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

Comparative Example 5 The same procedure as in Comparative Example 1 was repeated except that stearic acid was added to 2.7 parts by weight based on 100 parts by weight of titanium dioxide (75 parts by weight) and ground calcium carbonate (25 parts by weight). A mixed powder was obtained. Then, the obtained mixed powder was mixed and molded in the same manner as in Example 1 to obtain each test piece.

With respect to the test pieces of Examples 1 to 5 and Comparative Examples 1 to 5 obtained as described above, Izod impact strength, tensile strength and bending strength were measured by the following methods,
In addition, the colorability and dispersibility were evaluated by the following methods.

Izod impact strength: JIS K 711
It measured based on 0.

Tensile strength: Measured according to JIS K 7113.

Bending strength: Measured according to JIS K7203.

Colorability : It was evaluated by measuring the whiteness (L value) with a color difference meter (a color meter manufactured by Suga Test Instruments Co., Ltd.). In the evaluation of the colorability, the large whiteness (L value) is because the carbon black contained in the test piece is hidden by the hybrid powder, and therefore, the synthetic resin is mixed with the colorant. When this is done, the color possessed by the colorant will be reflected more appropriately, indicating that the colorability is excellent.

Dispersibility: Evaluated by observing the state of the powder dispersed in polypropylene with a scanning electron microscope [S-800 (trade name) manufactured by Hitachi, Ltd.]. In displaying the evaluation results, they are symbolized and shown according to the following evaluation criteria.

Evaluation criteria: ◯: The powder is uniformly dispersed. X: Aggregated particles of 10 μm or more are present.

Izod impact strength of Examples 1 to 5 above,
Table 1 shows the measurement results of tensile strength and bending strength, and the evaluation results of colorability and dispersibility. In addition, Comparative Examples 1 to
Table 2 shows the measurement results of Izod impact strength, tensile strength and bending strength of No. 5 and evaluation results of coloring property and dispersibility.
Shown in.

[0034]

[Table 1]

[0035]

[Table 2]

As is clear from the comparison between the characteristics of Examples 1 to 5 shown in Table 1 and the characteristics of Comparative Examples 1 to 5 shown in Table 2, Examples 1 to 5 have the same powder composition. Examples 1-
5, the Izod impact strength, the tensile strength and the bending strength are large, the L value showing the evaluation of the coloring property is large, and the dispersibility is excellent. It was clear that when blended with a synthetic resin, it has excellent dispersibility and improves the mechanical strength and colorability of the resulting synthetic resin molded product.

[0037]

As described above, according to the present invention, when blended with a synthetic resin such as polyolefin, the dispersibility is excellent and the mechanical strength and colorability of the obtained synthetic resin molded article can be improved. It was possible to provide a hybrid powder for compounding a synthetic resin.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroaki Moriyasu             Takeka, 1-3-4, Funamachi, Taisho-ku, Osaka             Within the corporation (72) Inventor Jun Kobayashi             2484 Takao, Niimi City, Okayama Prefecture Sankyo Seiko             Within the corporation (72) Inventor Daisuke Sasaki             2484 Takao, Niimi City, Okayama Prefecture Sankyo Seiko             Within the corporation F term (reference) 4J002 AA001 DE136 DE236 FB236                       FD016 FD096

Claims (4)

[Claims] 1. A hybrid powder for blending a synthetic resin, which is obtained by mixing titanium dioxide, calcium carbonate and a fatty acid or a salt thereof by dry high speed stirring. 2. The average particle diameter of titanium dioxide is 0.1 to 1.
μm, and the average particle size of calcium carbonate is 0.05 to
The hybrid powder for blending synthetic resin according to claim 1, having a size of 5 μm. 3. The synthetic resin blending hybrid powder according to claim 1, wherein the peripheral speed of the rotating blades of the mixer during dry high speed stirring is 20 m / s or more. 4. A method for producing a hybrid powder for blending a synthetic resin, which comprises uniformly mixing and pulverizing titanium dioxide, calcium carbonate, a fatty acid or salts thereof by dry high speed stirring.