JPS603431B2 - Surface modified inorganic filler - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface-modified inorganic filler suitable for use in thermoplastic resin composites, and more specifically, the present invention relates to a surface-modified inorganic filler suitable for use in thermoplastic resin composites. The present invention relates to a coated surface-modified inorganic filler.

Recently, interest in filler-containing plastic composite materials has increased due to the idea of resource conservation. Research and development of composite resin compositions with fillers have been actively conducted, and some such products have come to be commercially available. However, in general, thermoplastic resins and inorganic substances are
Due to their chemical structures, they lack compatibility, and it is impossible to obtain a composite material that exhibits sufficiently high strength by simply heating and melting the two, and appropriate reinforcing means have been sought.

Up until now, inorganic substances to be kneaded with thermoplastic resins have been mixed with silane coupling agents (for example, Japanese Patent Publication No. 39-1344, Japanese Patent Publication No. 55-1982).
5548), organic titanates (e.g. Japanese Patent Publication No. 49-39
169, Special Publication No. 55-4669, Special Publication No. 53-1106
44), etc., but these modifiers are expensive and have not been widely used. As a result of extensive research into surface-modified inorganic fillers that exhibit excellent physical strength when kneaded into thermoplastic resins, the present inventors found that specific organic phosphate esters or/and and force = addition of cellubonic acid ester, adsorption, coating the particle surface of the filler,
The present inventors have discovered that by modifying this resin, it can be heat-melted and kneaded with a thermoplastic resin to form a reinforced composite resin composition with extremely excellent physical strength, leading to the achievement of the present invention.

The inorganic filler according to L according to the present invention includes calcium carbonate,
Carbonates and hydroxides of metals in group B or group M of the periodic table, such as magnesium carbonate, basic magnesium carbonate, dolomite, aluminum hydroxide, and magnesium hydroxide, can be used.

The specific organic phosphate ester according to the present invention has the following formula (
1), as a carboxyl ester, the following formula (〇) (Nazugoshi, R in the above formula is hydrogen or a methyl group, R2 is an alkylene group having 2 to 6 carbon atoms or a halogen-substituted derivative thereof,
or polyoxyethylene group - or 2-CH2-(OC
H2-CH2)-n (n=1 to 20), or a polyoxypropylene group (n=1 to 20), R3 is a phenylene group, a naphthylene group, an alkylene group having 1 to 10 carbon atoms, or an alkenylene group, m=
1 to 2 are shown.

) Examples include ethylene acrylate phosphate, ethylene methacrylate phosphate, isopropylene acrylate phosphate, tetraethylene methacrylate phosphate, 1-chloromethylethylene methacrylate phosphate, 2-hydroxyethyl acrylate. Examples include phthalic acid monoester and succinic acid monoester, and maleic acid monoester of 2-hydroxyethyl methacrylate.

The surface-modified filler according to the present invention can be applied to general-purpose resins such as PVC resin, polystyrene, polyethylene, and polypropylene, or general thermoplastic resins such as engineering plastics such as ABS, polyamide resin, polycarbonate, acetal resin, and PBT. It can be applied to

In particular, when applied to polyolefin resins such as high-pressure polyethylene, medium-low pressure polyethylene, and polypropylene, a reinforced composite resin composition exhibiting excellent physical strength in terms of impact and tensile properties can be obtained. In the present invention, the amount of specific organic phosphoric acid ester and/or carboxylic acid ester added to the inorganic filler is 0.05 to 10.
0% by weight, preferably 0.2-5. The appropriate weight percentage is
If it is less than 0.05% by weight, the reinforcing effect on the thermoplastic resin will not be sufficient, and 10. (at weight percent or higher, the reinforcement of the thermoplastic resin is not significantly improved compared to the amount added)
death,.

The method of adding the organic phosphate ester or/and carboxylic ester to the inorganic filler is generally a dry method. Using a mixer, mix organic phosphate esters and/or carboxylic esters as they are, or mix them with alcohols, ketones, esters, etc.
It is dissolved in a suitable organic solvent such as a chlorinated solvent, added to the inorganic filler under the rope by spraying or passing through, mixed uniformly, and finished by drying, pulverizing, and classifying as necessary.

Furthermore, if necessary, the organic phosphoric acid ester and/or carboxylic acid ester can be vaporized and adsorbed onto the inorganic filler, or Z can also be flooded with the inorganic filler. On the other hand, in the wet method, organic phosphate esters and/or carboxylic esters or their alkali metal salts, ammonium salts, etc. are added to an aqueous suspension of an inorganic filler, mixed with a coagulation pestle, dehydrated, dried, pulverized, A surface-modified inorganic filler is obtained by classification. The blending ratio of the surface-modified inorganic filler of the present invention to the thermoplastic resin is 90 to 1
5% by weight and 10-85% by weight of surface-modifying inorganic filler, preferably 75-30% by weight of resin and 25% by weight of surface-modifying inorganic filler.
A weight percent of ~7 is suitable. If the blending ratio of the surface-modified inorganic filler is less than 1% by weight, a substantially reinforced composite material cannot be obtained, and if it is more than 85% by weight, a resin composition with appropriate impact strength as a composite material cannot be obtained. The thermoplastic resin and the surface-modified inorganic filler are kneaded into a resin composition using a general kneading machine such as a mixed wire roll heated to about 3000C, a Banbury mixer, a kneader mixer, or an extrusion type thickener. If necessary, we also perform pelletizing and molding processes.

The reason why the surface-modified inorganic filler of the present invention exhibits excellent reinforcing properties for thermoplastic resins is still unclear, but the reason why the surface-modified inorganic filler of the present invention exhibits excellent reinforcing properties for thermoplastic resins is unclear. When fused into a molten slurry, the appropriate long-chain molecular structure of specific phosphate esters and/or carboxylic esters adsorbed and bonded to the surface of filler particles by acid groups acts as a lubricant to form a thermoplastic resin. It is believed that the acryloyl or methacryloyl group helped disperse the inorganic filler therein, and that the acryloyl or methacryloyl group had some kind of bonding effect with the thermoplastic resin, resulting in the formation of a reinforced composite material.

The thermoplastic resin composition containing the surface-modified inorganic filler of the present invention can be used in addition to commercially available thermoplastic resins and the surface-modified inorganic filler of the present invention. There is no problem in adding additives, antioxidants, lubricants, nucleating agents, colorants, scale agents, glass fibers, fillers, elutriants, and the like. The present invention will be explained in more detail with reference to Examples below.

Examples 1 to 7 2-hydroxyethyl methacrylate and phosphoric anhydride were mixed in the presence of a polymerization inhibitor while using a Henschel-type high-speed mixer to mix calcium carbonate powder 2K9 with an average particle size of 4 grains obtained by the light transmission turbidity method. Phosphate ethylene methacrylate (abbreviated as phosphate ester) obtained by reacting with calcium carbonate was 0.1, 0.2, and 0.1, respectively. Fu 1.
0, 5. % by weight and were uniformly mixed to obtain five types of calcium carbonate surface-modified with phosphate ester.

Each of the surface-modified calcium carbonates and commercially available medium-low pressure IJ ethylene (abbreviation: HDPE, trade name: Shorex S6002) were mixed in the proportions shown in Table 1.
After roll kneading at 0, the tensile strength and Izod impact strength were measured by press molding at 1700, and the results are shown in Table 1. It can be seen that the quality of calcium carbonate and the resin composition thereof are excellent.

Comparative Examples 1 to 5 In Examples 1 to 7, the addition ratio of phosphate ester to calcium carbonate was 0, 0.02, and 15, respectively.
The mixture was kneaded and molded into HDPE in the same manner as above, and the tensile strength and Izod impact strength were measured. The results are shown in Table 1.

Examples 8 to 10 Ta Basic magnesium carbonate with an average particle size of 0.1 mm, dolomite powder with an average particle size of 5 mm, and aluminum hydroxide with an average particle size of 8 mm, each using a light transmission turbidity method.
9, 1.0 weight of phthalic acid monoester [B} of 2-hydroxyethyl acrylate obtained by reacting 2-hydroxyethyl acrylate and phthalic anhydride in the presence of a polymerization inhibitor. % to each filler in a ribbon blender and mixed uniformly to obtain basic magnesium carbonate, dolomite powder, and aluminum hydroxide each surface-modified with phthalic acid monoester legs.

Weight percent of each surface-modified inorganic filler 5 and commercially available polypropylene (abbreviation PP, trade name Sumitomo Noblen WIO)
I) 5% by weight after roll kneading at 200 ml.
The tensile strength and Izod impact strength were measured by injection molding at 230 pm. It can be seen that this resin composition is superior.

Comparative Examples 6-8 In Examples 8-10, phthalic acid monoester [B'
Using each inorganic filler that had not been surface-modified, the materials were kneaded and molded into PP in the same manner as above, and the physical strength was measured. The results are shown in Table 2.

Examples 11-12 Calcium carbonate 2 with an average particle diameter of 0.3 as determined by a turtle photograph
Isopropylene acrylate phosphate (abbreviated as phosphate ester {q
) and phosphate diethylene glycol acrylate (abbreviated as phosphate ester [D}) were added by spray at a ratio of 1.0% by weight, and mixed uniformly to obtain surface-modified calcium carbonate with each phosphate ester. .

As in Examples 1 to 7, each surface-depleted calcium carbonate was thickened and molded with medium-low pressure polyethylene, and the tensile strength and Izod impact strength were measured, and the results are shown in Table 3. However, all of them exhibited good physical strength, demonstrating that the surface-modified calcium carbonate and resin compositions thereof according to the present invention are superior.

Comparative Examples 9-10 In Examples 11-12, calcium carbonate to which no phosphate ester was added and isopropyl triisostearoyl titanate (abbreviated as titanate TTS) in place of the phosphate ester were used in 1. Calcium carbonate to which was added % by weight was mixed into medium-low pressure polyethylene, and the physical strength was measured in the same manner as above, and the results are shown in Table 3.

Example 13 ・A suspension of 1% by weight of calcium carbonate on the surface of a mountain with an average particle diameter of 0.08 as determined by exposure microphotograph 10% by weight of phosphoric acid 1-chloromethylethylene acrylate (abbreviated as phosphate ester 'E') in water 28.5k9 1.5 kg of an aqueous sodium salt solution was added thereto, mechanically heated for 10 minutes, then subjected to dehydration pressing, drying, crushing, and 100-mesh classification to obtain surface-modified calcium carbonate 2.6k9.

As in Examples 1 to 7, the surface-modified calcium carbonate was kneaded and molded with medium-low pressure polyethylene, and the tensile strength and Izod impact strength were measured, and the results showed good physical strength as shown in Table 3. , it can be seen that the surface-modified calcium carbonate and its resin composition according to the present invention are excellent.

Comparative Examples 11 to 14 In Example 13, calcium carbonate using palmitic acid, sorbic acid, and acrylic acid and 0.08A calcium carbonate without additives were used in place of phosphate ester, and other The samples were similarly drilled and molded into medium-low pressure polyethylene, and the tensile strength and Izod impact strength were measured, and the results are shown in Table 3.

Table 1 Table 2 Table 3

Claims (1)

[Claims] 1. Adsorption of 0.05 to 10.0% by weight of an organic phosphoric acid ester or/and carboxylic acid ester represented by general formula (I) or general formula (II), respectively, as an inorganic filler;
A surface-modified inorganic filler comprising coated inorganic filler particles. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 in the above formula is hydrogen or methyl group, R_2
is an alkylene group having 2 to 6 carbon atoms or a halogen-substituted derivative thereof, or a polyoxyethylene group -CH_2-CH
_2-(O-CH_2-CH_2)-n(n=1~20
), or polyoxypropylene group ▲ Numerical formulas, chemical formulas, tables, etc. ▼ R_3 is a phenylene group, naphthelene group, or alkylene group or alkenylene group having 1 to 10 carbon atoms, m =
1 to 2 are shown. )2 The inorganic filler is an average particle of carbonate or hydroxide of a metal in Group II or Group III of the periodic table, such as calcium carbonate, magnesium carbonate, basic magnesium carbonate, dolomite powder, magnesium hydroxide, aluminum hydroxide, etc. The surface-modified inorganic filler according to claim 1, which is a powder having a diameter of 20 μm or less.