JPS6010050B2 - polyolefin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an inorganic filler-filled composition that has excellent practical properties such as rigidity, hardness, and impact resistance.

Plastics containing inorganic fillers have recently attracted attention from various viewpoints, such as the depletion of raw material resources for plastics, the problem of plastic waste pollution, and the improvement of mechanical, thermal, chemical, or optical properties of base plastics. As a result, many products have come on the market, and its uses are gradually expanding.

Among plastics, polyolefins such as polyethylene and polypropylene do not generate harmful gases when incinerated, so the usefulness of inorganic filler-containing compositions containing polyolefins as a base polymer is attracting attention. By the way, compositions in which such polyolefins are blended with inorganic fillers at a high concentration have improved heat resistance and rigidity, but their impact resistance has significantly decreased, and their use is currently subject to certain restrictions.

For example, by mixing about 80 to 10 parts by weight of an inorganic filler such as heavy calcium carbonate or talc with 10 parts by weight of high-density polyethylene, the tensile modulus and flexural modulus can be adjusted to the original values of high-density polyethylene. However, on the other hand, the Izod impact strength decreases to 10% to 30%, making it unsuitable for applications requiring impact resistance. Therefore, in a polyolefin composition containing an inorganic filler, without reducing impact resistance,
If high rigidity can be obtained, the industrial value is extremely large.

Various proposals have been made to improve these drawbacks and to enhance the reinforcing effect of inorganic compounded polyolefins.

For example, a method of coating the surface of an inorganic filler with an organic substance that is compatible with polyolefin, a method of copolymerizing a gutter monomer with polyolefin to improve compatibility with the inorganic filler, or both methods. This is a method that uses both. However, since the latter two methods are complicated and involve copolymerizing polar monomers, they impair the original characteristics of polyolefins, resulting in decreased rigidity, stool resistance, and chemical resistance.Also, the former method For this purpose, a surface treatment agent such as a surfactant, metal soap, higher fatty acid, etc. is simply mixed with an inorganic filler, or an inorganic filler is mixed into an aqueous solution (suspension) of the surface treatment agent. It is known that the filler is filtered in an oven, dried, and then ground to form a surface-treated filler.

However, in these methods, the dispersibility and reinforcing properties of the filler in the polyolefin are low, and it is difficult to fill the filler into the polyolefin at a high concentration. In addition,
The known higher fatty acids used in the above usage examples usually have carbon atoms of 12 or more (lauric acid), and even in special cases, carbon atoms of 10 or more (capric acid).

Furthermore, for example, a method for obtaining an active filler by adding a fatty acid to an aqueous solution (suspension) of calcium hydroxide, passing carbon dioxide gas to form reactive calcium carbonate, drying and pulverizing it, and ``Journal of the Rubber Association of Japan,'' Vol. Lid, No. 3, No. 295
~302 pages) are known.

However, even with this method, when the reactive calcium carbonate obtained is mixed into synthetic resins, synthetic rubbers, etc., it exhibits superior reinforcing properties to calcium carbonate produced without using fatty acids, but it is still insufficient. However, it has been difficult to fill polyolefins in a high concentration as in the present invention. As a result of repeated research on the mechanism of action of saturated fatty acids and the types of surface activators, we have found that among saturated fatty acids, aliphatic saturated monocarboxylic acids with 4 to 9 carbon atoms, which are liquid at room temperature, The inventors have discovered that a large reinforcing effect can be achieved when used under these conditions, and have arrived at the present invention.

That is, in the present invention, 80 to 15 parts by weight of a polyolefin, 20 to 85 parts by weight of an inorganic filler, and 0.1 to 5 parts by weight of an aliphatic saturated monocarboxylic acid having 4 to 9 carbon atoms are mixed in the presence of a radical generator. The present invention provides a novel composition having excellent mechanical properties, thermal properties, etc. by subjecting it to a heating reaction.

More specifically, the effects of the composition of the present invention are as follows:
It is as follows. '11 A composition with outstanding rigidity and impact resistance.

{2} The composition has extremely excellent thermal properties such as heat resistance and dimensional stability.

{3} The composition has outstanding properties such as surface activity and flame resistance.

'4} The composition has excellent moldability, fluidity, etc.

[5} Can be manufactured extremely easily.

{6} This composition has an extremely wide range of applications.

For example, various compression molded products, extrusion molded products, flow molded products, injection molded products, aged molded products, rotary molded products, calendar molded products, various foam molded products, secondary processed products such as stretched or forged products, etc. These effects of the present invention were completely unexpected compared to the fact that activation of fillers with known saturated fatty acids did not show sufficient reinforcing properties.

Hereinafter, embodiments of the present invention will be described.

The polyolefin that is the base material of the composition in the present invention refers to one whose main component is a polymer or copolymer of monoolefin such as ethylene, propylene, and putene.

Examples include high-density polyethylene, medium- and low-density polyethylene, crystalline polypropylene, crystalline ethylene-propylene block copolymer, polybutene, poly-3-methylbutene-1, poly-4-methylbentene-1, etc., and mixtures thereof. . The inorganic fillers used in the present invention include Ca, Mg oxides, hydroxides, carbonates, or silicates, AI hydroxides, and alkali metal ions that are contained in the structure as cations. A collection of metal compounds selected from the group consisting of aluminosilicate minerals, including calcium oxide, magnesium oxide, zinc oxide, titanium oxide, lead oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, Examples include calcium silicate, magnesium silicate, and sodium aluminosilicate.Alternatively, hydrates or double salt minerals such as basic magnesium carbonate, dolomite, and pilsonite can also be used.

Moreover, these inorganic fillers may be naturally occurring natural minerals or may be synthetically synthesized artificial minerals.
Furthermore, these inorganic fillers may be used alone or as a mixture of two or more. In addition, some of the present inventors have developed active fillers obtained by reacting inorganic fillers with specific organic substances (Tokugan Showa 4).
6-102601, special face Showa 46-102602). That is, carbonates of metals of Group L or Group M of the periodic table,
This is an active filler obtained by coating the surface of a hydroxide or oxide with a polymerizable organic acid to a thickness of 5 A to 150 A on average as calculated by the BET specific surface area method. Furthermore, we have also developed active fillers that can improve the heat deterioration resistance of filling compositions (Tokuiso Sho 48-10850, Totokubuta Sho 49-159377). That is, oxides of Ca and Mg,
hydroxide, carbonate or silicate, hydroxide of N;
On the surface of powders such as aluminosilicate minerals containing alkali metal ions as enteric ions, polymerizable organic acid monomers having ethylenic double bonds form a monomolecular ultrathin film, and ethylenic It is an active filler that leaves double bonds and bonds to the metal elements on the powder surface. If such active fillers are used, the functionality of the filling compositions of the present invention is further significantly improved.

That is, the active filler used in the present invention is:
Selected from the group consisting of oxides, hydroxides, carbonates, or silicates of Ca, Mg, Zn, etc., hydroxides of N, and aluminosilicate minerals containing alkali metal ions as cations in the structure. The powder surface of the metal compound
The amount of the polymerizable organic acid monomer having ethylenic double bonds does not exceed the amount that can be coated with a thickness of a monomolecular thin film or more, and the amount of metal elements on the powder surface is such that the ethylenic double bonds remain. It is an active filler that is combined with

The method for producing the active filler requires that the inorganic filler in powder form is brought into direct contact reaction with the polymerizable organic acid at room temperature or above, preferably under dehydration conditions at a temperature of 50 to 200 oo. to form a polymerizable organic acid salt and/or a polymerizable organic acid salt polymer that is firmly bonded to the surface of the filler and remains an integral ethylenic double bond. That's true. In this case, the metal compound powder (hereinafter referred to as raw inorganic filler) used as the raw material for the active filler includes calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium carbonate, and magnesium carbonate. , calcium silicate, magnesium silicate (sodium aluminosilicate, potassium aluminosilicate, lithium aluminosilicate, etc.), or as part of the composition, such as basic magnesium carbonate, hydrates such as dolomite, pilsonite, or enoki salt minerals. It is also possible to use those containing

Moreover, these raw material inorganic fillers may be naturally occurring natural minerals, or may be artificially synthesized artificial minerals. Furthermore, these inorganic fillers may be used alone or as a mixture of two or more. The polymerizable organic acid used to produce the active filler has a hydrocarbon moiety having one or more ethylenic double bonds and one or more carboxyl groups. and unsaturated carboxylic acids having 10 or less carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, Q-chloroacrylic acid and its Q-8 substituted body, maleic acid,
Itaconic acid: Vinyl acetic acid, allyl acetic acid, etc.

These may be used alone or as a mixture of two or more. Alternatively, an acid anhydride may be used as a precursor of a polymerizable organic acid to convert it into an organic acid. When the above polymerizable organic acid is reacted with the raw material inorganic filler, the amount of the polymerizable organic acid used is one of the factors that influences the effectiveness of the filling composition.

In other words, the amount is such that the surface of the raw inorganic filler can be uniformly coated with a thickness greater than a monomolecular thin film and is not excessive. Furthermore, the amount used is roughly estimated from the BET specific surface area measured for the raw inorganic filler, and is an amount sufficient to uniformly coat the surface of the inorganic filler to a thickness of 2A to 150A. be. The BET specific surface area method referred to in this) is a commonly used adsorption method for measuring the specific surface area of powder, and the values used in the description of the present invention are based on the adsorption of nitrogen gas at liquid nitrogen temperature. It means the value of the specific surface area measured by the BET method.

Although there are various methods for measuring the specific surface area other than the BET method, the present inventors used the BET method to determine the amount used because it is the most common method and is particularly suitable for fine particle powders. was estimated. The weight of the polymerizable organic acid actually used can be calculated using the following formula. That is, the specific surface area a/
Let W be the weight of a polymerizable organic acid with a specific gravity d that can uniformly cover the surface of the inorganic filler with a thickness b arc, and W = a x w x b x d (w). It is.

For example, the amount of polymerizable organic acid reacted with an inorganic filler having an average grain size of 0.1 to 10 mm is most commonly 0.1 to 10 mm.
It is in the range of 0.01 to 5% by weight.

If the amount of the polymerizable organic acid used is outside this range, the effect as an active filler will be reduced. That is, when the amount is less than this range, the physical properties of the inorganic filler-containing composition obtained therefrom will have substantially little difference compared to the physical properties of an unactivated filler-containing composition. On the other hand, if the amount of the polymerizable organic acid used exceeds this range, the reinforcing effect of the obtained active filler will decrease,
Furthermore, secondary aggregates of the inorganic filler are formed, which impairs the dispersibility, and disadvantages include discoloration and foaming of the composition due to oozing and thermal decomposition. Next, in order to cause a surface reaction between the polymerizable organic acid and the raw material inorganic filler to produce the active filler referred to in the present invention, various mixing devices are used, generally a Henschel mixer, a Mewfu, a ribbon blender, etc. A high-efficiency mixer such as is preferred.
Furthermore, in order to increase the contact efficiency between the raw material inorganic filler and the polymerizable organic acid, it is desirable to add the polymerizable organic acid in the form of a mist or gas. If it is a liquid, it is preferable to use it as is, but if it is a relatively viscous liquid or solid, a small amount of non-polar solvent may be used as necessary. The temperature must be selected appropriately depending on the type, combination, properties, etc. of the raw material inorganic filler, polymerizable organic acid, etc. used, and must be between room temperature or higher and lower than the decomposition temperature of the polymerizable organic acid. 200
A temperature range of 0.00 is preferred.

The reaction time for this reaction is appropriately selected depending on various conditions, but is generally preferably in the range of 1 to 3 minutes. In addition, in order to avoid polymerization of the polymerizable organic acid or polymerizable organic acid salt during this reaction, the reaction atmosphere should be appropriately selected (air or oxygen atmosphere is preferable in the case of acrylic acid), or It is preferable to add a polymerization inhibitor to the acid.

As the polymerization inhibitor, general polymerization inhibitors such as hydroquinone, methoxyhydroquinone, p-penzoquinone, naphthoquinone, and t-butylcatechol can be used, and the amount used is 0 to 1% by weight based on the polymerizable organic acid. , especially 0
．． A range of 0.02 to 0.5% by weight is recommended. Furthermore, this reaction needs to be carried out in the substantial absence of liquid water, and is preferably carried out under conditions (dehydration conditions) such that water generated during the reaction is removed from the system.

If the reaction is carried out in the presence of excess liquid water, the polymerizable organic acid salt produced and the raw inorganic filler will separate, and the polymerizable organic acid salt will firmly adhere to the surface of the raw inorganic filler. It is not possible to obtain effective active fillers bound to. Therefore, it is desirable that the raw inorganic filler and polymerizable organic acid used be dehydrated and dried before use. mosquito)
Another method for producing an active filler is to react the raw inorganic filler with an excessive concentration of the polymerizable organic acid by the method described above, and then react the polymerizable organic acid and the free polymerizable organic acid. This method purifies the salt by washing it with a non-aqueous solvent that easily dissolves it, filtering it in an oven, and drying it.

Solvents that can be used in this method include methanol, ethanol, phenol, diethyl ether, acetone,
Low boiling point solvents such as methyl ethyl ketone and ethyl acetate are preferred. Another method for producing the active filler is to mix a sufficiently dried raw inorganic filler and a polymerizable organic acid in the non-aqueous solvent, and then refine the mixture by filtering, washing, and drying. It's a method.

In this method, a non-polar solvent such as benzene, toluene, xylene, hexane, heptane, tetralin, decalin, chloroform, carbon tetrachloride, etc. is used in addition to the above-mentioned gutter solvent, and the above-mentioned It is also possible to perform washing and purification with a gutter solvent. When such an improved active filler is used as the inorganic filler in the present invention or as a part of the inorganic filler, the function of the filling composition of the present invention becomes even more excellent.

The average particle diameter of the powdered inorganic filler used in the present invention is 0.
It is preferable to use fillers in the range of 0.01 to 100 mm, usually in the range of 0.1 to 20 mm.

The amount of inorganic filler used in the present invention varies depending on the desired filling composition, but is in the range of 20 to 85% by weight of the final composition. When the amount of the inorganic filler is 2% by weight or less, the degree of modification of mechanical properties, thermal properties, etc. by the inorganic filler is generally small, and the rigidity is low, so that the composition of the present invention is Features reduce. Further, if the amount is 85% by weight or more, it is substantially difficult to produce an inorganic filler-filled composition. Next, the aliphatic saturated monocarboxylic acids having 4 to 9 carbon atoms as used in the present invention include butyric acid, valeric acid, caproic acid, and hef.

Linear saturated monocarboxylic acids such as tannic acid and caprylic acid, isobutyric acid, isovaleric acid, methylethyl acetic acid, piberidic acid, incaproic acid, 8-methylvaleric acid, tert-butylacetic acid, diethyl acetate, methyl- n-propylacetic acid, methylisopropylacetic acid, dimethylethyl acetic acid,
It is a branched saturated monocarboxylic acid such as henanthic acid. These may be used alone or as a mixture of two or more. The amount of saturated monocarboxylic acid used in the present invention ranges from 0.1 to 5% by weight of the final fill composition.

If the amount of the saturated monocarboxylic acid used is less than this range, the physical properties of the final filled composition will be the same as those of a simple blend composition, and the reinforcing properties will be low. On the other hand, if the amount exceeds this range, troubles such as generation of secondary aggregates and oozing out of carboxylic acid occur, and the effect of improving physical properties is reduced. The method for producing the inorganic filler-filled composition of the present invention includes:
(2) A method of heating and kneading polyolefin, an inorganic filler, and a C' saturated monocarboxylic acid can be mentioned.

In this case, there is a method of heating and kneading the above three components at the same time, or a method of heating and kneading the two components (■ and [B} and the wind and 'C) in advance, and then adding the remaining ingredients and kneading them with heat. . As the heating kneading device, commonly used kneading machines such as various extruders, Banbury mixers, kneaders, mixing rolls, etc. can be used.

It is also recommended to carry out premixing continuously or intermittently before heating and thickening.

In particular, [premixing Bi and {C'] has a great effect on improving physical properties, and as a premixing device,
Commonly used mixing machines, for example drum blenders,
V-type blenders, ribbon blenders, Henschel mixers, and other mixing machines can be used. The temperature for heating and kneading is in the range from the melting and softening temperature of the base polymer to the thermal decomposition temperature, and is preferably in the range from 200 to 30,000 to particularly increase the effect of improving physical properties.

Even if the base polymer is in a molten state, if it is heated and kneaded at a temperature of 20,000 or less, the effect of improving physical properties will be reduced and the characteristics of the filling composition of the present invention will not be fully exhibited. Furthermore, in order to obtain a particularly excellent highly functional material, it is preferable to use a radical generator during heating and kneading. When using the above-mentioned active filler as an inorganic filler,
By using a radical generator, the effect of improving physical properties is further improved. In this case, usable radical generators include tetravalent tin compounds such as dibutyltin oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-215 -di(t-butylperoxy)hexine-3, dicumyl/g-oxide, t-butyl-'-oxymaleic acid, lauroyl peroxide, benzoyl/g-oxide,
Commonly used radicals such as organic peroxides such as t-butyl/guoxide, t-butylhydro/dioxide, and isopropyl percarbonate, azo compounds such as azobisisobutyronitrile, and inorganic peroxides such as ammonium persulfate. Generators, and one or a combination of two or more of these may be used.

The amount of the radical generator used is usually in the range of 0.001 to 0.5 parts by weight per 100 parts by weight of the inorganic filler-filled composition.

The filled composition according to the invention is not simply a mixture of a polyolefin, a saturated carboxylic acid and an inorganic filler, but the carboxyl groups of the carboxylic acid are bonded in some way to the metal in the filler, while the hydrocarbon chains are It is thought that they are in the form of coalescence, graft bonding, or mutual dissolution.

This is because these saturated monocarboxylic acids are liquid at room temperature, have a relatively low boiling point, and are easily monomolecularized at high temperatures such as in the reaction of the present invention, so they are highly reactive with inorganic fillers. On the other hand, in the high-temperature reaction of the present invention or the reaction in the presence of a radical generator, the radical reaction causes the carboxylic acid and the base polymer to be graft-bonded or dispersed in the base polymer in a very specific manner, resulting in the formation of molecules. This is thought to be due to entanglement, etc.

Furthermore, propionic acid with 3 carbon atoms has no effect at all, while caproic acid with 4 or more carbon atoms, especially caproic acid with 6 carbon atoms, has a remarkable effect. It is considered that the chain length is suitable for effective bonding or compatibility with the base polymer polyolefin.

Furthermore, when an active filler such as the one of the present invention is used as an inorganic filler, these carboxylic acids are coated or dispersed around the active filler, thereby forming a bond between the base polymer and the active filler. It is thought that a special layer is formed at the interface with the active filler and the active filler is bonded to the base polymer via this layer.

Therefore, it is considered that the filling composition according to the present invention is completely different from known mixtures of polyolefin and inorganic filler in the structure of the interface between the polyolefin serving as the base and the inorganic filler.

It is believed that the specificity of the microstructure changes the state of propagation of energy applied to the substrate and contributes to improving impact resistance and rigidity.In addition to the above composition, the filling composition of the present invention has It may contain stabilizers, plasticizers, lubricants, crosslinking agents, pigments, key fuel agents, antistatic agents, thickeners, foaming agents, fibrous reinforcing materials, and other additives. Although explained in detail, the scope of the present invention is not limited only to the scope of the examples.

In Examples and Reference Examples, "%" means parts by weight and % by weight, respectively. In addition, the Izod impact strength, tensile elongation, flexural modulus, and Rockwell hardness of polymers and compositions are determined by compression molding. The test was carried out using a test piece according to the following method.

Izod impact strength ASTM D256-7 Sae Unit k9' Skin/Notched tensile elongation ASTM D638-71a Unit % Flexural modulus ASTM D790-71 Rockwell hardness in k9' ASTM D785-65 R scale example 1-1 Melt index (hereinafter simply referred to as MI) (load 2.
16k9, temperature 190oo) 1.5, specific gravity 0.961 high density polyethylene 5 anchors, average particle size 1.8
After adding 48 parts of French carcass calcium carbonate and 2 parts of caproic acid and mixing well with a Henschel mixer, this mixture was kneaded with a Banbury mixer at 250 qo for 3 minutes to obtain a filled composition, and then rolled into sheets. turned into
It was granulated using a sheet beretizer to obtain a pellet-shaped filling composition.

Table 1 shows the results obtained by evaluating this filling composition.

Example 1-2 50 parts of high-density polyethylene, 48 parts of heavy calcium carbonate, 2 parts of caproic acid used in Example 1-1, and 2,5-dimethyl-2,5-di(t) as a radical generator.
-butylperoxy)hexane (0.01 part) were mixed and heated and kneaded in the same manner as in Example 1 to produce a filling composition.

Table 1 shows the results obtained by evaluating this filling composition.

Reference Example 1-1 A young calcium carbonate concentration of 48 was obtained from only the high-density polyethylene and heavy trade calcium carbonate used in Example 1-1.
% filling composition was mixed in the same manner as in Example 1-1,
A filling composition was produced by heating and kneading.

Table 1 shows the results obtained by evaluating this filling composition.

Reference Examples 1-2 *The high-density polyethylene used in Examples 1-1 was evaluated and the results are shown in Table 1.

Table 1 Examples 2-1 to 2-4 M15. & 64 parts of high-density polyethylene with a specific gravity of 0.969, 35 parts of heavy calcium carbonate used in Example 1-1, and 0.002 parts of the radical generator used in Example 1-2.
Filled compositions were prepared using the same mixing, heating and kneading conditions and method as in Example 1-1, using the same methods as in Example 1-1.

This composition was evaluated and the obtained results were evaluated in the second
Shown in the table.

Reference Examples 2-1 to 2-3 High-density polyethylene used in Examples 2-1 to 2-4,
Using heavy calcium carbonate, a radical generator, various carboxylic acids listed in Table 2*, the composition listed in Table 2, mixing, heating kneading conditions, and method are the same as in Example 2-1. Filling compositions were produced respectively.

This composition was evaluated and the obtained results were evaluated in the second
Shown in the table.

Reference Example 2-4 A filling composition was manufactured from the high-density polyethylene and heavy calcium carbonate used in Example 2-1 with the composition shown in Table 2.

The evaluation results are shown in Table 2.

Reference Example 2-5 Only the high-density polyethylene used in Example 2-1 was evaluated.

The results obtained are shown in Table 2.

Table 2 Example 3 A filling composition was produced using the same raw material composition as in Examples 1-1 and heating and kneading at a temperature of 22,000.

The evaluation results are shown in Table 3.

Reference Example 3 A filling composition was manufactured using the same raw material composition as in Example 1-1 and heating and kneading at a temperature of 160 qo.

The evaluation results are shown in Table 3. Table 3 Example 4-1 MIO. 3 High-density polyethylene with a specific gravity of 0.953, magnesium hydroxide with an average particle size of 0.2 mm, caproic acid, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane as a radical generator. A filling composition was produced using the four materials in the composition shown in Table 4 under the same mixing and heating kneading conditions as in Examples 1-1.

The results obtained from the evaluation are shown in Table 4.

Example 4-2 MF14.8 (melt index measured at load 2.16k9 and temperature 230°C), boiling n-heptane insoluble content 9
A filling composition was prepared by mixing 5% propylene polymer, talc with an average particle size of 8, and caproic acid in the composition shown in Table 4, and using the same mixing and heating kneading conditions as in Example 1-1. I did o
The results obtained from the evaluation are shown in Table 4.

Reference Example 4-1 The mixing and heating bran conditions for the two materials used in Example 4-1, high-density polyethylene and magnesium hydroxide, were as in Example 4.
A filling composition was produced in the same manner as in Example 1-1.

The results obtained from the evaluation are shown in Table 4.

Reference Example 4-2 A filling composition was produced from the crystalline polypropylene and talc used in Examples 4-2 using the same mixing and heating kneading conditions as in Examples 4-2.

The results obtained from the evaluation are shown in Table 4. Table 4 Example 5 10 parts of heavy calcium carbonate with an average particle size of 1.8 A, a BET specific surface area of 5.5 mm, and a moisture content of 0.15% were placed in a Henschel mixer, and at 150 pm. Acrylic acid containing 500 hydroquinone and 1
was gradually added in a mist using a spray addition device and mixed for 30 minutes at normal pressure to obtain an active filler.

The obtained active filler was a smooth powder with no acrylic acid odor. During the reaction, water vapor and carbon dioxide gas were generated, both of which were removed from the system in gaseous form.
The amount of acrylic acid used was sufficient to uniformly and uniformly coat the surface of the calcium carbonate to a theoretical thickness of 17A.
The above active filler was sufficiently extracted with diethyl ether, and the extract was re-extracted with water and neutralized and titrated with caustic soda. As a result, 0.0 part of unreacted acrylic acid was analyzed in terms of acrylic acid.

On the other hand, the active filler was sufficiently extracted with water and the extract was extracted with E.
When chelate titration was performed using DTA/state a solution using a BT indicator, 0.97 parts of calcium acrylate was analyzed in terms of acrylic acid. At the same time, this extract was titrated for ethylenic double bonds using the bromide bromate method, and calcium acrylate of 0.9 group was analyzed in terms of acrylic acid. At the same time, this extract was concentrated and purified by recrystallization using a methanol-jetyl ether mixed solvent, and calcium acrylate was identified in an amount almost the same as the above titration value by infrared absorption spectrum and elemental analysis. On the other hand, the above active filler was washed and extracted with excess methanol, the extracted residue was dried and thoroughly extracted with water, and the extract was subjected to chelate titration and bromide bromate titration in the same manner as above. Calculated as 0.21 part of calcium acrylate was analyzed. Therefore, on the surface of the active filler, approximately 0. It is thought that the acrylic acid in the group part is strongly bound. The above active filler, Example 1-1
The high-density polyethylene, caproic acid, and 2,5-dimethyl-2,5-di(t
-*butylperoxy)hexane in the composition shown in Table 5, and a filling composition was prepared using the same mixing and heating kneading conditions as in Example 1-1. Table 5 shows the results obtained by evaluating this filling composition.

Reference Example 5 In Example 5, except for caproic acid, three of the following were used: high-density polyethylene, activated heavy calcium carbonate, and radical generator.
Filling compositions were prepared from the same person with the compositions listed in Table 5.

Table 5 shows the results obtained by evaluating this filling composition. Table 5 Examples 6-1 to 6-2 Various inorganic fillers listed in Table 6 were used instead of heavy calcium carbonate in Example 5, and various active fillers were used in the same manner as in Example 5. Obtained.

However, the thickness of the acrylic acid thin film covering the surface of the inorganic filler is estimated from the BET specific surface area as shown in Table 6. In addition, for the various active fillers described above, the extracts obtained mainly from water extraction and methanol extraction were analyzed by the bromide bromate method, and the amount of bound acrylic acid was determined from the difference between the two analytical values. The values are shown in Table 6. Using the above active filler, the high density polyethylene used in Example 2-1 was used as the base polymer, and carboxylic acid,
The radical generator used in Example 5 was used, and the radical generator used in Example 6 was used.
A filling composition was produced in the same manner as in Example 5 except that the composition shown in the table was blended. The results obtained by evaluating this filling composition are shown in Table 6.

Reference Examples 6-1 to 6-2 Filling compositions having the compositions shown in Table 6 were prepared from the various active fillers, high-density polyethylene, and radical generator used in Examples 6-1 and 6-2. Manufactured.

Table 6 shows the results obtained by evaluating each of these filling compositions.

Reference Examples 6-3 to 6-4 The unactivated filler used as the raw material for the activated filler in Examples 6-1 and 6-2 and the high-density polyethylene used in Examples 6-1 and 6-2. Filling compositions were prepared from the two materials according to the formulations shown in Table 6.

Table 6 shows the results obtained by evaluating each of these filling compositions.

Table 6 Examples 7-1 to 7-2 In Example 5, a filling composition was produced in the same manner as in Example 5 except that various carboxylic acids shown in Table 7 were used instead of caproic acid. .

Table 7 shows the results obtained by evaluating these filling compositions.

*Reference Example 7 In Example 5,
A filling composition was produced in the same manner as in Example 5 except that propionic acid was used instead of caproic acid.

Table 7 shows the results obtained by evaluating this filling composition.

Table 7 Examples 8-1 to 8-2 Various active fillers were obtained in the same manner as in Example 5 using the various inorganic fillers shown in Table 8.

Using the above active filler, the base polymer was Mm12
．． 8. Using an ethylene-propylene block copolymer with an ethylene content of 8.8% and a boiling n-heptane content of 93%, the radical generator and carboxylic acid were the same as in Example 5, and the composition shown in Table 8 was used. A filling composition was produced using the same machine as in Example 5 except for the above.

The results obtained by evaluating these filling compositions are shown in Table 8.

Reference Examples 8-1 to 8-2 The unactivated filler used as the raw material for the activated filler in Examples 8-1 and 8-2, and the ethylene-propylene block copolymer 2 used in Example 8 Filling compositions were manufactured from the same person with the compositions shown in Table 8.

The evaluation results are shown in Table 8. Table 8 1): Analysis value 2): Kanata Ontario province chemical composition: Si02 61.0, AZ203 23.
3, Na20 9.8, k20 46, -Other 1.
3% The inorganic filler-filled composition of the present invention has excellent properties such as rigidity, hardness, and impact resistance, as well as excellent moldability, and is therefore extremely suitable for a wide variety of uses.

Claims (1)

[Scope of Claims] 1 (a) 80 to 15 parts by weight of polyolefin, (b) 20 to 85 parts by weight of inorganic filler, and (c) having 4 to 4 carbon atoms.
A polyolefin composition obtained by heat-reacting 0.1 to 5 parts by weight of the aliphatic saturated monocarboxylic acid No. 9 in the presence of a radical generator. 2 (a) 80 to 15 parts by weight of polyolefin, (b) The powder surface of the inorganic filler can be coated with a polymerizable organic acid monomer having an ethylenic double bond to a thickness greater than a monomolecular thin film. 20 to 85 parts by weight of an active filler which is bonded to the metal element on the powder surface with an ethylenic double bond remaining in an amount that is not excessive; and (c) an aliphatic filler having 4 to 9 carbon atoms. A polyolefin composition obtained by subjecting 0.1 to 5 parts by weight of a saturated monocarboxylic acid to a heating reaction.