JP2001302809A - Polyolefin-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a master batch composition which is superior in thermal oxidation stability, smell stability and color stability when an inorganic filler- compounded polyolefin-based resin is recycled, and to provide a compound improved in recycling property. SOLUTION: This master batch composition for improving the recyclable property of the inorganic filler-containing polyolefin-based resin, is characterized by blending the resin with a hydrotalcite compound, a compound represented by the general formula: R-CO-NH-(CH2)n=HN-CO-R [R is a 5 to 21C alkyl or alkenyl; (n) is 1 to 6] and a phosphite-based antioxidatnt, and the compound which is improved in recycling property is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a masterbatch composition having remarkably improved thermo-oxidative stability, odor and color stability when recycling a polyolefin resin containing an inorganic filler, and a compound having improved recyclability. About.

[0002]

2. Description of the Related Art In order to improve mechanical properties such as rigidity, impact resistance, dimensional stability and heat resistance of a polyolefin, a method of blending an inorganic filler is widely used. However, there is a drawback that the thermal oxidation stability, the odor and the hue stability are remarkably reduced by the addition of the inorganic filler as compared with those without the filler. In particular, this tendency appears remarkably due to heat history and the like in recycling use, and improvement thereof has been eagerly desired.

[0003] From this point, conventionally, thermal oxidation deterioration, odor,
Various methods have been proposed to improve discoloration (for example, JP-A-52-49254, JP-A-52-80345, JP-A-53-79938, and JP-A-56-90.
844, JP-A-56-11837, and JP-A-56-141339. However, these known methods are not sufficiently improved. As a cause of the decrease in thermal oxidation stability and hue stability of a system containing an inorganic filler, the thermal oxidation stabilizer added to prevent thermal oxidation deterioration is inactivated or decomposed by the inorganic filler. It is considered that the effect was not sufficiently exhibited.

[0004]

Under such circumstances,
The problem to be solved by the present invention, that is, the object of the present invention,
Masterbatch composition that improves thermal oxidation stability, odor, and hue stability by combining a specific thermal oxidation stabilizer and a specific compound with a polyolefin resin containing an inorganic filler, and an improvement in recyclability To provide a tailored compound.

[0005]

That is, the present invention relates to a polyolefin resin containing an inorganic filler and a hydrotalcite compound and a compound of the general formula R-CO-NH- (CH2).
a compound represented by n-HN-CO-R (wherein R represents an alkyl or alkenyl group having 5 to 21 carbon atoms, and n represents 1 to 6), a phenolic antioxidant and a phosphite antioxidant And a compound having improved recyclability and a masterbatch composition for improving the thermal oxidation stability, odor, and hue stability when the inorganic filler-containing polyolefin-based resin is used by recycling. The polyolefin resin containing an inorganic filler in the present invention is a polyolefin resin containing 1 to 60% by weight of an inorganic filler.

The aim of the present invention is to study a method for preventing or suppressing the deterioration of the thermal oxidation stability, odor and hue stability of a polyolefin resin by an inorganic filler, and as a result, a plurality of specific compounds are used in combination. It has been found that the above problems can be solved at once by blending. That is, a hydrotalcite compound and a general formula R-CO
A remarkable effect is obtained only when a bisamide compound represented by -NH- (CH2) n-HN-CO-R is combined with four compounds of a specific phenolic antioxidant and a phosphite antioxidant. They found it to work.

The compounding amount of these compounds is 0.005 to 0.5 parts by weight of a hydrotalcite compound based on 100 parts by weight of an inorganic filler-containing polyolefin resin, and the compound of the general formula R-CO-NH- (CH2) 0.01 to 1.0 part by weight of a compound represented by n-HN-CO-R, 0.005 to 0.5 part by weight of a phenolic antioxidant, and 0.01 to 1 part by weight of a phosphite antioxidant. 0.0 parts by weight The effect is remarkably exhibited when it is blended. In particular, the compounding ratio of these four types of compounds is such that the hydrotalcite compound: R-
Compound represented by CO-NH- (CH2) n-HN-CO-R: phenolic antioxidant: phosphite antioxidant = 1: 2-4: 1-2: 2-4 when combined effect Becomes big.

Further, the general formula R-CO-NH- (CH
2) Among the compounds represented by n-HN-CO-R, ethylene bisstearyl amide is most preferable in terms of cost performance. Among the phenolic antioxidants, hindered phenols having β- (4-hydroxy-3,5-di-t-butylphenyl) propionate and / or isocyanurate groups impart thermal oxidation stability. It is preferable from the viewpoint of great effect and small discoloration.

Among the phosphite-based antioxidants, tris (2,4-di-t-butylphenyl) phosphite is preferred because of its excellent hydrolysis resistance. It is effective to use a sulfur-containing antioxidant in combination only to improve the thermal oxidation stability, but there is a problem that odor is deteriorated, and it is preferable not to use it. Furthermore, the merits of making these compounding techniques master batch (high concentration) include practically improved workability, simplicity, and a wide range of applications as compared with direct compounding.

The polyolefin used in the present invention includes ethylene, propylene, butene-1, hexene-
Α-olefin homopolymers such as 1,4-methyl-pentene-1 or random and block copolymers composed of two or more kinds thereof, such as polyethylene, polypropylene, polybutene-1, polyisobutene, poly-3-methyl-butene -1, poly-4-methyl-pentene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, propylene-4-methyl-pentene-1 copolymer, propylene-butene-1 copolymer , Decene-1-4
-Methyl-pentene-1 copolymer, ethylene-propylene-butene-1 copolymer and the like. In the case of copolymerization, a copolymer containing a polyunsaturated compound such as a conjugated diene or a non-conjugated diene or acrylic acid, methacrylic acid, vinyl acetate or the like together with the α-olefin is also included.

These polymers may be acid-modified, for example, polymers modified by grafting with α, β-unsaturated fatty acids, alicyclic carboxylic acids, or derivatives thereof. Further, in the present invention, a mixture obtained by adding a synthetic rubber to these polyolefins can be used according to the application. As the synthetic rubber that can be used in the present invention, an ethylene-α-olefin copolymer rubber is preferable. Examples of the ethylene-α-olefin copolymer rubber include copolymer rubbers of ethylene and α-olefin, for example, propylene, butene-1, hexene-1, and the like, or non-conjugated dienes as a third component in an ethylene-propylene system. For example, a terpolymer rubber obtained by copolymerizing ethylidene norbornene, cyclopentadiene, or the like (hereinafter referred to as “EPD
M ”). Among them, ethylene-propylene copolymer rubber or EPDM is preferable.

Inorganic fillers that can be used in the present invention include talc, mica, wollastonite,
Calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, calcium sulfate, carbon fiber,
Glass fiber, metal fiber, silica sand, poppy, carbon black, titanium oxide, magnesium hydroxide, asbestos,
Examples include zeolite, molybdenum, diatomaceous earth, sericite, shirasu, calcium hydroxide, calcium sulfite, sodium sulfate, bentonite, and graphite. Among them, talc, mica, glass fiber, wollastonite and the like are preferable as those which improve low-temperature impact resistance, moldability and coatability.

The hydrotalcite compounds used in the present invention include natural products and synthetic products. Commercially, synthetic products having stable quality, large quantities, and stable availability are preferred. General formula R-CO-N used in the present invention
Specific examples of the compound represented by H- (CH2) n-HN-CO-R include methylene bisstearyl amide,
Examples include ethylene bisstearyl amide and hexamethylene bisstearyl amide. Particularly, ethylene bisstearyl amide is preferable.

The phenolic antioxidant used in the present invention includes tetrakis [methylene- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] methane, stearyl-β- (4-hydroxy-
3,5-di-t-butylphenyl) propionate,
2,2'-thio-diethylenebis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis- [3- (3-t
-Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 1,3,5-tris (3,5-di-
t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxyethyl]
And isocyanurate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbezyl) isocyanurate and the like.

Specific examples of the phosphite-based antioxidant include distearylpentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite and bis (2,4-di-t-butylphenyl). ) Pentaerythritol diphosphite, tetrakis (2,4
-Di-t-butylphenyl) 4,4'-biphenylenediphosphonite, trinonylphenylphosphite and the like. Particularly, tris (2,4-di-t-butylphenyl) phosphite is preferable. Other compositions of the present invention, as long as the properties are not impaired, other additives, such as process oils, plasticizers, lubricants, neutralizing agents, antioxidants,
A weathering agent, a heavy metal deactivator, a lubricant, a nucleating agent, an antistatic agent, a release agent, a pigment, a fungicide, and the like can be added.

The composition of the present invention can be obtained by kneading in a heated and melted state using a conventional kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll, a Brabender or a kneader. As described above, the product obtained from the polyolefin-based resin containing an inorganic filler of the present invention has excellent features such as extremely excellent thermal oxidation stability, little odor, and little discoloration.

[0017]

The present invention will be described more specifically with reference to the following examples. The test methods for melt flow rate and thermal oxidation stability, odor and coloring in the examples are as follows. (1) Melt flow rate (MFR) Evaluation was performed in accordance with JIS K 7210 (flow test method for thermoplastics). (2) Thermal Oxidation Stability Evaluation was performed in accordance with JIS K 7212 [General rules for heat aging test (oven method) of thermoplastics].
150 using a gear oven manufactured by Toyo Seiki Seisaku-sho, Ltd.
Measured in ° C. Then, the time until the test piece (press sheet having a thickness of 1 mm) was completely deteriorated, in other words, the time until the tensile strength became zero (GO life) was measured.

(3) Coloring Yellowness Index (YI) is converted to ASTM.
The measurement was performed according to -D1925. (4) Odor The odor was determined by placing 10 g of pellets in a 250 ml wide-mouthed reagent bottle, adjusting the state in an oven at 60 ° C. for 30 minutes, and determining the degree of odor in four stages as shown in the table below by five panelists.

[0019]

Example 1 (1) Preparation of Masterbatch Melt Flow Rate 15g / 1 manufactured by Sumitomo Chemical Co., Ltd.
9 kg of 0-minute homopolypropylene powder, 400 g of ethylene bisstearyl amide (trade name: Armowax EBS) manufactured by Lion Akzo, and synthetic hydrotalcite (trade name: DHT-) manufactured by Kyowa Chemical Industry Co., Ltd.
4A), 200 g of Irganox 1010 manufactured by Ciba Specialty Chemicals KK as a phenolic antioxidant, and 300 g of Irgaphos 168 manufactured by Ciba Specialty Chemicals KK as a phosphite-based antioxidant. The mixture was charged all at once into a mixer and mixed for 30 minutes. Next, this mixture was melt-extruded using a twin screw extruder TEM35B (two-way co-rotating type) manufactured by Toshiba Machine Co., Ltd. under the conditions of an extrusion temperature of 200 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 20 kg / hr. Granulation was performed by a strand cut method to obtain pellets.

(2) Preparation of Compound Containing Inorganic Filler Melt Flow Rate 15 g / 1 manufactured by Sumitomo Chemical Co., Ltd.
For a mixture of 8 kg of 0-minute homopolypropylene powder and 2 kg of talc (trade name: Micron White 5000S) manufactured by Hayashi Kasei Co., Ltd. as an inorganic filler, Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd. as an antioxidant. And 0.2% by weight (20 g) of calcium stearate (manufactured by Tannan Chemical Co., Ltd.) as a neutralizing agent.
After adding 0.5 parts by weight (5 g) and 2 parts by weight (200 g) of the masterbatch prepared in the above (1) and mixing with a tumbler for 30 minutes, the mixture was mixed with a twin screw extruder TEM35B (Toshiba Machine Co., Ltd.). Direction rotation two-row type) used, extrusion temperature 280 ° C, screw rotation speed 300rpm
The melt extrusion was performed under the conditions of m and a discharge rate of 20 kg / hr, and the mixture was granulated by a strand cut method to obtain a compound (pellet). The compound thus obtained is referred to as a single pass product for convenience.

For this compound, the melt flow rate (230 ° C./2160 g) and the yellowness index (YI) were measured with an SM color computer model SM-6 manufactured by Suga Test Instruments Co., Ltd. In addition, a press sheet with a thickness of 1 mm was created by hot pressing (200 ° C),
The GO life was measured at 150 ° C. for thermal oxidation stability evaluation. Further, the odor was evaluated using a compound (pellet). Table 1 shows the measurement results.

(3) Evaluation of effects on various physical properties due to repeated extrusion (recycling) of the compound The compound (single-passed product) prepared in the above (2) was subjected to twice and three times under the same conditions as in the above (2). The pellets were repeatedly extruded, and the obtained pellets were measured for melt flow rate, coloring, and odor. Table 1 shows the measurement results.

[0023]

Example 2 In the preparation of the compound containing an inorganic filler in item (2) of Example 1, 6 kg of a homopolypropylene powder was used.
Talc was changed to 4 kg, and 0.2 parts by weight of Irganox 1010, which is an antioxidant, and 4 parts by weight of the masterbatch prepared in (1) of Example 1 were mixed with the mixture of the two. Prepared a compound in the same manner as in item (2) of Example 1. This compound was repeatedly extruded in the same manner as in item (3) of Example 1, and the extruded product was similarly subjected to melt flow rate, 150 ° C GO life (single pass product only), coloring And the odor was evaluated. Table 1 shows the measurement results.

[0024]

Example 3 For a mixture of 8 kg of homopolypropylene powder having a melt flow rate of 15 g / 10 min manufactured by Sumitomo Chemical Co., Ltd. and 2 kg of talc (trade name: Micron White 5000S) manufactured by Hayashi Kasei Co., Ltd. as an inorganic filler. Then, 2 parts by weight (200 g) of the master batch prepared in (1) of Example 1 was added, and the mixture was mixed with a tumbler for 30 minutes.
A compound (referred to as a single pass product) was prepared in the same manner as in item (2) of Example 1. This compound was repeatedly extruded in the same manner as in item (3) of Example 1, and the extruded product was similarly subjected to melt flow rate, 150 ° C GO life (only once-through product), coloring,
The odor was evaluated. Table 1 shows the measurement results.

[0025]

[Comparative Example 1] Item (2) of Example 1 except that the masterbatch prepared in item (1) of Example 1 was not blended when preparing the compound containing an inorganic filler in item (2) of Example 1. The compound was created in the same way as. This compound was repeatedly extruded in the same manner as in item (3) of Example 1, and the extruded product was similarly subjected to melt flow rate, 150 ° C GO life (single pass product only), coloring And the odor was evaluated. Table 1 shows the measurement results.

[0026]

Comparative Example 2 When preparing the compound containing an inorganic filler in item (2) of Example 1, the masterbatch prepared in item (1) of Example 1 was not blended but added as an antioxidant. 0.4% Irganox 1010
A compound was prepared in the same manner as in item (2) of Example 1, except that the amount was increased to parts by weight. This compound was repeatedly extruded in the same manner as in item (3) of Example 1, and the extruded product was similarly subjected to melt flow rate, 150 ° C GO life (single pass product only), coloring And the odor was evaluated. Table 1 shows the measurement results.

[0027]

Comparative Example 3 A compound was prepared in the same manner as in item (2) of Example 1, except that the masterbatch prepared in item (1) of Example 1 was not used when preparing the compound containing an inorganic filler in Example 2. It was created. This compound was repeatedly extruded in the same manner as in item (3) of Example 1, and the extruded product was similarly subjected to melt flow rate, 150 ° C GO life (single pass product only), coloring And the odor was evaluated. Table 1 shows the measurement results.

[0028]

[Table 1-1]

[Table 1-2]

[0029]

Example 4 In preparing the compound containing an inorganic filler in item (2) of Example 1, calcium carbonate (trade name: Softon 1800) manufactured by Bihoku Powder Chemical Industry Co., Ltd. was used instead of talc as the inorganic filler. A compound was prepared in the same manner as in the item (2) of Example 1 except that the compound was prepared. This compound was repeatedly extruded in the same manner as in item (3) of Example 1, and the extruded product was similarly subjected to melt flow rate, 150 ° C GO life (single pass product only), coloring And the odor was evaluated. Table 2 shows the measurement results.

[0030]

Comparative Example 4 The compound was prepared in the same manner as in item (2) of Example 1, except that the masterbatch prepared in item (1) of Example 1 was not used when preparing the compound containing calcium carbonate of Example 3. Created. This compound was repeatedly extruded in the same manner as in item (3) of Example 1, and the extruded product was similarly subjected to melt flow rate, 150 ° C GO life (single pass product only), coloring And the odor was evaluated. Table 2 shows the measurement results.

[0031]

[Table 2-1]

[Table 2-2]

[0032]

Example 5 8 kg of low-density polyethylene (trade name: Sumikacene L705) manufactured by Sumitomo Chemical Co., Ltd. with a melt flow rate of 7 g / 10 min and Hayashi Kasei Co., Ltd. as an inorganic filler
Talc (trade name: Micron White 5000S) 2k
g mixture as an antioxidant, Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.
0.05 parts by weight, 0.1 parts by weight of Irgafos 168 manufactured by Ciba Specialty Chemicals Co., Ltd., and 0.1 parts by weight of ethylene bisstearyl amide (trade name: Armowax EBS) manufactured by Lion Akzo. A mixture obtained by adding 0.05 parts by weight of synthetic hydrotalcite (trade name: DHT-4A) manufactured by Kyowa Chemical Industry Co., Ltd. was mixed by a tumbler for 30 minutes, and the mixture was twin-screw extruder manufactured by Toshiba Machine Co., Ltd. Uses TEM35B (same-rotation two-row type), extrusion temperature 200 ° C, screw rotation speed 30
Melt extrusion was performed under the conditions of 0 rpm and a discharge rate of 20 kg / hr, and the mixture was granulated by a strand cut method to obtain a compound (pellet). The compound thus obtained is referred to as a single pass product for convenience.

With respect to this compound, the melt flow rate (190 ° C./2160 g) and the yellowness index (YI) were measured with an SM color computer model SM-6 manufactured by Suga Test Instruments Co., Ltd. Further, the odor was evaluated using a compound (pellet). Next, the single pass product was repeatedly extruded with a twin screw extruder twice and three times under the same conditions as above, and the melt flow rate, coloring, and odor of the obtained pellets were measured. Table 3 shows the measurement results.

[0034]

Comparative Example 5 8 kg of low-density polyethylene (trade name: Sumikacene L705) manufactured by Sumitomo Chemical Co., Ltd. with a melt flow rate of 7 g / 10 min and Hayashi Kasei Co., Ltd. as an inorganic filler
Talc (trade name: Micron White 5000S) 2k
g mixture as an antioxidant, Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.
Was added in a tumbler for 30 minutes, melt-kneaded in a twin-screw extruder in the same manner as in Example 4, and then processed in the same manner to obtain a compound (pellet). For this compound, the melt flow rate,
Coloring and odor were evaluated. Table 3 shows the measurement results.

[0035]

[Table 3-1]

[Table 3-2]

[0036]

According to the present invention, there is provided a masterbatch composition and a compound having good thermal oxidation stability, odor and color stability when a polyolefin resin blended with an inorganic filler is recycled. be able to.

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Claims (10)

[Claims] 1. A polyolefin resin, a hydrotalcite compound and a compound represented by the general formula: R-CO-NH- (CH2) n-HN-CO-R, wherein R is an alkyl group or alkenyl group having 5 to 21 carbon atoms, n represents 1 to 6), and a masterbatch composition for improving recyclability of an inorganic filler-containing polyolefin-based resin, comprising a compound represented by formula (1), a phenolic antioxidant and a phosphite-based antioxidant. 2. The polyolefin resin, a hydrotalcite compound, a compound represented by the general formula R-CO-NH- (CH2) n-HN-CO-R, a phenolic antioxidant and a phosphite antioxidant. The polyolefin resin is 70 to 97% by weight, the hydrotalcite compound is 0.5 to 5% by weight, and the general formula R-CO-NH- (CH2) n- The compound represented by HN-CO-R is 1 to 10% by weight, the phenolic antioxidant is 0.5 to 5% by weight, and the phosphite antioxidant is 1 to 10% by weight. Master batch composition. 3. The compound of the general formula R-CO-NH- (CH2)
The masterbatch composition according to claim 1, wherein the compound represented by n-HN-CO-R is ethylene bisstearyl amide. 4. The method according to claim 1, wherein the phenolic antioxidant is β- (4-
The masterbatch composition according to claim 1 or 2, which is a hindered phenol having a hydroxy-3,5-di-t-butylphenyl) propionate and / or an isocyanurate group. 5. The master batch composition according to claim 1, wherein the phosphite-based antioxidant is tris (2,4-di-t-butylphenyl) phosphite. 6. The masterbatch composition according to claim 1 in a weight ratio to the amount of the inorganic filler in the inorganic filler-containing polyolefin resin. Inorganic filler amount: masterbatch composition = 1: 0. A polyolefin-based resin compound containing an inorganic filler and having improved recyclability, which is obtained by blending at a ratio of 0.05 to 0.2. 7. An inorganic filler-containing polyolefin resin is blended with an inorganic filler, melted and kneaded to obtain an inorganic filler-containing polyolefin resin. Items containing the masterbatch composition according to any one of Items 1 to 5 in a weight ratio of inorganic filler: masterbatch composition = 1: 0.05 to 0.2, containing an inorganic filler having improved recyclability. Polyolefin resin compound. 8. An inorganic filler-containing polyolefin resin, which is repeatedly melted and extruded, wherein the amount of the inorganic filler in the present inorganic filler-containing polyolefin resin is based on the amount of the inorganic filler.
Inorganic filler-containing polyolefin-based resin compound having improved recyclability obtained by blending the masterbatch composition described in 1 in a weight ratio of inorganic filler: masterbatch composition = 1: 0.05 to 0.2 . 9. An inorganic filler-containing polyolefin resin comprising 100 parts by weight of a polyolefin resin and 1 to 150 parts by weight of an inorganic filler, wherein 0.005 to 0.5 parts by weight of the hydrotalcite compound is added to a compound represented by the general formula: R-CO-N
0.01 to 1 part by weight of a compound represented by H- (CH2) n-HN-CO-R, 0.005 to 0.5 part by weight of a phenolic antioxidant, and 0 to 1 part by weight of a phosphite antioxidant. 9. The polyolefin resin compound containing an inorganic filler having improved recyclability according to claim 6, wherein the compound contains 0.11 to 1 part by weight. 10. The polyolefin resin compound containing an inorganic filler and a masterbatch composition according to claim 1, wherein the polyolefin resin is a polypropylene resin.