JPH07292068A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To provide a polyolefin resin compsn. having excellent bending modulus of elasticity, Izod impact strength, and rheological properties in a melted state. CONSTITUTION:A polyolefin resin compsn. comprising: (i) 100 pts.wt. olefin polymer at least part of which has been modified with an unsatd. org. acid or/and a deriv. thereof; (ii) 0.1 to 100 pts.wt. carboxylate of at least one group Ia, group IIa metal of the Periodic Table; (iii) 0.1 to 100 pts.wt. hydroxide or oxide of at least one group Ia, group IIa metal; and (iv) 0.1 to 100 pts.wt. epoxy resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition for polyolefin. More specifically, it relates to a metal ion-crosslinked polyolefin resin composition which remarkably improves mechanical properties, particularly impact strength, tensile strength and flexural modulus, as well as rheological properties upon melting.

[0002]

2. Description of the Related Art Conventionally, a method of introducing an ionic cross-linkage into an olefin polymer is, for example, by copolymerizing ethylene with an α-β unsaturated carboxylic acid, or by using polyethylene, polypropylene, or ethylene. -A propylene copolymer or the like is subjected to a graft reaction with an α-β unsaturated organic acid to first produce a base / polyolefin resin having a carboxyl group introduced into the polymer. Then, a resin composition having a high melt tension can be obtained by forming an ionic cross-linking bond between carboxyl groups with a metal ion cross-linking agent such as calcium stearate or magnesium hydroxide.
It is known from No. 5356.

The resin composition obtained by this method has a high melt tension as described above, but in order to significantly improve the melt tension and the mechanical strength, a large amount of additives such as calcium stearate and magnesium hydroxide is used. Must be added. As a result, the surface of these molded products is extremely rough, and thus the obtained resin has poor transparency and gloss, and as a result, the value as a product is greatly impaired. Further, the resin obtained by the method according to the above-mentioned known technique has an insufficient melt tension, which has a great influence on the quality of the molding processability, and further, the tensile strength and the impact strength of the molded product are insufficient. In blow molding, the parison is stretched longitudinally by its own weight as it is extruded from the die. This phenomenon is called drawdown or sagging and causes uneven thickness of the molded product. On the other hand, the drawdown property is related to the melt tension, and the resin obtained by the known method lacks the melt tension, resulting in a parison with many drawdowns. As a result, the molded product has uneven thickness. There will be many. Further, when foam molding is performed, the resin must have a high melt tension in order to form closed cells in which gas is confined inside the molten resin. As can be seen from the above description,
The resin obtained by the method described in No. 25356,
Although the melt tension and the mechanical strength were improved as described in the patent, it was still insufficient for practical use. Further, when zinc acetate, magnesium acetate, etc. are used as the above-mentioned metal ion cross-linking agent according to JP-A-61-2364, JP-A-61-252204, etc., they are corrosive, and therefore anticorrosion treatment is required in the production of the resin. Requires applied equipment.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a polyolefin resin composition obtained by a conventional technique, which has improved rheological properties and / or mechanical properties. The inventors have conducted intensive research to solve the above problems. As a result, a polyolefin-based polymer modified with an unsaturated organic acid or its derivative is added to a compound of the following three groups B, C and D, that is, a metal selected from B, Group Ia and Group IIa of the periodic table of the elements. Of 1
1 of the above-mentioned carboxylates C, metals selected from Group Ia and Group IIa of the Periodic Table of the Elements
The polyolefin resin composition obtained by blending the above-mentioned hydroxides and / or oxides D and epoxy resin in a specific weight ratio has the above-mentioned problems, that is, insufficient melt tension, rough surface of molded products and insufficient mechanical strength. The present invention has been completed with the knowledge that it can be greatly improved. As is clear from the above description, an object of the present invention is to provide a polyolefin resin composition having the above-mentioned properties of the polyolefin resin composition obtained by known techniques improved.

[0005]

The present invention includes the following (1).
It has the main composition of. (1) A polyolefin-based polymer at least a part of which is modified with an unsaturated organic acid or a derivative thereof, a carboxylate of Group Ia or Group IIa of the Periodic Table of Elements, and Group Ia of the Periodic Table of Elements or And a Group IIa hydroxide or and oxide, and an epoxy resin are blended, which is a polyolefin resin composition.

The structure and effect of the present invention will be described in detail below. As the constituent component other than the polyolefin-based polymer of the composition of the present invention, in particular, an unsaturated organic acid, or a derivative thereof is maleic anhydride or methacrylic acid,
The carboxylate of Group Ia or Group IIa of the Periodic Table of Elements is calcium stearate or magnesium stearate, and the hydroxide or oxide of Group Ia or Group IIa of the Periodic Table of Elements is magnesium hydroxide or magnesium oxide or Calcium hydroxide or calcium oxide, which is a mixture of these with an epoxy resin.

The polyolefin-based polymer used in the present invention includes propylene homopolymer, propylene as a main component, propylene and ethylene, butene-1, and pentene-.
1 selected from 1, 1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, decene-1.
A copolymer with the above, or polyethylene, ethylene-
Propylene block copolymers, poly-4-methylpentene-1, ethylene-propylene rubber and mixtures of two or more selected from these. Particularly, polypropylene, polyethylene, a copolymer of propylene and ethylene, and a copolymer of propylene, ethylene and butene-1 are preferable from the viewpoint of exhibiting the effect of the present invention. In order to obtain a resin composition having a melt tension equivalent to that of the resin composition obtained by the method of the present invention by the above-mentioned known method, the metal carboxylate or metal hydroxide or metal oxide of the present invention is used. It is impossible to achieve it without adding a larger amount than the method according to. However, if a large amount of these is added, the surface roughness of the molded product will occur as described above, and the commercial value will be impaired. As is apparent from the above description, the present invention makes it possible to reduce the compounding amount of a carboxylic acid metal salt or metal hydroxide or metal oxide as compared with known methods in order to improve the above-mentioned problems. became.

Next, these modification methods will be described. First, as the component A, the above-mentioned polyolefin polymer is first modified with an unsaturated organic acid or a derivative thereof. Specifically, one or more compounds selected from acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, etc. are added to 100 parts by weight of the polyolefin-based polymer. .01-1
Add 0 parts by weight and modify by the grafting method. Above all, it is preferable to modify the polyolefin polymer with maleic anhydride or methacrylic acid. Regarding this modification, in order to improve the graft ratio, benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-
2,5- (t-butylperoxy) hexane, 1,3-
Bis (t-butylperoxyisopropyl) benzene,
An organic peroxide such as The blending amount of the unsaturated organic acid or its derivative is preferably 0.005 to 3.0 parts by weight with respect to 100 parts by weight of the polyolefin polymer. The modification method is to specifically mix an unsaturated organic acid or a derivative thereof and the above-mentioned organic peroxide into a polyolefin-based polymer, and after sufficiently mixing and stirring, above the melting point of the polyolefin-based polymer, generally 170 to Melt kneading is carried out at a temperature of 280 ° C., for example, with an extruder. Further, in the composition of the present invention, it is also an effective method to replace part A with an unmodified polyolefin resin. The modification method including the compounding amount does not limit the scope of this patent.

Next, as the component B, the periodic table of elements Ia group, II
8 or more carbon atoms as one or more carboxylates selected from group a
~ 28 carboxylic acid metal salts, such as 2-ethylhexyl carboxylate, lauric acid metal salt, myristic acid metal salt, palmitic acid metal salt, stearic acid metal salt, behenic acid metal salt, 12-hydroxystearic acid metal salt, montan. Examples thereof include acid metal salts. Of these, calcium stearate, magnesium stearate, lithium stearate, sodium stearate, potassium stearate, and zinc stearate are preferable. More preferred are calcium stearate and magnesium stearate. The blending amount of these is 0.1 to 100 parts by weight with respect to 100 parts by weight of the modified polyolefin polymer.

Next, the component C is one or more hydroxides and / or oxides selected from the groups Ia and IIa of the Periodic Table of the Elements, as sodium oxide, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium oxide, Examples thereof include beryllium hydroxide and barium hydroxide, but magnesium hydroxide, magnesium oxide, calcium hydroxide and calcium oxide are preferable. The compounding amount is 0.1-10 with respect to 100 parts by weight of the modified polyolefin-based polymer.
0 parts by weight. Further, a basic metal soap which is a double salt instead of blending the components B and C, for example, (C ₁₇ COO)
It is also possible to use ₂ Mg / MgO or the like. Also,
The weight ratio of the component B to the component C is 0.01 to 100, preferably 0.05 to 50, and more preferably 0.05 to 10 for the component B with respect to 1.

Component D is bisphenol type, tetrahydroxyphenylmethane type, polyalcohol type, polyglycol type, glycerin triether type, novolak type,
Examples thereof include cycloaliphatic epoxy resins, and cycloaliphatic and / or novolac epoxy resins are particularly preferable.

The order of compounding the components A, B, C and D is not particularly limited as long as they are uniformly mixed. For example, stirring is performed for 3 minutes or more using a stirring device such as a Henschel mixer, a ribbon blender, and a tumbler. In order to melt-knead the mixture thus obtained, a normal kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader may be used, but a twin-screw extruder is more preferable. When the amount of component B added is large when kneading using an extruder, from the first-stage charging port having a multi-stage charging port, the component A or the mixture of the component A and the components C and D is mixed in two stages. The addition of the component B or the mixture of the component B and the components C and D from the eye inlet has a great effect on facilitating the production of the intended polyolefin resin composition.

During the melt-kneading for producing the composition of the present invention, in addition to the above-mentioned components, various coloring agents usually used in polyolefin resins, ultraviolet absorbers, antistatic agents, copper damage inhibitors, flame retardants, It is possible to further add a light stabilizer, an organic filler (for example, wood powder), an inorganic filler (for example, glass fiber, mica) and the like as long as the original purpose is not impaired.

Component B will be described in more detail. Normally, additives such as polyolefin resin are used to improve slip properties, catalyst residual chains are neutralized, and, for example, calcium stearate is used as a dispersant for pigments. It is 0.3 parts by weight or less based on 100 parts by weight of the polyolefin resin. If it is blended in an amount exceeding 0.5 part by weight, bleeding from the surface of the molded product or the film is severe and it cannot be practically used. If a larger amount is blended, melt-kneading with an extruder will result in slippage inside the extruder, making extrusion impossible.

However, when a polyolefin resin modified with an organic acid and a specific metal oxide or hydroxide are used in combination, a larger amount of component B exceeding 0.5 parts by weight is obtained.
Can be blended. As shown in the present invention, the effect is remarkably improved by further adding an epoxy resin thereto. At this time, at the same time, the metal ions of the component B and the component C generate a metal ion bond with the modified polyolefin resin, and improved mechanical strength and viscoelastic modification can be obtained. Obtaining this finding is the basis of the present invention.

Example 1 As a method for producing an unsaturated organic acid-modified α-olefin polymer, Chisso Polypro, P1000 (propylene homopolymer, MFR 0.9 (MFR; temperature 23
Discharge amount of molten resin for 10 minutes when a load of 2.16 kg is applied at 0 ° C., unit: g)) is 100 parts by weight, and 0.5 parts by weight of maleic anhydride, 1,3-bis- (t- 0.05 parts by weight of butylperoxyisopropyl) benzene and 0.07 parts by weight of tetrakis (methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane as an antioxidant and a processability stabilizer. , 2,6-di-t-butyl-p-cresol and 0.1 part by weight of calcium stearate were mixed and stirred with a Henschel mixer for 3 minutes, and then melt-kneaded.
The melt-kneading was carried out by using a twin screw extruder PCM-45 manufactured by Ikegai Tekko Co., Ltd. at a cylinder temperature of 230 ° C.

The concentration of maleic acid in the resin pellet thus obtained was 0.19% by weight as measured by infrared absorption spectrum. When the exemplary composition of the present invention was formed into a film and the infrared spectrum was examined, the characteristic peak of maleic anhydride at 1785 cm ⁻¹ decreased, and the peak increase due to ionic bond was inversely proportional to 156.
It was clearly recognized at 0 cm ^-1 . Further, when the composition was pulverized and subjected to Soxhlet extraction for 8 hours using a xylene solvent, insoluble components were generated in the components A + B + C and the components A + B + C + D. On the other hand, component A, component A + B, component A
Only + C and component A + D were all dissolved. The MFR was 55. 90 parts by weight of Chisso Polypro, P6000M (highly crystalline propylene homopolymer, MFR 6.6), manufactured by Chisso Corporation, was added to 10 parts by weight of the pellet obtained in order to form an ionic cross-link. Magnesium and calcium stearate and Araldite CY179 manufactured by Nippon Ciba Geigy Co., Ltd.
(Cyclic aliphatic epoxy resin, epoxy equivalent 140) was blended in the amounts shown in Table 1 and stirred for 3 minutes with a Henschel mixer, and then a Yamaguchi Seisakusho single screw extruder YE20V.
Was used for melt kneading at a cylinder temperature of 230 ° C. The definition and production method of the highly crystalline propylene homopolymer are as shown in Japanese Patent Publication No. 63-191809.
The pellets of the present composition thus obtained have a resin temperature of 25
Injection molding was performed under the condition of 0 ° C., a predetermined test piece was prepared, and the mechanical strength was measured. The tensile yield strength, flexural modulus, and Izod impact strength of the test piece thus obtained at room temperature were 420 Kgf / cm ² and 22000 Kgf / cm, respectively.
² and 6.9 Kgf · cm / cm ² . The melt tension was measured using a melt tension tester manufactured by Toyo Seiki Co., Ltd.
At a cylinder temperature of ° C, the discharge port diameter was 2.095 mm, the extrusion speed was 20 mm / min, and the winding speed was 4600 mm / min. The melt tension value was 7.0 g. The MFR was 3.8 g / 10 minutes. The skin roughness was evaluated by a plurality of persons by visually observing the surface of each of the above-mentioned test pieces in five stages. The evaluation of the rough skin was “good”.

Example 2 The polyolefin resin modified in Example 1 and P6000
Except for the compounding amount of M, it was the same as in Example 1. Maleic acid modified α
The blending amounts of the olefin polymer and P6000M are shown in Table 1. The methods of measuring MFR, melt tension, mechanical strength, and evaluating rough skin were in accordance with Example 1. MFR is 0.7 g /
The melt tension at 190 ° C. for 10 minutes was 25 g or more. Tensile yield strength, flexural modulus and Izod impact strength at room temperature are 440Kgf / cm ² and 23000Kg, respectively.
The values were f / cm ² and 8.8 Kgf · cm / cm ² . The evaluation of the rough skin was “bad”.

Example 3 The unsaturated organic acid-modified α-olefin polymer produced in Example 1 was used. Ionic crosslinking reaction is P6000
Chisso Polypro manufactured by Chisso Corporation instead of M, P10
Example 1 except that 00 (propylene homopolymer, MFR 0.9) was used and the compounding amount thereof and the compounding amounts of magnesium hydroxide, calcium stearate and epoxy resin were used.
According to. The compounding amounts of P1000, magnesium hydroxide, calcium stearate and epoxy resin are shown in Table 1. The method for measuring MFR, melt tension, mechanical strength and evaluation of rough skin and the method for measuring MFR, melt tension, mechanical strength and rough skin were the same as in Example 1. MFR is 0.6g / 10min, melt tension at 190 ℃ is 25g
That was all. Tensile yield strength, flexural modulus and Izod impact strength at room temperature are 460 Kgf / cm ² and 2, respectively.
The values were 1500 Kgf / cm ² and 9.1 Kgf · cm / cm ² . The evaluation of the rough skin was “good”.

Example 4 The unsaturated organic acid-modified α-olefin polymer used in Example 1 was used. The reaction for forming an ionic cross-link was the same as in Example 1 except that Chisso Polypro, P6000 (propylene homopolymer, MFR 4.6) manufactured by Chisso Corporation was used in place of P6000M in Example 1. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MFR is 2.2 g / 10 minutes, and the melt tension at 190 ° C. is 24.
5g, tensile yield strength at room temperature, flexural modulus, Izod impact strength is 430Kgf / cm ² , 19000 respectively.
The values were Kgf / cm ² and 8.5 Kgf · cm / cm ² . The evaluation of the rough skin was “good”.

Example 5 The unsaturated organic acid-modified α-olefin polymer produced in Example 1 was used. The reaction for forming an ionic cross-link was the same as in Example 1 except that Chisso Polypro P9005 (propylene homopolymer, MFR51) manufactured by Chisso Corporation was used in place of P6000M.
According to. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. The MFR is 8.4 g / 10 minutes and the melt tension at 190 ° C. is 15.
5g, tensile yield strength at room temperature, flexural modulus, Izod impact strength is 410Kgf / cm ² , 21000 respectively.
The values were Kgf / cm ² and 6.8 Kgf · cm / cm ² . The evaluation of the rough skin was “good”.

Example 6 Example 4 was followed except that magnesium stearate was used in place of calcium stearate and the amounts of magnesium stearate, magnesium hydroxide and epoxy resin were each compounded. The blending amounts of magnesium stearate, magnesium hydroxide and CY179 are shown in Table 1. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MFR is 9.2g
/ 10 min, the melt tension is 5.3g at 190 ° C., yield tensile strength at room temperature, flexural modulus, Izod impact strength, respectively ^{380Kgf / cm 2, 17200Kgf / cm} 2,
It was 5.2 Kgf · cm / cm ² . The evaluation of the rough skin was “bad”.

Example 7 Example 4 was followed except that zinc stearate was used in place of calcium stearate in Example 4 and the amounts of magnesium stearate, magnesium hydroxide and epoxy resin were each compounded. The compounding amounts of zinc stearate, magnesium hydroxide and epoxy resin are shown in Table 1. Also MF
The methods of measuring R, melt tension, mechanical strength and evaluating rough skin were the same as in Example 1. MFR is 11.2g / 10 minutes,
Melt tension at 190 ° C is 4.8g, tensile yield strength at room temperature, flexural modulus, Izod impact strength are 370Kgf / cm ² , 16500Kgf / cm ² , 4.8Kgf ・
It was cm / cm ² . The evaluation of the rough skin was “bad”.

Example 8 In Example 3, instead of P1000, Chisso Polypro manufactured by Chisso Corporation, P7020 (ethylene-propylene random copolymer, ethylene concentration 2.5 wt%, MFR8.
Same as Example 3 except that 0) was used. Also MF
The methods of measuring R, melt tension, mechanical strength and evaluating rough skin were the same as in Example 1. MFR is 11.8g / 10 minutes,
Melt tension at 190 ° C is 5.2g, tensile yield strength at room temperature, flexural modulus, Izod impact strength are 340Kgf / cm ² , 15000Kgf / cm ² , 8.2Kgf ・, respectively.
It was cm / cm ² . The evaluation of the rough skin was “good”.

Example 9 According to Example 3, except that Chisso Polyethylene Q6910P (high density polyethylene, methyl branch number: 3/1000 carbon, MFR38) manufactured by Chisso Corporation was used in place of P1000 in Example 3. It was In addition, MFR, melt tension,
The method for measuring the mechanical strength and evaluating the skin roughness was in accordance with Example 1. The MFR was 0.8 g / 10 minutes, and the melt tension at 190 ° C. was 25 g or more. Tensile yield strength, flexural modulus, and Izod impact strength at room temperature are 3 each
30Kgf / cm ² , 12000Kgf / cm ² , 6.9Kgf · cm / cm ²
Met. The evaluation of the rough skin was “good”.

Example 10 In Example 3, P5070 (ethylene-propylene block copolymer, total ethylene concentration 6.8 wt%, MFR 5.
Same as Example 3 except that 0) was used. Also MF
The methods of measuring R, melt tension, mechanical strength and evaluating rough skin were the same as in Example 1. MFR is 5.0g / 10min, 1
Melt tension at 90 ° C is 5.8g, tensile yield strength at room temperature, flexural modulus, Izod impact strength are 340Kgf / cm ² , 15000Kgf / cm ² , 21.5Kgf ・
It was cm / cm ² . The evaluation of the rough skin was "normal".

Example 11 The procedure of Example 4 was followed except for the amount of the epoxy resin compounded. The compounding amount of the epoxy resin is shown in Table 1. Also MF
The methods of measuring R, melt tension, mechanical strength and evaluating rough skin were the same as in Example 1. MFR is 3.9g / 10 minutes, 1
Melt tension at 90 ° C is 12.9g, tensile yield strength at room temperature, flexural modulus and Izod impact strength are 420Kgf / cm ² , 19500Kgf / cm ² and 7.9Kgf ・, respectively.
It was cm / cm ² . The evaluation of the rough skin was "normal".

Example 12 The procedure of Example 4 was repeated except that methacrylic acid was used instead of maleic anhydride in Example 4. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MFR is 2.8 g / 10 minutes, melt tension at 190 ° C. is 10.5 g, tensile yield strength at room temperature, flexural modulus, and Izod impact strength are 42 respectively.
The values were 0 Kgf / cm ² , 18500 Kgf / cm ² and 5.2 Kgf · cm / cm ² . The evaluation of the rough skin was “good”.

Example 13 The procedure of Example 4 was repeated except that magnesium oxide was used in place of magnesium hydroxide in Example 4. Also MF
The methods of measuring R, melt tension, mechanical strength and evaluating rough skin were the same as in Example 1. MFR is 3.0g / 10min, 1
Melt tension at 90 ° C is 7.5g, tensile yield strength at room temperature, flexural modulus and Izod impact strength are 400Kgf / cm ² , 17000Kgf / cm ² and 6.1Kgf · cm, respectively.
It was / cm ² . The evaluation of the rough skin was “good”.

Example 14 Instead of the cycloaliphatic epoxy resin in Example 4, novolac was used.
Use of black epoxy resin (epoxy equivalent 175)
Other than that was based on Example 4. Also MFR, melt tension, machine
The method for measuring the physical strength and the evaluation of the rough skin are the same as in Example 1.
It was MFR is 4.5g / 10min, melting at 190 ℃
Tension is 8.9g, tensile yield strength at room temperature, bending elastic
Sex ratio and Izod impact strength are 410 Kgf / cm each ² ,
18500Kgf / cm² , 6.6Kgf · cm / cm²Met. Rough skin
The evaluation was "good".

Control Example 1 The unsaturated organic acid-modified α-olefin polymer prepared in Example 1 was used. For 30 parts by weight of this pellet, Chisso Polypro, P6000 manufactured by Chisso Corporation
(Propylene homopolymer, MFR 4.6) was mixed in an amount of 70 parts by weight and stirred for 3 minutes with a Henschel mixer, and then melt-kneaded at a cylinder temperature of 230 ° C. using the above twin-screw extruder. The methods of measuring MFR, melt tension, mechanical strength, and evaluating rough skin were in accordance with Example 1.
MFR is 13.5 g / 10 min, melt tension at 190 ° C. is 0.7 g, tensile yield strength at room temperature, flexural modulus, and Izod impact strength are 350 Kgf / cm ² , 1 respectively.
It was 2000 Kgf / cm ² , 2.8 Kgf · cm / cm ² . The evaluation of the rough skin was “very excellent”.

Comparative Example 2 Instead of P6000 in Comparative Example 1, Chisso Polypro, P7020 (ethylene-propylene random copolymer, ethylene concentration 2.5 wt%, MFR8.
Comparative Example 1 except that 5) was used, and the unsaturated organic acid-modified α-olefin polymer used was that produced in Example 8.
According to. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MFR is 2
1.0 g / 10 min, melt tension at 190 ° C. is 0.6
g, tensile yield strength at room temperature, flexural modulus, Izod impact strength are 280 Kgf / cm ² , 9500 Kgf /
It was cm ² , 5.1 Kgf · cm / cm ² . The evaluation of the rough skin was “very excellent”.

Control Example 3 In Control Example 1, instead of P6000, Chisso Polyethylene Q6910P (high density polyethylene, 3 methyl branches / 1000 carbons, MFR 38) manufactured by Chisso Corporation was used, and the modified polyolefin resin was used in Example 9. The procedure of Control Example 1 was followed except that the one manufactured in 1. was used. Also MFR,
The melt tension, the measurement of mechanical strength, and the method of evaluating the rough skin were the same as in Example 1. MFR is 26.8g / 10 minutes, 19
Melt tension at 0 ° C is 0.5g, tensile yield strength at room temperature, flexural modulus and Izod impact strength are 270Kgf / cm ² , 9000Kgf / cm ² , 3.9Kgf · cm / cm ^{2 respectively.}
Met. The evaluation of the rough skin was “very excellent”.

Control Example 4 Instead of P6000 in Control Example 1, Chisso Polypro, P5070 (ethylene-propylene block copolymer, total ethylene concentration 6.8 wt%, MFR5.
0) was used, and the unsaturated organic acid-modified α-olefin polymer was the same as in Control Example 1 except that the one prepared in Example 10 was used. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MFR is 9.5 g / 10 minutes, melt tension at 190 ° C. is 0.8
g, tensile yield strength at room temperature, flexural modulus and Izod impact strength are 260 Kgf / cm ² and 10500 Kg, respectively.
It was f / cm ² and 11.7 Kgf · cm / cm ² . The evaluation of the rough skin was “good”.

Comparative Example 5 Instead of P6000 in Comparative Example 1, Chisso Polypro, P1000 (propylene homopolymer, MF, manufactured by Chisso Corporation) was used.
R0.9) was used, and the unsaturated organic acid-modified α-olefin polymer was the same as in Control Example 1 except that the one produced in Example 1 was used. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 3.2 g / 10 min, melt tension at 190 ° C. is 2.1 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 350 Kgf / cm ² , 130 respectively
It was 00 Kgf / cm ² , 2.8 Kgf · cm / cm ² . The evaluation of the rough skin was “very excellent”.

Comparative Example 6 Instead of P6000 in Comparative Example 1, Chisso Polypro P9005 (propylene homopolymer, MF, manufactured by Chisso Corporation) was used.
R51) was used, and the unsaturated organic acid-modified α-olefin polymer was the same as in Control Example 1 except that the one produced in Example 1 was used. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MFR
Is 55 g / 10 minutes, and the melt tension at 190 ° C. is 0.1
It was less than or equal to g. Tensile yield strength, flexural modulus and Izod impact strength at room temperature are 330 Kgf / cm ² , respectively.
It was 12,500 Kgf / cm ² , 2.6 Kgf · cm / cm ² . The evaluation of the rough skin was “very excellent”.

Control Example 7 The polyolefin resin modified in Control Example 1 was used in Example 12
The procedure of Control Example 1 was followed except that the one manufactured in 1. was used. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MFR is 15.0
g / 10 min, melt tension at 190 ° C is 0.6 g, tensile yield strength at room temperature, flexural modulus and Izod impact strength are 360 Kgf / cm ² and 13500 Kgf / cm, respectively.
^{2 was} 2.6 Kgf · cm / cm ² . The evaluation of the rough skin was “good”.

Comparative Example 1 Example 1 was repeated except that the epoxy resin was not added in Example 1. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 5.1 g / 10 minutes, melt tension at 190 ° C. is 3.1 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 370 Kgf / cm ² , 140 respectively
It was 00 kgf / cm ² , 3.2 Kgf · cm / cm ² . The evaluation of the rough skin was "normal".

Comparative Example 2 The procedure of Example 2 was repeated except that the epoxy resin was not added in Example 2. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 4.4 g / 10 minutes, and the melt tension at 190 ° C. is 1.
2.4 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 390 Kgf / cm ² , 145 respectively
The values were 00 Kgf / cm ² and 3.1 Kgf · cm / cm ² . The evaluation of the rough skin was "very bad".

Comparative Example 3 The procedure of Example 6 was repeated except that the epoxy resin was not added in Example 6. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 11.9 g / 10 minutes, melt tension at 190 ° C. is 2.6 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 380 Kgf / cm ² , 140 respectively
The values were 00 Kgf / cm ² and 3.5 Kgf · cm / cm ² . The evaluation of the rough skin was "very bad".

Comparative Example 4 The procedure of Example 7 was repeated except that the epoxy resin was not added in Example 7. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 12.1 g / 10 minutes, melt tension at 190 ° C. is 2.4 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 360 Kgf / cm ² , 140 respectively
The values were 00 Kgf / cm ² and 3.1 Kgf · cm / cm ² . The evaluation of the rough skin was "very bad".

Comparative Example 5 The procedure of Example 8 was repeated except that the epoxy resin was not added in Example 8. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 15.2 g / 10 minutes, melt tension at 190 ° C. is 1.9 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 320 Kgf / cm ² , 110 respectively
The values were 00 Kgf / cm ² and 6.8 Kgf · cm / cm ² . The evaluation of the rough skin was "normal".

Comparative Example 6 The procedure of Example 9 was repeated except that the epoxy resin was not added in Example 9. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 4.0 g / 10 minutes, and the melt tension at 190 ° C. is 1
8.9 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 310 Kgf / cm ² , 100 respectively
It was 00 Kgf / cm ² , 5.2 Kgf · cm / cm ² . The evaluation of the rough skin was "normal".

Comparative Example 7 The procedure of Example 10 was repeated except that the epoxy resin was not added in Example 10. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1.
MFR is 9.1 g / 10 minutes, melt tension at 190 ° C. is 3.4 g, tensile yield strength at room temperature, flexural modulus, and Izod impact strength are 300 Kgf / cm ² , 1 respectively.
It was 1000 Kgf / cm ² and 16.8 Kgf · cm / cm ² . The evaluation of the rough skin was “bad”.

Comparative Example 8 The procedure of Example 4 was repeated except that the epoxy resin was not added in Example 4. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 6.1 g / 10 min, melt tension at 190 ° C. is 6.5 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 370 Kgf / cm ² , 144 respectively
It was 00 Kgf / cm ² , 5.5 Kgf · cm / cm ² . The evaluation of the rough skin was “bad”.

Comparative Example 9 The procedure of Example 3 was repeated except that the epoxy resin was not added in Example 3. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 1.5 g / 10 minutes, and the melt tension at 190 ° C. is 1
5.2 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 380 kgf / cm ² , 150 respectively
It was 00 Kgf / cm ² , 4.1 Kgf · cm / cm ² . The evaluation of the rough skin was “bad”.

Comparative Example 10 The procedure of Example 5 was repeated except that the epoxy resin was not added in Example 5. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1. MF
R is 17.3 g / 10 minutes, melt tension at 190 ° C. is 8.2 g, tensile yield strength at room temperature, flexural modulus,
Izod impact strength is 380 Kgf / cm ² , 115 respectively
The values were 00 Kgf / cm ² and 3.5 Kgf · cm / cm ² . The evaluation of the rough skin was “bad”.

Comparative Example 11 The procedure of Example 12 was repeated except that the epoxy resin was not added in Example 12. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1.
MFR is 5.5 g / 10 minutes, melt tension at 190 ° C. is 3.5 g, tensile yield strength at room temperature, flexural modulus, and Izod impact strength are 390 kgf / cm ² , 1 respectively.
It was 5000 Kgf / cm ² and 3.8 Kgf · cm / cm ² . The evaluation of the rough skin was “bad”.

Comparative Example 12 The procedure of Example 13 was repeated except that the epoxy resin was not added in Example 13. The methods for measuring MFR, melt tension, mechanical strength and evaluating rough skin were in accordance with Example 1.
MFR is 6.2 g / 10 minutes, melt tension at 190 ° C. is 3.1 g, tensile yield strength at room temperature, flexural modulus and Izod impact strength are 360 Kgf / cm ² , 1 respectively.
It was 2800 Kgf / cm ² and 4.2 Kgf · cm / cm ² . The evaluation of the rough skin was “bad”.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

Claims (8)

[Claims] 1. A polyolefin resin composition comprising the following respective component compounds A, B, C and D. A, 100 parts by weight of a polyolefin-based polymer, at least a part of which is modified with an unsaturated organic acid or a derivative thereof, B, 1 of metals selected from Group Ia and Group IIa of the Periodic Table of the Elements
0.1 to 100 parts by weight of the above-mentioned carboxylates, C, 1 of metals selected from Ia group and IIa group of the periodic table of the elements
0.1 to 100 parts by weight of the above hydroxides and / or oxides. D, 0.1 to 100 parts by weight of epoxy resin. 2. The polyolefin resin composition according to claim 1, wherein the unsaturated organic acid or its derivative is maleic anhydride or methacrylic acid. 3. The polyolefin resin composition according to claim 1, wherein the one or more carboxylates of a metal selected from the groups Ia and IIa of the periodic table of the elements are calcium stearate and magnesium stearate. 4. The one or more hydroxides and / or oxides of metals selected from Group Ia and Group IIa of the Periodic Table of the Elements are magnesium hydroxide, magnesium stearate, calcium hydroxide and calcium oxide. The polyolefin resin composition described in 1. 5. The polyolefin resin composition according to claim 1, wherein the epoxy resin is an aliphatic epoxy resin or a novolac type epoxy resin. 6. The polyolefin resin composition according to claim 2, wherein the one or more carboxylates of a metal selected from the groups Ia and IIa of the periodic table of the elements are calcium stearate and magnesium stearate. 7. The one or more hydroxides and / or oxides of metals selected from Group Ia and Group IIa of the Periodic Table of the Elements are magnesium hydroxide, magnesium stearate, calcium hydroxide and calcium oxide. The polyolefin resin composition described in 1. 8. The polyolefin resin composition according to claim 7, wherein the epoxy resin is a cycloaliphatic epoxy resin or a novolac type epoxy resin.