JP2006291171A - Polyolefin resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin resin composition which has excellent mechanical strength, in particular, impact strength and tensile strength, and a pellet thereof, and provide a molded article comprising the resin composition or the pellet thereof. <P>SOLUTION: The polyolefin resin composition contains (A) all aromatic polyester fibers and (B) a polyolefin resin, wherein the weight ratio A/B ranges 5/95 to 70/30. The present invention provides the polyolefin resin composition, a pellet comprising the polyolefin resin composition, and a molded article comprising the polyolefin resin composition or the pellet thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyolefin resin composition and pellets thereof, and a molded body comprising the resin composition or pellets. More specifically, the present invention relates to a polyolefin resin composition excellent in mechanical strength, in particular excellent in impact strength and tensile strength, and a pellet thereof, and a molded body made of the resin composition or the pellet.

Conventionally, it is known to use synthetic fibers as means for improving the mechanical strength of polypropylene resin.
For example, in JP-A-5-86234, as a resin composition for molding intended to prevent the strength and synthesis of a remolded product from being lower than the original synthetic resin, the matrix resin is polypropylene, There is described a molding resin composition containing a liquid crystalline polymer having a melting point higher than that of a matrix resin and having a liquid crystal polymer compounded in the molding having an aspect ratio of 3 or more.

  Japanese Patent Application Laid-Open No. 2001-49012 discloses that long fiber reinforced resin pellets having excellent recyclability and high impact resistance can be obtained by suppressing damage due to thermal deterioration of synthetic organic fibers as much as possible. The purpose is to manufacture the organic fiber reinforced resin pellets containing a polyolefin resin as a matrix component and synthetic organic fibers as reinforcing fibers by a melt drawing method. Polyethylene terephthalate fibers and polybutylene terephthalates as synthetic organic fibers are described. It is described that fibers, nylon 6 fibers, and nylon 66 fibers can be used.

  In JP-A-2002-97313, for the purpose of providing a resin molded product excellent in design properties, 0.1 to 5% by mass of a melt-anisotropic aromatic polyester fiber containing 0.1 to 5% by mass of a colorant is disclosed. A molded article made of a polyolefin resin containing ˜5 mass% is described.

JP-A-5-86234 JP 2001-49012 A JP 2002-97313 A

  However, regarding the polyolefin resin composition and its pellets described in the above-mentioned publications and the like, and the mechanical strength of the molded body made of the resin composition or pellets, in particular, the impact strength and the tensile strength are further increased. Improvement was desired.

  Under such circumstances, an object of the present invention is to provide a polyolefin resin composition having excellent mechanical strength, in particular, excellent impact strength and tensile strength, and pellets thereof, and a molded body comprising the resin composition or pellets. It is in.

In view of the actual situation, the present inventors have found that the present invention can solve the above problems as a result of intensive studies, and have completed the present invention.
That is, one aspect of the present invention is
A polyolefin resin composition containing a wholly aromatic polyester fiber (A) and a polyolefin resin (B),
The ratio (A / B) between the weight of (A) and the weight of (B) relates to a polyolefin resin composition having a ratio of 5/95 to 70/30.

Also, one aspect of the present invention is
A polyolefin resin composition comprising a wholly aromatic polyester fiber (A) and a modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof,
The ratio (A / C) of the weight of (A) to the weight of (C) relates to a polyolefin resin composition having a ratio of 5/95 to 70/30.

Also, one aspect of the present invention is
A polyolefin containing a wholly aromatic polyester fiber (A), a polyolefin resin (B), and a modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof A resin composition comprising:
The ratio (A / (B + C)) of the weight of (A) and the sum of the respective weights of (B) and (C) is 5/95 to 70/30,
The ratio (B / C) between the weight of (B) and the weight of (C) relates to a polyolefin resin composition having a ratio of 99.5 / 0.5 to 60/40.

Also, one aspect of the present invention is
The present invention relates to a pellet made of the above polyolefin resin composition and a molded body made of the above polyolefin resin composition or the pellet.

  According to the present invention, it is possible to obtain a polyolefin resin composition excellent in mechanical strength, in particular, excellent in impact strength and tensile strength, pellets thereof, and a molded body made of the resin composition or pellets.

  The wholly aromatic polyester fiber (A) used in the present invention is obtained by polycondensing at least one compound selected from the group consisting of aromatic dicarboxylic acids, aromatic dihydroxy compounds, aromatic oxycarboxylic acids and ester compounds thereof. The resulting polymer.

  Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylether dicarboxylic acid, methylterephthalic acid, methylisophthalic acid, etc. Illustrated.

  As aromatic dihydroxy compounds, hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, ethylhydroquinone, t-butylhydroquinone, t-amylhydroquinone, t-butylhydroquinone, (α-phenylethyl) hydroquinone, (2-phenylprop- 2-yl) hydroquinone, phenylhydroquinone, benzylhydroquinone, methoxyhydroquinone, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, bis (4-hydroxyphenoxy) ethane, 2,2 ′ -Dimethyl-4,4'-dihydroxydiphenyl, 3,3'-dimethoxy-4,4'-dihydroxydiphenyl ether, bis (2-chloro-4-hydroxyphenoxy) Emissions, 2,2-bis (4'-hydroxyphenyl) propane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, and the like.

  As aromatic oxycarboxylic acids, p-oxybenzoic acid, 4-oxydiphenyl-4′-carboxylic acid, 3-chloro-4-oxybenzoic acid, 3-methoxy-4-oxybenzoic acid, 3-ethoxy-4- Oxybenzoic acid, 2-methyl-4-oxybenzoic acid, 3-methyl-4-oxybenzoic acid, 2-phenyl-4-oxybenzoic acid, 3-phenyl-4-oxybenzoic acid, 2-chloro-4- Examples thereof include oxydiphenyl-4′-carboxylic acid and 2-hydroxynaphthalene-6-carboxylic acid.

  Examples of the aromatic dicarboxylic acid ester compounds include the lower alkyl esters and aryl esters of the aromatic dicarboxylic acids exemplified above, such as dimethyl ester, diethyl ester or diphenyl ester, ditolyl ester, dinaphthyl ester, and the like. Illustrated. Examples thereof include diphenyl terephthalate and diphenyl isophthalate.

  Examples of the ester compound of the aromatic dihydroxy compound include lower fatty acid esters of the aromatic dihydroxy compound exemplified above, such as acetate ester and propionate ester. For example, hydroquinone diacetate and hydroquinone dipropionate are exemplified.

  Examples of the ester compound of aromatic oxycarboxylic acid include lower alkyl esters, aryl esters and lower fatty acid esters of aromatic oxycarboxylic acids exemplified above. The lower alkyl ester or aryl ester is an ester compound derived from a carboxyl group of an aromatic oxycarboxylic acid, and the lower fatty acid ester is an ester compound derived from a hydroxyl group of an aromatic oxycarboxylic acid. For example, ester compounds derived from p-oxybenzoic acid include methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl p-oxybenzoate, tolyl p-oxybenzoate, p-acetoxybenzoic acid, Examples thereof include p-propionyloxybenzoic acid.

The wholly aromatic polyester fiber (A) used in the present invention is preferably a wholly aromatic polyester fiber exhibiting melt anisotropy. The melt anisotropy referred to in the present invention is to show optical anisotropy (liquid crystallinity) in the melt phase.
Melting anisotropy (that is, exhibiting optical anisotropy (liquid crystallinity) in the molten phase) is achieved by, for example, placing a sample on a hot stage, heating it in a nitrogen atmosphere, and observing the transmitted light of the sample. I can confirm.
The wholly aromatic polyester fiber exhibiting melt anisotropy used in the present invention is preferably a wholly aromatic polyester fiber comprising repeating structural units derived from an aromatic diol, aromatic dicarboxylic acid or aromatic hydroxycarboxylic acid. , More preferably
(1) A wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formulas (1-1) and (1-2):
(2) wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formula (2-1), formula (2-2) and formula (2-3):
(3) wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formula (3-1), formula (3-2) and formula (3-3):
(4) wholly aromatic polyester fiber comprising a combination of each repeating structural unit of formula (4-1) and formula (4-2) shown below,
(5) wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formulas (5-1) and (5-2):
(6) A wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formula (6-1), formula (6-2) and formula (6-3):
(7) wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formula (7-1), formula (7-2) and formula (7-3):
(8) A wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formula (8-1), formula (8-2), formula (8-3) and formula (8-4):
(9) A wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formula (9-1), formula (9-2), formula (9-3) and formula (9-4):
(10) Composed of combinations of repeating structural units of formula (10-1), formula (10-2), formula (10-3), formula (10-4) and formula (10-5) shown below. Wholly aromatic polyester fiber,
(11) A wholly aromatic polyester fiber comprising a combination of repeating structural units of the following formulas (11-1) and (11-2).

More preferably,
(5) wholly aromatic polyester fiber comprising a combination of each repeating structural unit of formula (5-1) and formula (5-2),
Wholly aromatic polyester fiber consisting of a combination of
(8) wholly aromatic polyester fiber comprising a combination of repeating structural units of formula (8-1), formula (8-2), formula (8-3) and formula (8-4),
(9) A wholly aromatic polyester fiber comprising a combination of repeating structural units of the formula (9-1), the formula (9-2), the formula (9-3) and the formula (9-4),

  More preferably, (5) a wholly aromatic polyester fiber comprising a combination of repeating structural units of the formula (5-1) and the formula (5-2), wherein the repeating structural unit of the formula (5-2) It is a wholly aromatic polyester fiber having a content of 4 to 45 mol%. (However, the total amount of wholly aromatic polyester fibers composed of combinations of the repeating structural units of the formulas (5-1) and (5-2) is 100 mol%.)

  The wholly aromatic polyester fiber (A) used in the present invention contains polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyetheresterketone, fluororesin, etc. as necessary. You may not. Moreover, you may include various additives, such as inorganic substances, such as a titanium oxide, a silica, and barium oxide, antioxidant, a ultraviolet absorber, and a light stabilizer.

  The weight average fiber length of the wholly aromatic polyester fiber (A) used in the present invention is 1 to 50 mm from the viewpoint of improvement in mechanical strength such as rigidity and impact strength and ease of production and molding. Is preferable, more preferably 2 to 30 mm, and particularly preferably 3 to 30 mm. The weight average fiber length of component (A) is the length in the polyolefin resin composition of the present invention. After removing the polyolefin resin by a known method such as solvent extraction, JP-A-2002-5924 The weight average fiber length measured by the method described.

  The fiber diameter of the wholly aromatic polyester fiber (A) used in the present invention is such that the damage of the wholly aromatic polyester fiber is prevented and the productivity of the wholly aromatic polyester fiber bundle is not lowered. From the viewpoint of sufficiently exhibiting the reinforcing effect without reducing the aspect ratio, it is preferably 1 to 40 μm, more preferably 3 to 35 μm, and further preferably 5 to 30 μm.

  The decomposition start temperature of the wholly aromatic polyester fiber (A) used in the present invention is from the ease of production of the polyolefin resin composition of the present invention, the incineration of the polyolefin resin composition of the present invention, and the ease of disposal. Preferably it is 300-700 degreeC, More preferably, it is 350-700 degreeC, Especially preferably, it is 400-650 degreeC, More preferably, it is 450-600 degreeC. The decomposition starting temperature of the wholly aromatic polyester fiber (A) is calculated by thermogravimetry (TG measurement) measured from room temperature to 600 ° C. at a heating rate of 10 ° C./min in an air atmosphere. The calculation method of the decomposition start temperature from a TG curve is performed by the method described in the reading of the TG curve of JIS K7120-1987.

  The melting point of the wholly aromatic polyester fiber (A) used in the present invention is preferably 300 ° C. or higher, more preferably 350 ° C. or higher, and particularly preferably 400 ° C. or higher because of the ease of production of the polyolefin resin composition. . The melting point of the wholly aromatic polyester fiber (A) is calculated from a melting endothermic curve obtained by measuring with a differential scanning calorimeter.

  The wholly aromatic polyester fiber (A) can be produced by melt spinning a wholly aromatic polyester resin. Examples of a method for producing a wholly aromatic polyester fiber include, for example, Japanese Patent Publication No. 7-72367, Japanese Patent Publication No. 55-20008, Japanese Patent Application Laid-Open No. 60-239600, Japanese Patent No. 2588533, Japanese Patent Publication No. 3-27643. The method described in etc. is mentioned.

  Examples of the method for producing a wholly aromatic polyester resin include, for example, JP-B-64-484, JP-B-3-27643, JP-B-47-47870, JP-B-63-3888, and JP-B-63. -3891 gazette, Japanese Patent Publication No. 56-18016 gazette, Japanese Patent Publication No. 2-51523 gazette etc. are mentioned.

  Examples of the polyolefin resin (B) used in the present invention include a polypropylene resin, a polyethylene resin, and an α-olefin resin mainly containing an α-olefin having 4 or more carbon atoms. The polyolefin resin is preferably a polypropylene resin. These polyolefin resins may be used alone or in combination of at least two kinds.

Examples of the polypropylene resin include propylene homopolymer, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, propylene-ethylene-α-olefin random copolymer, propylene homoethylene, and ethylene. Examples include a propylene block copolymer obtained by copolymerizing propylene.
In addition, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, ethylene content contained in propylene-ethylene-α-olefin random copolymer, α-olefin content or ethylene and α -The total content of olefins is less than 50 mol% (provided that the total content of propylene, ethylene and α-olefin is 100 mol%). For the ethylene content, α-olefin content, or ethylene and α-olefin content, please refer to the “New Edition Polymer Analysis Handbook” (Kinokuniya Bookstore, 1995) It is measured using IR method or NMR method described in the above.

Examples of the polyethylene resin include an ethylene homopolymer, an ethylene-propylene random copolymer, an ethylene-α-olefin random copolymer, and the like.
In addition, the content of propylene contained in the ethylene-propylene random copolymer, ethylene-α-olefin random copolymer, ethylene-propylene-α-olefin random copolymer, α-olefin content or propylene and α -The total content of olefins is less than 50 mol% (provided that the total content of ethylene, propylene and α-olefin is 100 mol%).

Examples of the α-olefin resin mainly containing an α-olefin having 4 or more carbon atoms include an α-olefin-propylene random copolymer and an α-olefin-ethylene random copolymer.
In addition, content of propylene contained in α-olefin-propylene random copolymer, α-olefin-ethylene random copolymer, α-olefin-propylene-ethylene random copolymer, ethylene content or propylene and ethylene The total content of is less than 50 mol% (provided that the total content of each of the α-olefin, propylene and ethylene is 100 mol%).

  Examples of the α-olefin having 4 or more carbon atoms used for the polyolefin resin (B) include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1 -Hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl -1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, Ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl 1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like. 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

  As a manufacturing method of polyolefin resin (B) used by this invention, the method of manufacturing by solution polymerization method, slurry polymerization method, bulk polymerization method, a gas phase polymerization method, etc. is mentioned. Moreover, the method of using these polymerization methods independently may be used, and the method of combining at least 2 types may be used.

As a method for producing the polyolefin resin (B), for example, “new polymer production process” (edited by Koji Saeki, Industrial Research Committee (published in 1994)), JP-A-4-323207, JP-A-61-287917. And polymerization methods described in Japanese Patent Publication No. Gazette.
When the polyolefin resin (B) used by this invention is a polypropylene resin, said manufacturing method is mentioned as a preferable manufacturing method of a polypropylene resin.

As a catalyst used for manufacture of polyolefin resin (B), a multi-site catalyst and a single site catalyst are mentioned. As the multi-site catalyst, a catalyst obtained by using a solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom is preferable. As the single-site catalyst, a metallocene complex is preferable.
When the polyolefin resin (B) used by this invention is a polypropylene resin, said catalyst is mentioned as a preferable catalyst used for the manufacturing method of a polypropylene resin.

Examples of the modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof used in the present invention include the following (Ca) to (Cd): Modified polyolefin resin is mentioned. These modified polyolefin resins may be used alone or in combination of at least two kinds.
(Ca) A modified polyolefin resin obtained by graft polymerization of at least one compound selected from the group consisting of an unsaturated carboxylic acid and a derivative thereof onto an olefin homopolymer.
(Cb) A modified polyolefin resin obtained by graft polymerization of at least one compound selected from the group consisting of an unsaturated carboxylic acid and a derivative thereof onto a copolymer obtained by copolymerizing at least two kinds of olefins. .
(Cc) Graft polymerization of at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof onto a block copolymer obtained by homopolymerizing an olefin and then copolymerizing at least two olefins Modified polyolefin resin obtained by
(Cd) A modified polyolefin resin obtained by copolymerizing at least one olefin and at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof.

  Examples of the method for producing the modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof used in the present invention include solution method, bulk method, melt kneading method and the like. A method is mentioned. Moreover, the manufacturing method which combined these at least 2 types of methods may be sufficient.

  Examples of the solution method, bulk method, melt kneading method and the like include “practical polymer alloy design” (Fumio Ide, Industrial Research Committee (1996)), Prog. Polym. Sci. 24, 81-142 (1999), JP 2002-308947 A, JP 2004-292581 A, JP 2004-217753 A, JP 2004-217754 A, and the like. It is done.

  As the modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof used in the present invention, commercially available modified polyolefin resins may be used. , Trade name Modiper (manufactured by NOF Corporation), trade name BLEMMER CP (manufactured by NOF Corporation), trade name Bond First (manufactured by Sumitomo Chemical Co., Ltd.) , Trade name Lexpearl (manufactured by Nippon Petrochemical Co., Ltd.), trade name Admer (manufactured by Mitsui Chemicals), trade name Modic AP (manufactured by Mitsubishi Chemical Corporation), trade name Polybond (made by Crompton Co., Ltd.) , And trade name Umex (manufactured by Sanyo Chemical Co., Ltd.)

  Examples of the unsaturated carboxylic acid used in the modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof include maleic acid, fumaric acid, itaconic acid, acrylic An acid, methacrylic acid, etc. are mentioned.

Further, examples of the unsaturated carboxylic acid derivative include acid anhydrides, ester compounds, amide compounds, imide compounds, metal salts, and the like of the above unsaturated carboxylic acids. Specific examples thereof include maleic anhydride, itaconic anhydride. Acid, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, monoethyl maleate, diethyl maleate Examples include ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, sodium methacrylate and the like.
Moreover, you may use what dehydrates and produces | generates unsaturated carboxylic acid at the process grafted to polyolefin like citric acid and malic acid.

  The at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof is preferably acrylic acid, glycidyl ester of methacrylic acid, maleic anhydride, or 2-hydroxyethyl methacrylate.

The modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof used in the present invention is preferably the following (Ce), (Cf) ) Or a mixture thereof.
(Ce) Graft polymerization of maleic anhydride or glycidyl methacrylate or 2-hydroxyethyl methacrylate on a polyolefin resin containing as a main constituent unit a unit derived from at least one olefin selected from ethylene and propylene The modified polyolefin resin obtained by doing.
(Cf) A modified polyolefin resin obtained by copolymerizing at least one olefin selected from ethylene and propylene with maleic anhydride, glycidyl methacrylate or 2-hydroxyethyl methacrylate.

  Selected from the group consisting of the unsaturated carboxylic acid and its derivative contained in the modified polyolefin resin (C) modified with at least one compound selected from the group consisting of the unsaturated carboxylic acid and its derivative used in the present invention. The content of the structural unit derived from at least one compound is preferably 0.1 to 10% by weight from the viewpoint of mechanical strength such as impact strength, fatigue characteristics, and rigidity. The content of the structural unit derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and their derivatives is determined by the unsaturated carboxylic acid and its derivatives used for modification by infrared absorption spectrum or NMR spectrum. This is a value obtained by quantifying the absorption based on at least one compound selected from the group consisting of:

  The modified polyolefin resin (C) modified with at least one compound selected from the group consisting of an unsaturated carboxylic acid and a derivative thereof is the above (Cd) at least one olefin, an unsaturated carboxylic acid and its In the case of a modified polyolefin resin obtained by copolymerizing at least one compound selected from the group consisting of derivatives, structural units derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof The content is preferably 3 to 10% by weight. The content of the structural unit derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and their derivatives is determined by the unsaturated carboxylic acid and its derivatives used for modification by infrared absorption spectrum or NMR spectrum. This is a value obtained by quantifying the absorption based on at least one compound selected from the group consisting of:

A modified polyolefin resin (C) modified with at least one compound selected from the group consisting of an unsaturated carboxylic acid and a derivative thereof is converted to an unsaturated carboxylic acid and its When it is a modified polyolefin resin obtained by graft polymerization of at least one compound selected from the group consisting of derivatives, or
When (Cb) is a modified polyolefin resin obtained by graft polymerization of at least one compound selected from the group consisting of an unsaturated carboxylic acid and a derivative thereof to a copolymer of at least two olefins, Or
At least one compound selected from the group consisting of an unsaturated carboxylic acid and a derivative thereof is added to a block copolymer obtained by homopolymerizing the (Cc) olefin and then copolymerizing at least two olefins. In the case of a modified polyolefin resin obtained by graft polymerization, the content of structural units derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof is preferably 0.1 to 10% by weight It is.

  When the polyolefin resin composition of the present invention contains the wholly aromatic polyester fiber (A) and the polyolefin resin (B), the ratio (A / B) of the weight of (A) to the weight of (B) is 5 / 95 to 70/30, preferably 8/92 to 68/32, more preferably from the viewpoint of improving mechanical strength such as rigidity and impact strength, and from the viewpoint of production stability. Is 10 / 90-60 / 40.

  The polyolefin resin composition of the present invention contains a modified polyolefin resin (C) modified with at least one compound selected from the group consisting of wholly aromatic polyester fibers (A), unsaturated carboxylic acids and derivatives thereof. The ratio (A / C) between the weight of (A) and the weight of (C) is 5/95 to 70/30, preferably from the viewpoint of improving mechanical strength such as rigidity and impact strength. From the viewpoint of production stability, it is preferably 8/92 to 68/32, more preferably 10/90 to 60/40.

Modified polyolefin in which the polyolefin resin composition of the present invention is modified with at least one compound selected from the group consisting of wholly aromatic polyester fibers (A), polyolefin resins (B), unsaturated carboxylic acids and derivatives thereof When the resin (C) is contained,
The ratio (A / (B + C)) of the weight of (A) and the sum of the weights of (B) and (C) is 5/95 to 70/30, and preferably the rigidity, impact strength, etc. From the viewpoint of improving the mechanical strength of the film and from the viewpoint of production stability, it is 8/92 to 68/32, more preferably 10/90 to 60/40.

  And the ratio (B / C) of the weight of (B) and the weight of (C) is 99.5 / 0.5-60 / 40, and it says that mechanical strength, such as rigidity and impact strength, is improved. From a viewpoint and a viewpoint of manufacturing stability, Preferably, it is 99.5 / 0.5-70 / 30, More preferably, it is 99.5 / 0.5-80 / 20.

As a manufacturing method of the polyolefin resin composition of this invention, well-known various methods are mentioned, For example, the method of following (1)-(3) etc. are mentioned.
(1) A method in which all the components are mixed to form a uniform mixture, and then the mixture is melt-kneaded.
(2) A method in which the respective components are arbitrarily combined and mixed individually to form a uniform mixture, and then the mixture is melt-kneaded.
(3) Protrusion method.
In the above method (1) or (2), examples of a method for obtaining a uniform mixture include a method of mixing with a Henschel mixer, a ribbon blender, a blender or the like. Examples of the melt kneading method include a melt kneading method using a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder, and the like.

The method for producing the polyolefin resin composition of the present invention is preferably the above (3) pultrusion method from the viewpoint of ease of production, mechanical strength such as rigidity and impact strength. The pultrusion method is basically a method of impregnating a resin into a fiber bundle while drawing a continuous fiber bundle. Examples thereof include the following methods (3-1) to (3-3). .
(3-1) A method in which a fiber bundle is passed through an impregnation tank containing a resin emulsion, suspension, or solution, and the fiber bundle is impregnated with the resin.
(3-2) A method of impregnating a fiber bundle by spraying the resin powder onto the fiber bundle, or after passing the fiber bundle through a powder tank and adhering the resin to the fiber. .
(3-3) A method of impregnating the fiber bundle by supplying resin from the extruder or the like to the cross head while passing the fiber bundle through the cross head.

  The pultrusion method using the crosshead of (3-3) is preferable, and the pultrusion method using the crosshead described in JP-A-3-272830 is more preferable.

  In the pultrusion method (3), the resin impregnation operation may be performed in one stage or in at least two stages. Moreover, you may blend the pellet manufactured by the pultrusion method, and the pellet manufactured by the melt-kneading method.

  The pellet of the present invention is a pellet made of the composition of the present invention, and when applied to injection molding, from the viewpoint of obtaining a molded product having excellent strength without impairing injection moldability. The length of the pellets is preferably 2 to 50 mm, more preferably 2 to 30 mm, and even more preferably 3 to 20 mm.

  The molded product of the present invention is a molded product comprising the composition of the present invention or a pellet thereof. Examples of the molding method include an injection molding method, an injection compression molding method, a gas assist molding method, and an extrusion molding method.

Applications of the molded article of the present invention include automotive plastic parts, exterior parts that require mechanical strength, durability and good appearance, interior parts that require heat-resistant rigidity, parts in engines, etc. Is mentioned.
Examples of exterior parts include fenders, over fenders, grill guards, cowl louvers, wheel caps, side protectors, side moldings, side lower skirts, front grills, side steps, roof rails, rear spoilers, bumpers, and tailgates. Examples of interior parts include instrument panels, trims, tailgates, etc., and examples of internal parts of the engine include bumper beams, cooling fans, fan shrouds, lamp housings, car heater cases, fuse boxes, air cleaner cases, etc. Is mentioned.

  In addition, examples of the use of the molded body of the present invention include parts of various electrical products, parts of various machines, parts of structures, etc. Examples of parts of various electrical products include, for example, electric tools, cameras, video cameras, Examples include microwave ovens, electric kettles, pots, vacuum cleaners, personal computers, copiers, printers, FDD, CRT machine housings, etc. Examples of various machine parts include pump casings and the like, and parts such as structures Examples include tanks, pipes, and architectural forms.

Hereinafter, the present invention will be described with reference to examples and comparative examples. In Examples or Comparative Examples, the following fibers or resins were used.
(1) Fiber A-1: Kuraray Co., Ltd. fully aromatic polyester fiber (trade name: Vectran)
(167 tex, fiber diameter 20 μm)
D-1: Polyethylene terephthalate fiber (110 tex, fiber diameter 20 μm)

(2) Polypropylene B-1: Propylene homopolymer (MFR = 120 g / 10 min)
(Product name: Nobren U501E-1 manufactured by Sumitomo Chemical Co., Ltd.)
B-2: Propylene homopolymer (MFR = 320 g / 10 min)
Manufactured by a gas phase polymerization method using a solid catalyst component described in JP-A-7-216017

(3) Modified polypropylene resin C-1: Maleic anhydride modified polypropylene resin (MFR = 60 g / 10 min, maleic acid graft amount = 0.6 wt%)
C-2: 2-hydroxyethyl methacrylate modified polypropylene resin (MFR = 77 g / 10 min, graft amount = 2.3 wt%)
C-3: Glycidyl methacrylate modified polypropylene resin (MFR = 13 g / 10 min, graft amount = 0.7 wt%)

The molding conditions of the samples for evaluation using Examples and Comparative Examples are shown below.
(1) Manufacturing method of fiber reinforced pellets According to the method described in JP-A-3-121146, fiber reinforced pellets were manufactured with the compositions shown in Table 1.
Impregnation temperature: 220 ° C. (Examples 1 to 4)
200 ° C. (Comparative Examples 1 and 2)
Take-off speed: 13m / min

(2) Method for producing sample for evaluation The sample for measurement is for evaluation by injection-molding the fiber reinforced pellet obtained in (1) above under the following conditions using a molding machine manufactured by Nippon Steel Works. Samples were manufactured.
〔Molding machine〕
Molding machine: Japan Steel Works molding machine J150E
Clamping force: 150t
Screw: Deep groove screw for long fibers Screw diameter: 46mm
Screw L / D: 20.3
〔Molding condition〕
Cylinder temperature: 220 ° C. (Examples 1 to 4)
200 ° C. (Comparative Examples 1 and 2)
Mold temperature: 50 ℃

Evaluation methods in Examples and Comparative Examples are shown below.
(1) Tensile strength (unit: MPa)
A. S. T. T. et al. M.M. According to D638, the measurement was performed under the following conditions.
Measurement temperature: 23 ° C
Sample thickness: 3.2 mm
Tensile speed: 10 mm / min

(2) Flexural modulus (unit: MPa)
A. S. T. T. et al. M.M. According to D790, the measurement was performed under the following conditions.
Measurement temperature: 23 ° C
Sample thickness: 3.2 mm
Span: 50mm
Tensile speed: 2 mm / min

(3) Bending strength (unit: MPa)
A. S. T. T. et al. M.M. According to D790, the measurement was performed under the following conditions.
Measurement temperature: 23 ° C
Sample thickness: 3.2 mm
Span: 50mm
Tensile speed: 2 mm / min

(4) IZOD impact strength (unit: KJ / m ² )
A. S. T. T. et al. The measurement was performed under the following conditions according to MD256.
Measurement temperature: 23 ° C
Sample thickness: 3.2 mm [with V notch]

Example 1
According to the method described in JP-A-3-121146, fiber-reinforced pellets having the composition shown in Table 1 and a fiber content of 19% by weight and a pellet length of 9 mm were prepared. One strand was composed of four fibers. As the component (A), Kuraray Co., Ltd., wholly aromatic polyester fiber (trade name: Vectran) (167 tex, fiber diameter 20 μm) was used. Kuraray Co., Ltd. fully aromatic polyester fiber (trade name: Vectran) has a melting point of 450 ° C. or higher and a decomposition start temperature of 495 ° C.
The polyolefin resin (B) used was a propylene homopolymer (MFR = 120 g / 10 min, trade name: Nobrene U501E-1 manufactured by Sumitomo Chemical Co., Ltd.) (B-1).
The obtained fiber reinforced pellets were injection-molded, and the tensile strength, bending elastic modulus, bending strength, and IZOD impact strength of the obtained samples were measured. The results are shown in Table 1.

Example 2
According to the method described in JP-A-3-121146, fiber-reinforced pellets having the composition described in Table 1 and a fiber content of 17% by weight and a pellet length of 9 mm were prepared. One strand was composed of four fibers. As the component (A), a wholly aromatic polyester fiber (trade name: Vectran) (167 tex, fiber diameter 20 μm) manufactured by Kuraray Co., Ltd. was used.
The polyolefin resin (B) used was a propylene homopolymer (MFR = 120 g / 10 min, trade name: Nobrene U501E-1 manufactured by Sumitomo Chemical Co., Ltd.) (B-1), the unsaturated carboxylic acid used and its The modified polyolefin resin (C) modified with at least one compound selected from the group consisting of derivatives is a maleic anhydride-modified polypropylene resin (MFR = 60 g / 10 min, maleic anhydride graft amount = 0.6% by weight). (C-1). The modified polyolefin resin (C-1) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof was described in Example 1 of JP-A-2004-197068. Created according to the method.
The obtained fiber reinforced pellets were injection molded, and the obtained samples were measured for flexural modulus, flexural strength, and IZOD impact strength, and the results are shown in Table 1.

Example 3
According to the method described in JP-A-3-121146, fiber-reinforced pellets having the composition described in Table 1 and a fiber content of 17% by weight and a pellet length of 9 mm were prepared. One strand was composed of four fibers. As the component (A), Kuraray Co., Ltd., wholly aromatic polyester fiber (trade name: Vectran) (167 tex, fiber diameter 20 μm) was used.
The polyolefin resin (B) used was a propylene homopolymer (MFR = 120 g / 10 min, trade name: Nobrene U501E-1 manufactured by Sumitomo Chemical Co., Ltd.) (B-1), the unsaturated carboxylic acid used and its The modified polyolefin resin (C) modified with at least one compound selected from the group consisting of derivatives is a 2-hydroxyethyl methacrylate-modified polypropylene resin (MFR = 77 g / 10 min, 2-hydroxyethyl methacrylate graft amount = 2.3 wt%) (C-2).
The modified polyolefin resin (C-2) modified with at least one compound selected from the group consisting of the unsaturated carboxylic acid and its derivative used was a polypropylene resin powder ([η] = 3.0 dl / g). , Ethylene content 0.2 wt%) 100 parts by weight, 8 parts by weight of 2-hydroxyethyl methacrylate, 2 parts by weight of t-butylperoxybenzoate, 3 parts by weight of organic porous powder (MP-1000 manufactured by MEMBRANA), Sodium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate (0.3 parts by weight) was added and sufficiently premixed, and then fed from the feed port of the twin screw extruder. Kneaded and manufactured.
A twin-screw extruder KZW15-45MG (L / D = 45, cylinder diameter = 15 mm) manufactured by Technobel was used, the cylinder temperature was set to 180 ° C., and the screw rotation speed was 500 rpm.
MFR (unit: g / 10 min) is A.M. S. T. T. et al. According to MD1238, measurement was performed at a measurement temperature of 230 ° C. and a load of 21.2 N.
The amount of 2-hydroxyethyl methacrylate grafted was quantified by the following procedure.
The sample was dissolved in boiling xylene, and the obtained sample solution was dropped into a large amount of methanol with stirring to reprecipitate and collect the sample. The collected sample was vacuum-dried (80 ° C., 8 hours), and a film having a thickness of about 100 μm was formed by hot pressing. The infrared absorption spectrum of this prepared film was measured, and the amount of grafting was quantified from the absorption near 1730 cm ⁻¹ .

Example 4
According to the method described in JP-A-3-121146, fiber-reinforced pellets having the composition described in Table 1 and a fiber content of 17% by weight and a pellet length of 9 mm were prepared. One strand was composed of four fibers. As the component (A), Kuraray Co., Ltd., wholly aromatic polyester fiber (trade name: Vectran) (167 tex, fiber diameter 20 μm) was used.
The polyolefin resin (B) used was a propylene homopolymer (MFR = 120 g / 10 min, trade name: Nobrene U501E-1 manufactured by Sumitomo Chemical Co., Ltd.) (B-1), the unsaturated carboxylic acid used and its The modified polyolefin resin (C) modified with at least one compound selected from the group consisting of derivatives is a glycidyl methacrylate-modified polypropylene resin (MFR = 13 g / 10 min, glycidyl methacrylate graft amount = 0.7 wt%). (C-3).
The obtained fiber reinforced pellets were injection molded, and the obtained samples were measured for flexural modulus, flexural strength, and IZOD impact strength, and the results are shown in Table 1.
The glycidyl methacrylate-modified polypropylene resin was produced by the following method.
100 parts by weight of polypropylene resin powder ([η] = 3.0, ethylene content 0.2% by weight), 2 parts by weight of glycidyl methacrylate, 2 parts by weight of styrene, 1,3-bis (t-butyl peroxy isopropyl) After 0.8 parts by weight of benzene, 0.05 parts by weight of calcium stearate and 0.1 parts by weight of antioxidant IRG1010 were sufficiently premixed, they were supplied from the supply port of the twin screw extruder and kneaded.
Using a Toyo Seiki twin screw extruder 2D25-S (L / D = 25, cylinder diameter = 20 mm), the cylinder temperature was set to 250 ° C., and the screw speed was 70 rpm.
MFR (unit: g / 10 min) is A.M. S. T. T. et al. According to MD1238, measurement was performed at a measurement temperature of 230 ° C. and a load of 21.2 N.
The amount of glycidyl methacrylate graft was quantified by the following procedure.
1.0 g of sample was dissolved in 10 ml of xylene. The sample solution was added dropwise to 300 ml of methanol with stirring to re-precipitate the sample and collected. The collected sample was vacuum-dried (80 ° C., 8 hours), and a film having a thickness of 100 μm was formed by hot pressing. The infrared absorption spectrum of the prepared film was measured, and the amount of grafting was quantified from the absorption near 1730 cm-1.

Comparative Example 1
Component (A) Kuraray Co., Ltd. fully aromatic polyester fiber (trade name: Vectran) (167 tex, fiber diameter 20 μm) (A-1), polyethylene terephthalate fiber (110 tex, fiber diameter 20 μm) Evaluation was made in the same manner as in Example 1 except that the content of was changed to 16 wt%.

Comparative Example 2
Instead of the fully aromatic polyester fiber (trade name: Vectran) (167 tex, fiber diameter 20 μm) manufactured by Kuraray Co., Ltd., component (A), polyethylene terephthalate fiber (110 tex, fiber diameter 20 μm) was used. Example 2 except that the content of the modified polyolefin resin (C) modified with at least one compound selected from the group consisting of derivatives was changed to 2% by weight and the fiber content was changed to 27% by weight. Evaluation was performed in the same manner.

Ａ−１：クラレ株式会社製全芳香族ポリエステル繊維（商品名：ベクトラン）（１６７ｔｅｘ，繊維径２０μｍ）
Ｂ−１：プロピレン単独重合体（ＭＦＲ＝１２０ｇ／１０分，商品名住友化学株式会社製ノーブレンＵ５０１Ｅ−１）
Ｂ−２：プロピレン単独重合体（ＭＦＲ＝３２０ｇ／１０分）特開平７−２１６０１７記載の固体触媒成分を用いて気相重合法により製造した。
Ｃ−１：無水マレイン酸変性ポリプロピレン樹脂（ＭＦＲ＝６０ｇ／１０分、マレイン酸グラフト量＝０．６重量％）
Ｃ−２：２−ヒドロキシエチルメタクリレート変性ポリプロピレン樹脂（ＭＦＲ＝７７ｇ／１０分、グラフト量＝２．３重量％）
Ｃ−３：グリシジルメタクリレート変性ポリプロピレン樹脂（ＭＦＲ＝１３ｇ／１０分、グラフト量＝０．７重量％）
Ｄ−１：ポリエチレンテレフタレート繊維（１１０ｔｅｘ，繊維径２０μｍ）

A-1: Kuraray Co., Ltd. wholly aromatic polyester fiber (trade name: Vectran) (167 tex, fiber diameter 20 μm)
B-1: Propylene homopolymer (MFR = 120 g / 10 min, trade name: Nobrene U501E-1 manufactured by Sumitomo Chemical Co., Ltd.)
B-2: Propylene homopolymer (MFR = 320 g / 10 min): Produced by a gas phase polymerization method using a solid catalyst component described in JP-A-7-216017.
C-1: Maleic anhydride modified polypropylene resin (MFR = 60 g / 10 min, maleic acid graft amount = 0.6 wt%)
C-2: 2-hydroxyethyl methacrylate-modified polypropylene resin (MFR = 77 g / 10 min, graft amount = 2.3 wt%)
C-3: Glycidyl methacrylate-modified polypropylene resin (MFR = 13 g / 10 min, graft amount = 0.7 wt%)
D-1: Polyethylene terephthalate fiber (110 tex, fiber diameter 20 μm)

It can be seen that Examples 1 to 4 satisfying the requirements of the present invention are excellent in mechanical strength, and particularly excellent in impact strength and tensile strength.
On the other hand, it can be seen that Comparative Examples 1 and 2 that do not satisfy the component (A), which is a requirement of the present invention, have insufficient mechanical strength.

Claims (7)

A polyolefin resin composition containing a wholly aromatic polyester fiber (A) and a polyolefin resin (B),
The polyolefin resin composition whose ratio (A / B) of the weight of (A) and the weight of (B) is 5 / 95-70 / 30. A polyolefin resin composition comprising a wholly aromatic polyester fiber (A) and a modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof,
The polyolefin resin composition whose ratio (A / C) of the weight of (A) and the weight of (C) is 5 / 95-70 / 30. A polyolefin containing a wholly aromatic polyester fiber (A), a polyolefin resin (B), and a modified polyolefin resin (C) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof A resin composition comprising:
The ratio (A / (B + C)) of the weight of (A) and the sum of the respective weights of (B) and (C) is 5/95 to 70/30,
The polyolefin resin composition whose ratio (B / C) of the weight of (B) and the weight of (C) is 99.5 / 0.5-60 / 40.   The polyolefin resin composition according to any one of claims 1 to 3, wherein the polyolefin resin (B) is polypropylene.   The polyolefin resin composition according to any one of claims 1 to 3, wherein the wholly aromatic polyester fiber (A) has a weight average fiber length of 1 to 50 mm.   A pellet comprising the polyolefin resin composition according to any one of claims 1 to 5, which is obtained by a pultrusion method and has a pellet length of 2 to 50 mm.   The molded object which consists of the polyolefin resin composition in any one of Claims 1-5, or the pellet of Claim 6.