JP2008031451A - Inorganic fiber-containing polyolefin resin composition and molded article obtained therefrom - Google Patents

Abstract

An object of the present invention is to provide an inorganic fiber-containing polyolefin resin composition that maintains rigidity and has excellent impact strength, and a molded product thereof.
SOLUTION: 5 to 70% by weight of inorganic fiber (A);
Inorganic fiber-containing polyolefin resin composition containing 30 to 95% by weight of modified polyolefin resin (B) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. (However, the amount of the inorganic fiber (A) and the amount of the modified polyolefin resin (B) are based on the total amount of the inorganic fiber (A) and the modified polyolefin resin (B), respectively),
An inorganic fiber-containing polyolefin resin composition, wherein the inorganic fiber (A) contains 30 to 50% by weight of SiO ₂ .
[Selection figure] None

Description

  The present invention relates to an inorganic fiber-containing polyolefin resin composition and a molded body thereof. More specifically, the present invention relates to an inorganic fiber-containing polyolefin resin composition that maintains rigidity and is excellent in impact strength, and a molded article thereof.

Conventionally, polyolefin resin compositions containing fibers are known as means for improving the mechanical strength of polyolefin resins.
For example, Japanese Patent Laid-Open No. 10-176085 obtained by melt-kneading a propylene-based polymer and a propylene-based resin-reinforced glass fiber structure for the purpose of improving the mechanical strength and direction appearance of an injection-molded product. A glass fiber reinforced resin composition having a weight average fiber length / number average fiber length of less than 5 is described.

  Japanese Patent Application Laid-Open No. 2004-122549 discloses an automotive interior material obtained by molding a multi-layered product in which a basalt fiber mat is laminated on both surfaces of a thin plate-like urethane foam and a skin material is laminated on the surface of the basalt fiber. Are listed.

  In addition, JP 2005-502755 A contains a fibrous filler such as sized basalt fiber sized with polyamide for the purpose of shortening the cycle time of production of a molded body and improving mechanical properties and burst pressure. Thermoplastic molding materials are described.

  Japanese Patent Application Laid-Open No. 2005-199891 discloses an automobile interior material laminated sheet having sound absorption and dimensional stability, on the hole forming surface of a modified polyphenylene ether-based resin foam sheet, which is made of a shape-retaining fiber such as basalt fiber. An automobile interior material laminated sheet is described in which a surface sheet made of work cloth is laminated.

JP-A-10-176085 JP 2004-122549 A JP 2005-502755 A JP 2005-199891 A

  However, the resin composition and its molded body described in the above publications and the like have also been required to be improved in rigidity and impact strength. An object of the present invention is to provide an inorganic fiber-containing polyolefin resin composition excellent in rigidity and impact strength and a molded product thereof.

In one aspect of the present invention,
5 to 70% by weight of inorganic fibers (A),
Inorganic fiber-containing polyolefin resin composition containing 30 to 95% by weight of modified polyolefin resin (B) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. (However, the amount of the inorganic fiber (A) and the amount of the modified polyolefin resin (B) are based on the total amount of the inorganic fiber (A) and the polyolefin resin (B), respectively),
The inorganic fiber (A) contains 30 to 50% by weight of SiO ₂ and relates to an inorganic fiber-containing polyolefin resin composition.

In another aspect of the present invention,
5 to 70% by weight of inorganic fibers (A),
Inorganic fiber-containing polyolefin resin composition containing 30 to 95% by weight of polyolefin resin composition (I) (however, the amount of the inorganic fiber (A) and the amount of the polyolefin resin composition (I) are Based on the total amount of inorganic fiber (A) and polyolefin resin composition (I)),
The polyolefin resin composition (I) is:
0.5 to 40% by weight of a modified polyolefin resin (B) in which the polyolefin resin is modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives;
99.5 to 60% by weight of polyolefin resin (C) (wherein the amount of the modified polyolefin resin (B) and the amount of the polyolefin resin (C) are respectively the modified polyolefin resin (B) and the polyolefin resin. (Based on the total amount of (C)),
The inorganic fiber (A) contains 30 to 50% by weight of SiO ₂ and relates to an inorganic fiber-containing polyolefin resin composition.

Moreover, the present invention in still another aspect,
The present invention relates to a molded body obtained from any one of the above inorganic fiber-containing polyolefin resin compositions.

  The inorganic fiber-containing polyolefin resin composition of the present invention and its molded product are excellent in rigidity and impact strength.

The inorganic fiber (A) in the present invention contains silicon oxide (SiO ₂ ), and its content is 30 to 50% by weight. From the viewpoint of mechanical strength such as impact strength and rigidity of the inorganic fiber-containing polyolefin resin composition and the molded article, and from the viewpoint of productivity of the inorganic fiber-containing polyolefin resin composition, the SiO ₂ content of the inorganic fiber (A) is The content is preferably 35 to 50% by weight, more preferably 40 to 50% by weight, and still more preferably 45 to 50% by weight.

In addition to silicon oxide (SiO ₂ ), the inorganic fiber (A) includes aluminum oxide (Al ₂ O ₃ ), iron oxide (FeO), calcium oxide (CaO), magnesium oxide (MgO), and sodium oxide (Na ₂ O). ) And the like. From the viewpoint of mechanical strength such as impact strength and rigidity of the inorganic fiber-containing polyolefin resin composition and the molded product, and from the viewpoint of productivity of the inorganic fiber-containing polyolefin resin composition, the content of Al ₂ O ₃ is preferably 13.0 to 16.3% by weight, more preferably 14.0 to 15.3% by weight, and the content of FeO is preferably 5.3 to 10.1% by weight, more preferably Is 6.3 to 9.1% by weight, and the CaO content is preferably 9.8 to 12.9% by weight, more preferably 10.8 to 11.9% by weight. The content is preferably 7.2 to 10.7% by weight, more preferably 8.2 to 9.7% by weight; the Na ₂ O content is preferably 2.0 to 2.5%. % By weight, more preferably 2.3% by weight.

  As an inorganic fiber (A), a calcium silicate fiber, a basalt fiber (basalt fiber), rock wool etc. are mentioned, for example, Preferably, it is a basalt fiber. Basalt fiber is a fiber obtained by spinning molten basalt. As a manufacturing method of a basalt fiber, the manufacturing method described in WO93 / 17975 is mentioned, for example.

  A sizing agent may be applied to the inorganic fiber (A). Examples of the sizing agent include polyolefin resin, polyurethane resin, polyester resin, acrylic resin, epoxy resin, starch, vegetable oil and the like. Furthermore, you may mix | blend lubricants, such as modified polyolefin resin, a coupling agent, and paraffin wax, with a sizing agent.

  In order to improve the wettability and adhesion between the inorganic fiber (A) and the resin, a coupling agent may be added to the sizing agent. Examples of the coupling agent include silane coupling agents, titanate coupling agents, aluminum coupling agents, chromium coupling agents, zirconium coupling agents, borane coupling agents, and the like. A silane coupling agent or a titanate coupling agent, more preferably a silane coupling agent.

  Examples of the silane coupling agent include triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4). -Epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc., preferably γ-aminopropyltriethoxysilane, N-β- (aminoethyl) ) -Γ-aminopropyltrime It is an aminosilane such as Kishishiran.

  The heat loss starting temperature of the sizing agent applied to the inorganic fiber (A) is the appearance of the molded product obtained from the inorganic fiber-containing polyolefin resin composition of the present invention or the production of the inorganic fiber-containing polyolefin resin composition of the present invention. From the viewpoint of easiness, it is preferably 180 to 300 ° C, more preferably 190 to 270 ° C, still more preferably 200 to 250 ° C, and still more preferably 220 to 250 ° C. The heat loss start temperature of the sizing agent is calculated by thermogravimetry (TG measurement) measured from room temperature to 600 ° C. at an increase rate of 10 ° C./min in an air atmosphere. The calculation of the heating loss start temperature from the TG curve is performed by the method described in the TG curve reading method described in JIS K7120-1987.

  Examples of the method for treating the inorganic fiber (A) with the above sizing agent include conventionally used methods such as an aqueous solution method, an organic solvent method, and a spray method. The aqueous solution method is described in the description of the immersion heating method (wet) in Chapter 4 of “Interface control and composite material design” by Fumio Ide, Sigma Publishing (1995). Further, Journal of Japan Adhesion Association, 22 (4), 214-225 (1986) can also be referred to. The organic solvent method is also described in the description of the immersion stirring method (dry method) in Chapter 4 of “Interface control and composite material design” by Fumio Ide, Sigma Publishing (1995). The spray method is described in the description of “5. Inorganic fibers” in the “Industrial Textile Handbook”, edited by Textile Society, Nikkan Kogyo Shimbun (1994).

  The weight average fiber length of the inorganic fiber (A) is determined from the viewpoint of mechanical strength such as rigidity and impact strength of the inorganic fiber-containing polyolefin resin composition and its molded body, and the production and molding of the inorganic fiber-containing polyolefin resin composition. From the viewpoint of ease, it is preferably 1 to 50 mm, more preferably 2 to 30 mm, and further preferably 3 to 15 mm. In addition, after removing resin by solvent extraction etc., the weight average fiber length of an inorganic fiber (A) is measured by the method described in Unexamined-Japanese-Patent No. 2002-5924.

  The fiber diameter of the inorganic fiber (A) is preferably 1 to 40 μm, more preferably 3 to 30 μm, from the viewpoint of preventing damage to the inorganic fiber (A) and the reinforcing effect by the inorganic fiber (A). Preferably it is 5-20 micrometers.

The modified polyolefin resin (B) used in the present invention is a modified polyolefin resin in which the polyolefin resin is modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. Here, the polyolefin resin used as the raw material of the modified polyolefin resin (B) is a resin composed of a homopolymer of one kind of olefin or a copolymer of two or more kinds of olefins. In other words, the modified polyolefin resin (B) is selected from the group consisting of a homopolymer of one olefin or a copolymer of two or more olefins and an unsaturated carboxylic acid and an unsaturated carboxylic acid derivative. A resin produced by reacting at least one compound, and having a partial structure derived from an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative in the molecule. Examples of the modified polyolefin resin (B) include the following modified polyolefin resins (Ba) to (Bc). As the modified polyolefin resin (B), these modified polyolefin resins may be used alone or in combination of two or more.
(Ba) A modified polyolefin resin obtained by graft polymerization of at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid derivative to an olefin homopolymer.
(Bb) Obtained by graft polymerizing at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives onto a copolymer obtained by copolymerizing two or more olefins. Modified polyolefin resin.
(Bc) At least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives in block copolymers obtained by homopolymerizing olefins and then copolymerizing two or more olefins Modified polyolefin resin obtained by graft polymerization.

  The modified polyolefin resin (B) can be produced by a solution method, a bulk method, a melt kneading method or the like. Moreover, you may use together these 2 or more types of methods.

  Specific examples of the solution method, bulk method, melt kneading method and the like include, for example, “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 (B), a commercially available modified polyolefin resin may be used. For example, the product name Modiper (manufactured by NOF Corporation), the brand name BLEMMER CP (manufactured by NOF Corporation), the product Name Bond First (manufactured by Sumitomo Chemical Co., Ltd.), product name Bondine (manufactured by Sumitomo Chemical Co., Ltd.), product name Lexpearl (manufactured by Nippon Polyethylene Co., Ltd.), product name Admer (manufactured by Mitsui Chemicals, Inc.), product Name modic AP (manufactured by Mitsubishi Chemical Co., Ltd.), trade name Polybond (manufactured by Crompton Co., Ltd.), trade name Umex (manufactured by Sanyo Chemical Co., Ltd.), and the like.

  As unsaturated carboxylic acid used for manufacture of modified polyolefin resin (B), maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid etc. are mentioned, for example.

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

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

The modified polyolefin resin (B) is preferably the following (Bd).
(Bd) 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.

  The content of the structural unit derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid derivative contained in the modified polyolefin resin (B) is impact strength, fatigue characteristics, rigidity, etc. From the viewpoint of mechanical strength, it is preferably 0.1 to 10% by weight. The content of the structural unit derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid derivative is determined by an infrared absorption spectrum or an NMR spectrum according to the unsaturated carboxylic acid and the unsaturated carboxylic acid. It is a value obtained by quantifying absorption based on at least one compound selected from the group consisting of acid derivatives.

  When the modified polyolefin resin (B) is the above (Ba), (Bb), or (Bc), at least selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid derivative. The content of structural units derived from one compound is preferably 0.1 to 10% by weight.

  The polyolefin resin (C) is a resin composed of a homopolymer of one kind of olefin or a copolymer of two or more kinds of olefins, and a resin modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative falls under this category. do not do. Examples of the polyolefin resin (C) 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 independently and may use 2 or more types together.

  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 thereof include a propylene-based block copolymer obtained by copolymerizing propylene. From the viewpoint of heat resistance, the polypropylene resin is preferably a propylene homopolymer, or a propylene block copolymer obtained by homopolymerizing propylene and then copolymerizing ethylene and propylene.

  The content of ethylene contained in the propylene-ethylene random copolymer (however, the total amount of propylene and ethylene is 100 mol%), the α-olefin contained in the propylene-α-olefin random copolymer Content (provided that the total amount of propylene and α-olefin is 100 mol%), the total content of ethylene and α-olefin contained in the propylene-ethylene-α-olefin random copolymer (provided that propylene And the total amount of ethylene and α-olefin are 100 mol%). The content of ethylene, the content of α-olefin and the total content of ethylene and α-olefin are described in “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, content of propylene contained in the ethylene-propylene random copolymer (however, the total amount of ethylene and propylene is 100 mol%), α-olefin contained in the ethylene-α-olefin random copolymer Content (provided that the total amount of ethylene and α-olefin is 100 mol%), the total content of propylene and α-olefin contained in the ethylene-propylene-α-olefin random copolymer (provided that ethylene , And the total amount of 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.
It should be noted that the content of propylene contained in the α-olefin-propylene random copolymer (however, the total amount of α-olefin and propylene is 100 mol%), contained in the α-olefin-ethylene random copolymer. Ethylene content (provided that the total amount of α-olefin and ethylene is 100 mol%), and the total content of propylene and ethylene contained in the α-olefin-propylene-ethylene random copolymer (provided that (The total amount of α-olefin, propylene and ethylene is 100 mol%) is less than 50 mol%.

  Examples of the α-olefin having 4 or more carbon atoms, which is a component of the polyolefin resin (C), include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, and 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, di Chill-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like. Preferred are α-olefins having 4 to 8 carbon atoms (for example, 1-butene, 1-pentene, 1-hexene, 1-octene).

  The polyolefin resin (C) can be produced by a solution polymerization method, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like. Moreover, these polymerization methods may be used independently and may combine 2 or more types.

  Examples of a more specific production method of the polyolefin resin (C) include, for example, “new polymer production process” (edited by Koji Saeki, Industrial Research Committee (issued in 1994)), JP-A-4-323207, Examples thereof include polymerization methods described in JP-A-61-287917.

As a catalyst used for manufacture of polyolefin resin (C), a multi-site catalyst and a single site catalyst are mentioned. A preferable multi-site catalyst includes a catalyst obtained by using a solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom, and a preferable single-site catalyst includes a metallocene catalyst.
As a preferable catalyst used for the production of the polypropylene resin as the polyolefin resin (C), a catalyst obtained by using the above-described solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom can be mentioned.

  A modified polyolefin resin (B) modified with at least one compound selected from the group consisting of inorganic fibers (A), unsaturated carboxylic acids and unsaturated carboxylic acid derivatives, wherein the inorganic fiber-containing polyolefin resin composition of the present invention is used. When contained, the content of the inorganic fiber (A) is 5 to 70% by weight, and the content of the modified polyolefin resin (B) is 30 to 95% by weight. However, the amount of the inorganic fiber (A) and the amount of the modified polyolefin resin (B) are based on the total amount of the inorganic fiber (A) and the modified polyolefin resin (B), respectively. From the viewpoint of mechanical strength such as rigidity and impact strength, and from the viewpoint of production stability of the inorganic fiber-containing polyolefin resin composition, the content of the inorganic fiber (A) is preferably 10 to 65% by weight, and the modified polyolefin The resin (B) content is 35 to 90% by weight. More preferably, the content of the inorganic fiber (A) is 20 to 60% by weight, and the content of the modified polyolefin resin (B) is 40 to 80% by weight.

  The inorganic fiber-containing polyolefin resin composition of the present invention contains an inorganic fiber (A) and a polyolefin resin composition (I), and the polyolefin resin composition (I) contains a polyolefin resin (C), a modified polyolefin resin (B), and Is contained, the content of the inorganic fiber (A) is 5 to 70% by weight, and the content of the polyolefin resin composition (I) is 30 to 95% by weight. However, the amount of the inorganic fiber (A) and the amount of the polyolefin resin composition (I) are based on the total amount of the inorganic fiber (A) and the polyolefin resin composition (I), respectively. From the viewpoint of mechanical strength such as rigidity and impact strength of the inorganic fiber-containing polyolefin resin composition and the molded product thereof, and from the viewpoint of production stability of the inorganic fiber-containing polyolefin resin composition, preferably, the inorganic fiber (A) is contained. The amount is 10 to 65% by weight, and the content of the polyolefin resin composition (I) is 35 to 90% by weight. More preferably, the content of the inorganic fiber (A) is 20 to 60% by weight, and the content of the polyolefin resin composition (I) is 40 to 80% by weight.

  And content of polyolefin resin (C) contained in polyolefin resin composition (I) is 99.5 to 60 weight%, and content of modified polyolefin resin (B) is 0.5 to 40 weight%. is there. However, the amount of the modified polyolefin resin (B) and the amount of the polyolefin resin (C) are based on the total amount of the modified polyolefin resin (B) and the polyolefin resin (C), respectively. From the viewpoint of mechanical strength such as rigidity and impact strength of the inorganic fiber-containing polyolefin resin composition and the molded product thereof, and from the viewpoint of production stability of the inorganic fiber-containing polyolefin resin composition, the polyolefin resin (C) is preferably contained. The amount is 99.5 to 70% by weight, the content of the modified polyolefin resin (B) is 0.5 to 30% by weight, and more preferably the content of the polyolefin resin (C) is 99.5 to 80%. The content of the modified polyolefin resin (B) is 0.5 to 20% by weight.

  The method for producing the polyolefin resin composition (I) includes, for example, a method in which all of the polyolefin resin (C) and the modified polyolefin resin (B) are mixed to form a uniform mixture, and then the mixture is melt-kneaded. Can be mentioned.

The inorganic fiber-containing polyolefin resin composition of the present invention can be produced, for example, by any of the following methods (1) to (3).
(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 mixing device such as a Henschel mixer and a ribbon blender. 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.

As the method for producing the polyolefin resin composition of the present invention, preferably, the ease of production of the inorganic fiber-containing polyolefin resin composition, the mechanical strength such as the rigidity and impact strength of the inorganic fiber-containing polyolefin resin composition and its molded product From the point of view, the pultrusion method. The pultrusion method is a method of impregnating a resin into the fiber bundle while drawing a continuous fiber bundle. Examples thereof include the following methods (3-1) to (3-3).
(3-1) A method of passing a fiber bundle through an impregnation tank containing a resin emulsion, suspension or solution, impregnating the fiber bundle with resin, and then removing the solvent.
(3-2) A method in which resin powder is adhered to the surface of the fiber bundle, and then the resin is melted and impregnated into the fiber bundle.
(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 a crosshead described in JP-A-3-272830 is more preferable.

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

  When applied to injection molding, the inorganic fiber-containing polyolefin resin composition of the present invention can be obtained by a pultrusion method because a molded article having excellent strength and injection molding equivalent to a polyolefin resin not containing inorganic fibers can be obtained. It is preferably manufactured and is in the form of pellets having a length of 2 to 50 mm, and the pellet length is more preferably 2 to 30 mm, and further preferably 3 to 15 mm.

  The molded product of the present invention is a molded product obtained from the inorganic fiber-containing polyolefin resin composition of the present invention. 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 body of the present invention include automotive parts, such as exterior parts that require mechanical strength, durability and good appearance, interior parts that require heat-resistant rigidity, parts in engines, etc. Can be 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. the interior parts, for example instrumentation preparative panels, trim, tailgate and the like, as a component in the engine, for example a bumper beam, a cooling fan, a fan shroud, a lamp housing, car heater cases, fuse boxes, air cleaner case Etc.

  Further uses of the molded article of the present invention include parts of various electrical products, parts of various machines, parts of structures, etc. Examples of parts of electrical products include electric tools, cameras, video cameras, electronic devices, etc. Ranges, electric kettles, pots, vacuum cleaners, personal computers, copiers, printers, FDD, CRT machine housings, etc., examples of machine parts include pump casings, etc. Examples thereof include tanks, pipes, and architectural forms.

Hereinafter, the present invention will be described with reference to examples and comparative examples. In Examples and Comparative Examples, the following inorganic fibers and resins were used.
(1) Inorganic fiber A-1: Basalt fiber manufactured by Kammeny Vek (fineness: 1200 tex, fiber diameter: 13 μm)
Composition: 48.5% by weight of SiO ₂
Al ₂ O ₃ 14.7% by weight
FeO 7.7% by weight
CaO 11.4% by weight
MgO 9.0 wt%
Na ₂ O 2.3 wt%

D-1: Glass fiber FT157C manufactured by Asahi Fiber Glass Co., Ltd.
(Fineness: 2200 tex, fiber diameter: 16 μm)
Composition: SiO ₂ 54.9% by weight
Al ₂ O ₃ 14.2% by weight
FeO 0.2 wt%
CaO 22.9% by weight
MgO 0.4 wt%
B ₂ O ₃ 6.0 wt%
TiO ₂ 0.2 wt%
K ₂ 0, Na ₂ O 0.6 wt%
Other 0.6% by weight
D-2: Glass fiber T-441 manufactured by Nippon Electric Glass Co., Ltd.
(Fineness: 2310 tex, fiber diameter: 17 μm)

(2) Modified polyolefin resin B-1: Maleic anhydride-modified polypropylene resin (Melt flow rate (MFR): 60 g / 10 minutes,
(Maleic anhydride grafting amount: 0.6% by weight, rubber content: 21% by weight)
This resin was described in Example 1 of Japanese Patent Application Laid-Open No. 2004-197068 using a propylene-based block copolymer (intrinsic viscosity [η] = 2.8 dl / g, rubber content = 21 wt%). Prepared by method.

(3) Polyolefin resin C-1: Propylene homopolymer (melt flow rate (MFR): 120 g / 10 min)
(Product name: Nobren U501E-1 manufactured by Sumitomo Chemical Co., Ltd.)

The molding conditions of the samples for evaluation used in 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: 270 ° C
Take-off speed: 15m / min

(2) Evaluation Sample Manufacturing Method The measurement sample was manufactured by injection molding the fiber reinforced pellet obtained in (1) above under the following conditions using the following molding machine. .
〔Molding machine〕
Molding machine: Japan Steel Works molding machine J150E
Clamping force: 150t
Screw: Deep groove screw Screw diameter: 46mm
Screw L / D: 20.3
〔Molding condition〕
Cylinder temperature: 250 ° C
Mold temperature: 50 ℃

The evaluation method of the sample for evaluation used for the Example and the comparative example was shown below.
(1) Flexural modulus (unit: MPa)
The measurement was performed under the following conditions in accordance with ASTM D790.
Measurement temperature: 23 ° C
Sample thickness: 3.2 mm
Span: 50mm
Tensile speed: 2 mm / min

(2) IZOD impact strength (unit: kJ / m ² )
The measurement was performed under the following conditions in accordance with ASTM D256.
Measurement temperature: 23 ° C
Sample thickness: 3.2 mm [with V notch]

(3) Remaining weight average fiber length (unit: mm)
A weight average fiber length was measured using a sample for evaluation by the method described in JP-A No. 2002-5924.
(4) Melt flow rate (MFR) (unit: g / 10 minutes)
The melt flow rate was measured under the following conditions according to ASTM D1238.
Measurement temperature: 230 ° C
Load: 21.2N

Example 1
According to the method described in JP-A-3-121146, the inorganic fiber (A-1), the modified polyolefin resin (B-1), and the polyolefin resin (C-1) are mixed at a weight ratio described in Table 1. Then, a fiber reinforced pellet having a fiber (A-1) content of 40% by weight and a pellet length of 9 mm was prepared. One strand was composed of two fibers.
The obtained fiber reinforced pellets were injection-molded, and the bending elastic modulus, IZOD impact strength and residual weight average fiber length of the obtained evaluation samples were measured. The results are shown in Table 1.

Example 2
The fiber reinforced pellets obtained in Example 1 and the polyolefin resin (C-1) were blended at a weight ratio shown in Table 3, and injection molding was performed. The bending elastic modulus and IZOD impact strength of the obtained sample for evaluation were measured, and the results are shown in Table 3.

Example 3
The same operation as in Example 2 was performed except that the weight ratio of the fiber reinforced pellets obtained in Example 1 and the polyolefin resin (C-1) was changed as described in Table 3. The results are shown in Table 3.

Example 4
The same operation as in Example 2 was performed except that the weight ratio of the fiber reinforced pellets obtained in Example 1 and the polyolefin resin (C-1) was changed as described in Table 3. The results are shown in Table 3.

Example 5
According to the method described in JP-A-3-121146, the inorganic fibers (A-1) and the modified polyolefin resin (B-1) are mixed in the weight ratios shown in Table 2, and the fibers (A-1) A fiber reinforced pellet having a content of 40% by weight and a pellet length of 9 mm was prepared. One strand was composed of two fibers.
The obtained fiber reinforced pellets were injection-molded, and the bending elastic modulus, IZOD impact strength and residual weight average fiber length of the obtained evaluation samples were measured. The results are shown in Table 2.

Example 6
The same operation as in Example 2 was performed except that the weight ratio of the fiber reinforced pellets obtained in Example 5 and the polyolefin resin (C-1) was changed as described in Table 3. The results are shown in Table 3.

Comparative Example 1
The same operation as in Example 1 was performed except that the inorganic fiber (A-1) used in Example 1 was changed to the inorganic fiber (D-1) and one strand was composed of one fiber. . The results are shown in Table 1.

Reference Example According to the method described in JP-A-3-121146, the inorganic fibers (D-2), the modified polyolefin resin (B-1), and the polyolefin resin (C-1) were mixed at a weight ratio shown in Table 4. The mixture was mixed to prepare a fiber reinforced pellet having a pellet length of 9 mm.

Comparative Example 2
The fiber reinforced pellets obtained in the reference example and the polyolefin resin (C-1) were blended at a weight ratio shown in Table 5 and injection molded, and the bending elastic modulus and IZOD impact strength of the obtained evaluation samples were measured. The results are shown in Table 5.

Comparative Example 3
The same operation as in Comparative Example 2 was performed except that the weight ratio of the fiber reinforced pellets obtained in the reference example and the polyolefin resin (C-1) was changed as described in Table 5. The results are shown in Table 5.

Comparative Example 4
The same operation as in Comparative Example 2 was performed except that the weight ratio of the fiber reinforced pellets obtained in the reference example and the polyolefin resin (C-1) was changed as described in Table 5. The results are shown in Table 5.

Comparative Example 5
The same operation as in Example 5 was performed except that the inorganic fiber (D-1) was used instead of the inorganic fiber (A-1). The results are shown in Table 2.

The products of Examples 1 to 6 are excellent in rigidity and impact strength.
On the other hand, the products of Comparative Examples 1 to 5 that did not use the inorganic fiber (A) have insufficient impact strength.

Claims (8)

5 to 70% by weight of inorganic fibers (A),
Inorganic fiber-containing polyolefin resin composition containing 30 to 95% by weight of modified polyolefin resin (B) modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. (However, the amount of the inorganic fiber (A) and the amount of the modified polyolefin resin (B) are based on the total amount of the inorganic fiber (A) and the modified polyolefin resin (B), respectively),
An inorganic fiber-containing polyolefin resin composition, wherein the inorganic fiber (A) contains 30 to 50% by weight of SiO ₂ .   The inorganic fiber-containing polyolefin resin composition according to claim 1, wherein the inorganic fiber (A) is a basalt fiber.   The inorganic fiber-containing polyolefin resin composition according to claim 1 or 2, which is produced by a pultrusion method and is in the form of pellets having a length of 2 to 50 mm. 5 to 70% by weight of inorganic fibers (A),
Inorganic fiber-containing polyolefin resin composition containing 30 to 95% by weight of polyolefin resin composition (I) (however, the amount of the inorganic fiber (A) and the amount of the polyolefin resin composition (I) are Based on the total amount of inorganic fiber (A) and polyolefin resin composition (I)),
The polyolefin resin composition (I) is a modified polyolefin resin (0.5 to 40% by weight) in which the polyolefin resin is modified with at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. B) and 99.5 to 60% by weight of a polyolefin resin (C) (wherein the amount of the modified polyolefin resin (B) and the amount of the polyolefin resin (C) are respectively ) And polyolefin resin (C) based)
An inorganic fiber-containing polyolefin resin composition, wherein the inorganic fiber (A) contains 30 to 50% by weight of SiO ₂ .   The inorganic fiber-containing polyolefin resin composition according to claim 4, wherein the inorganic fiber (A) is a basalt fiber.   The inorganic fiber-containing polyolefin resin composition according to claim 4 or 5, wherein the polyolefin resin (C) is a polypropylene resin.   The inorganic fiber-containing polyolefin resin composition according to any one of claims 4 to 6, which is produced by a pultrusion method and has a pellet shape with a length of 2 to 50 mm.   The molded object obtained from the inorganic fiber containing polyolefin resin composition in any one of Claims 1-7.