JP2010043204A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which gives a molded body suitable for an automobile outer plate member. <P>SOLUTION: The resin composition contains (A) a resin containing a polyamide resin, (B) a polymer having a maleimide-based monomer unit, and (C) reinforcing fibers, wherein the reinforcing fibers (C) are bundled in the longitudinal direction and combined by at least the components (A) and (B) to form a reinforcing fiber bundle, and the content of the maleimide-based monomer unit in the polymer having the maleimide-based monomer units of the component (B) is ≥40 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition from which a molded article suitable for use in an automobile outer plate member can be obtained.

  For the purpose of increasing the mechanical strength of a thermoplastic resin molded body, a molded body using a mixture of a thermoplastic resin and a fibrous filler (reinforced fiber) is known.

  The invention of Patent Document 1 describes a fiber reinforced thermoplastic resin molded article including a crystalline thermoplastic resin such as polypropylene and nylon, an amorphous thermoplastic resin such as polystyrene and ABS resin, and a fibrous reinforcing material. . However, this molded article does not describe any use of a compatibilizing agent for a crystalline thermoplastic resin and an amorphous thermoplastic resin.

  The invention of Patent Document 2 describes a long fiber reinforced thermoplastic resin composition for an automobile outer plate member including thermoplastic polyurethane, styrene resin, and reinforcing fibers, and polyamide resin is described as an optional component. . However, in this invention, the reinforcing fiber is used as being integrated with the thermoplastic polyurethane.

  In the invention of Patent Document 3, it is described in the Examples that a resin-impregnated fiber bundle was produced using polyamide, ABS resin, and stainless fiber, but there is no description about using a compatibilizing agent.

The invention of Patent Document 4 describes a thermoplastic resin composed of other resins such as maleimide copolymer, polyamide, modified polyolefin polymer, and ABS resin, but glass fiber and the like are described as optional components. And are not used in the examples.
Japanese Patent No. 3665660 JP 2008-13693 A JP 2004-14990 A Japanese Patent No. 2820956

  An object of the present invention is to provide a resin composition that has a high mechanical strength and heat resistance, and that is small in dimensional change due to water absorption of the resin and that can be used to obtain a molded article suitable for use in an automobile outer plate member.

The present invention provides the following inventions as means for solving the problems.
(1) (A) a resin containing a polyamide-based resin, (B) a polymer having a maleimide-based monomer unit, and (C) a reinforcing fiber, and the reinforcing fiber of (C) component is bundled in the length direction , A resin composition comprising a reinforcing fiber bundle integrated with at least the components (A) and (B),
(B) The resin composition whose content of the maleimide-type monomer unit in the polymer which has a maleimide-type monomer unit of a component is 40 mass% or more.
(2) The resin composition according to claim 1, wherein the resin containing the polyamide resin as the component (A) contains (A-1) a polyamide resin and (A-2) a styrene resin.
(3) A polymer having a maleimide monomer unit as component (B) is maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenyl. It has a monomer unit selected from maleimide, N-toluylmaleimide, N-xylylmaleimide, N-naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, N-orthomethoxyphenylmaleimide. The resin composition according to claim 1, which is a product.
(4) The resin composition according to any one of claims 1 to 3, wherein the reinforcing fiber of component (C) is selected from glass fiber, carbon fiber, stainless steel fiber, and aramid fiber.
(5) The resin composition according to any one of claims 1 to 4, wherein the reinforcing fiber of component (C) is a glass fiber surface-treated with an epoxysilane coupling agent.
(6) The resin composition according to any one of claims 1 to 5, further comprising a thermoplastic resin in addition to the reinforcing fiber bundle.
(7) The resin composition according to any one of claims 1 to 6, which is used for an outer plate member of an automobile.

  The molded body obtained from the resin composition of the present invention has high mechanical strength and heat resistance, and has a small dimensional change due to moisture absorption, and is particularly suitable for use as an automobile outer plate member.

<Resin composition>
The resin composition of the present invention includes the reinforcing fiber bundle in addition to the reinforcing fiber bundle in which the reinforcing fibers of the component (C) are bundled in the length direction and integrated by at least the components (A) and (B). And thermoplastic resins, various resin additives, and the like.

<(A) component>
The component (A) can be used in combination with a polyamide resin and other thermoplastic resins in addition to the polyamide resin alone. The combination is preferably a combination of (A-1) polyamide resin and (A-2) styrene resin.

[(A-1) Polyamide resin]
As the polyamide-based resin of component (A-1), polyamide resins formed from diamine and dicarboxylic acid and copolymers thereof, specifically nylon 66, polyhexamethylene sebacamide (nylon 6 · 10) , Polyhexamethylene dodecanamide (nylon 6/12), polydodecamethylene dodecanamide (nylon 1212), polymetaxylylene adipamide (nylon MXD6), polytetramethylene adipamide (nylon 46) and mixtures thereof Nylon 6/66, nylon 66 / 6T (6T: polyhexamethylene terephthalamide) in which 6T component is 50 mol% or less, nylon 66 / 6I (6I: 6I component in which 6I component is 50 mol% or less) Polyhexamethylene isophthalamide), nylon 6T / 6I / 66, nylon 6T / 6I / 61 Copolymers such as polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), poly (2-methylpentamethylene) terephthalamide (nylon M5T), poly (2-methylpentamethylene) isophthal Copolymers such as amide (nylon M5I), nylon 6T / 6I, nylon 6T / M5T, and the like, may also be copolymer nylon such as amorphous nylon. As amorphous nylon, polycondensation of terephthalic acid and trimethylhexamethylenediamine And the like.

  Further, a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, and a copolymer comprising these components, specifically, nylon 6, poly-ω-undecanamide (nylon 11), poly-ω-dodecanamide. (Nylon 12) and other aliphatic polyamide resins and copolymers thereof, and copolymers with polyamides comprising diamines and dicarboxylic acids, specifically nylon 6T / 6, nylon 6T / 11, nylon 6T / 12, Mention may be made of nylon 6T / 6I / 12, nylon 6T / 6I / 610/12, and mixtures thereof.

[(A-2) Styrene resin]
Examples of the styrene resin as the component (A-2) include polymers of styrene and styrene derivatives such as α-substituted and nucleus-substituted styrene. Also included are copolymers composed mainly of these monomers and monomers of vinyl compounds such as acrylonitrile, acrylic acid and methacrylic acid and / or conjugated diene compounds such as butadiene and isoprene. For example, polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-styrene copolymer (AS resin), styrene-methacrylate copolymer (MS resin), styrene-butadiene A copolymer (SBS resin) etc. can be mentioned.

[(B) Polymer having maleimide monomer unit]
Examples of the polymer having a maleimide monomer unit (B) include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, Units derived from maleimide monomers selected from N-toluylmaleimide, N-xylylmaleimide, N-naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, N-orthomethoxyphenylmaleimide; The thing containing the unit derived from the other monomer which can be copolymerized with the said monomer as needed can be mentioned.

  Examples of other monomers that can be copolymerized with maleimide monomers include styrene and maleic anhydride.

  In the polymer of the component (B), the content of the maleimide monomer unit is 40% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more.

[(C) Reinforcing fiber]
(C) Component reinforcing fiber is glass fiber made of E-glass, D-glass; carbon fiber made of polyacrylonitrile, pitch, rayon, etc .; inorganic fiber such as boron fiber, mineral fiber; stainless steel, brass, etc. Metal fibers comprising: ultra-high molecular polyethylene fibers, polyoxymethylene fibers, polyvinyl alcohol fibers, liquid crystalline aromatic polyester fibers, polyethylene naphthalate fibers, polyethylene terephthalate fibers, aramid fibers (poly-p-phenylene terephthalamide, poly-m) -Phenylene isophthalamide, etc.), and cellulose fibers such as cotton and jute. Among these, those selected from glass fiber, carbon fiber, stainless steel fiber, and aramid fiber are preferable.

  The reinforcing fiber preferably has a diameter of 0.1 to 50 μm, more preferably 5 to 30 μm, and still more preferably 6 to 20 μm.

[Content ratio of components (A) to (C)]
60-99 mass% is preferable, as for the content rate in the (A) and (B) component total amount of resin containing the polyamide-type resin of (A) component, 70-98 mass% is more preferable, and 80-97 mass%. Is more preferable.

When component (A-1) and component (A-2) are used together as component (A), the polyamide resin of component (A-1) contains the styrene resin of component (A-2) It is desirable to exceed the amount, but it is not limited to this,
In the total amount of the component (A-1) and the component (A-2), the content ratio of the component (A-1) is preferably 50 to 95% by mass, more preferably 50 to 80% by mass, and 50 to 75% by mass. Is more preferred,
In the total amount of the component (A-1) and the component (A-2), the content ratio of the component (A-2) is preferably 50 to 5% by mass, more preferably 50 to 20% by mass, and 50 to 25% by mass. Is more preferable.

  The content of the (B) component-containing polymer having a maleimide monomer unit in the total amount of the components (A) and (B) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass. -20 mass% is still more preferable.

  The content ratio of the reinforcing fiber (C) component in the composition is preferably 8 to 220 parts by mass and more preferably 20 to 150 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). 25-120 mass parts is still more preferable.

[Method for producing reinforcing fiber bundle]
The reinforcing fiber bundle contained in the composition of the present invention is integrated by at least the components (A) and (B), and is, for example, a pultrusion molding described in paragraph 0008 of Japanese Patent No. 3665660. (Particularly preferably, a pultrusion method using a crosshead die), and a pultrusion method using a crosshead die described in Examples 1 to 7 (FIG. 1) of paragraph No. 0047 of JP-A-2004-14990. Can be manufactured.

  The number of reinforcing fibers in the bundle is preferably 100 to 30,000, more preferably 1000 to 25,000, and still more preferably 2000 to 12,000.

(Resin composition)
The resin composition of the present invention may be composed only of reinforcing fiber bundles, or may be composed of reinforcing fiber bundles, thermoplastic resins, various resin additives, and the like.

  The thermoplastic resin is not particularly limited, and the same polyamide resin as the component (A-1), the same styrene resin as the component (A-2), and those compatible with them are preferable. A thermoplastic resin selected from polyester resins, polyolefin resins, acrylic resins, urethane resins, polycarbonate resins, vinyl resins, polyphenylene oxide resins, and thermoplastic elastomers can be used.

  When the reinforcing fiber bundle and the thermoplastic resin are used in combination, the amount of the thermoplastic resin is not particularly limited, but it is desirable to determine the total amount (resin total amount) with the resin amount contained in the reinforcing fiber bundle. . For example, the reinforcing fiber amount of the component (C) with respect to 100 parts by mass of the total resin is preferably 8 to 220 parts by mass, more preferably 25 to 150 parts by mass, and 30 to 100 parts by mass. Is more preferable.

  As additives for various resins, antioxidants, heat stabilizers, light stabilizers, weather stabilizers, hydrolysis inhibitors, plasticizers, colorants, flame retardants, foaming agents, nucleating agents, talc, silica And powdery inorganic fillers such as pigments, lubricants, spreading agents and the like.

  The resin composition of the present invention is used for automobile outer plate members, for example, bumpers, bonnets, roofs, hoods, front panels, canopies, trunk lids, door panels, pillars, spoilers, rear garnishes, radiator grills, side panels, back doors. It is suitable as an inner panel, a back door outer panel, and a similar outer plate member.

Examples 1-5, Comparative Examples 1-4
A fiber bundle (a bundle of about 4000 fibers) composed of reinforcing fibers of component (C) shown in Table 1 was passed through a crosshead die through heating at 150 ° C. by a preheating device. At that time, the resin shown in Table 1 in a molten state was supplied from a twin-screw extruder, cylinder temperature 290 ° C. to the crosshead die, and the fiber bundle was impregnated with the resin. Then, after shaping with a shaping nozzle at the exit of the crosshead die and shaping with a shaping roll, the pellet was cut into a predetermined length by a pelletizer to obtain a pellet-like (columnar) reinforcing fiber bundle. In the reinforcing fiber bundle (resin composition of the present invention) thus obtained, the fibers were almost parallel to the length direction, and they were integrated with the resin.

In the production of the reinforcing fiber bundle, the composition (reinforcing fiber) productivity was evaluated according to the following criteria. The occurrence of discoloration is due to the burning of the resin component.
◯: When there is no discoloration on the cut surface of the reinforcing fiber bundle obtained after 4 hours from the start of production.
X: When the cut surface of the reinforcing fiber bundle obtained within 1 hour from the start of production has discoloration.

  In Comparative Example 1, only the components shown in Table 1 were mixed with a tumbler blender, melted and kneaded with an extruder set at 250 ° C., extruded, and cut to obtain pellets.

  Next, using each fiber bundle, in accordance with ISO multi-purpose test piece preparation method and 150 square plate preparation method, injection molding machine (J150EII, manufactured by Nippon Steel Works, screw: screw for long fiber) injection molding The body was subjected to the following measurements. The results are shown in Table 1.

ISO multi-purpose specimen creation method
Mold: ISO multipurpose specimen (t = 4)
Molding temperature: 260 ° C Mold temperature: 100 ° C (setting)
150 square plate making method
Mold: 150 square flat plate (t = 3)
Molding temperature: 260 ° C
Mold temperature: 120 ° C (setting)
Tensile test: conforms to ISO527-1 Bend test: conforms to ISO178 Charpy impact strength: conforms to ISO179 / 1eA (edgewise) Deflection temperature under load: conforms to ISO75-1 (1.80 MPa: flatwise) It measured with the test piece of an absolutely dry state.

  Dimensional change rate due to water absorption (dimensional change rate changed from flat plate size in completely dry state to flat plate size in moisture absorption state): Using the flat plate injection molded under the above conditions, obtain the dimensional change rate due to water absorption at the location shown in FIG. It was. Water absorption conditions were performed in a saturated water absorption state in a 23 ° C./50% RH atmosphere.

PA6: UBE nylon 1013B
ABS1: Santac AT-05 (Nippon A & L Co., Ltd.)
ABS2: Santac ST-55 (Nippon A & L Co., Ltd.)
Maleimide polymer: Styrene-N-phenylmaleimide-maleic anhydride copolymer (styrene 47% by mass, N-phenylmaleimide 51% by mass, maleic anhydride 2% by mass, weight average molecular weight 145,000)
Maleic anhydride-modified ABS: maleic anhydride 4% by mass, styrene 43% by mass, acrylonitrile 15% by mass, rubber 38% by mass)
GF1: Glass fiber roving 1 (fiber diameter 17 μm, surface treated with epoxysilane coupling agent)
GF2: Glass fiber roving 2 (fiber diameter 17 μm, surface-treated with an aminosilane coupling agent)
GF3: Glass fiber chopped strand (fiber diameter 13 μm, length 3 mm, surface treated with epoxysilane coupling agent)

Explanatory drawing of the measuring method of the dimensional-change rate by water absorption.

Claims (7)

(A) a resin including a polyamide-based resin, (B) a polymer having a maleimide-based monomer unit, and (C) a reinforcing fiber, wherein the reinforcing fiber of the component (C) is bundled in the length direction, and at least ( A) a resin composition comprising a bundle of reinforcing fibers integrated by components (B),
(B) The resin composition whose content of the maleimide-type monomer unit in the polymer which has a maleimide-type monomer unit of a component is 40 mass% or more.   The resin composition according to claim 1, wherein the resin containing the polyamide resin as the component (A) contains (A-1) a polyamide resin and (A-2) a styrene resin.   The polymer having a maleimide monomer unit (B) is maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N It has a monomer unit selected from -toluylmaleimide, N-xylylmaleimide, N-naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, N-orthomethoxyphenylmaleimide The resin composition according to claim 1.   The resin composition according to any one of claims 1 to 3, wherein the reinforcing fiber of component (C) is selected from glass fiber, carbon fiber, stainless steel fiber, and aramid fiber.   The resin composition according to any one of claims 1 to 4, wherein the reinforcing fiber of component (C) is a glass fiber surface-treated with an epoxysilane coupling agent.   The resin composition according to any one of claims 1 to 5, further comprising a thermoplastic resin in addition to the reinforcing fiber bundle.   The resin composition according to any one of claims 1 to 6, which is used for an outer plate member of an automobile.

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