JP2009013330A - Filament-reinforced composite resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a filament-reinforced composite resin composition having good dispersibility of an organic filament, providing excellent appearance, and having excellent mechanical strength such as rigidity and impact resistance, and to provide a molded article formed therefrom. <P>SOLUTION: The filament-reinforced composite resin composition comprises an olefinic resin, the organic filament and talc regulated so that the proportions of the organic filament and the talc to 100 pts.wt. of the olefinic resin may be 10-200 pts.wt. and 10-200 pts.wt. respectively. The molded article is obtained therefrom. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a long fiber reinforced composite resin composition and a molded article. Specifically, the long fiber reinforced composite resin composition has excellent dispersion of long fibers, excellent appearance, and excellent mechanical strength such as rigidity and impact resistance. And a molded article obtained therefrom.

  Today, resin products are required to have high rigidity in various fields. For example, in applications such as housings for home appliances, building materials, and structural materials for automobiles, higher rigidity is imparted to the resin while balancing the physical properties. Many attempts have been made (Patent Documents 1 to 6). As one of them, a method is known in which a rubber component and talc are blended in a resin, and the former provides impact resistance and the latter provides rigidity. According to this method, since the raw material is relatively inexpensive, there are advantages that the manufactured product is inexpensive, can be ductile fractured under normal temperature use conditions, and can obtain a smooth molded product appearance.

  However, usually, brittle fracture occurs under low temperature usage conditions below zero, it is difficult to balance physical properties such as rigidity due to a large composition ratio of rubber components, and rubber components and compatibilizing components as time-dependent changes There are problems such as deterioration or separation.

  Therefore, many attempts have been made to add a larger amount of the rubber component in order to improve the ductile fracture under low temperature use conditions, but the rubber component is more expensive than the matrix resin and the price of the manufactured product is also high. Another problem is caused, such as being expensive, and adding a large amount of a filler component to compensate for the balance of physical properties such as rigidity, and thereby the fluidity at the time of molding is remarkably lowered.

Japanese Patent Laid-Open No. 51-136735 JP 58-1111846 A Japanese Patent Laid-Open No. 58-129037 Japanese Patent Laid-Open No. 61-187859 Japanese Patent Publication No. 60-3420 JP-A-3-250040

  The present invention has been made in view of the above circumstances, and its purpose is to provide a long fiber reinforced composite resin composition having good long fiber dispersion, excellent appearance, and excellent mechanical strength such as rigidity and impact resistance. It is in providing a molded article obtained from this.

  That is, the first gist of the present invention comprises an olefin resin, an organic long fiber, and talc, and the organic fiber has a ratio of 10 to 200 parts by weight and the ratio of talc to 100 parts by weight of the olefin resin. The present invention resides in a long fiber reinforced composite resin composition characterized by being 10 to 200 parts by weight, and the second gist of the present invention is characterized by forming the above long fiber reinforced composite resin composition. It exists in long fiber reinforced composite resin molded products.

  The resin composition of the present invention containing an olefin resin, organic long fibers, and talc weakens the interfacial adhesion between the organic long fibers and the matrix resin because the organic long fibers are dispersed and reinforced in a network. By doing so, it is possible to obtain mechanical strength such as impact resistance that cannot be achieved by a conventionally known long-fiber composite resin assembly.

  Moreover, the molded product formed by shape | molding the resin composition of this invention can provide rigidity, without reducing the impact resistance obtained by the composite of organic long fiber by containing a talc. As a result, it becomes possible to easily design without impairing the balance of physical properties such as impact resistance and rigidity required for each of various product applications, and as a result, the range of applications in which the long fiber composite resin composition can be applied. It can be widely spread.

  The olefin resin used in the present invention is not particularly limited, and various olefin resins can be used. For example, ethylene-based resins such as ethylene homopolymers, copolymers of ethylene as a main component and one or more of other α-olefins such as propylene and 1-butene; A propylene-based resin such as a copolymer, a copolymer of propylene as a main component and one or more of other α-olefins such as ethylene and 1-butene; 1-butene homopolymer, 1- Examples include butene-based resins such as copolymers of butene as a main component and one or more of other α-olefins such as ethylene and propylene. These olefin-based resins may be homopolymers or copolymers, may be random copolymers, or may be block copolymers. In addition, said "main component" refers to that whose content of the said component in an olefin resin is 50 weight% or more normally, Preferably it is 60 weight% or more.

  Among these, a propylene resin is preferable from the viewpoint of excellent heat resistance. Specific examples thereof include a propylene homopolymer, a propylene-ethylene random copolymer resin mainly composed of propylene, and a propylene-ethylene block copolymer. Examples include coalesced resins. Two or more olefin resins may be used in combination. The polymerization mode of the olefin resin is not particularly limited, but a gas phase method or a solution method is preferable.

  The melt flow rate of the olefin resin (based on JIS K7210, measured at a temperature of 230 ° C. and a load of 21.18 N) is usually 0.05 to 200 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes. is there. When the melt flow rate is less than 0.05 g / 10 minutes, the moldability tends to be deteriorated, and the surface appearance of the resulting molded product tends to be poor, and when it exceeds 200 g / 10 minutes, Mechanical strength and dispersion of organic long fibers tend to be poor.

  The organic long fiber used in the present invention can have a polar resin attached to its surface. Here, the polar resin refers to a resin having a higher polarity than a non-polar olefin resin. Examples of such polar resins include unsaturated polyesters, vinyl ester resins, epoxy resins (including epoxy compounds), phenol (resole type) resins, urea / melamine resins, polyimides, urethane resins, copolymers thereof, and modified And thermosetting resins such as body. Moreover, thermoplastic resins, such as saturated polyester, polyamide, acrylic resin, these copolymers, and a modified body, are also mentioned. As the polar resin, a thermosetting resin epoxy resin or urethane resin is particularly preferable from the viewpoint of handling / workability and mechanical properties, and an epoxy resin is particularly preferable. Specific examples of the epoxy resin include the following compounds.

  That is, in the diglycidyl ether compound, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether , Polytetramethylene glycol diglycidyl ether, polyalkylene glycol diglycidyl ether, and the like. In addition, in the polyglycidyl ether compound, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol poly Examples thereof include glycidyl ethers and polyglycidyl ethers of aliphatic polyhydric alcohols. Preferably, it is an aliphatic polyglycidyl ether compound having a highly reactive glycidyl group. More preferred are polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, and alkanediol diglycidyl ethers.

  By the way, in the present invention, as the olefin resin, for example, an acid-modified olefin resin modified with maleic anhydride is preferably excluded. Moreover, it is preferable to remove the organic long fiber described later from the surface treated with the acid-modified olefin resin. Furthermore, it is preferable to exclude the acid-modified olefin resin as the polar resin to be attached to the organic long fiber. By satisfying such conditions, the interfacial strength between the olefin resin as the matrix resin and the organic long fibers can be further reduced, and the tensile elongation at break and impact resistance can be further enhanced.

  Examples of the acid-modified olefin resin include (A) an olefin homopolymer or a copolymer of two or more olefins, for example, a polyolefin obtained by graft polymerization of an unsaturated carboxylic acid or a derivative thereof, and (B) a polyolefin. A copolymer of one or more olefins and one or two or more unsaturated carboxylic acids or derivatives thereof, which is a polymerization raw material monomer of (C), and (C) those obtained in (B) above. Examples include those obtained by graft polymerization of saturated carboxylic acids or derivatives thereof.

  Examples of the organic long fibers include polyester fibers, polyamide fibers, polyurethane fibers, polyacrylonitrile fibers, kenaf, and cellulose fibers. These organic long fibers may be used in combination of two or more. Among these, polyester fiber or polyamide fiber is preferable from the viewpoint of handling / workability and mechanical properties, and in particular, polyethylene terephthalate (PET) fiber (melting point 260 ° C., glass transition temperature 67 ° C.), polyethylene naphthalate ( PEN) fibers (melting point 272 ° C., glass transition temperature 113 ° C.) are preferred. Since the polyester fiber is well dispersed in the injection molded product and has high physical properties as a fiber, an injection molded product having good mechanical properties can be obtained.

  By the way, when the resin composition of the present invention is molded by injection molding, it is preferable to use an organic long fiber that does not melt during injection molding because it is molded at a temperature equal to or higher than the melting point of the olefin resin. That is, the melting point of the olefin resin is usually selected from the range of 70 to 170 ° C., and the molding temperature (the outlet temperature of the molding machine) is usually selected from the range of 150 to 210 ° C. The melting point of the organic long fiber is preferably higher than the molding temperature by 10 ° C. or more, preferably 20 ° C. or more. Therefore, the melting point of the organic long fiber is usually selected from a range of 200 ° C. or higher.

  Moreover, if the fiber diameter of the organic long fiber is too large, the Izod impact strength of the molded product is lowered. On the other hand, there is no problem even if the fiber diameter is too thin, and it seems that nano-sized fibers can be used, and good results are obtained depending on the application of the molded product. Thus, since the fiber diameter covers a wide range, the number of organic long fibers used cannot be uniquely defined. However, considering the cross-sectional area of the bundle of fibers, the number of the organic long fibers is preferably about 5 to 60% of the cross-sectional area in the direction substantially perpendicular to the pellet fibers. The single yarn fineness of the organic long fiber is usually 1 to 20 dtex, preferably 2 to 15 dtex. The total fineness of the organic long fibers is usually 150 to 3,000 dtex, preferably 250 to 2000 dtex. Furthermore, the number of filaments of the organic long fiber is usually 10 to 1,000 filaments, preferably 50 to 500 filaments.

  As a method for attaching the polar resin to the organic long fiber, (A) a method of providing a polar compound that is not compatible with or reacts with the olefin-based resin before being wound into a cheese shape in the step of producing the organic long fiber. (B) After winding up the organic long fiber, a method of impregnating the organic long fiber with a polar compound that does not dissolve or react with the olefin-based resin and heat-treats it may be mentioned.

  The adhesion amount of the polar resin to the organic long fiber is usually 0.01 to 5% by weight, preferably 0.03 to 3.5% by weight. When the adhesion amount of the polar resin is less than 0.01% by weight, it is difficult to obtain the effect of weakening the interfacial adhesion between the organic long fibers and the matrix resin, and the fibers are entangled with each other during molding. As a result, appearance quality deteriorates. On the other hand, when the adhesion amount of the polar resin exceeds 5% by weight, the organic long fiber becomes too hard, so that the processability is lowered and it is difficult to combine with the organic long fiber.

  In the resin composition of the present invention, the length of the organic long fiber in the pellet corresponds to the length of the pellet. The average fiber length of the organic long fibers contained in the pellet made of olefin resin is usually 4 to 50 mm, preferably 4 to 20 mm, and more preferably 4 to 10 mm. When the average fiber length of the organic long fibers is less than 4 mm, the effect of improving the impact resistance is not sufficiently obtained. On the other hand, when the average fiber length exceeds 50 mm, molding becomes difficult.

  The average particle diameter of talc used in the present invention is usually 15 μm or less, preferably 12 μm or less, more preferably 10 μm or less, and its lower limit is usually 0.5 μm. When the average particle size exceeds 15 μm, the impact resistance of the product tends to decrease. When the average particle size is 0.5 μm, talc itself is expensive, and the fluidity of the composition is significantly reduced. The average particle size referred to here is a particle size value measured by a liquid phase precipitation type light transmission method and having a cumulative amount of 50% by weight read from a cumulative particle size distribution curve. The talc having an average particle diameter as described above is generally produced by dry classification after dry pulverization.

The specific surface area of talc is usually 1.5 m ² / g or more, preferably 2.0 m ² / g or more, more preferably 3.0 m ² / g or more, and the upper limit is usually 20 m ² / g. When the specific surface area is less than 1.5 m ² / g, the impact resistance of the product tends to be insufficient. On the other hand, when the specific surface area exceeds 20 m ² / g, talc itself is expensive, and the fluidity of the composition tends to decrease. The specific surface area here is a value measured by an air permeation method.

  The resin composition of the present invention contains an olefin resin, organic long fibers, and talc. And as a ratio with respect to 100 weight part of olefin resin, the ratio of an organic long fiber is 10-200 weight part, Preferably it is 20-180 weight part, The ratio of talc is 10-200 weight part, Preferably it is 20- 180 parts by weight. When the ratio of the organic long fibers is less than the above range, the reinforcing effect tends to be insufficient, and when it is more than the above range, molding tends to be difficult and the appearance of the molded product tends to deteriorate. On the other hand, when the ratio of talc is less than the above range, the desired rigidity tends not to be imparted, and when it is more than the above range, the fluidity is remarkably lowered and the molding becomes difficult and the appearance of the molded product tends to be poor In addition, the specific gravity tends to increase.

  The resin composition (pellet) of the present invention is obtained by a method (pulling molding method) in which continuous organic long fibers are impregnated with a molten resin while being drawn through a crosshead die. For example, if necessary, a resin additive is added to the olefin resin, and the olefin resin is supplied from the extruder to the crosshead die in a molten state while being drawn through the crosshead die. It is obtained by impregnating and coating an olefin-based resin, heating the melt-impregnated material, cooling, and cutting it at right angles to the drawing direction. According to this method, a resin composition (pellet) in which organic long fibers are arranged in parallel with the same length in the length direction of the obtained pellet can be obtained without causing damage to the organic long fibers.

  The pultrusion method is basically a method of impregnating a resin while drawing a continuous reinforcing fiber bundle. In addition to the method of supplying and impregnating the resin to the crosshead from an extruder or the like while passing the fiber bundle through the crosshead, as an aspect thereof, the fiber is contained in an impregnation bath containing a resin emulsion, suspension or solution. There are known methods of impregnating through bundles, methods of spraying resin powder onto fiber bundles, or attaching resin powder to fibers through fiber bundles in a tank containing the powder, and then melting and impregnating the resin. Therefore, any aspect can be used in the present invention. Particularly preferred is the crosshead method. Further, the resin impregnation operation in these pultrusion methods is generally performed in one stage, but it may be divided into two or more stages, and may be performed by different impregnation methods.

  In addition, it is also possible to supplementarily use a small amount of one or more other thermoplastic resins and rubbers as needed in combination with the olefin resin. In addition, in order to impart desired properties according to the purpose, known substances generally added to thermoplastic resins, for example, stabilizers such as antioxidants, heat stabilizers, UV absorbers, antistatic agents, flame retardants, etc. In addition, flame retardant aids, colorants (dyes and pigments), lubricants, plasticizers, crystallization accelerators, crystal nucleating agents, and the like can be further blended.

  The above impregnation operation is usually performed at 150 to 300 ° C, preferably 170 to 260 ° C, more preferably 190 to 230 ° C. The impregnated material is heated at the above temperature. When the heating temperature is too low, the impregnation is insufficient, and when it is too high, the olefin resin is decomposed.

  The melt impregnated product is extruded to a strand after the heating reaction, cooled to a temperature capable of being cut, and cut by a cutter into pellets. Examples of the shape of the pellet include a columnar shape, a prismatic shape, a plate shape, and a die shape. In the pellet thus obtained, the organic long fibers have substantially the same length, and the direction of each fiber is aligned in the extruded direction (that is, the length direction of the pellet). In addition, the above pellets may be those using two or more types of organic long fibers having different types and concentrations, and those using a mixture of olefinic resins. In the present invention, “pellet” is used in a broad sense including strand shape, sheet shape, flat plate shape and the like in addition to the above-mentioned narrowly defined pellets.

  The size of the pellet made of the resin composition of the present invention is the length of the organic long fiber, and is usually 4 to 50 mm, preferably 4 to 20 mm, and more preferably 4 to 10 mm. When the length of the organic long fiber in the pellet is too short, the desired mechanical strength as a composite material cannot be obtained. On the other hand, when the length is too long, it becomes difficult to supply the pellet to an injection molding machine or the like.

  The pellets obtained as described above are used alone or diluted with another thermoplastic resin, preferably the same type of resin as the olefin resin, and used as a raw material for injection molding or the like. The kind and ratio of the resin to be diluted are determined by the physical property values of the desired molded product. A molded product obtained by injection molding using the resin composition (pellet) of the present invention has little breakage during the injection molding of organic long fibers, and the organic long fibers are uniformly dispersed. The molded product obtained from the resin composition of the present invention has excellent appearance and mechanical strength such as rigidity and impact resistance, and is extremely useful for vehicles, construction / civil engineering, mechanical parts, electronic parts, etc. It is.

  In the present invention, as described above, in addition to the production of a resin composition (pellet) containing an olefin resin, organic long fibers, and talc, the molded product is formed into a molded product. After manufacturing the resin composition (pellet A) containing a fiber and the resin composition (pellet B) containing an olefin resin and talc, the pellets A and B may be mixed and molded. That is, it is sufficient that the resin composition of the present invention is completed when it is formed into a molded product. Moreover, since the resin composition (pellet) of the present invention has no fear of cutting organic long fibers in addition to the above-described pultrusion molding method, a method of forming a composition by kneading necessary components can also be employed. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by a following example, unless the summary is exceeded. The materials and evaluation methods used in the following examples are as shown below.

  Ingredient (a): Polypropylene ["Novatec BC10AHA" manufactured by Nippon Polypro Co., Ltd., melt flow rate 100 g / 10 min (230 ° C., 21.2 N load)]

  Component (b): PET long fiber (“P903AL BHT1670T250” manufactured by Teijin Fibers Ltd., average fiber diameter: 24 μm, epoxy resin adhesion amount = 0.2% by weight) with a polyglycidyl ether epoxy resin attached as an epoxy resin

Component (c): Talc [“K-1” manufactured by Nippon Talc Co., Ltd., average particle size of 7.4 μm, specific surface area of 7.0 m ² / g]

  Long glass fiber reinforced polypropylene [Nippon Polypro Co., Ltd. "Funkster LR23C", glass content 30% by weight] (used as a comparative material)

(1) Maximum bending stress and flexural modulus:
A bar having a thickness of 4 mm, a width of 10 mm, and a length of 80 mm obtained by molding was measured in accordance with JIS-K7171 under the following conditions. The test speed was 2 mm / min, and the distance between fulcrums was 64 mm.

(2) Izod impact strength:
A bar having a thickness of 4 mm, a width of 12.7 mm, and a length of 63.5 mm obtained by molding was measured according to JIS-K7110 under the following conditions. The rotation speed of notch processing was 400 rpm, the feed speed of notch processing was 120 mm / min, the hammer capacity was 5.5 J, and the measurement temperatures were 23 ° C. and −40 ° C.

(3) Tensile breaking strength and tensile breaking elongation:
A dumbbell bar having a thickness of 3.2 mm and a width of 10 mm obtained by molding was measured at a test speed of 50 mm / min in accordance with JIS-K7161.

(4) Appearance:
The surface of a flat plate of 100 mm × 100 mm × thickness 3 mm obtained by molding was visually observed and evaluated according to the following criteria.

○: The fiber dispersion is good, there is almost no bundle of unopened fibers, and the flat plate surface is smooth.
(Triangle | delta): The bundle | flux of the fiber which is not opened is seen for a while, or a flat surface has a little unevenness.
X: Many bundles of unopened fibers are seen, and the flat plate surface is rough.

Examples 1-4 and Comparative Examples 1-6:
Polypropylene, PET long fiber components and talc were used in the composition shown in Table 1, and pultrusion molding was performed to produce long fiber reinforced polyolefin resin pellets. As a manufacturing apparatus, a twin screw extruder having a crosshead die (“TEX30” manufactured by Nippon Steel Works Co., Ltd., L / D = 42, cylinder diameter 30 mm, cylinder temperature: 190 to 220 ° C., cross die head temperature: 220 ° C. )It was used. The pellet length was adjusted to 8 mm. Next, the obtained long fiber-containing polyolefin resin pellets were subjected to an injection molding machine, and flat plates and bars were molded at a cylinder temperature of 210 ° C., a mold temperature of 70 ° C., a back pressure of 10 kg / cm ² , and a screw rotation speed of 50 rpm. did. The evaluation results are shown in Tables 1 and 2.

  From Tables 1 and 2, it can be seen that according to the present invention, a molded product having excellent appearance and excellent mechanical strength such as rigidity and impact resistance can be obtained.

Claims (10)

Olefin resin, the organic filaments, an antifoaming agent, talc, and characterized in that for 100 parts by weight of olefin resin, the proportion of the organic filaments 10 to 200 parts by weight, the proportion of talc is 10 to 200 parts by weight A long fiber reinforced composite resin composition.   The long fiber reinforced composite resin composition according to claim 1, wherein the olefin resin is a propylene resin.   3. The long fiber reinforced composite resin composition according to claim 1 or 2, wherein the organic long fiber has a polar resin attached to the surface.   The long fiber reinforced composite resin composition according to claim 3, wherein the polar resin is an epoxy resin.   The long fiber reinforced composite resin composition according to claim 3 or 4, wherein the adhesion amount of the polar resin is 0.01 to 5% by weight with respect to the organic long fiber.   The long-fiber reinforced composite resin composition according to any one of claims 1 to 5, wherein the organic long fiber has a melting point of 200 ° C or higher.   The long organic fiber reinforced composite resin composition according to any one of claims 1 to 6, wherein the organic long fiber is a polyester fiber or a polyamide fiber. The long fiber reinforced composite resin composition according to any one of claims 1 to 7, wherein the talc used has an average particle size of 15 µm or less and a specific surface area of 1.5 m ² / g or more.   A long fiber reinforced composite resin molded product, comprising the long fiber reinforced composite resin composition according to any one of claims 1 to 8.   The long fiber reinforced composite resin molded article according to claim 9, wherein the molding method is an injection molding method.