JP5211658B2 - Composition for automotive interior parts - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a composition for automobile interior parts, and more particularly to a composition for automobile interior parts such as instrument panels, console boxes, pillars, trims, and the like made of a propylene-based resin composition reinforced with organic long fibers.

  2. Description of the Related Art Conventionally, as a structural material for automobile instrument panels and safety-compliant interior materials, a rubber component and talc are blended in a propylene resin, and the former provides impact resistance and the latter imparts rigidity. According to this method, since the raw material is relatively inexpensive, there are advantages such as that the manufactured product is also inexpensive, can be ductile fractured under normal temperature use conditions, and can obtain a smooth molded product appearance. 1-6).

  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. Addition of a large amount of talc, etc. to compensate for the balance of physical properties such as heat resistance and rigidity, resulting in significantly reduced fluidity during molding, increased specific gravity, increased product thickness and ribs Problems such as the need for reinforcement or the need for reinforcement from the back with metal parts make the design very complicated.

  On the other hand, in order to particularly improve the heat-resistant rigidity, it has also been proposed to blend propyl, mica, glass flakes, glass fibers and the like with a propylene resin (Patent Document 7). However, in this case, since the rigid glass fibers are oriented at the time of molding, anisotropy occurs in the shrinkage of the resin, and the molded product is warped or deformed.

JP 51-136735 A JP 58-1111846 JP-A-58-129037 JP 61-187859 A Special Exchange Sho 60-3420 JP-A-3-250040 JP-A-62-36428

  The present invention has been made in view of the above circumstances, and its purpose is good dispersion of fibers, excellent appearance, excellent mechanical strength such as rigidity and impact resistance, and further required for automobile interior materials. An object of the present invention is to provide a composition for automobile interior parts that has good scratch resistance, little warping deformation, and high fluidity during injection molding.

That is, the gist of the present invention comprises 10 to 200 parts by weight of organic long fibers with respect to 100 parts by weight of propylene resin (however, talc is added at a ratio of 10 to 200 parts by weight with respect to 100 parts by weight of propylene resin. except when containing), a fiber-reinforced composite resin composition obtained by the pultrusion method, the adhesion amount of the polar resin is an organic continuous fiber organic filaments are made by attaching the polar resin to the surface It exists in the composition for motor vehicle interior components characterized by being 0.01-3.5 weight% with respect to an organic long fiber .

  The composition for automobile interior parts of the present invention containing organic long fibers in a propylene-based resin (hereinafter abbreviated as “resin composition”) has long fibers dispersed and reinforced, and By weakening the interfacial adhesion between the fiber and the matrix resin, it is possible to easily balance mechanical properties such as impact resistance and heat-resistant rigidity that cannot be achieved by a conventionally known resin composition.

  Furthermore, since the resin composition of the present invention does not need to contain a large amount of rubber component, talc, glass component, etc. in order to obtain heat-resistant rigidity, impact resistance, and mechanical strength with desired performance, it is an automobile interior material. Therefore, it is possible to satisfy the performance required for automobile interior materials, such as good scratch resistance, low warpage deformation, and high fluidity during injection molding. Moreover, according to the resin composition of the present invention, when the impact is applied to the molded product and the fracture occurs, the fracture point does not become brittle fracture and does not become a sharp edge. There is no secondary damage such as cuts.

  The propylene-based resin used in the present invention is not particularly limited. For example, a propylene homopolymer, one or more of other α-olefins such as ethylene and 1-butene having propylene as a main component, and And the like. The copolymer may be a random copolymer or a block copolymer. In addition, said "main component" refers to what is contained in a propylene-type resin 50weight% or more, Preferably it is 60weight% or more.

  As a polymerization mode of the propylene-based resin, any polymerization mode may be adopted as long as a resinous material can be obtained, but a gas phase method or a solution method is particularly preferable.

  The melt flow rate of propylene 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.

  In the resin composition of the present invention, two or more types of propylene-based resins may be used in combination, and further, conventionally known components such as thermoplastic resins, rubbers, fillers, additives and the like within the range not impairing the effects of the present invention. Can be blended.

  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 propylene 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. Polyglycidyl ether compounds include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, sorbitol polyglycidyl ethers, arabitol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, 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 propylene-based resin, for example, an acid-modified propylene-based resin 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 interface strength between the propylene-based resin as the matrix resin and the organic long fiber can be further reduced, and the tensile breaking elongation 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 organic long fibers that do not melt during the injection molding because they are molded at a temperature higher than the melting point of the propylene resin. That is, the melting point of the propylene-based 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 usually 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 of attaching a polar resin to an organic long fiber, (A) a method of providing a polar compound that is not compatible with or reacts with a propylene-based resin before being wound into a cheese shape in the step of producing the organic long fiber (B) A method of once winding an organic long fiber and then impregnating the organic long fiber with a polar compound that does not dissolve or react with the propylene-based resin and heat-treats the organic long fiber.

  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 propylene-based 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 resin 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 resin 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 a propylene-based resin and organic long fibers as essential components. And as a ratio with respect to 100 weight part of propylene-type resin, the ratio of an organic long fiber is 10-200 weight part, Preferably it is 20-180 weight part. 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. When the resin composition of this invention contains a talc, the ratio is 10-200 weight part as a ratio with respect to 100 weight part of propylene-type resin, Preferably it is 20-180 weight part. 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 molding becomes difficult, and the appearance of the molded product tends to deteriorate. Also, 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 propylene resin and the propylene 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 with a propylene-based resin, heating the melt-impregnated product, 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 possible to supplementarily use a small amount of one or more other thermoplastic resins and rubbers as needed in combination with the propylene 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, impregnation is insufficient, and when it is too high, the propylene-based 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). Further, 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 propylene 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 a resin of the same type as the propylene 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.

  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.

<Materials used>

(1) Polypropylene:
“NOVATEC PP BC10AHA” manufactured by Nippon Polypro Co., Ltd. (melt flow rate 100 g / 10 min (230 ° C., 21.2 N load)

(2) PET long fiber 1 (adhesive product with polyglycidyl ether epoxy resin):
“P903AL BHT1670T250” manufactured by Teijin Fibers Limited (average fiber diameter: 24 μm, epoxy resin adhesion amount: 0.2% by weight)

(3) PET long fiber 2:
“P900M BHT1670T250” manufactured by Teijin Fibers Limited (average fiber diameter: 24 μm)

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

(5) Comparative material 1 (long glass fiber reinforced polypropylene):
“Funkster LR23C” manufactured by Nippon Polypro Co., Ltd. (glass content 30% by weight)

(6) Comparative material 2 (PP / rubber / talc composite material for automobile interior materials):
MFR 25 g / 10 min ethylene propylene block copolymer containing 40 g / 10 min PP homopolymer: 65 wt%, ethylene propylene copolymer rubber with PP content 22 wt% and melting temperature 40 ° C .: 5 wt%, 1 butene as comonomer An ethylene α-olefin copolymer having a melting temperature of 80 ° C .: 10 wt%, a specific surface area of 4.0 m ² / g and an average particle size of 2.8 μm talc: 20 wt% It was prepared by melt-kneading at "TEX30") at 210 ° C.

<Evaluation method>

(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 the dispersibility and fiber opening property were evaluated according to the following criteria.

○: Good fiber dispersion, almost no bundle of unopened fibers, and good texture transfer.
(Triangle | delta): The bundle | flux of the fiber which is not opened is seen for a while, and a wrinkle transfer is inadequate or uneven.
X: Many bundles of unopened fibers are seen, and the flat plate surface is rough.

(5) Fluidity:
The surface of a 100 mm × 100 mm × 3 mm thick flat plate obtained by molding was visually observed, and jetting, flow marks, and filling unevenness were evaluated according to the following criteria.
○: Jetting and flow marks are not observed, and are filled uniformly.
(Triangle | delta): Jetting or a flow mark is seen slightly and filling irregularity may appear.
X: Molding is difficult and often cannot be fully filled.

(6) Scratch resistance:
100 mm x 100 mm x 3 mm thick flat plate obtained by molding, using a fully automatic scratch testing machine (manufactured in-house), and applying a marking needle vertically. A scratch test was conducted by moving the test piece under load. The conditions were a pitch of 0.75 mm, a number of 30, a stroke of 50 mm, a speed of 500 mm / min, only one direction of movement, a load of 200 g, and no tip-shaped tungsten steel R. The results were visually evaluated according to the following criteria. The difference in brightness before and after damage, L, is also noted.

◯: No scratches at the scratched edge and no sliding of filler components, and scratches are not noticeable visually.
(Triangle | delta): The crack of a crack edge part and sliding of a filler component are seen slightly, and a scar looks white.
X: Scattering of the scratched edge and sliding of the filler component is remarkable, and the scar remains clearly.

(7) Warpage deformation:
The gate side end of a 100 mm × 350 mm × 3 mm thick flat plate obtained by molding was fixed to the base, and the height of the end side end farthest from the base was measured.

Examples 1 to 12 , Reference Example 1 and Comparative Examples 1 to 2:
Polypropylene, PET long fibers and talc were used in the formulation shown in Table 1, and pultrusion molding was performed to produce long fiber reinforced polypropylene 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 polypropylene 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. The evaluation results are shown in Tables 1 to 3.

  From Tables 1 and 2, the composition of the present invention has good fiber dispersion, excellent appearance, excellent mechanical strength such as rigidity and impact resistance, and scratch resistance required for automotive interior materials. Good, less warping deformation and high fluidity during injection molding. Therefore, the molded product obtained from the resin composition of the present invention is extremely useful for automobile interior parts.

Claims (5)

It is composed of 10 to 200 parts by weight of organic long fibers per 100 parts by weight of propylene resin (except for the case of containing talc at a ratio of 10 to 200 parts by weight with respect to 100 parts by weight of propylene resin) . A long fiber reinforced composite resin composition obtained by a molding method, wherein the organic long fiber is an organic long fiber formed by attaching a polar resin to the surface, and the amount of the polar resin attached to the organic long fiber is 0.01. A composition for automobile interior parts, characterized by being -3.5% by weight. The composition for automotive interior parts according to claim 1, wherein the propylene resin is a propylene resin not acid-modified. The composition for automotive interior parts according to claim 1 or 2 , wherein the polar resin is an epoxy resin. The composition for automobile interior parts according to any one of claims 1 to 3 , wherein the organic long fiber has a melting point of 200 ° C or higher. The composition for automobile interior parts according to any one of claims 1 to 4 , wherein the organic long fibers are polyester fibers or polyamide fibers.