CN101018656A - Exterior molding body comprising a long fiber reinforced thermoplastic resin - Google Patents

Abstract

The present invention provides a long-fiber-reinforced automobile exterior mounting molding, which has excellent mechanical strength such as flexural modulus and flexural strength, chemical resistance, and heat resistance, is lightweight, has a high degree of freedom in product design, and can reduce The anisotropy of the linear expansion coefficient of the molded product due to the fiber orientation during filling. This long-fiber-reinforced thermoplastic resin exterior mounting molded body has a content rate of reinforcing fibers dispersed in the molded body of 30% by weight to 90% by weight, a weight average fiber length of 1.5 mm to 10 mm, and a maximum projected area of the molded body. 20000mm2 ^or more, the channel length of the narrow channel with a cross-sectional area of ^100mm2 or less during molding is 150mm or less, and the maximum linear expansion coefficient of the molded body part with a thickness of 2mm or more is 5×10 ^-5 K ^-1 or less, the maximum The ratio of the coefficient of linear expansion/the minimum coefficient of linear expansion is 1.8 or less.

Description

Long fiber reinforced thermoplastic resin exterior mounting molded body

technical field

The present invention relates to an injection-molded article of a long-fiber-reinforced thermoplastic resin excellent in mechanical properties such as impact resistance and fluidity, and relates to reduction of the anisotropy of the molded article due to fiber orientation during injection molding Long-fiber reinforced thermoplastic resin exterior mounting moldings, especially automotive exterior mounting moldings.

Background technique

At present, in terms of exterior parts for automobiles, a structure in which a metal exterior panel (exterior panel) is attached to a metallic structural part has been adopted. However, in recent years, there has been a tendency to reduce the weight of various automobile parts for the purpose of increasing fuel consumption and driving performance of automobiles, and resins have also been used in exterior panels and structures supporting them.

For example, in Patent Document 1, in order to further reduce the weight of automotive panels, an automotive panel made of FRP using a fabric base material made of continuous fibers as a reinforcing fiber is disclosed. In terms of efficiency, it cannot be satisfied.

Also, Patent Document 2 proposes a rear door whose outer panel is made of polyphenylene ether/polyamide alloy and whose inner panel is made of long-fiber-reinforced polyamide/polyolefin from the viewpoint of weight reduction and modularization. Alloy, however, due to the water absorption dimensional change caused by PA, there are problems of inconvenient switching and poor streamlined appearance. In order to solve the problem of water absorption dimensional change, the use of polycarbonate/polybutylene terephthalate alloy, etc. has also been proposed. However, since the inner panel is made of long fiber reinforced polypropylene, a bonded structure is required. In addition, the inner panel is made of The anisotropy of linear expansion caused by fiber orientation affects the outer plate, but there is no relevant description of the magnitude or anisotropy of linear expansion.

Patent Document 3 discloses, as an exterior part for vehicles, a carbon fiber-reinforced polyamide whose average value of the linear expansion coefficient in the flow direction during injection molding and the linear expansion coefficient in a direction perpendicular to the flow direction is 6× 10 ^-5 K ^-1 , however, there is no record about its anisotropy. When the anisotropy is large, the deformation state caused by the temperature change is different depending on the direction, which affects the appearance quality, and there may be fractures or cracks caused by stress concentration, so it is not ideal.

In addition, Patent Document 4 discloses that in a thermoplastic resin molded article obtained by injection molding a fiber-reinforced thermoplastic resin material containing 3 to 70% by weight of a fibrous reinforcing material, (volume)/(surface area)<2mm, The linear expansion coefficient of the molten resin containing fiber reinforcement in the flow direction (MD) and the direction (TD) at right angles to the flow direction at 23°C to 100°C is 0.6<(linear expansion coefficient in TD direction)/(MD direction The coefficient of linear expansion) <2.5. However, as an automotive exterior structure, it is necessary to reduce the anisotropy, and if the absolute value is still large, it may cause switchability, influence on peripheral parts, and poor coating or coating crack due to linear expansion. The reduction in appearance quality caused by cracking. Furthermore, when a narrow channel with a small cross-sectional area exists in the molded body, the orientation of the reinforcing fibers becomes stronger and the anisotropy becomes larger, which may adversely affect the entire molded body due to the length of the narrow channel. There is no description regarding the shape of the molded body.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2002-127944

Patent Document 2: Japanese Unexamined Patent Application Publication No. 2003-118379

Patent Document 3: Japanese Patent Application Laid-Open No. 2002-226703

Patent Document 4: Japanese Patent Application Laid-Open No. 9-296053

Contents of the invention

The problem to be solved by the present invention is to provide a long-fiber-reinforced automotive exterior molded body, which has excellent mechanical strength such as flexural modulus and flexural strength, excellent chemical resistance, heat resistance, and light weight. The degree of freedom in product design is high, and the anisotropy of the linear expansion coefficient of the molded body caused by the fiber orientation during filling is reduced.

In order to solve the above-mentioned problems, the inventors have repeatedly studied intensively, and as a result, they have found that by limiting the resin flow path in the mold cavity during molding, the maximum linear expansion coefficient and linear expansion coefficient of long-fiber-reinforced automotive exterior mounting moldings due to fiber orientation can be reduced. The anisotropy of the coefficient and the maximum moisture absorption dimensional change rate are all reduced, and the present invention has been completed.

That is, the gist of the present invention is a long-fiber-reinforced thermoplastic resin exterior mounting molded body in which the content of reinforcing fibers dispersed in the molded body is 30% by weight to 90% by weight, and the weight average fiber length is 1.5 mm to 1.5 mm. 10mm, the maximum projected area of the molded body is more than ^20000mm2 , the length of the narrow flow channel with a cross-sectional area of less than ^100mm2 during molding is less than ^150mm2 , and the maximum linear expansion coefficient of the molded body part with a thickness of more than 2mm is 5×10 ^-5 K ^-1 or less, and the ratio of the maximum linear expansion coefficient/minimum linear expansion coefficient is 1.8 or less.

In the long-fiber-reinforced thermoplastic resin exterior mounting molded body of the present invention, a long fiber having a reinforcing fiber content of 30% by weight to 90% by weight in which the reinforcing fibers are dispersed at a weight average fiber length of 1.5 mm to 15 mm is used. Fiber-reinforced resin, and the flow channel length of the narrow channel with a cross-sectional area of 100 mm ^or less in the mold cavity during molding is less than 150 mm. Therefore, it is possible to manufacture the size caused by the reduction of the linear expansion coefficient and its anisotropy Excellent stability, excellent mechanical strength such as flexural modulus and flexural strength, excellent chemical resistance and heat resistance, light weight, high degree of freedom in product design, suitable for large molded parts for automotive exterior mounting molded parts.

Description of drawings

Fig. 1 is a plan view and a side view of the external mounting molded body obtained in Examples 1, 2, 4 and Comparative Examples 1, 2, 5.

FIG. 2 is a plan view and a cross-sectional view of an external mounting molded body obtained in Example 3. FIG.

3 is a plan view and a cross-sectional view of an external mounting molded body obtained in Comparative Example 3. FIG.

4 is a plan view and a cross-sectional view of an exterior mounting molded body obtained in Comparative Example 4. FIG.

5 is a plan view and a side view of the external mounting molded body obtained in Examples 6 to 8 and Comparative Examples 7, 8, and 11.

FIG. 6 is a plan view and a cross-sectional view of an exterior mounting molded body obtained in Example 9. FIG.

7 is a plan view and a schematic cross-sectional view of an exterior mounting molded body obtained in Comparative Example 9. FIG.

8 is a plan view and a cross-sectional view of an exterior mounting molded body obtained in Comparative Example 10. FIG.

Detailed ways

The present invention will be described in detail below.

The long-fiber-reinforced thermoplastic resin exterior mounting molded article of the present invention (hereinafter referred to as "the molded article of the present invention") is suitable for a large molded article in which the anisotropy of the linear expansion coefficient is significantly affected, and is the largest projected area of the molded article Formed body larger than ^20000mm2 . When using fiber-reinforced resin molding, generally speaking, the surface layer in thickness, the fibers are oriented along the flow direction of the resin, and the center layer is oriented at right angles to the flow direction. When the reinforcing fibers are short fibers, since the degree of freedom of movement (rotation) of the fibers increases during molding, the surface layer is oriented in the flow direction due to shear force from the wall surface, but the vicinity of the center layer is often oriented in random directions. When the reinforcing fiber is a long fiber, due to the influence of its fiber length, the degree of freedom of movement (rotation) of the reinforcing fiber becomes smaller. It can be said that the surface layer tends to have a clear orientation along the flow direction, and the center layer tends to have a clear orientation along its perpendicular direction. . In addition, the upper limit of the maximum projected area is usually 2m ² (2 million mm ² ).

Another feature of the molded body of the present invention is that, preferably, in the relationship between the cross-sectional area of the narrow flow channel and its flow channel length during molding, the flow channel length of the narrow flow channel having a cross-sectional area of 100 mm ^or less is 150 mm or less, more preferably The flow path length of the narrow flow path having a cross-sectional area of 80 mm ² or less is 100 mm or less. If the flow path length of the narrow flow path having a cross-sectional area of 100 mm ^or less at the time of molding exceeds 150 mm, the orientation direction of the reinforcing fibers is more oriented along the filling direction of the molten resin, and thus the effect of reducing the coefficient of linear expansion in the filling direction becomes less Large, but its effect in the right angle direction is reduced, thus, the anisotropy becomes larger. Once the anisotropy becomes large, it may affect the switchability required as an exterior part, the matching with surrounding parts, and the amount of clearance, and further lead to the appearance quality caused by poor coating and coating cracks caused by linear expansion. decrease.

In addition, another feature of the molded article of the present invention is that, with regard to the reinforcing fibers dispersed in the molded article, the content of the reinforcing fibers is 30% by weight to 90% by weight, and the weight average fiber length of the reinforcing fibers is 1.5mm to 10mm. The length is dispersed therein; and the linear expansion coefficient at 23°C to 80°C is measured at any position (multiple places) of the molded body part having a thickness of 2mm or more, and the maximum value of these measured values (maximum linear expansion coefficient) is 5× 10 ^-5 K ^-1 or less, and the ratio to the minimum value (minimum linear expansion coefficient) of these measured values was calculated, and the ratio of the maximum linear expansion coefficient/minimum linear expansion coefficient was 1.8 or less.

However, when the content of the reinforcing fiber is less than 30% by weight, or the weight average fiber length is less than 1.5 mm, mechanical strength represented by flexural modulus and flexural strength and dimensional stability will decrease, which is not preferable. Moreover, when the content rate of the said reinforcing fiber exceeds 90 weight%, or when the weight average fiber length exceeds 10 mm, formability will fall, and it is unpreferable. In addition, when the linear expansion coefficient exceeds 5×10 ^-5 K ^-1 and the ratio of the maximum linear expansion coefficient/minimum linear expansion coefficient exceeds 1.8, the amount of deformation of the entire molded body with respect to the temperature change becomes large, which may cause damage to the molded body as The opening and closing properties required for exterior parts, the influence of matching with peripheral parts and the amount of voids, the occurrence of cracks due to deformation, deformation of the appearance, coating cracks, and even linear expansion caused by the coating of molded objects It is unpreferable because of a decrease in appearance quality due to poor coating and cracks in the coating.

The reinforcing fibers constituting the molded body of the present invention are long fibers with a weight-average fiber length of 1.5 mm to 10 mm, and preferably long fibers of 2 mm to 7 mm in order to produce a front structure with more excellent mechanical strength and dimensional stability. , and there is no particular limitation as long as it can be dispersed in the molded body. Generally, glass fiber, carbon fiber, metal fiber, synthetic fiber, etc. for reinforcement of resin can be used, but glass fiber and carbon fiber are practical. The carbon fiber preferably has a diameter of 5 μm to 15 μm. In addition, in order to improve the interfacial adhesion with the thermoplastic resin, the reinforcing fibers are preferably used with astringents or surface treatment agents (for example, epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, titanate compounds, etc. functional compounds) for surface treatment.

When the reinforcing fibers constituting the molded article of the present invention are glass fibers, the diameter is preferably 10 μm to 20 μm from the viewpoint of further improving the breakage of the glass fibers and the balance of physical properties. The glass fibers actually used are composed of glass components such as A glass, C glass, and E glass. From the viewpoint of not adversely affecting the thermal stability of thermoplastic resins, E glass (alkali-free glass) is particularly preferable. As a method for producing glass fiber, for example, the following method is employed. First, the melted glass is formed into a glass ball of a predetermined size called a marble, and heated and softened in a drawing furnace called a pushing type. It flows down, while extending the base material at a high speed, in the sizing agent coating device installed on the way, the sizing agent (sizing material) is applied by dipping to make it bundled, and then dried, in the rotating drum (rotating drum) ) wrapped around. At this time, the diameter of the nozzle, the drawing speed, the temperature of the drawing atmosphere, etc. are adjusted so that the average diameter of the glass fibers becomes a predetermined size.

When the reinforcing fibers constituting the molded article of the present invention are carbon fibers, the diameter is preferably 5 μm to 15 μm from the viewpoint of further improving the breakage of the carbon fibers and the balance of physical properties.

The carbon fiber actually used is generally made of acrylic fiber, petroleum or carbon-based special pitch, cellulose fiber, lignin, etc. restricted to certain types.

From the viewpoint of having excellent mechanical strength, oil resistance, chemical resistance, heat resistance, durability, formability, dimensional change due to water absorption, impact strength at high temperature, fatigue properties, and creep properties, as the structure of the present invention A particularly preferable example of the thermoplastic resin of the molding is selected from polyester resins such as polybutylene terephthalate and polyethylene terephthalate, aromatic polycarbonate resins, and alloys of these resins, for example , Alloy of polyester resin/aromatic polycarbonate resin. In addition, as a polyester resin, from the viewpoint of degradation of mechanical properties due to breakage of reinforcing fibers and hydrolysis resistance, the polyester resin is 1:1 (weight ratio) of phenol and tetrachloroethane at 30°C. The intrinsic viscosity measured in the mixed solution is polybutylene terephthalate of 0.30dl/g～1.20dl/g, and the titanium content is preferably below 50ppm according to the weight basis of the titanium metal in the resin, more preferably Preferably it is 33 ppm or less. If the intrinsic viscosity of polybutylene terephthalate is less than 0.30dl/g, the mechanical properties of the base resin constituting the matrix of the long-fiber-reinforced resin (matrix) will be reduced, and it will not be satisfactory as a long-fiber-reinforced exterior. The mechanical properties required to install the shaped body. In addition, if the intrinsic viscosity of polybutylene terephthalate constituting the molded body exceeds 1.20dl/g, the base resin constituting the matrix of the long-fiber reinforced resin will become high-viscosity, the formability will decrease, and the long-fiber The breakage becomes large and the mechanical strength falls, which is not preferable. Furthermore, in order to suppress the reduction in strength due to hydrolysis of polybutylene terephthalate constituting the long fiber material, the titanium content is preferably 33 ppm or less.

Another particularly preferable example of the thermoplastic resin constituting the molded article of the present invention is a polyamide resin. Polyamide resins are resins that are used in many fields including the automotive field and electrical and electronic fields, taking advantage of excellent properties such as heat resistance, toughness, oil resistance, gasoline resistance, friction resistance, and formability. Especially in the automotive field, there are many actual results of using its heat resistance and oil resistance, including parts around the engine.

As the polyamide resin, various polymers and copolymers obtained by polymerization (polycondensation) of ω-amino acid or its lactams and/or polycondensation of diamine and dicarboxylic acid can be used. Specifically, α-pyrrolidone, α-piperidone (α-piperidon), ε-caprolactam, aminocaproic acid, enantholactam (oenantholactam), 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc., by making hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, Amines, diamines such as m-xylylenediamine, and terephthalic acid, isophthalic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and undecanedioic acid , dodecanedioic acid and other dicarboxylic acid polycondensation polymers or their copolymers, for example, polyamide 4, polyamide 6, polyamide 7, polyamide 8, polyamide 11, polyamide 12 , polyamide 6-6, polyamide 6-9, polyamide 6-10, polyamide 6-11, polyamide 6-12, polyamide 6T, copolymer polyamide 6/6-6, copolymer polyamide 6 /12, copolymer polyamide 6/6T, copolymer polyamide 6I/6T, etc. Preferable examples include polyamide 6, polyamide 6-6 and copolymer polyamide 6/6-6, with polyamide 6 being particularly preferred. In addition, an aromatic polyamide resin mainly composed of a polyamide obtained by a polycondensation reaction of an aromatic diamine and an aliphatic dicarboxylic acid is also preferable. Examples of the aromatic diamine include p-xylylenediamine and m-xylylenediamine, and it is preferable to use a mixed diamine of p-xylylenediamine and m-xylylenediamine. The reason why the long-fiber-reinforced polyamide resin is selected as the material of the exterior mounting molded body of the present invention is that, compared with other long-fiber-reinforced thermoplastic resins such as polyester, the long-fiber-reinforced polyamide resin has excellent mechanical strength, oil resistance, A material with chemical resistance, heat resistance, durability, and formability, and especially excellent impact strength at high temperatures, fatigue properties, and creep properties.

In addition, the polyamide resin constituting the molded article of the present invention preferably has a degree of polymerization within a certain range, that is, a relative viscosity within a specific range. The preferred relative viscosity is 1.5-2.5 for polyamide 6 at 23°C in 98% sulfuric acid at a concentration of 1%, and for aromatic polyamides at 23°C in 96% sulfuric acid at a concentration of 1%. 1.5 to 2.5, more preferably 1.7 to 2.4. When the relative viscosity is less than 1.5, the mechanical strength is low; when it exceeds 2.5, the fluidity decreases, the breakage of long fibers during molding increases, and the mechanical strength decreases, so it is not preferable.

In addition, the molded article of the present invention made of polyamide resin may have a maximum moisture absorption dimensional change rate of 0.3% or less in the molded article with a thickness of 2 mm or more in addition to the above-mentioned features. Measure the dimensional change on the surface of the molded product by performing the water absorption treatment at the time of saturated water absorption at a temperature of 23°C and a relative humidity of 50% at any position (multiple places) of the molded body part having a thickness of 2mm or more, and calculate from these measured values The moisture absorption dimensional change rate of the following formula can be easily judged by confirming the maximum value (maximum moisture absorption dimensional change rate) of these calculated values.

[Formula 1]

Hygroscopic dimensional change rate = [(dimensions after water absorption - dimensions before water absorption)/dimensions before water absorption] × 100

When the maximum value of the above-mentioned maximum moisture absorption dimensional change rate exceeds 0.3%, there are problems such as inconvenient opening and closing due to dimensional changes caused by water absorption, influence on matching and clearance with peripheral parts, and poor streamlined appearance. preferred. By the way, there is no description on the dimensional change by hygroscopicity in the above-mentioned prior art.

The thermoplastic resin constituting the molded article of the present invention is not particularly limited as long as it can be molded. In addition to the above-mentioned thermoplastic resins, for example, olefin resins such as polyethylene and polypropylene, polyvinyl chloride, polystyrene resin, etc., can also be used. Vinyl resins such as ethylene, acrylonitrile/styrene/butadiene copolymer, polyacetal resin, polymethacrylate resin, polysulfone resin, polyphenylene ether resin, etc. These thermoplastic resins may be used alone or in combination of two or more.

The molded article of the present invention is molded by using the long-fiber-reinforced thermoplastic resin (A) or a mixture in which (A) is mixed with a recycled resin (B) described later as the molding material as required. The method includes various molding methods generally used for thermoplastic resins, such as injection molding, injection compression molding, hollow molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, and press molding. However, from the viewpoint of the degree of freedom of appearance and design of the molded product, and the reduction of the manufacturing process, molding by injection molding is preferable. When molding long-fiber-reinforced thermoplastic resin (A), usually, when melting and kneading in the cylinder of the molding machine or when filling the mold, there is a risk that the reinforcing fibers will be broken and the length of the fibers will be shortened. However, adjust The length of the pellet, the shape of the inner wall of the cylinder of the molding machine and the shape of the screw, molding conditions (for example, resin temperature during molding, injection speed), mold shape including the aspect of the above-mentioned narrow runner, etc., contribute to The weight-average fiber length of the reinforcing fibers dispersed in the molded article of the present invention is kept within a range of 1.5 mm to 10 mm. In addition, a highly rigid and high-strength vehicle body front structure can also be obtained by providing bosses, rib structures, and the like. Also, pressurized gas may be injected into the ribs and protrusions. In addition, in order to further increase the rigidity, a movable part is provided in the mold, and pressurized gas is injected into the volume expansion part caused by the movement of the movable part, thereby forming a hollow, forming a cross-sectional shape with high cross-sectional rigidity, and forming The hollow part is filled with foam and low-melting point metal, etc., and can also be reinforced to further increase the rigidity.

In addition, other components may be added to the long-fiber-reinforced thermoplastic resin (A) of the molding material of the molded article of the present invention as needed. Examples of other components include compatibility improvers, stabilizers, flame retardants, weather resistance improvers, foaming agents, lubricants, fluidity improvers, impact resistance improvers, and antistatic agents. , dyes, pigments, dispersants, inorganic reinforcing agents, release agents, antioxidants, weather resistance modifiers, alkaline soaps, metal soaps, hydrotalcites, plasticizers, nucleating agents, anti-dripping agents, etc. Examples of impact modifiers include polyolefin resins such as polyethylene and polypropylene, α-olefin-based rubbers, styrene-based rubbers, acrylic rubbers, silicone-based rubbers, MBS, core-shell polymers, and the like. Specific examples of the inorganic reinforcing agent include glass fibers other than long fibers, carbon fibers, aramid fibers, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, and the like.

The method for producing the long-fiber-reinforced thermoplastic resin (A) as the molding material of the molded article of the present invention is preferably a drawing method. The drawing method is basically a method of impregnating a resin while drawing a continuous fiber bundle for reinforcement. There is known a method of impregnating the fiber by passing it through an immersion bath of an emulsion, suspension, or solution containing a resin. The method is to spray the resin powder on the fiber or pass the fiber through the tank containing the powder, make the resin powder adhere to the fiber, and then melt the resin and impregnate the method, while making the fiber pass through the cross head, from the extruder to the cross head Any method of feeding molten resin to the head and impregnating it can be used. As a molding material, it is particularly preferable to supply molten thermoplastic resin from the extruder to the crosshead while passing the fiber through the crosshead, impregnate and cool it, and cut it into a length of 3.0 to 50 mm, preferably 4.0 to 30 mm in length. The granular (pellet) method. Since the reinforcing fibers in the thus obtained pellets are substantially parallel to the pellets, the length of the reinforcing fibers is shorter than the length of the pellets. When the length of the pellets is less than 3.0 mm, the length of the reinforcing fibers becomes short and the reinforcing effect is small. On the contrary, when the length of the pellets exceeds 50 mm, there may be cases where the bulk density becomes large, and the hopper during the forming process may occur. Bridging causes poor penetration into the screw, and stable molding cannot be performed.

When using a mixture in which a recycled resin (B) is mixed with a long-fiber-reinforced thermoplastic resin (A) as a molding material of the molded article of the present invention, it is preferable that the composition ratio thereof is expressed on a weight basis of the mixture to be in the range of

(A): 30% by weight to 100% by weight

(B): 0% by weight to 70% by weight

In the range. When the long-fiber-reinforced thermoplastic resin (A) is less than 30% by weight, it is not preferable because the mechanical strength, dimensional stability, appearance, and the like are greatly reduced. In addition, in order to prevent the classification phenomenon in the molding process, it is preferable that the shapes and sizes of the long-fiber-reinforced thermoplastic resin (A) and the recycled resin (B) are as similar as possible.

As the molding material of the molded article of the present invention, the recycled resin (B) blended with the long fiber reinforced thermoplastic resin (A) is not particularly limited, and recycled products of the thermoplastic resin (A) can be used from the viewpoint of compatibility. , but the following combinations are preferred.

(1) When the thermoplastic resin of the long fiber reinforced thermoplastic resin (A) is polyester resin, aromatic polycarbonate resin, or an alloy of these resins, if the recycled resin (B) is an aromatic resin with a viscosity average molecular weight of 10,000 to 17,000 The recycled product of polycarbonate resin has excellent fluidity, less breakage of long fibers during the molding process, and eliminates the molding shrinkage and linear expansion coefficient caused by alloying with crystalline resins. The reduction effect makes it suitable for use as a molding material for large moldings. In this case, if necessary, a compatibility improver may be used in combination.

(2) When the thermoplastic resin of the long fiber reinforced thermoplastic resin (A) is a polyamide resin, if the recycled resin (B) is selected from polypropylene, polyethylene, polystyrene and acrylonitrile-styrene-butadiene copolymer The recycled product of at least one thermoplastic resin in the product has excellent fluidity and is very suitable for use as a molding material for large molded objects. In this case, if necessary, a compatibility improver can be used in combination.

Examples of the recycled resin (B) include purging resin (purgeresin) during molding, in the sprue, in the runner (runner), during molding, during secondary processing, during mounting, etc. Recycled products from various stages, such as defective products generated, molded products recovered after being used for the intended purpose, etc. Of course, the shape of the molded product is not limited. Specifically, recycled products obtained by pulverizing outer panels of automobiles, electrical, electronic, and OA equipment, mechanical parts, and other molded products can also be used. However, molded articles with a lot of adherent substances such as solvents and fats and oils are not preferable because they cause reductions in mechanical strength, thermal stability, and appearance.

In addition, the compounding method of the recycled resin (B) and the long-fiber-reinforced thermoplastic resin (A) is not particularly limited, and various known mixing machines can be used, for example, Henschel mixer, ribbon mixer, V type mixer, extruder, Banbury mixer, Laboplastomill mixer (Brabender mixer), kneader (kneader), etc.

In order to make the molded body of the present invention an exterior molded body for automobiles, considering the required dimensional accuracy, it is preferably a bonnet, a roof, a hood, a front panel, or a roof. (canopy), trunk lid (trunk lid), door panel (doorpanel), pillar (pillar) and these similar exterior panels for automobiles or their structures.

In the present invention, the long-fiber-reinforced thermoplastic resin outer mounting molded body has at least one non-reinforced resin layer laminated on its outer surface, and a long-fiber-reinforced layer/non-reinforced layer on a cross-section perpendicular to the lamination surface. The layer thickness ratio of the reinforcing resin layer is preferably 1.0 or more, more preferably 1.2 or more. If the layer thickness ratio of the long-fiber-reinforced layer/non-reinforced resin layer is less than 1.0, wires between the long-fiber-reinforced layer and the non-reinforced resin layer may occur during molding of the long-fiber-reinforced molded article and/or due to changes in the temperature environment. Bending due to differential expansion. In addition, the non-reinforced resin used in the above-mentioned lamination is not particularly limited, but it is preferably the same type of resin as the long-fiber-reinforced thermoplastic resin, or a resin mainly composed of the resin, from the viewpoint of adhesion. alloy. In addition, at the time of the above lamination, a decorative portion including letters, symbols and/or marks may be enclosed between the long fiber reinforced molded body and the non-reinforced resin layer. Such a molded article is useful as an automotive exterior molded article having excellent appearance characteristics, designability, and design durability.

In the present invention, as a method of forming at least one non-reinforced resin layer laminated on the outer surface of a long-fiber reinforced thermoplastic resin exterior mounting molded body, there may be mentioned a processing method generally used for thermoplastic resins, that is, with Injection molding method of simultaneously laminating at least one non-reinforced resin layer such as non-reinforced resin film or plate, replication molding, two-color molding, double molding, and welding methods such as hot plate welding, vibration welding, laser welding, etc., However, the method of laminating the film and sheet simultaneously with injection molding is particularly preferable from the viewpoint of the appearance of the molded product, degree of design freedom, and reduction of manufacturing steps.

In the present invention, when the film or sheet is laminated at the same time as injection molding, in order to promote thermal fusion with the resin composition at the time of melt injection and make the lamination more reliable, the film or sheet may also be provided with a primer layer. Primer coating. As the resin used for primer coating, a resin having a melt viscosity higher than that of the thermoplastic resin constituting the molded article and which adheres well to the film or sheet is selected. For example, a resin of the same type as the thermoplastic resin and having a higher molecular weight, or a resin based on it, or a resin cured by heat or ultraviolet rays.

The molded article of the present invention may be provided with at least one functional layer selected from a hard coat layer, anti-fogging, anti-static, anti-reflection, and infrared shielding on one side as required, or may be provided on a surface formed by painting or copying. decorate. In order to form the functional layer, various methods known in the prior art are used. For the formation of the hard coat layer, the following method can be used. After setting the primer as necessary, apply a hard coat agent such as epoxy, acrylic, amino resin, polysiloxane, silicone, etc., and then apply heat or ultraviolet rays. and so on to harden it. For the formation of the anti-fog layer, a method of applying and hardening an anti-fog paint containing a water-soluble or hydrophilic resin and a surfactant as essential components may be used. In addition, the antistatic layer, antireflection layer, infrared shielding layer, etc. can also be formed by coating and curing a paint having these functions, or forming a thin film layer having these functions by methods such as vacuum evaporation. In addition, these functional layers may be formed into a composite layer to form a layer having two or more functions at the same time. In addition to these functional layers, or on the functional layers, a design-imparting layer may be formed by preliminarily applying a coating treatment for aesthetic appearance to impart design properties.

Example

Hereinafter, the present invention will be described in detail based on preferred embodiments with reference to the drawings, but the present invention is not limited to these scopes. In the following examples, unless otherwise specified, % means % by weight.

[evaluate]

Evaluation 1. Fiber content, weight average fiber length

Randomly cut a test piece from any position of the molded long-fiber-reinforced thermoplastic resin outer mounting molded body, burn only the plastic resin component in an electric furnace at 500°C, measure the weight and length of the remaining fibers, and compare them with those before burning The ratio of the weight of the test piece was taken as the content rate, and the weight average of the fiber length was taken as the weight average fiber length.

Evaluation 2. Intrinsic viscosity, viscosity average molecular weight

Using a sample randomly cut from any position of the molded long-fiber-reinforced thermoplastic resin external mounting molded body, in the case of polybutylene terephthalate resin, it is tested with phenol and tetrachloroethane at 30°C. Intrinsic viscosity measured in a mixed solvent with a weight ratio of 1:1 is expressed. For the polycarbonate resin, the viscosity average molecular weight (Mv) was determined based on the value (unit dl/g) of the intrinsic viscosity ([η]) measured in methylene chloride at 25°C.

Evaluation 3. Mechanical Properties

Cut out a rectangular test piece of 80 mm × 10 mm at any position of the long-fiber reinforced thermoplastic resin external mounting molded body with a thickness of 2 mm or more, and measure the flexural modulus and flexural strength in accordance with ISO 178, Charpy notched impact strength (Charpy notched) impactstrength) determined in accordance with ISO 179. In addition, when carrying out the measurement, the number of test pieces was n=10.

Evaluation 4. Coefficient of linear expansion

A rectangular test piece of 30 mm x 10 mm was cut out at any position of the molded long-fiber-reinforced thermoplastic resin outer mounting molding with a thickness of 2 mm or more, and the linear expansion coefficient was measured in the temperature range of 23°C to 80°C. Then, the measurement was carried out so that the number of test pieces was n=10, and the measurement was carried out in two directions perpendicular to each other on each test piece, and the maximum linear expansion coefficient was divided by the minimum linear expansion coefficient to calculate a ratio. The smaller this ratio is, the lower the anisotropy is evaluated.

Evaluation 5. Maximum moisture absorption dimensional change rate

The molded long-fiber reinforced polyamide resin external mounting molded body is water-absorbed to a saturated water-absorbed state at a temperature of 23°C and a relative humidity of 50%. Mark the positions of the four corners of at least 5 squares (the length of one side is about 25 to 50 mm) drawn at any position on the surface of the body part, measure the vertical and horizontal dimensions before and after water absorption, and calculate the water absorption of the following formula Dimensional change rate (%) is represented by their maximum value.

[Formula 2]

Hygroscopic dimensional change rate = [(dimensions after water absorption - dimensions before water absorption)/dimensions before water absorption] × 100

In addition, in Example 10 and Comparative Example 12, marking as shown in FIG. 5 was made on the surface of the obtained molded body, and it was used for calculating the maximum moisture absorption dimensional change rate.

[Example 1]

Preparation of Glass Long Fiber Reinforced Polyester Resin Pellets

Using the drawing method, that is, while opening and drawing continuous glass fiber bundles (rovings), they pass through the impregnation mold, impregnate the molten resin supplied to the impregnation mold, shape, cool, and cut, thereby producing Glass long-fiber-reinforced polyester resin pellets with a fiber content of 30% and a length of 10 mm. As the resin, polybutylene terephthalate resin (manufactured by Mitsubishi Engineering Plastics Corporation, product name NOVADURAN 5008, intrinsic viscosity 0.85 dl/g, titanium content 30 ppm) was melted and used. In the obtained pellets, the glass fibers had a diameter of 16 μm, had the same length as the pellets, and were substantially arranged in parallel in the longitudinal direction of the pellets.

Injection molding of molded parts for external mounting

Using Toshiba Machinery's IS-150 injection molding machine, a flat plate-shaped external mounting molded body with a thickness of 3 mm, 150 mm x 150 mm, and a maximum projected area of 22500 mm ² was formed as shown in Figure 1 . That is, the long-fiber-reinforced polyester resin pellets prepared as described above were fed into a heating cylinder of an injection molding machine heated to 270° C., plasticized, melted, and measured. Further, plasticization and measurement were performed while applying a back pressure of 5 MPa with the gauge pressure of the injection molding machine. After measuring, inject and fill in the cavity of the mold through the resin injection port as shown in the figure. The injection time is 2 seconds, plus a 20-second holding pressure of 100 MPa according to the metering pressure of the injection molding machine. After a cooling time of 25 seconds, the mold is opened, and the external mounting molded body made of long-fiber-reinforced thermoplastic resin is taken out to complete the molding. The temperature of the mold at this time was 70°C.

The thus obtained long-fiber-reinforced exterior mounting molded body is a highly rigid structure. In addition, the results of evaluating the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity of the test pieces cut out from the molded body are shown in Table-1 below. The mechanical properties in the evaluation results were all very high, and the coefficient of linear expansion and the anisotropy of linear expansion were all small, which satisfied the function as an exterior molded body for automobiles.

[Example 2]

In Example 1, when preparing the long-fiber-reinforced thermoplastic resin pellets, the long-fiber-reinforced exterior mounting molding was formed in the same manner as in Example 1, except that the fiber content was 30% instead of 50%.

The thus obtained long-fiber-reinforced exterior mounting molded body is a highly rigid structure. In addition, the results of evaluating the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity of the test pieces cut out from the molded body are shown in Table-1 below. The mechanical properties in the evaluation results were all very high, and the coefficient of linear expansion and the anisotropy of linear expansion were all small, which satisfied the function as an exterior molded body for automobiles.

[Example 3]

In Example 2, when the molded body for external mounting is injection-molded, the flat molded body shown in FIG. 1 is replaced with the one shown in FIG. A long-fiber-reinforced outer mounting molded body was molded in the same manner as in Example 2 except that the outer mounting molded body had a 27300 mm ² cross-sectional area of 90 mm ² and a narrow channel length of 45 mm.

The thus obtained long-fiber-reinforced exterior mounting molded body is a highly rigid structure. In addition, the evaluation results of the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity of the test piece cut out from the molded body are shown in Table-1 below. The mechanical properties in the evaluation results were all very high, and the coefficient of linear expansion and the anisotropy of linear expansion were all small, which satisfied the function as an exterior molded body for automobiles.

[Example 4]

In Example 2, at the time of injection molding of the exterior mounting molding, as a molding material, instead of the long-fiber-reinforced polyester resin pellets, the same long-fiber-reinforced polyester resin (A) pellets were used relative to 80% by weight. A mixture of aromatic polycarbonate resin (B) with a viscosity average molecular weight of 14,000 (fiber content: 40%) was blended at 20% by weight. The aromatic polycarbonate resin (B) was placed in a warm water bath to which a chemical treatment agent was added A recycled product obtained by peeling off a design film and a functional film from a recording medium (CD) and pulverizing them. Except for this, a long-fiber-reinforced exterior mounting molded body was molded in the same manner as in Example 2.

The long-fiber-reinforced exterior mounting molded body obtained in this way has a high rigidity. In addition, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, intrinsic viscosity, and viscosity average molecular weight of the test piece cut out from the molded body are shown in Table 1 below. The mechanical properties in the evaluation results were all very high, and the coefficient of linear expansion and the anisotropy of linear expansion were all small, which satisfied the function as an exterior molded body for automobiles.

[Example 5]

In Example 2, when the external mounting molded body is injection molded, the size of the cavity of the mold is changed to a thickness of 4mm, 150mm×150mm, and a pre-formed 0.5mm thick surface with a hard surface is installed on the two cavity surfaces. A polycarbonate sheet (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name Iupilon Sheet CFI-5) for coating the functional layer. Except for this, in the same manner as in Example 2, an exterior mounting molded body (maximum projected area: 22500 mm ² ) was molded in which non-reinforced resin layers were laminated on both sides of the long fiber reinforced resin layer. The thickness ratio of the long-fiber-reinforced resin layer/non-reinforced resin layer in this laminated flat-plate exterior mounting molded body was 3. A polycarbonate thin plate with a hard coat on one side and a cross mark printed on the other side is attached so that the hard coat is in contact with the mold surface (enclosed marks) and molded.

The thus obtained long-fiber-reinforced exterior mounting molded body has excellent surface smoothness and high rigidity. In addition, the evaluation results of the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity of the test piece cut out from the molded body are shown in Table-1 below. The mechanical properties in the evaluation results were all very high, and the coefficient of linear expansion and the anisotropy of linear expansion were all small, which satisfied the function as an exterior molded body for automobiles.

[Table 1]

Example 1 2 3 4 5 raw material Resin type PBT PBT PBT PBT/recycled PC PBT intrinsic viscosity [dl/g] 0.85 0.85 0.85 0.85 0.85 Viscosity average molecular weight - - - 14000 - GF Content rate [weight%] 30.5 49.6 50.4 40.5 37.9 weight average fiber length [mm] 2.97 2.65 3 1.96 2.88 diameter [μm] 16 16 16 16 16 shaped body Maximum projected area [mm ² ] 22500 22500 27300 22600 22500 intrinsic viscosity [sl/g] 1.10 1.15 1.12 1.16 1.10 Viscosity average molecular weight - - - 13500 - narrow runner cross-sectional area [mm ² ] - - 90 - - Runner length [mm] - - 45 - - lamination Enhancement layer/non-enhancement layer - - - - 3 bending elastic rate [GPa] 10.2 12.3 12.5 10.6 8.9 strength [MPa] 230 250 242 200 196 Charpy impact strength [kJ/mm ² ] 28 42 39 35 48 Linear expansion coefficient maximum [×10 ^-5 K ^-1 ] 4.8 4.6 4.2 4.4 4.7 the smallest [×10 ^-5 K ^-1 ] 4.1 3.4 3.5 3.2 3.6 Max/Min Ratio (Anisotropy) 1.2 1.4 1.2 1.4 1.3

[Comparative example 1]

In Example 1, a long-fiber-reinforced exterior molded body was molded in the same manner as in Example 1 except that the fiber content was replaced by 30% to 15% when preparing glass long-fiber-reinforced polyester resin pellets.

The long-fiber-reinforced exterior mounting molded body thus obtained has a low rigidity. In addition, the evaluation results of the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity of the test piece cut out from the molded body are shown in Table-2 below. Although there is a result that the weight average fiber length of the molded product is 2.6mm long, the mechanical properties in the evaluation results are all low, and although the anisotropy of the linear expansion coefficient (ratio of the maximum linear expansion coefficient/minimum linear expansion coefficient) is low It reached 1.5, but the maximum coefficient of linear expansion was as large as 7.1×10 ^-5 K ^-1 , which could not satisfy the function as an exterior molded body for automobiles.

[Comparative example 2]

In Example 1, instead of the preparation of glass long fiber reinforced polyester resin pellets, polybutylene terephthalate (manufactured by Mitsubishi Engineering Plastics, trade name NOVADURAN (ノバデュラン) 5010G45) with a fiber content of 30% was used. Viscosity 0.10dl/g). Except for this, in the same manner as in Example 1, a long-fiber-reinforced exterior mounting molded body was molded.

The long-fiber-reinforced exterior mounting molded body obtained in this way is a molded body with high rigidity. In addition, for the test piece cut out from the molded body, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity are shown in Table-2 below. Since the weight average fiber length of the molded body The length is as short as 0.35 mm, the impact strength in the evaluation results is low, the maximum linear expansion coefficient is 6.2×10 ^-5 K ^-1 , and the anisotropy is 1.9, all of which are too large to satisfy the function as an exterior mounting molded body for automobiles. .

[Comparative example 3]

In Example 2, when the molded body for external mounting is injection-molded, the flat molded body shown in FIG. A long-fiber-reinforced exterior mounting molded body was molded in the same manner as in Example 2 except that the maximum projected area was 20400 mm ² , and the cross-sectional area was 40 mm ² , and the channel length was 160 mm.

The long-fiber-reinforced exterior mounting molded body obtained in this way is a molded body with a high sense of rigidity. In addition, the evaluation results of the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity of the test piece cut out from the molded body are shown in Table-2 below. In the evaluation results, the maximum coefficient of linear expansion was 5.6×10 ^-5 K ^-1 and the anisotropy was 2.7, both of which were too large, and could not satisfy the function as an automotive exterior molding.

[Comparative example 4]

In Example 2, when the molded body for external mounting is injection-molded, the flat-shaped molded body shown in FIG. 1 is replaced with the one shown in FIG. ^2. An external mounting molded body having a narrow channel with a cross-sectional area of 90 mm ² and a channel length of 160 mm. In the same manner as in Example 2, a long-fiber-reinforced external mounting molded body was molded.

The long-fiber-reinforced exterior mounting molded body obtained in this way is a molded body with high rigidity. In addition, the evaluation results of the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and relative viscosity of the test piece cut out from the molded body are shown in Table-2 below. In the evaluation results, the maximum linear expansion coefficient was 6.4×10 ^-5 K ^-1 , and the anisotropy was 3.4, both of which were relatively large, and could not satisfy the function as an automotive exterior molded body.

[Comparative Example 5]

In Example 2, when the glass long fiber reinforced polyester resin pellets were prepared, polybutylene terephthalate (manufactured by Mitsubishi Engineering Plastics, trade name NOVADURAN 5020, intrinsic viscosity 1.20dl/ g) instead of polybutylene terephthalate (manufactured by Mitsubishi Engineering Plastics, trade name NOVADURAN (Novadulan) 5008, intrinsic viscosity 0.85dl/g, titanium content 30ppm), except that, the same molding as in Example 2 Long-fiber reinforced exterior mounting shapes.

The long-fiber-reinforced molded article thus obtained is a molded article with high rigidity. In addition, for the test piece cut out from the molded body, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity are shown in Table-2 below. Since the weight average fiber length of the molded body The length is as short as 0.94 mm, so the impact strength in the evaluation results is low, and the maximum linear expansion coefficient is as large as 5.2×10 ^-5 K ^-1 , which cannot satisfy the function as an exterior molded body for automobiles.

[Comparative Example 6]

In Example 5, when the external mounting molded body is injection molded, a 1.1 mm thick polycarbonate sheet with a hard coat functional layer on the surface is installed on the two cavity surfaces of the mold instead of a 0.5 mm thick polycarbonate sheet. A thin plate made of polycarbonate (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name Iupilon Sheet (ュピロンシート) CFI-5) with a hard coat functional layer on the surface, except that, in the same way as in Example 5, the external mounting A molded body having non-reinforced resin layers laminated on both sides of a long fiber reinforced resin layer. The thickness ratio of the long-fiber-reinforced resin layer/non-reinforced resin layer in this laminated flat-plate exterior mounting molded body was 0.82.

The thus obtained long-fiber-reinforced exterior mounting molded body is a molded body having excellent surface smoothness. In addition, the evaluation results of the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and intrinsic viscosity of the test piece cut out from the molded body are shown in Table-2 below. The impact strength in the evaluation results is high, but the mechanical properties such as rigidity and strength are all low, and the maximum and minimum values of the linear expansion coefficient are both 5×10 ^-5 K ^-1 or more, which cannot be used as an exterior mount for automobiles. The function of the shaped body.

[Table 2]

Comparative example 1 2 3 4 5 6 raw material Resin type PBT PBT PBT PBT PBT PBT intrinsic viscosity [dl/g] 0.85 0.85 0.85 0.85 1.20 0.85 GF Content rate [weight%] 15.4 45.6 50.3 50.2 49.9 24.7 weight average fiber length [mm] 2.64 0.35 2.65 2.39 0.94 2.44 diameter [μm] 16 16 16 16 16 16 shaped body Maximum projected area [mm ² ] 22500 22500 20400 20400 22500 22500 intrinsic viscosity [dl/g] 1.10 0.85 1.13 1.08 1.56 1.09 narrow runner cross-sectional area [mm ² ] - - 40 90 - - Runner length [mm] - - 160 160 - - lamination Enhancement layer/non-enhancement layer - - - - - 0.82 bending elastic rate [GPa] 5.7 12.9 12.4 12.4 12.8 5.2 strength [MPa] 143 238 246 251 245 196 Charpy impact strength [kJ/mm ² ] 13 10 40 42 12 60 Linear expansion coefficient maximum [×10 ^-5 K ^-1 ] 7.1 6.2 5.6 6.4 6.2 6 the smallest [×10 ^-5 K ^-1 ] 4.9 3.3 2.1 1.9 2.9 5.2 Max/Min Ratio (Anisotropy) 1.5 1.9 2.7 3.4 1.8 1.2

[Example 6]

Preparation of Glass Long Fiber Reinforced Polyamide Resin Pellets

Using the drawing method, that is, while opening and drawing continuous glass fiber bundles (rovings), they are passed through an impregnation die, impregnated with molten resin supplied to the impregnation die, shaped, cooled, and cut to produce Glass fiber-reinforced polyamide resin pellets with a fiber content of 30% and a length of 10 mm. As the resin, polyamide 6 (manufactured by Mitsubishi Engineering Plastics Corporation, product name NOVAMID (Novamid) 1007J, relative viscosity 2.2) was melted and used. In the obtained pellets, the glass fibers had a diameter of 16 μm, had the same length as the pellets, and were substantially arranged in parallel in the longitudinal direction of the pellets.

Injection molding of molded body for external mounting

Using an IS-150 injection molding machine manufactured by Toshiba Machinery, a flat plate-shaped external mounting molded body having a thickness of 3 mm, 150 mm×150 mm, and a maximum projected area of 22500 mm ² was formed as shown in FIG. 5 . That is, the long-fiber-reinforced polyamide resin pellets prepared as described above were fed into a heating cylinder of an injection molding machine heated to 270° C., plasticized, melted, and measured. Further, plasticization and measurement were performed while applying a back pressure of 5 MPa with the gauge pressure of the injection molding machine. After measuring, inject and fill into the cavity of the mold through the resin injection port as shown in the figure. The injection time is 2 seconds, and the metering pressure of the injection molding machine is added to the holding pressure of 100 MPa for 20 seconds. After a cooling time of 25 seconds, the mold is opened, and the external mounting molded body made of long fiber reinforced polyamide resin is taken out to complete the molding. In addition, the mold temperature at this time was 70 degreeC.

The thus obtained long-fiber-reinforced exterior mounting molded body is a highly rigid structure. In addition, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, moisture absorption dimensional change rate, and relative viscosity of the test piece cut out from the molded body are shown in Table-3 below. The mechanical properties in the evaluation results are all very high, and the coefficient of linear expansion, anisotropy of linear expansion, and dimensional change due to moisture absorption are all small, and it can satisfy the function as an exterior molded body for automobiles.

[Example 7]

In Example 6, when the long-fiber-reinforced polyamide resin pellets were prepared, the fiber content was replaced from 30% to 50%, and a long-fiber-reinforced exterior mounting molded body was formed in the same manner as in Example 6.

The thus obtained long-fiber-reinforced exterior mounting molded body is a highly rigid structure. In addition, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, moisture absorption dimensional change rate, and relative viscosity of the test piece cut out from the molded body are shown in Table-3 below. The mechanical properties in the evaluation results are all very high, and the linear expansion coefficient, linear expansion anisotropy, and moisture absorption dimensional change rate are all small, and can satisfy the function as an automotive exterior molding.

[Example 8]

In Example 7, when preparing long-fiber reinforced polyamide resin pellets, aromatic polyamide (manufactured by Mitsubishi Engineering Plastics, product name Reny (レニ) 6002, relative viscosity 2.1, abbreviated as MXD6-PA) was used instead Polyamide 6; during injection molding, the temperature of the heating cylinder of the injection molding machine is 280°C instead of 270°C, and the temperature of the mold is 135°C instead of 70°C; in addition, the same as in Example 7, the formed long fiber reinforced external mounting molding body.

The thus obtained long-fiber-reinforced exterior mounting molded body is a highly rigid structure. In addition, the evaluation results of the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and moisture absorption dimensional change rate of the test piece cut out from the molded body are shown in Table-3 below. The mechanical properties in the evaluation results are all very high, and the linear expansion coefficient, linear expansion anisotropy, and moisture absorption dimensional change rate are all small, and can satisfy the function as an automotive exterior molding.

[Example 9]

In Example 7, when the molded body for external mounting is injection-molded, the flat molded body shown in FIG. 5 is replaced with the one shown in FIG. ^2. An external mounting molded body having a narrow channel with a cross-sectional area of 90 mm ² and a channel length of 45 mm. In the same manner as in Example 7, a long fiber reinforced external mounting molded body was molded.

The thus obtained long-fiber-reinforced exterior mounting molded body is a highly rigid structure. In addition, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, moisture absorption dimensional change rate, and relative viscosity of the test piece cut out from the molded body are shown in Table-3 below. The mechanical properties in the evaluation results are all very high, and the linear expansion coefficient, linear expansion anisotropy, and moisture absorption dimensional change rate are all small, and can satisfy the function as an automotive exterior molding.

[Example 10]

In Example 7, when the external mounting molding is injection molded, the size of the mold cavity is changed to a thickness of 4 mm, 150 mm × 150 mm, and a pre-formed 0.5 mm thick polyamide 6 film is installed on the two cavity surfaces. , except that, in the same manner as in Example 7, an exterior mounting molded body (maximum projected area: 22500 mm ² ) was molded in which non-reinforced resin layers were laminated on both sides of the long fiber reinforced resin layer. The thickness ratio of the long-fiber-reinforced resin layer/non-reinforced resin layer in this laminated flat-plate exterior mounting molded body was 3. A cross mark for evaluation of misalignment etc. was printed on one side of the polyamide 6 film by screen printing, and it was molded so as to enclose the printed side.

The thus obtained long-fiber-reinforced exterior mounting molded body is a molded body having excellent surface smoothness and high rigidity. In addition, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, moisture absorption dimensional change rate, and relative viscosity of the test piece cut out from the molded body are shown in Table-3 below. The mechanical properties in the evaluation results are all very high, and the coefficient of linear expansion, anisotropy of linear expansion, and dimensional change rate of moisture absorption are all very small, which can satisfy the function as an exterior molded body for automobiles.

[table 3]

Example 6 7 8 9 10 resin PA6 PA6 MXD6-PA PA6 PA6 GF Content rate [weight%] 30.2 50.3 50.1 49.8 40.5 weight average fiber length [mm] 2.99 2.78 2.58 2.23 2.65 diameter [μm] 16 16 16 16 16 shaped body Maximum projected area [mm ² ] 22500 22500 22500 27300 22500 intrinsic viscosity [dl/g] 2.2 2.2 2.1 2.2 2.2 narrow runner cross-sectional area [mm ² ] - - - 90 - Runner length [mm] - - - 45 - lamination Enhancement layer/non-enhancement layer - - - - 3 bending elastic rate [GPa] 6.9 12.5 15.1 12.9 11.8 strength [MPa] 239 265 318 270 240 Charpy impact strength [kJ/mm ² ] twenty four 31 29 34 26 Linear expansion coefficient maximum [×10 ^-5 K ^-1 ] 4.8 4.2 3.0 4.8 4.6 the smallest [×10 ^-5 K ^-1 ] 3.3 3.3 2.4 3.0 3.0 Max/Min Ratio (Anisotropy) 1.5 1.3 1.3 1.6 1.5 Maximum moisture absorption dimensional change rate [%] 0.22 0.16 0.11 0.28 0.26

[Comparative Example 7]

In Example 6, when preparing the glass long-fiber-reinforced polyamide resin pellets, the long-fiber-reinforced exterior mounting molding was formed in the same manner as in Example 6 except that the fiber content was 30% instead of 10%.

The long-fiber-reinforced exterior mounting molded body thus obtained is a molded body with low rigidity. In addition, the evaluation results of the fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and relative viscosity of the test piece cut out from the molded body are shown in Table-4 described later. As a result, the weight-average fiber length of the molded body was as long as 2.8 mm, but the mechanical properties in the evaluation results were all low, and the maximum linear expansion coefficient was 7.0×10 ^-5 K ^-1 , and the anisotropy (maximum linear expansion coefficient/minimum The linear expansion coefficient) increased to 1.9, and the maximum moisture absorption dimensional change rate reached 0.65%, both of which were too large to satisfy the function as an exterior mounting molded body for automobiles.

[Comparative Example 8]

In Example 6, instead of preparing glass long-fiber-reinforced polyamide resin pellets, polyamide 6 (manufactured by Mitsubishi Engineering Plastics, trade name NOVAMID (Novamid) 1013GH30) with a fiber content of 30% was used. Example 6 Similarly, shaped long fiber reinforced exterior mounting shaped body.

The long-fiber-reinforced exterior mounting molded body obtained in this way is a molded body with high rigidity. In addition, for the test piece cut out from the molded body, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and relative viscosity are shown in Table-4 below. Since the weight average fiber length of the molded body The length is as short as 0.41mm, the impact strength in the evaluation results is low, and the maximum linear expansion coefficient is 7.1×10 ^-5 K ^-1 , anisotropy is 2.2, and the maximum moisture absorption dimensional change rate is 0.32%, which are too large to be satisfied. Functions as exterior molded body for automobiles.

[Comparative Example 9]

In Example 7, when the molded body for external mounting is injection-molded, the flat molded body shown in FIG. 5 is replaced with the one shown in FIG. ^2. The external mounting molded body having a narrow channel with a cross-sectional area of 100 mm ² and a channel length of 160 mm. In the same manner as in Example 7, a long fiber reinforced external mounting molded body was molded.

The long-fiber-reinforced exterior mounting molded body obtained in this way is a molded body with high rigidity. In addition, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, hygroscopic dimensional change rate, and relative viscosity of the test piece cut out from the molded body are shown in Table 4 below. In the evaluation results, the maximum linear expansion coefficient was 6.0×10 ^-5 K ^-1 , the anisotropy was 2.3, and the maximum moisture absorption dimensional change rate was 0.36%, all of which were relatively large, and could not satisfy the function as an automotive exterior molding.

[Comparative Example 10]

In Example 7, when the molded body for external mounting is injection-molded, the flat molded body shown in FIG. 5 is replaced with the one shown in FIG. 20400 mm ² , a long-fiber-reinforced exterior mounting molded body was molded in the same manner as in Example 7 except that the cross-sectional area was 90 mm ² , and the channel length was 160 mm.

The long-fiber-reinforced exterior mounting molded body obtained in this way is a molded body with high rigidity. In addition, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, moisture absorption dimensional change rate, and relative viscosity of the test piece cut out from the molded body are shown in Table-4 below. In the evaluation results, the maximum linear expansion coefficient was 6.5×10 ^-5 K ^-1 , the anisotropy was 3.0, and the maximum moisture absorption dimensional change rate was 0.41%, all of which were relatively large, and could not satisfy the function as an automotive exterior molded article.

[Comparative Example 11]

In Example 7, when the glass long fiber reinforced polyamide resin pellets were prepared, polyamide 6 (manufactured by Mitsubishi Engineering Plastics Corporation, product name NOVAMID (Novamid) 1030J, relative viscosity 4.5) was used instead of polyamide 6 (Mitsubishi Engineering Plastics Co., Ltd. Made by Plastics Co., Ltd., product name NOVAMID (Novamid) 1007J, relative viscosity 2.2), except that, in the same manner as in Example 7, a long-fiber-reinforced exterior mounting molded body was molded.

The long-fiber-reinforced exterior mounting molded body obtained in this way is a molded body with high rigidity. In addition, for the test piece cut out from the molded body, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, moisture absorption dimensional change rate, and relative viscosity are shown in Table-4 below. The weight average fiber length of the body is as short as 0.91mm, so the impact strength in the evaluation results is low, and the maximum linear expansion coefficient reaches 6.5×10 ^-5 K ^-1 , the anisotropy reaches 2.0, and the maximum moisture absorption dimensional change rate reaches 0.32%. , all of which are too large to satisfy the function as an exterior mounting molded body for automobiles.

[Comparative Example 12]

In Example 10, when the external mounting molded body was injection-molded, a polyamide 6 film with a thickness of 1.1 mm was placed on both cavity surfaces of the mold instead of a polyamide 6 film with a thickness of 0.5 mm. Except for this, in the same manner as in Example 10, an exterior mounting molded body in which non-reinforced resin layers were laminated on both surfaces of the long fiber reinforced resin layer was formed. The thickness ratio of the long-fiber-reinforced resin layer/non-reinforced resin layer in this laminated flat-plate exterior mounting molded body was 0.82.

The thus obtained long-fiber-reinforced exterior mounting molded body is a molded body having excellent surface smoothness. In addition, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, moisture absorption dimensional change rate, and relative viscosity of the test piece cut out from the molded body are shown in Table-4 below. The mechanical properties such as rigidity and strength in the evaluation results are very low, and the linear expansion coefficient reaches 7.0×10 ^-5 K ^-1 , the anisotropy reaches 2.1, and the maximum moisture absorption dimensional change rate reaches 0.37%, which are too large to satisfy Functions as exterior molded body for automobiles.

[Comparative Example 13]

In Comparative Example 8, an aromatic polyamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name MX nylon S6121, relative viscosity 3.65, referred to as MX) with a fiber content of 50% was used instead of polyamide 6 with a fiber content of 30% (Mitsubishi Engineering Co., Ltd. Plastic Co., Ltd. (trade name: NOVAMID (Novamid) 1030GH30), except that, in the same manner as in Comparative Example 8, a long-fiber-reinforced exterior mounting molded body was molded.

The long-fiber-reinforced exterior mounting molded body obtained in this way is a molded body with high rigidity. In addition, for the test piece cut out from the molded body, the evaluation results of fiber content, weight average fiber length, mechanical properties, linear expansion coefficient, and relative viscosity are shown in Table-4 below. Since the weight average fiber length of the molded body Since the length is as short as 0.55 mm, the impact strength in the evaluation results is significantly lowered, and the function as an exterior molded body for automobiles cannot be satisfied.

[Table 4]

comparative example 7 8 9 10 11 12 13 raw material type of resin PA6 PA6 PA6 PA6 PA6 PA6 MX GF Content rate [weight%] 10.6 29.8 49.7 50.4 50.1 25.3 49.5 weight average fiber length [mm] 2.76 0.41 2.32 2.41 0.91 2.22 0.55 diameter [μm] 16 16 16 16 16 16 16 shaped body Maximum projected area [mm ² ] 22500 22500 20400 20400 22500 22500 22500 Intrinsic viscosity [dl/g] 2.2 2.2 2.2 2.2 4.5 2.2 3.65 narrow runner cross-sectional area [mm ² ] - - 100 90 - - - Runner length [mm] - - 160 160 - - - lamination Enhancement layer/non-enhancement layer - - - - - 0.82 - bending elastic rate [GPa] 2.6 7.2 12.6 12.3 12.2 6.2 15.6 Strength [MPa] 102 250 260 270 250 231 320 Charpy impact strength [kJ/mm ² ] 10 10 33 30 16 10 7 Linear expansion coefficient maximum [×10 ^-5 K ^-1 ] 7.0 7.1 6.0 6.5 6.5 7.0 4.2 minimum [×10 ^-5 K ^-1 ] 3.7 3.3 2.6 2.2 3.2 3.3 2.8 Max/Min Ratio (Anisotropy) 1.9 2.2 2.3 3.0 2.0 2.1 1.5 Maximum moisture absorption dimensional change rate [%] 0.65 0.32 0.36 0.41 0.32 0.37 0.12

Claims (16)

1. exterior formed article made of long fiber-reinforced thermoplastic resin is characterized in that:

The containing ratio that is dispersed in the fortifying fibre in the formed body is 30 weight %～90 weight %, and the weight average fiber length that is dispersed in the fortifying fibre in the formed body is 1.5mm～10mm, and the maximal projection area of formed body is 20000mm ²More than, sectional area 100mm during shaping ²The runner of following narrow runner is long for below the 150mm, and the max line coefficient of expansion of the formed body part that thickness 2mm is above is 5 * 10 ^-5K ^-1Below, and the ratio of the max line coefficient of expansion/minimum line coefficient of expansion of the part of the formed body more than the thickness 2mm is below 1.8.

2. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 1 is characterized in that:

Thermoplastic resin is to be selected from the alloy of mylar, aromatic polycarbonate resin, these resins and the resin of polyamide.

3. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 1 is characterized in that:

Thermoplastic resin is a polyamide, and the above formed body maximum moisture absorption size changing rate partly of thickness 2mm is below 0.3%.

4. fiber reinforced thermoplastic resin as claimed in claim 2 is made body, it is characterized in that:

Thermoplastic resin is the polybutylene terephthalate (PBT) resin, the inherent viscosity that this polybutylene terephthalate (PBT) resin is measured in 1 to 1 (weight ratio) mixed liquor of 30 ℃ of phenol and tetrachloroethanes is 0.30dl/g～1.20dl/g, and the titanium amount is below the 33ppm.

5. as claim 2 or 3 described continuous fiber reinforcing polyamide resin exterior formed article mades, it is characterized in that:

Polyamide is that to measure the relative viscosity that obtains with concentration 1% in 23 ℃, 98% sulfuric acid be 1.5～2.5 polyamide 6.

6. as claim 2 or 3 described continuous fiber reinforcing polyamide resin exterior formed article mades, it is characterized in that:

Polyamide is that to measure the relative viscosity that obtains with concentration 1% in 23 ℃, 96% sulfuric acid be 1.5～2.5 aromatic polyamide.

7. as claim 2 or 3 described continuous fiber reinforcing polyamide resin exterior formed article mades, it is characterized in that:

Polyamide is to be the aromatic polyamide resin of main component with the polyamide that the polycondensation reaction by aromatic diamine and aliphatic dicarboxylic acid obtains.

8. as each described exterior formed article made of long fiber-reinforced thermoplastic resin of claim 1～7, it is characterized in that:

Use has cooperated mixture that recycled resin (B) forms as moulding material in fiber reinforced thermoplastic resin (A), its ratio of components, according to the weight basis of this mixture, in following scope:

(A): 30 weight %～100 weight %;

(B): 0 weight %～70 weight %.

9. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 8 is characterized in that:

The thermoplastic resin of fiber reinforced thermoplastic resin (A) is the alloy of mylar, aromatic polycarbonate resin or these resins, and recycled resin (B) is the recirculation product of the aromatic polycarbonate resin of viscosity-average molecular weight 10000～17000.

10. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 8 is characterized in that:

The thermoplastic resin of fiber reinforced thermoplastic resin (A) is a polyamide, and recycled resin (B) is the recirculation product that are selected from least a thermoplastic resin in polypropylene, polyethylene, polystyrene and the acrylonitrile styrene-butadiene-copolymer.

11. each the described exterior formed article made of long fiber-reinforced thermoplastic resin as claim 1～10 is characterized in that:

Fortifying fibre is the glass fibre of diameter 10 μ m～20 μ m.

12. each the described exterior formed article made of long fiber-reinforced thermoplastic resin as claim 1～11 is characterized in that:

Formed body is the formed body that obtains by injection molded.

13. each the described exterior formed article made of long fiber-reinforced thermoplastic resin as claim 1～12 is characterized in that:

As be selected from hood (bonnet), roof (roof), hood (hood), panel (front panel), top (canopy), luggage-boot lid (trunk lid), door-plate (doorpanel), post (pillar), with these similar automobiles with any the automobile exterior formed article in outer dress plate and the tectosome thereof.

14. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 13 is characterized in that:

Have the non-enhancing resin bed of lamination one deck at least on the outer surface, and the bed thickness ratio of the long fibre enhancement layer on the cross section vertical with this lamination face/non-enhancing resin bed is more than 1.0.

15. automobile exterior formed article as claimed in claim 14 is characterized in that:

Non-enhancing resin is and the congener resin of this fiber reinforced thermoplastic resin, or is the alloy of main component with this resin.

16., it is characterized in that as claim 14 or 15 described automobile exterior formed articles:

When lamination, being enhanced between body and this non-enhancing resin bed to enclose at this long fibre has the ornamental portion that comprises literal, symbol and/or mark.

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