JPH09208756A - External part of vehicle using long glass fiber-reinforced polypropylene resin composition stabilized for weathering resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide long parts for external parts of vehicles having extraordinary little changes in the appearances such as color, capable of holding various characteristics such as strength and having high reliability for long period uses. SOLUTION: A part having a long shape is formed from a formed article of a long glass fiber reinforced-polypropylene composition comprising (A) long glass fiber-reinforced polypropylene resin pellets, having 2-100mm length in the fiber direction, obtained by impregnating a polyolefin resin in a glass fiber bundle by drawing the continuous glass fiber bundle for reinforcing the resin in the polyolefin resin and cutting the glass fiber-reinforced resin, and containing 15-75wt.% glass which substantially have the same length as the pellet and are arranged in parallel, (B) a polyolefin resin, (C) an antioxidant, (D) a light stabilizer and (E) a UV absorber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a long vehicle exterior component which is excellent in weather resistance such as color and strength and various other characteristics and which can maintain its beautiful appearance for a long period of time.

[0002]

2. Description of the Related Art Glass fiber reinforced polyolefin, especially polypropylene resin, is widely used in various industrial parts because of its excellent mechanical strength, heat resistance and moldability. In particular, long-fiber-reinforced polyolefin resin obtained by so-called drawing method, in which resin is impregnated while drawing continuous fibers, is a short-fiber-reinforced polyolefin resin obtained by kneading chopped strands of glass fiber and resin in an extruder or a molding machine. It has the advantages of superior impact strength, creep characteristics and vibration fatigue characteristics. Further, the long fiber reinforced polyolefin resin produced by the drawing method has a feature that the glass fibers can be filled with extremely high density because the glass fibers are arranged in the same direction.
By utilizing such characteristics of long glass fiber reinforced polyolefin resin, automobile parts, parts of electric products, etc. are manufactured by melt molding, but when used outdoors for a long time, May be deteriorated by the action of heat, oxygen and light, and its mechanical properties may be significantly deteriorated.

Generally, a polyolefin resin is inexpensive as a general-purpose plastic and is widely used. Therefore, if the materials of the plastics are unified, the recyclability is expected to be improved. However, polyolefin resin is
It has the drawback that it deteriorates due to the effects of heat, oxygen, and light during use and becomes unusable for practical use. Various efforts have hitherto been made to improve this point, and techniques for adding weathering agents such as antioxidants, ultraviolet absorbers, and light stabilizers have been disclosed.

In JP-A-60-124642, 0.1 to 1 part by weight of a specific hindered amine compound, a specific high molecular weight phenol compound and a specific phosphite compound are added to 100 parts by weight of polyolefin. A stabilized polyolefin composition is described which is formulated. JP-A-62-4733 discloses a composition comprising 100 parts by weight of a polyolefin and 1 to 100 parts by weight of an inorganic filler, and (1) 0.01 to 0.5 parts by weight of a benzotriazole-based or benzophenone-based UV absorber. , (2) 0.01 to 1 part by weight of a hindered amine-based or phenylbenzoate-based light stabilizer and (3) 0.01 to 1 part by weight of an organophosphorus compound are disclosed. JP-A-3-265638 discloses a stabilized polypropylene resin composition containing a specific hindered piperidine. JP-A-6-2120
No. 32 discloses a polyolefin resin 1 containing a crystalline polyolefin and / or an olefin elastomer.
(A) 0.05 to 0.20 part by weight of a hindered phenolic antioxidant, (b) 0.05 to 0.20 part by weight of a phosphorus antioxidant, and (c) ultraviolet Absorbent 0.
10-0.50 parts by weight and (d) N-O-R type or N-CO
-R type hindered amine light stabilizer 0.10 to 0.5
A composition containing 0 parts by weight is disclosed.

[0005]

However, in the above-mentioned prior art, the degree of weather resistance is insufficient, and it withstands long-term use and harsh conditions naturally required for exterior parts of vehicles such as automobiles. I can't. For example, the weather resistance such that there is no change in appearance including color change for 10 years or more under the condition of being exposed to direct sunlight containing a large amount of ultraviolet rays, and various properties are retained is not sufficient. Therefore, there is a problem in that the properties of the polyolefin resin are impaired if the amount of the additive is increased.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems in the prior art and to have excellent weather resistance, so there is very little change in appearance such as color that is naturally required for exterior parts. Various properties such as strength are retained. Another object of the present invention is to provide a long vehicle exterior component that has high impact strength and is not easily broken, and that the impact mode is cracked, but is not easily cracked so that it is highly reliable for long-term use. Another object of the present invention is to reduce the equipment cost because the molding die for the short fiber reinforced engineering plastic, which is a conventional product, can be used as it is because the shrinkage rate is small. It is intended to provide a long vehicle exterior component that can be reduced in cost because of its low specific gravity as compared with a product, and can improve recyclability because a general-purpose plastic is a base resin.

That is, the present invention relates to a long-shaped component used for the exterior of a vehicle, wherein at least the main part of the long-shaped component is for resin reinforcement in (A) a polyolefin resin. While pulling out the continuous glass fiber bundle,
A pellet having a length of 2 to 100 mm in the fiber direction obtained by impregnating the glass fiber bundle with the resin and cutting the glass fiber, wherein the glass fiber is aligned substantially in parallel with the pellet in a parallel manner. Long glass fiber reinforced polyolefin resin pellets having a content of 15 to 75 wt%, (B) polyolefin resin, (C) antioxidant, (D) light stabilizer, and (E) ultraviolet absorber Provided is a long component for vehicle exterior, which is formed from a polyolefin composition molded product. Further, it is preferable that the long glass fiber reinforced polyolefin resin composition further contains a sulfur compound. Further, in the long glass fiber reinforced polyolefin resin composition, further preferably,
It contains carbon black and / or zinc sulfide, and in this case, the antioxidant, the light stabilizer, the ultraviolet absorber, optionally a sulfur compound, and both carbon black and zinc sulfide, or It is necessary that the total weight of either one is 1.0 to 8.0 parts by weight with respect to 100 parts by weight of the polyolefin resin.

Hereinafter, the present invention will be described in detail. The long-shaped vehicle exterior component of the present invention (hereinafter, also referred to as a long member)
Is an exterior component mainly arranged on a side surface and a roof of a vehicle such as an automobile, and is referred to as a side molding (side protector) and a roof molding, respectively. By mounting these on an actual vehicle, the appearance is enhanced by hiding the mating portion of the vehicle body outer plate, and it is possible to prevent damage to the door or the like due to contact. As shown in a concrete example in FIG. 1, the method of attaching to the automobile outer plate is as follows. The long member is formed into a flat plate or into a hollow flat tubular shape, and the flat surface that contacts the automobile outer plate or the contact surface is bonded. In order to facilitate the process, a method of roughening or the like and attaching with an adhesive or double-sided tape 14 (FIG. 1A), a long member is formed into a T-shaped cross-section having leg portions 16 for attachment, A method of attaching to the hollow space of the joints of the steel plates or the space of the crimped joints (FIG. 1 (b)), a member having a mounting hole (joint portion 18) is formed in the long member, and the screw or the Examples of the method include a method of attaching the bolt and nut 18 (FIG. 1C), but the method is not limited thereto. The shape is basically a shape in which the length / width dimension ratio of the planar shape is 10 or more, preferably 12 or more, and does not have an enlarged diameter portion or a narrowed diameter portion, and the thickness is not particularly limited. , 0.5 to 3.5 mm is preferable. Further, when the long molded product of the present invention is molded by hollow extrusion molding, the proper range of the dimensional ratio is such that the planar length / width dimension ratio is 10 or more, preferably 12 or more. Part and narrow diameter part are not included. The thickness of the molded product is not particularly limited, but 0.5 to 5.0 is preferable. As exterior parts for vehicles,
The bottom flat surface is caulked and held by the steel plate for car body,
It is used by being adhered to a steel plate, or by being provided with a rib shape on the back surface and being mechanically fixed with a grip or the like, or by being fixed by a means that combines these, and the cross section may have any shape, and the vehicle to which it is applied. It may be determined in consideration of the design and design of the. For example, a shape in which the central portion of the cross section is recessed, a shape in which the central portion of the cross section is projected, and the like can be mentioned. Generally, a width of 5 to 50 mm, a thickness of 2 to 3 mm, and a recessed central portion of the cross section are often used, but the present invention is not limited to this.

Since the long-shaped exterior part of the present invention is formed from the long glass fiber resin composition described below, it has an advantage that the shrinkage ratio during melt molding in the width direction (short direction) can be reduced. Have. Especially for the dimension control of long shaped members, the length can be adjusted appropriately by truncating, but the shape in the width direction needs to be recreated from the shape of the mold, so the conventionally used mold When the composition is used as it is for cost reduction, it is required that the shrinkage ratio of the composition in the width direction is as small as that of the conventional product. The long glass fiber resin composition used in the present invention can be used as it is in a conventional mold by reducing the shrinkage ratio in the width direction. Further, since it is excellent in weather resistance, even when it is installed on the roof of an automobile, even if it is used for a long period of time by directly receiving sunlight, its appearance color tone does not change much, so that the designability is not impaired.

Next, the long glass fiber resin composition constituting the long vehicle exterior component of the present invention will be described. (A) The glass fiber-reinforced polyolefin resin pellet (A) used in the present invention is a fiber obtained by impregnating the resin bundle with the resin while pulling out the resin-reinforced continuous glass fiber bundle in at least the polyolefin resin and cutting the fiber bundle. A length of 2 to 100, preferably 3 to 50 mm, in which the glass fibers are substantially parallel and aligned in parallel with the pellet, and the glass fiber content is 15 to 75 wt, preferably 30 to 70 wt% long glass fiber reinforced polyolefin resin pellets.

The continuous glass fiber used in the present invention is E
-Glass, S-Glass, C-Glass, AR-Glass, T
-Glass, D-glass, R-glass and the like, and usually in the form of so-called glass roving, which is a bundle of a plurality of glass filaments wound into a coil. A glass fiber having a diameter of 3 to 40 μm is suitable. If it is less than 3 μm, it becomes difficult to impregnate the resin with the same glass content because the number of glass fibers is relatively increased, and if it exceeds 40 μm, the surface appearance of the molded product is remarkably deteriorated. The optimum glass fiber diameter is 9 to 20 μm.

The glass fiber used in the present invention may be surface-treated with a surface-treating agent containing a coupling agent. As the coupling agent, silane coupling agents such as aminosilane, epoxysilane, amidosilane, azidosilane, acrylsilane, titanate coupling agents and mixtures thereof can be used. Of these,
Aminosilane and epoxysilane are preferable, and an aminosilane coupling agent is particularly preferable.

The polyolefin resin used in the present invention includes homopolymers and copolymers of ethylene, propylene, butene, 4-methylpentene, etc., and polar monomers such as vinyl acetate, acrylic acid, acrylic acid esters, maleic anhydride, etc. Also included are random, block or graft copolymers with. In addition, ethylene-α-
Compositions containing synthetic rubber such as olefinic copolymer rubber, isoprene rubber, and isobutylene rubber in an amount of less than half weight% are also included. Specifically, high-pressure ethylene homopolymer, ethylene-propylene copolymer, low-pressure ethylene homopolymer, ethylene-propylene copolymer, ethylene-
1-butene copolymer, same ethylene-1-hexene copolymer, medium pressure ethylene copolymer, high pressure ethylene-vinyl acetate copolymer, propylene homopolymer, propylene-ethylene random or block copolymer, etc. There is.
Among them, the crystalline propylene-based polymer, especially polypropylene has a more remarkable effect.

Polypropylene is not only a propylene homopolymer but also a copolymer containing propylene as a main component and an ethylene component, for example, a propylene-ethylene block copolymer, a block copolymer of propylene and ethylene-propylene rubber, and the like. May be. Among these, the latter, in particular, a block copolymer containing an ethylene component is preferably used. When a copolymer containing an ethylene component is used, the ethylene component is usually contained in the range of 20% by weight or less based on the weight of the copolymer. The polypropylene resin targeted by the present invention may further contain an α-olefin copolymer rubber in addition to such polypropylene.
The α-olefin-based copolymer rubber here is a rubber-like polymer obtained by copolymerizing two or more types of α-olefins, and the α-olefin serving as a copolymerization component has, for example, 2 to 2 carbon atoms. Twelve. Among the α-olefin copolymer rubbers, preferred are ethylene and other α-olefin rubbers.
It is a copolymer rubber with olefin. The α-olefin that is a copolymerization partner of ethylene is, for example, one having 3 to 12 carbon atoms, and specifically, propylene, 1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
Examples thereof include 1-octene and a mixture thereof, and among them, propylene or 1-butene is preferable.

The long glass fiber reinforced polyolefin produced by the drawing method is a hydrophilic glass fiber and a non-polar glass fiber which is completely impregnated with a polyolefin resin while drawing glass fibers consisting of thousands to tens of thousands of filaments. Methods for improving wettability with certain polyolefin resins are disclosed in U.S. Pat. Nos. 4,479,998, 4,549,920, and 4
The component (A) of the present invention described in Japanese Patent No. 559262 may be produced by these methods. Also,
For example, in JP-A-5-17631, in order to facilitate impregnation of a molten resin, a melt flow rate measured by a method of ASTM D-1238 (load: 2.16 kg, temperature: 230 ° C.) 30 g / 10 min. The method using the above low-viscosity polypropylene, the method of impregnating an extremely low molecular weight resin in Japanese Patent Publication No. 3-25340, and the surface treatment of glass fiber in order to improve the wettability in Japanese Patent Laid-Open No. 3-181528. In addition, there is a method of using a modified polypropylene resin, and the component (A) of the present invention may be produced by these methods.

The long glass fiber reinforced polyolefin resin pellet (A) used in the present invention is obtained by impregnating a glass fiber with a polyolefin resin while drawing continuous reinforcing glass fiber, and then cutting the fiber in a direction perpendicular to the direction of drawing the fiber. Is obtained by Any method may be used for impregnating the resin. For example, a method of impregnating glass fiber with an emulsion of a polyolefin resin, applying a coating, and then drying,
A method in which a powder suspension of a polyolefin resin is adhered to glass fibers and dried and then heat-melted and impregnated, a method in which glass fibers are charged and a polyolefin resin powder is adhered, and then heat-melted and impregnated, a solvent-dissolved polyolefin resin After impregnating the glass fiber with a solvent, a method of removing the solvent, a method of heating a mixed fiber of a continuous fiber of polyolefin and a continuous fiber of glass, and impregnating with a molten polyolefin resin or a heat-melted polyolefin resin, a bar, a roll, a die. Any method such as impregnation while opening the glass fiber may be used. Among these methods, the method of impregnating the heat-melted polyolefin resin while opening the glass fiber on a bar, a roll or a die is most preferable because of the simplicity of the apparatus and the process.

In the pellets thus obtained after cutting, glass fibers are present in a state of being aligned in parallel with each other in the same length as the pellets. The pellets contain 15 to 15 glass fibers.
It is contained in an amount of 75% by weight, and the pellet length is 2 to 100 mm in the fiber direction. Glass fiber content is 15% by weight
If the amount is less than the above, the advantage as a masterbatch cannot be utilized, which is economically disadvantageous, and the product application range of the molded product after dilution is narrowed, so that the industrial value is reduced. If it exceeds 75% by weight, the resin cannot be sufficiently impregnated and the production becomes extremely difficult. This preferred glass fiber content is 1
5 to 75% by weight. If the pellet length is less than 2 mm, the glass fiber length in the molded product becomes short and the strength, particularly the impact strength, decreases. If it exceeds 100 mm, high strength, high impact, creep resistance, and vibration fatigue resistance, which are the characteristics of long fiber reinforcement, will not be further improved. Instead, it will be clogged in the hopper during injection molding or extrusion molding, and polyolefin. Segregation occurs in a mixture with a resin, which is not preferable. The preferred pellet length is 3 to 50 mm. The pellet shape may be any shape as long as the length is 2 to 100 mm, and for example, the cut surface may be circular, oval or quadrangular. Further, the length of the cut surface in the longitudinal direction is preferably such that the aspect ratio (ratio between the pellet length and the cut surface length) is 1 to 10, more preferably 2 to 5.

(B) Polyolefin resin (B) of the present invention
Means a resin containing no glass fiber for resin reinforcement, a polyolefin resin (B) for dilution mixed with pellets (A) of long glass fiber reinforced polyolefin resin, and containing 70% by weight or more of olefin as a constitutional unit. Good,
For example, in addition to the polyolefin described in the component (A), propylene homopolymer, less than 30% by weight of a vinyl group-containing monomer copolymerizable with propylene, and 70% propylene.
There are copolymers and mixtures of these which comprise more than weight%. Examples of the copolymer include ethylene-propylene random copolymer, ethylene-propylene block copolymer, propylene-butene copolymer, propylene-EPD.
An example of the copolymer is M.

Particularly when impact resistance is required, ethylene-propylene copolymer and propylene-EPDM copolymer have high melt viscosity and it is difficult to impregnate glass fiber. It is difficult to manufacture reinforced melt-molded products. Therefore, the use of the mixture of the polyolefin resin pellets (A) in the low viscosity range of the present invention and the polypropylene resin (B) for these high impact copolymers is effective for producing long glass fiber reinforced molded articles of these resins. It is a means.

The mixing ratio of the long glass fiber reinforced polyolefin resin pellets (A) used for the present invention and the dilution polyolefin resin (B) is such that the master batch pellets (A) are mixed.
/ Polyolefin resin (B) = 10/90 to 90/10
(Weight ratio). When the mixing ratio of the masterbatch is less than 5% by weight, the glass fiber content in the molded product after dilution is too low, and the high strength and high impact characteristics of the long fiber reinforced molded product cannot be fully exhibited.

The shape of the diluting polyolefin resin (B) is not particularly limited, but powder and pellets are preferable. More preferably, the masterbatch pellet (A)
It is preferable that the size and shape are close to each other. If the sizes of both pellets are extremely different, there is a drawback that they separate in the hopper during melt molding. Preferred polyolefin resin (B)
The shape is a granular shape having a diameter of 2 to 5 mm or a cylindrical shape having a diameter of 1 to 5 mm and a length of 1 to 10 mm.

The antioxidant used in the present invention is preferably a phenol compound or a phosphorus compound, and the phenol compound is 2,6-di-t-butyl-4-.
Methylphenol, 1,3,5-tris (3,5-di-
t-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionyloxymethyl] methane and the like, and among them, hindered phenol compounds are preferable, for example, 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, Stearyl (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl)
Phosphonate, 2,2'-methylenebis (4-methyl-
6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), bis [3,3-bis (4-hydroxy-3-t-butylphenyl) butyric acid] glycol ester , 4,
4'-butylidene bis (6-t-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-t-butylphenol), 2,2'-ethylidene bis (4-s)
ec-butyl-6-t-butylphenol), 1,1,
3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) ) Phenyl] terephthalate, 1,3,5
-Tris (2,6-dimethyl-3-hydroxy-4-t
-Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-
Di-t-butyl-4-hydroxybenzyl) -2,4
6-trimethylbenzene, 1,3,5-tris [(3,
5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2-t- Butyl-4-methyl-6- (2'-acryloyloxy-
3'-t-butyl-5'-methylbenzyl) phenol, 3,9-bis (1 ', 1'-dimethyl-2'-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane, bis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate and the like can be mentioned. Among these, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate] methane and the like are preferred.

Examples of the phosphorus-based compound include phosphorus-based stabilizers such as alkyl phosphite, alkyl allyl phosphite, allyl phosphite, alkyl phosphonite, and allyl phosphonite. Specifically, distearyl penta Erythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,
4'-biphenylene phosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, 1 ，
Examples thereof include 1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane.

The amount of the hindered phenol compound and phosphorus compound compounded is 0.2 to 2.5 parts by weight, preferably 0.3 to 2.
0 parts by weight. The weight ratio of the hindered phenol compound to the phosphoric acid compound is preferably in the range of 1/10 to 10/1, and more preferably in the range of 1/5 to 5/1.

Examples of the light stabilizer used in the present invention include amine compounds and phenylbenzoate light stabilizers.
Among them, examples of the hindered amine-based or phenylbenzoate-based light stabilizer include, for example, bis (2,2,6,
6-Tetramethyl-4-piperidyl) sepacate, succinic acid and N- (2-hydroxypropyl) -2,2,6,6
Condensate with 6-tetramethyl-4-hydroxypiperidine, tetrakis (2,2,6,6-tetramethyl-4-
Piperidyl), 1,2,3,4-butanetetracarboxylate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,
Polycondensation product with 2-dibromoethane, bis (2,2,6,
6-tetramethylpiperidyl) adipate, bis (2,2
2,6,6-Tetramethylpiperidyl) fumarate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 2,4-di-t-
Butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 4-octylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t- Butyl-4-hydroxybenzoate and the like can be mentioned. The addition amount of these is 0.2 to 3.0 parts by weight based on 100 parts by weight of the resin components in total. If it is less than this, the effect is not exhibited, and if it exceeds the upper limit, it is uneconomical and causes problems such as bleeding. A particularly preferable blending amount is 0.3 to 2.0 parts by weight.

Examples of the ultraviolet absorber used in the present invention include salicylic acid derivatives, benzophenone-based, benzotriazole-based, and benzoate-based ones. Among these, benzotriazole type and benzoate type are preferable. Examples of the benzotriazole-based ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and 2- (3,5-di-t-butyl-2). -Hydroxyphenyl) -5-chlorobenzotriazole, 2-
(5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy5-t-octylphenyl) benzotriazole, Two
Examples thereof include-(2-hydroxy-3,5-di-t-amylphenyl) benzotriazole. Examples of the benzoate-based ultraviolet absorber include 2,4-
Di-t-butylphenyl-3,5-di-t-butyl-4
-Hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and the like can be mentioned.

The amount of the above ultraviolet absorber blended is 0.05 to 3.0 parts by weight, based on 100 parts by weight of the resin component in total.
It is preferably 0.1 to 2.0 parts by weight. If the amount of the ultraviolet absorber blended is less than 0.05 parts by weight, the weather resistance will be insufficient, and if it exceeds 0.3 parts by weight, the corresponding effect cannot be obtained.

The sulfur-based compound used according to the present invention is preferably a sulfur-containing ester compound, and is pentaerythritol tetra (β-alkylthiopropionate), dilauryl, thiodipropionate, pentaerythritol tetrakis (3-dodecyl). Thiopropionate) is preferred.

The long vehicle exterior component of the present invention can be colored black or gray without painting, and has a good appearance according to the color of the vehicle to which the present invention is applied. You can select such a color. In the case of coloring in black, it can be carried out by adding carbon black, which is preferable in that the weather resistance is superior to that by coating. The compounding amount is 0.2 to 2.5 parts by weight, preferably 0.3 to 2.
0 parts by weight. When the blending amount of carbon black is within this range, the weather resistance is effective.

When carbon black is used in the composition of the present invention, (C) an antioxidant, (D) a light stabilizer,
The total content of the (E) ultraviolet absorber and the sulfur-based compound optionally contained is preferably 1.0 to 8.0 with respect to the total 100 parts by weight of the resin component in total with the amount of carbon black. Parts by weight, more preferably 1.2-6.
0 parts by weight. The reason for this is that carbon black absorbs light and therefore the weather resistance is improved.

Further, in the case of coloring in gray, it is preferable to use a carbon black using zinc sulfide / a pigment for gray obtained from zinc sulfide as a white pigment because the impact strength can be reduced to a small extent. Although general titanium oxide can be used as the white pigment, it is not preferable because it damages the glass fiber and lowers the impact resistance.

The method for producing a long component for vehicle exterior according to the present invention comprises: (A) long glass fiber reinforced polyolefin resin pellets, (B) polyolefin resin, (C) antioxidant,
The (D) light stabilizer, (E) ultraviolet absorber and other necessary additives may all be kneaded and produced at the same time. Preferably, the components (C), (D), and (E) are kneaded in a master pellet based on an olefin resin such as polypropylene or high-density polyethylene, and this is produced at an arbitrary timing to produce the composition of the present invention. Add at times. The master pellet containing the components (C), (D) and (E) may be kneaded with the component (A) in advance and then with the component (B), or the component (A) and the component (B). May be added when kneading.

Dyes / pigments for coloring, higher fatty acids, higher fatty acid metal salts, amides of higher fatty acids, lubricants such as waxes, and the like can be added to the composition of the present invention.

The melt-molding of the long parts for vehicle exterior of the present invention is carried out by a usual injection molding machine, injection-press molding machine, single-screw extruder, twin-screw extruder, heating press molding machine, extrusion molding, hollow extrusion molding. Etc.

The average fiber length (median length) of the residual fiber length in the molded product obtained by melt-molding the composition of the present invention is 0.8-10, preferably 1.0-8.0 mm. .
If it is less than 0.8 mm, the high strength, high elastic modulus, excellent creep characteristics and vibration fatigue characteristics, which are features of the long fiber reinforced molded product, cannot be sufficiently exhibited. Further, if it exceeds 10 mm, the characteristics of the long fiber reinforced molded product are not further improved, and the surface appearance is rather deteriorated, which is not preferable.

In order to maintain the residual average glass fiber length of 0.8-10, preferably 1.0-8.0 mm, the melt-forming mixture of the present invention has a relatively mild melt-forming condition, that is, a weak kneading force. However, it is necessary to reduce the shearing force applied to the molten resin. For example, it is necessary to use a deep groove screw and reduce the back pressure of the screw to 0 to 3 kg / cm ² , or to reduce the screw rotation speed. In the composition of the present invention, the glass fiber is sufficiently dispersed even if the kneading force is weak as described above.

Although the long parts for vehicle exterior have been specifically described above, the present invention is not limited to these and may be any design known and used in the art. .

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples. The present invention is not limited to these specific examples.

[Examples 1 to 4] Verton ^R MFX700-10 (5
Polypropylene resin containing 0% long glass fiber: 50 parts by weight of Kawasaki Steel Co., Ltd., 48 parts by weight of polypropylene pellets having MI of 50 (granular particles having a diameter of 3 mm), and 2 parts by weight of low-density polyethylene containing 30% by weight of carbon black. ,
The polypropylene resin pellets were mixed with the additive components shown in Table 1 (Examples) so that the additive amount shown in Table 1 was added to the total amount of the polyolefin resin, and the injection molding temperature 24
Injection molding was performed under the conditions of 0 ° C. and a mold temperature of 60 ° C. to obtain a No. 1 test piece conforming to ASTM. Bending strength of the obtained molded product (A
STM) and flexural modulus (ASTM) were measured. The results are shown in Table 1.

[Examples 5 to 10] Verton ^R MFX700-10
(Polypropylene resin containing 50% long glass fiber: manufactured by Kawasaki Steel Co., Ltd.) 50 parts by weight, polypropylene pellets with MI of 45 (granular particles having a diameter of 3 mm), and the total amount of low-density polyethylene and polypropylene containing 30% by weight of carbon black. On the other hand, the additives were mixed with the polypropylene resin pellets in the amounts shown in Table 2 and injection-molded at the injection molding temperature of 240 ° C and the mold temperature of 60 ° C.
The No. 1 test conforming to STM was obtained. Example 5 obtained in Table 2
The molded products of Nos. 10 to 10 had no glass float observed at the time of the following 2000 hours of the weather resistance accelerated test, and the bending strength was 2000 as compared with the respective test pieces before the accelerated test was started.
85% or more was maintained when HR passed.

The initial flexural strength and flexural modulus were measured, and an accelerated weathering test with an ultraviolet fluorescent lamp was carried out for 500 hours, 1000 hours, 15 hours in accordance with ASTM G-53.
The results are shown for each 00 hours. The irradiation condition is 8 hours, the black panel temperature is 70 ° C., 2.7 w / m ² of ultraviolet rays are irradiated, and then the black panel temperature is 50 hours.
A cycle of keeping in the dark under steam conditions of ° C was repeated as one cycle. The retention rate was expressed in% by dividing the strength after the accelerated weathering test by the initial strength. The GF float was judged by whether or not the float of the glass fiber was observed when the surface of the plate material was magnified 200 times.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

The components used in the composition of Table 1 are as follows.

[0046] Bio soap 80 is a trademark of Sumitomo Chemical Co., Ltd. Other than that, additives made by Asahi Denka Co., Ltd.

[Embodiment 11] Further, using the same materials as in Embodiment 1, polypropylene resin pellets were mixed in the same manner as in Embodiment 1, and the mixture was heated at a resin temperature in an injection molding machine with a mold clamping force of 150 t. Injection molding was performed under the conditions of 240 ° C and mold temperature of 60 ° C to produce a long vehicle exterior component having a length of 500 mm, a width of 12 mm, a thickness of 2 mm and a central portion of 4 mm. The characteristics were tested and evaluated.

(Heat Deformability) The product was mounted in an actual vehicle and exposed to an ambient temperature of 85 ± 2 ° C. for 5 hours. afterwards,
The presence / absence of defects such as cracking, discoloration, deformation, shrinkage, change in gloss, stickiness, change in hardness, swelling, looseness at the mounting portion, looseness, etc., which impair the commercial property, was evaluated. The following two types of mounting methods were tested as actual vehicle mounting conditions. (1) The roof panel of the vehicle has a width of 10 mm and a thickness of 0.8
mm acrylic foam tape (Sumitomo 3M # 421
Bonded via 2). The primer K500 (Sumitomo 3M) was applied to the double-sided tape adhered surface of this product. (2) The product was placed on the roof panel of the vehicle, a 2 mm hole was drilled at a position 6 mm from the center and both ends, and fixed at three points with hop rivets.

(Thermal cycle resistance) The product was mounted in a state where it was mounted on an actual vehicle, and the following items (1) to (5) were repeated for 5 cycles. −30 ± 2 ° C. × 7.5 hours Room temperature × 0.5 hours or more 80 ± 2 ° C. × 15.5 hours Room temperature × 0.5 hours or more −30 ± 2 ° C. × 7.5 hours Room temperature × 0.5 hours or more 49 ± 1 ° C, relative humidity 98% or more x 15.5 hours Room temperature x 0.5 hours or more After that, cracking, discoloration, deformation, shrinkage, change in gloss, stickiness, change in hardness, swelling, surface peeling, The presence or absence of defects such as backlash and looseness that impair the commercialability was evaluated. The deformation and shrinkage were evaluated according to the same criteria as in the heat deformability test.

(Weather Resistance) The weather resistance test and evaluation were carried out in accordance with ASTM G-53.

(Impact resistance) The product was mounted in a state of being mounted on an actual vehicle, and at room temperature and -30 ± 2 ° C., 0.5 kg, diameter 50
A steel ball of mm was freely dropped vertically from a height of 300 mm. Then, the presence or absence of defects such as cracking, deformation, looseness, loosening, and whitening of the commercial property, which impair the commercial property, was evaluated.

(Results) As a result of the above-mentioned test, no defects such as those impairing the commercial property were found in any of the heat deformability, the thermocycle resistance, the weather resistance and the impact resistance.

[0053]

EFFECTS OF THE INVENTION The long vehicle exterior component of the present invention can be colored without painting and is excellent in weather resistance, so that the change in appearance such as color can be extremely reduced. , The aesthetics can be maintained for a long time. In addition to being excellent in various properties such as strength and elasticity, the strength and elasticity can be maintained for a long time due to the weather resistance. Furthermore, since the shrinkage in the width direction during molding is as small as that of conventional products, the conventional molding dies can be used as they are, and moreover, compared to conventional short fiber reinforced engineering plastic molded products. Since it has a low specific gravity, cost reduction can be realized. Moreover, since general-purpose plastic is a base resin, recyclability can be improved.

[Brief description of drawings]

FIG. 1 is a view showing an example in which various vehicle exterior long components according to the present invention are attached to an automobile outer plate. (A)
In the example, an adhesive or a double-sided tape is used, (b) is a clip, and (c) is a screw or a bolt.

[Explanation of symbols]

 10a, 10b, 10c Long parts for vehicle exterior 12 Automobile outer plate 14 Adhesive or double-sided tape 16 Legs 18 Joints

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location // B29K 23:00 105: 12 309: 04 B29L 31:30 (72) Inventor Seiji Hanatani Kawasaki Steel Co., Ltd., Chuo-ku, Chiba-shi, Chiba Prefecture (72) Inventor Hiroshi Oshita 1 Kawasaki-machi, Chuo-ku, Chiba, Chiba Prefecture (1) Kawasaki Steel Co., Ltd. (72) Inventor Small Taichi Kawa, 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Prefectural Institute of Technology, Kawasaki Steel Co., Ltd. (72) Inventor Junichi Kasai 3-25-1 Tonomachi, Kawasaki-ku, Kawasaki-shi, Kanagawa Isuzu Motors Ltd. Kawasaki Plant

Claims (3)

[Claims] 1. A long-shaped component used for the exterior of a vehicle, wherein the long-shaped component is (A) a polyolefin resin, while the continuous glass fiber bundle for resin reinforcement is drawn out. A pellet having a length of 2 to 100 mm in the fiber direction obtained by impregnating a fiber bundle with the resin and cutting, wherein the glass fibers are substantially aligned in parallel with the pellet and have a glass fiber content rate. Is 15-7
Formed from a long glass fiber reinforced polyolefin composition containing 5 wt% long glass fiber reinforced polyolefin resin pellets, (B) polyolefin resin, (C) antioxidant, (D) light stabilizer, and (E) ultraviolet absorber Long parts for vehicle exterior. 2. The long component for exterior of a vehicle according to claim 1, wherein the long glass fiber reinforced polyolefin resin composition further contains a sulfur compound. 3. The long glass fiber reinforced polyolefin resin composition further contains carbon black and / or zinc sulfide, and contains the antioxidant, the light stabilizer, and the ultraviolet absorber. The total weight of the sulfur-based compound and / or carbon black and / or zinc sulfide is 100% of that of the polyolefin resin.
The long component for vehicle exterior according to claim 1 or 2, which is 1.0 to 8.0 parts by weight with respect to parts by weight.