JPH1134097A - Outer door handle molded product composed of long fiber glass reinforced propylene resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an outer door handle molded product composed of long fiber glass reinforced propylene resin of lightweight, high mechanical strength and superior weather resistance. SOLUTION: An outer door handle molded product is manufactured by injection molding a glass fiber reinforced propylene resin composition formed by adding a hindered amine light stabilizer of molecular weight of 1000 or more of 0.3-2.0 pts.wt. and carbon black of the structural length of 60 nm or less at the time of primary coagulation of 1-2 pts.wt. into a glass fiber containing resin mixture of 100 pts.wt. formed by mixing a glass fiber containing resin molded body which is manufactured by impregnating rovings formed of filament- shaped glass fibers with molten propylene resin, carrying out pultrusion for the rovings and cutting the ravings into the pellet shape, with propylene resin so that the ratio in which propylene resin is 70-90 wt.% and the glass fibers is 10-30 wt.% is provided in the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article of an outer door handle made of long fiber glass reinforced propylene resin. More specifically, the present invention relates to an injection-molded article containing long-fiber glass, which is lightweight, has high mechanical strength, and is excellent in long-term weather resistance and is formed of a long-fiber glass-reinforced propylene resin outer door handle.

[0002]

2. Description of the Related Art Conventional outer door handles for automobiles are preferably made of a polyacetal resin having a high mechanical strength or a glass fiber reinforced polyacetal resin composition in which a glass fiber is added to a polyacetal resin to further improve the mechanical strength. in use. However, the polyacetal resin is a resin having a relatively high specific gravity, and has a drawback that if the glass fiber is added to the resin, the specific gravity is further increased, so that the weight cannot be reduced. In addition, the added glass fiber jumps out of the molded product, and while the molded product is used, the exposure of the glass fiber gradually increases, thereby deteriorating the appearance of the molded product, and cracking due to the exposure of the fiber. Are liable to occur, which causes deterioration of weather resistance.

[0003] In recent years, for the purpose of solving the above problems, a glass fiber-reinforced olefin resin composition in which glass fibers are added to an olefin resin, particularly a propylene resin, instead of the polyacetal resin has been studied. However, even if glass fibers are added to the resin, the glass fibers are cut short by the shearing action during the granulation step, the molding step, and the like, so that it is difficult to improve the mechanical strength. There is also a method of changing the glass fiber to be added to a longer glass fiber.However, most of the glass fiber is shortened by the shearing action, and the improvement in mechanical strength is not so much expected. Since it is easy to be exposed from the molded product, it may cause deterioration of the appearance and weather resistance of the molded product.

[0004] Usually, carbon black is used to color a molded product black, but if this carbon black is blended, the shearing action becomes stronger, so that the added glass fiber becomes extremely short. Even when glass fibers are added, the mechanical strength of the molded product obtained hardly improves.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that it is effective to use a glass fiber reinforced propylene resin composition of a specific composition. The present invention has been completed.
As is apparent from the above description, an object of the present invention is to provide a long fiber glass reinforced propylene resin outer door handle molded article which is lightweight, has high mechanical strength, and is excellent in weather resistance.

[0006]

The molded article of the present invention is a glass fiber obtained by impregnating a roving made of filamentous glass fiber with a molten propylene resin, then drawing and cutting into a pellet. The propylene resin containing the resin molded article and the propylene resin is 70 to 9
0.3 to 2.0 parts by weight of a hindered amine light stabilizer having a molecular weight of 1000 or more based on 100 parts by weight of a glass fiber-containing resin mixture mixed so as to have a ratio of 0% by weight to 10 to 30% by weight of glass fibers. It can be easily obtained by injection molding a glass fiber reinforced propylene resin composition to which 1-2 parts by weight of carbon black having a structure length of 60 nm or less at the time of primary aggregation is added.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The propylene resin used in the present invention includes crystalline propylene homopolymer, crystalline propylene-α-olefin copolymer, and those obtained by modifying the homopolymer or copolymer with an unsaturated carboxylic acid or an acid anhydride thereof. Can be mentioned. As the propylene resin used when obtaining the glass fiber-containing resin molded product, an α-olefin content of 8 in consideration of compatibility with glass fibers and fusibility.
It is preferable that an unsaturated carboxylic acid or an acid anhydride thereof is modified by 0.1 to 1% by weight with respect to 10 to 10% by weight of a crystalline propylene-α-olefin copolymer. on the other hand,
The propylene resin mixed with the glass fiber-containing resin molded product is preferably a crystalline propylene homopolymer in consideration of rigidity.

The glass fibers used in the present invention include E glass (Electrical glass) and C glass (Chemical glas).
s), A glass (Alkali glass), S glass (High st
and glass obtained by melt-spinning glass such as alkali glass and alkali-resistant glass into filamentous fibers. Fiber diameter is 6-20μ as glass fiber
m is preferably used. When the fiber diameter is used, a molded article having a good appearance can be obtained.

[0009] The glass fiber-containing resin molded article used in the present invention is obtained by introducing a roving of several thousand glass fibers into an impregnating die, uniformly impregnating the molten propylene resin between the filaments, and then performing pultrusion. Length (4
To 20 mm), but can be easily obtained, but the production method is not particularly limited. When the molded article is used, the long fiber glass can be held in a relatively long state inside the molded article, and since the long fiber glass is hardly exposed from the molded article, the long fiber glass and the propylene resin are simply blended. Unlike a molded product obtained from the conventional conventional long-fiber glass reinforced propylene resin composition, the appearance and weather resistance of the molded product are not easily deteriorated.

The glass fiber-containing resin mixture used in the present invention is a mixture of a glass fiber-containing resin molded product and a propylene resin. The total amount of 70 to 90% by weight of the propylene resin and 10 to 30% by weight of the glass fiber is 100% by weight. It is configured. When the glass fiber-containing resin molded body used is in this range, only the glass fiber-containing resin molded body may be used as the glass fiber-containing resin mixture without blending the propylene resin. If the blending ratio of the propylene resin in the glass fiber-containing resin mixture used in the present invention is less than 70% by weight, the appearance of the molded product will be poor, and if it exceeds 90% by weight, the mechanical strength will not be sufficiently improved.

The hindered amine light stabilizer used in the present invention has a molecular weight of 1,000 or more. Molecular weight 1
If it is less than 000, the hindered amine light stabilizer is likely to bleed from the molded article. Molecular weight 1000-1000
Those in the range of 0 are preferred. As the hindered amine light stabilizer, specifically, dimethyl succinate 1- (2
-Hydroxyethyl) -4-hydroxy-2,2,6
6-tetramethylpiperidine polycondensate, poly [｛6-
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl {(2,2,
6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-
Piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino ] -6-chloro-1,3,5 triazine condensate and the like. Among them, poly [(6-morpholino-s-triazo-2,4-diyl)} 2,2,6
6-Tetramethyl-4-piperidyl) imino {-hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] is preferred. As a commercially available hindered amine-based light stabilizer, a trade name of “Siasorb UV334” is used.
6 ″ (Made by Cytec, molecular weight: 1600) is effective.
The amount of the hindered amine light stabilizer added is 0.3 to 2.0 parts by weight based on 100 parts by weight of the glass fiber-containing resin mixture.
Parts by weight. If the amount is less than 0.3 part by weight, sufficient weather resistance cannot be obtained. If the amount exceeds 2.0 parts by weight, bleeding increases and the appearance of a molded product deteriorates.

[0012] The carbon black used in the present invention is not particularly limited as long as the structure length at the time of primary aggregation is 60 nm or less. Structure length at the time of primary aggregation is 6
When the carbon black exceeds 0 nm, the action of cutting the glass fiber becomes strong, and the glass fiber becomes extremely short, so that it is difficult to obtain sufficient mechanical strength. In the carbon black, the carbon basic particles do not exist as single particles but form a structure. The structure here refers to a primary aggregate (aggregate) in which carbon basic particles are fused, and is distinguished from a secondary aggregate (agglomerate) in which the primary aggregate is aggregated by van der Waals force. is there. The addition amount of the carbon black is the same as the glass fiber-containing resin mixture 1
It is 1-2 parts by weight with respect to 00 parts by weight.

The glass fiber reinforced propylene resin composition used in the present invention contains various additives such as an antioxidant, an antistatic agent, a copper damage inhibitor, a neutralizing agent, as long as the object of the present invention is not impaired. Additives such as pigments, dispersants, antioxidants, lubricants, mineral oils, silane coupling agents, titanate coupling agents and the like can be appropriately compounded.

The following method is effective as an example of a method for obtaining the glass fiber reinforced propylene resin composition used in the present invention. First, a masterbatch (H) in which a propylene resin and a hindered amine-based light stabilizer are mixed at a predetermined mixing ratio is formed into a pellet (H) by using a general propylene resin granulator to form a pellet. Similarly, a molded article (B) comprising a propylene resin and carbon black is obtained. Next, in a tumbler, these molded body (H) and molded body (B) are added to a glass fiber-containing resin molded body,
A propylene resin for adjusting the composition and various additives as necessary are mixed to obtain a glass fiber reinforced propylene resin composition.

The long fiber glass reinforced propylene resin outer door handle molded product of the present invention can be easily molded from the above glass fiber reinforced propylene resin composition by a general propylene resin injection molding machine. At this time, it is desirable to mold while adjusting the glass fiber contained in the molded article to have an average fiber length of 0.5 to 6 mm. The average fiber length of the glass fibers in the molded product is 0.5
If it is less than mm, the mechanical strength and impact strength of the molded product will not be sufficiently exhibited, and if the average fiber length of the glass fibers in the molded product exceeds 6 mm, the moldability will deteriorate. Factors that change the average fiber length in the molded product include the specifications of the molding machine,
Molding conditions, gate diameter, fiber content, molten resin viscosity and the like can be mentioned. Among them, the specifications of the molding machine, particularly the screw used, are a major factor. However, the average fiber length of the fibers in the molded product of the glass fiber reinforced propylene resin composition used in the present invention does not fall significantly below 0.5 mm as long as a general thermoplastic resin molding machine is used.

[0016]

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention should not be limited by these.

Example 1 A glass fiber (G1) obtained by roving several thousand filamentous glass fibers having a fiber diameter of 17 μm was led to an impregnation die, and the melt flow rate melted between the filaments was 1%.
20g / 10min (temperature 230 ° C, load 2.16kg
f), which is impregnated with a crystalline propylene-ethylene copolymer (P1) modified with 0.5 part by weight of maleic anhydride and having an ethylene content of 9% by weight, and thereafter, is subjected to pultrusion molding and has a length of 6%.
The glass fiber-containing resin molded product (X1) containing 50% by weight of glass fiber was obtained. Also, poly [(6-morpholino-s-triazo-2,4-diyl)]
{2,2,6,6-tetramethyl-4-piperidyl) imino} -hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (trade name “Siasorb UV3346” (Sytec) 10% by weight
And a melt flow rate of 24 g / 10 min (temperature 2
A mixture composed of 90% by weight of a propylene resin having a load of 2.16 kgf) at 30 ° C. was melt-kneaded by an extruder to obtain a pellet-shaped molded body (H1). The molded article (H1)
Carbon black (brand # 900) 25 having a structure length of 44 nm at the time of primary aggregation by the same manufacturing method
Propylene resin 7 whose weight% and melt flow rate are 24 g / 10 min (temperature 230 ° C., load 2.16 kgf)
A pellet-shaped compact (B1) consisting of 5% by weight was obtained. Next, the compact (X1) 40% by weight and the compact (H1)
8 parts by weight, molded part (B1) 6 parts by weight and crystal melting point 165
° C, melt flow rate 75g / 10min (temperature 23
Propylene resin (P2) with 0 ° C and load of 2.16 kgf)
46% by weight was put into a tumbler mixer and mixed to obtain a glass fiber reinforced propylene resin composition. The obtained glass fiber reinforced propylene resin composition was molded into a handle part and an outer frame part, which are parts of an outer door handle, by an injection molding machine.

Comparative Example 1 A commercially available weather-resistant glass fiber 20% reinforced polyacetal resin (POM-G) was molded by an injection molding machine into a handle part and an outer frame part which are parts of an outer door handle.

Comparative Example 2 Instead of the molded article (H1) used in Example 1, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name “TINUVIN 770” (Ciba.
Geigy), molecular weight 480.7) 10% by weight and a melt flow rate of 24 g / 10 min (temperature 230 ° C,
An outer door was prepared in the same manner as in Example 1 except that a pellet-shaped molded product (H2) obtained by melt-kneading a mixture consisting of 90% by weight of a propylene resin having a load of 2.16 kgf) and an extruder was used. Handle parts and outer frame parts, which are parts of the handle, were molded.

Comparative Example 3 Instead of the compact (B1) used in Example 1, 25% by weight of carbon black (brand # 10) having a structure length of 248 nm upon primary aggregation and a melt flow rate of 2 were used.
4g / 10min (temperature 230 ° C, load 2.16kg
A handle part and an outer frame part, which are parts of the outer door handle, were formed in accordance with Example 1 except that the pellet-shaped molded body (B2) composed of 75% by weight of the propylene resin of f) was used. .

Comparative Example 4 Instead of the compact (X1) and the propylene resin (P2) used in Example 1, 20% by weight of a chopped strand glass fiber (G2) having a fiber diameter of 13 μm and a fiber length of 3 mm and a melt flow rate were used. 5g / 10min (temperature 23
Propylene resin (P3) 66 at 0 ° C. under a load of 2.16 kgf) modified with 0.5 part by weight of maleic anhydride.
A handle part and an outer frame part which are parts of the outer door handle were formed in accordance with Example 1 except that the weight% was used.

Comparative Example 5 The molded article (X1) used in Example 1 and a propylene resin (P
2) and the molded body (B1), glass fiber (G)
2) Except for using 20% by weight, propylene resin (P3) 66% by weight, and the molded body (B2), a handle part and an outer frame part which are parts of the outer door handle are formed in accordance with Example 1 respectively. did.

The molded articles obtained in Example 1 and Comparative Examples 1 to 5 were subjected to the following test methods (fracture strength of the product, remaining fiber length in the product, product weight, suitability in appearance of the product, suitability of the outer door handle). It was measured according to the propriety of physical properties, weather resistance evaluation, and comprehensive judgment as an outer door handle). Table 1 shows the results.

[0024]

[Table 1]

(Fracture strength of product) The handle part and the outer frame part, which are the molded products obtained in Example 1 and Comparative Examples 1 to 5, are integrated with a hinge and a spring to form an outer door handle molded product. After being fixed, the handle was pulled while adding to the handle, and the strength at which the handle was broken was measured. The higher the value, the higher the mechanical strength of the molded product.

(Remaining fiber length in product) A part (about 5 g) of the handle part obtained in Example 1 and Comparative Examples 1 to 5 was left in an electric furnace set at 600 ° C. for 5 hours to be carbonized. After that, the carbide was stirred in water, transferred to a glass petri dish, dried, and only the fiber portion was taken out. The length of the taken out fiber was measured. The average length of these fibers indicates the average fiber length in the molded article.

(Product weight) Example 1 and Comparative Examples 1 to 5
The weight of the handle part and the outer frame part, which are the molded products obtained in the above, was measured. The smaller the value, the lighter the weight.

(Appearance of Product) It was visually judged whether or not the outer door handle molded product obtained in the above (measurement of breaking strength of product) had an appearance suitable for practical use.
If the determination is no, it means that the product cannot be used.

(Appropriateness of outer door handle in terms of physical properties) (Evaluation of (fracture strength of product), (length of remaining fiber in product), (product weight) and (appropriateness of appearance of product) in the above evaluation test
From the results, it was determined whether or not the molded products obtained in Example 1 and Comparative Examples 1 to 5 were suitable as outer door handles.

(Evaluation of weather resistance) Example 1 and Comparative Examples 1 to
The molded product obtained in 5 was left in a metal weather tester (manufactured by Die Plus Wintes) set under the following conditions, and the appearance of the molded product was periodically observed with a microscope at a magnification of 50 times. Cracks were checked, and the time when the crack generation ratio occupied about 70% was defined as the weather resistance time. Wavelength: 295-780 nm Light cycle: temperature 80 ° C., humidity 50 RH%, irradiation intensity 80 mW / cm ² , cycle time 10 Hr Work cycle: temperature 30 ° C., humidity 98 RH%, dew condensation, cycle time 4 Hr Shower: 10 sec cycle: Light cycle → shower → work cycle → shower → light cycle

(Comprehensive Judgment as Outer Door Handle) The suitability as an outer door handle was comprehensively determined from the results of (the suitability of the outer door handle in terms of physical properties) and (evaluation of weather resistance) in the evaluation test.

From the results shown in Table 1, the sample of Example 1 which is a molded product of the present invention is different from the sample of Comparative Example 1 which is a molded product using a glass fiber reinforced polyacetal resin corresponding to a conventional molded product. It turns out that it is lightweight, has high mechanical strength, and is excellent in weather resistance. In addition, the sample of Example 1 can hold the glass fiber in the molded product in a longer state than the samples of Comparative Examples 2 to 5 obtained by using a different formulation from the composition of the present invention, and have a weather resistance. It can be seen that, because of its excellent properties, it has high mechanical strength and can be used for a long time.

[0033]

The present invention is molded using a special glass fiber reinforced propylene resin, and is extremely useful as an outer door handle for automobiles because of its light weight, high mechanical strength, and excellent weather resistance. Things.

Claims (2)

[Claims] 1. A glass fiber-containing resin molded article obtained by impregnating a roving made of filamentous glass fiber with a molten propylene resin, followed by pultruding and cutting into pellets, and a propylene resin. A hindered amine-based light stabilizer having a molecular weight of 1000 or more is used in an amount of 0.3 to 2 to 100 parts by weight of a glass fiber-containing resin mixture mixed so as to have a resin content of 70 to 90% by weight and a glass fiber of 10 to 30% by weight. Molding of a long fiber glass reinforced propylene resin outer door handle obtained by injection molding a glass fiber reinforced propylene resin composition containing 0 parts by weight and 1-2 parts by weight of carbon black having a structure length of 60 nm or less at the time of primary aggregation. Goods. 2. The glass fiber in the molded product has an average fiber length of 0.5.
The outer door handle molded article made of long fiber glass reinforced propylene resin having a thickness of about 6.0 mm to 6.0 mm.