JPS63193944A - Glass fiber reinforced polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having highly balanced impact strength, rigidity, heat-deformation temperature, surface hardness, moldability, etc., and giving a molded article free from surface roughness and color mottling and having excellent surface appearance, by using polypropylene, polybutene-1 and glass fiber at specific ratios. CONSTITUTION:The objective composition can be produced by compounding (A) 15-80wt.% polypropylene, preferably a propylene-ethylene block copolymer or a propylene homopolymer having a melt flow index (MI) of 5-6g/10min and a density of 0.810-0.910g/cm<3>, (B) 20-60% polybutene-1 preferably having an MI of 10-25g/10min and a density of 0.901-0.910g/cm<3> and (C) 5-60% glass fiber preferably having a fiber length of 2-7mm and fiber diameter of 3-15mum and surface-treated with a silane coupling agent. If necessary, 100pts.wt. of the composition is further compounded with (D) <=5pts. preferably 0.2-4pts. of a modified polyolefin (preferably added with 0.01-5% unsaturated carboxylic acid).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyolefin resin composition, and more specifically, the present invention relates to a polyolefin resin composition, and more specifically, it has an excellent surface appearance when molded into a molded product with almost no surface roughness and no color unevenness, and has high impact strength. The present invention relates to a glass fiber-reinforced polyolefin resin composition that has an excellent balance of rigidity, heat distortion temperature, surface hardness, moldability, etc., and is suitable as a molding material in, for example, the automobile, home appliance, or other industrial fields.

[Prior art and its problems] For example, glass fiber reinforced polypropylene resin (CF-
Glass fiber-reinforced polyolefin resins such as PP) have improved tensile strength, rigidity, etc. compared to conventional polypropylene resins.
It has significantly superior kA characteristics and heat resistance, and is comparable to so-called engineering plastics.In recent years, it has been used as a material for industrial parts such as automobile parts and electrical parts.
Its uses have been expanded.

However, conventional glass fiber-reinforced polyolefin resins such as CF-PP have the disadvantage that surface roughness and color unevenness occur due to the orientation of glass fibers, deteriorating the surface appearance of molded products. 0
At present, its use in fields where surface appearance is important, such as A411 products, automobile interior parts, etc., is limited.

Therefore, in order to improve the surface appearance of molded products using GF-PP, various methods have been attempted in the past. For example, compositions made by blending polystyrene and modified polymers have been proposed. (Refer to Japanese Patent Application Laid-Open No. 50-58153).

However, when this composition is made into a molded article, surface roughness and color unevenness are still not sufficiently improved, and further improvements have been desired.

[Purpose of Departure 1J] This invention has been made based on the above circumstances.

In other words, the purpose of this IJJ is to obtain a good appearance without surface roughness or color unevenness when molded products are made, and
It is an object of the present invention to provide a glass fiber reinforced polyolefin resin composition having an excellent balance of impact strength, rigidity, heat distortion temperature, surface hardness, moldability, etc.

[Means for achieving the above object] In order to achieve the above object, as a result of extensive research by the present inventor, a molded article was created by blending glass fiber and a specific compound with polypropylene in a specific ratio. The inventors have discovered that it is possible to obtain a glass m-fiber-reinforced polyolefin resin composition that has a good appearance and an excellent balance of impact strength, rigidity, heat distortion temperature, surface hardness, moldability, etc., and has thus arrived at the present invention.

That is, the outline of the first invention for achieving the above object is as follows: 15 to 80% by weight of polypropylene, 20 to 60% by weight of polybutene-1, and 5 to 80% by weight of glass fiber.
A glass fiber reinforced polyolefin resin composition characterized in that it contains 15 to 80% by weight of polypropylene, 20 to 60% by weight of polybutene-1, and glass fibers. 5-60% by weight
and the resin composition 1 containing the resin composition at a blending ratio of
This is a glass fiber-reinforced polyolefin resin composition characterized in that it contains a modified polyolefin in a blending ratio of 5 parts by weight or less to 00 parts by weight.

As the polypropylene, for example, a so-called Ziegler-Natsuta catalyst is used, which is made of a combination of a nickel compound and an aluminum compound, a combination of a titanium compound and an organoaluminum compound, or a combination of a transition metal compound and an organometallic compound other than these. polypropylene homopolymers, propylene-ethylene random copolymers obtained by the production method or other methods, and mixtures of polypropylene homopolymers and propylene-ethylene random copolymers produced by multistage polymerization methods (so-called propylene-ethylene random copolymers). Block copolymers (such as block copolymers that are popular on the market), etc. can be suitably used. Furthermore, propylene, ethylene and carbon number 4
Copolymers with olefins of -6 can also be included in the polypropylene in this invention.

Among these, those having a melt flow ratio (MI) of 5 to 0.910 minutes and a density of 0.810 to 0.910 g/am"+7) are particularly preferred.

So-called propylene-ethylene block copolymers and propylene homopolymers having such melt flow ratios and densities are preferred.

Examples of the polybutene-1 include homopolymers of butene-1 produced by gas phase polymerization, bulk polymerization, slurry polymerization, etc., and butenes containing 30% by weight or less of other α-olefins. -1 copolymers can be used.

Among these, MI is Ig/10 minutes or more, preferably within the range of 10 to 25, and density is 0.900 g/c
m3 or more, preferably in the range of 0.901 to 0.910. If the OMI is less than 1 g/10 min, the moldability of the composition of the invention may deteriorate. If the density is less than 0.900g/cm3,
When the composition of the present invention is made into a molded article, surface roughness and color unevenness may not be sufficiently improved.

Examples of the glass fibers include non-alkali glass fibers and low-alkali glass mII, which have been conventionally used for resin reinforcement. Glass fibers such as can be used as appropriate.

There is no particular restriction on the form of the glass fibers, and they may be in any form such as roving, chopped strands, or strands, but if the fiber diameter is too large, the strength of the composition may decrease and the appearance may deteriorate. On the other hand,
If it is too thin, the fibers may break during kneading or molding, resulting in a decrease in strength.

In order to obtain a composition having better heat resistance and mechanical strength, the glass fibers may be optionally treated with a coupling agent such as an aminosilane type, an epoxysilane type, a poran type, a vinyl silane type, or a methacrylosilane type, or a chromium complex. It may be used after being surface treated with a compound, a boron compound, etc.

Among these, the fiber length is 1 to 8 mm, especially 2 to 7 mm.
mm, the fiber diameter is 20 ILm or less, particularly 3 to 153 zm, and those that have been surface-treated with a silane coupling agent are particularly preferred.

The resin composition of the first invention contains the polypropylene, polybutene-1, and glass fiber in a specific ratio.

The content of the polypropylene is usually 15 to 80% by weight, preferably 20 to 70% by weight. Content rate is 15
If the weight percentage is unsaturated, the moldability of the resin composition may deteriorate. On the other hand, if it exceeds 80% by weight, the rigidity and heat resistance of the resin composition may decrease, and the effect of improving the appearance of the molded product may not be sufficiently obtained.

The content of polybutene-1 is usually 20 to 60% by weight, preferably 30 to 50% by weight. Content rate is 20
If the weight percentage is unmatched, the effect of improving the appearance of the molded product of the resin composition may not be sufficiently obtained.

On the other hand, if it exceeds 60% by weight, the rigidity and heat resistance of the resin composition may decrease significantly.

The content of the glass fiber is usually 5 to 60% by weight, preferably 10 to 30% by weight. If the content is 5% by weight, the rigidity and heat resistance of the resin composition may decrease. On the other hand, if it exceeds 80% by weight, the moldability of the resin composition may deteriorate.

The glass fiber reinforced resin composition of the second invention further contains a modified polyolefin in a specific proportion based on 100 parts by weight of the first glass fiber reinforced resin composition.

Examples of the modified polyolefin include unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, polyethylene modified with chlorine or vinyl silane, polypropylene, and ethylene propylene copolymers.

Examples of the unsaturated carboxylic acid used for the modification include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
itaconic acid, crotonic acid, citraconic acid, sorbic acid,
Examples of the unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, metal salts, and the like, such as maleic anhydride, itaconic anhydride, citraconic anhydride, Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, Examples include sodium acrylate and sodium methacrylate.

Among these modified polyolefins, polypropylene modified with maleic anhydride, acrylic acid, etc. is particularly preferred.

There are no particular restrictions on the method for producing modified polyolefins, but 1. For example, polyolefins, unsaturated organic acids or derivatives thereof, and organic peroxides are blended, thoroughly mixed using a Henschel mixer, etc., and heated and melt-kneaded at a temperature above the melting point of the polyolefins. This method can be used.

The amount of added acid of the unsaturated carboxylic acid or its derivative in the modified polyolefin thus obtained is 0.01 to
It is desirable that the amount is in the range of 5% by weight. In this case, the unmodified polyolefin is modified to increase the amount of acid added from 0.01 to
The amount may be in the range of 5% by weight, or alternatively, a modified polyolefin with a high acid addition amount may be produced and this and an unmodified polyolefin may be blended to have an acid addition amount of 0.01 to 5% by weight.
During this modification, organic peroxides such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, and t-butyl hydroperoxide may be used to accelerate the degree of modification. Usually used, the amount of polyolefin is 10
It is preferably selected in the range of 0.01 to 3.0 parts by weight relative to 0 parts by weight.

The content of the modified polyolefin is 5 parts by weight per 10 parts by weight of the glass miscellaneous reinforced resin composition according to the first invention.
Parts by weight or less, particularly preferably 0.2 to 4 parts by weight.
Even if the content exceeds 5 parts by weight, the mechanical strength improvement effect corresponding to the content may not be obtained.

In the first invention and the second invention, in addition to the above-mentioned components, additives, elastomers, resins, inorganic fillers, etc. may be blended as necessary.

Examples of the additives include argylphenols,
Antioxidants such as amines and quinones; UV absorbers such as salicylate esters and benzene esters; chlorinated paraffin, tricresyl phosphate, chlorinated oil, antimony oxide, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, Combustion inhibitors such as tetrabromobisphenol A1 dibromopropyl phosphate, tri(2,3-dibromopropyl) phosphate; aliphatic sulfone hydrochloric acid, higher alcohol sulfate ester, ethylene oxide higher alcohol addition sulfate ester, higher alcohol phosphate ester, ethylene Antistatic agent such as oxide higher alcohol added phosphate ester, quaternary ammonium salt type cation activator, ethylene oxide higher alcohol ether, polyethylene glycol fatty acid ester, polyhydric alcohol fatty acid ester, gold salt of nistearate, isobutyl stearate, etc. lubricants; molding agents such as carnauba wax, paraffin wax, silicone oil, silicone emulsion, and silicone spray molding agents; foaming agents such as azonitrile compounds, benzenesulfohydrazine compounds, and diazoamide compounds; carbon black, titanium white, chrome yellow, oil yellow,
Examples include coloring agents such as oil blue and oil red.

Examples of the elastomer include ethylene propylene rubber, ethylene propylene diene rubber, styrene butadiene rubber, styrene butadiene ethylene styrene rubber, acrylic rubber, epichlorohydrin rubber, and butadiene rubber.

Examples of the resin include high-pressure low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and polystyrene.

Examples of the inorganic filler include granular or plate-like materials such as calcium carbonate, talc, mica, carbon black, titanium white, white carbon, and slate powder, and fibrous materials such as magnesium oxysulfate and titanic acid. Examples include potassium, calcium silicate, ceramic, and carbon mix.

In the first and second inventions, there is no particular restriction on the method of blending each component, for example, a method of premixing all the components and then kneading, and a method of premixing the resin resin component and then blending the glass m fiber. method etc. can be used. At this time, mixing and kneading can be carried out according to conventional methods.

The glass reinforced resin compositions according to the first and second inventions can be molded by, for example, injection molding, extrusion molding, blow molding, or the like.

The glass fiber reinforced resin composition according to the present invention contains polypropylene, glass fibers, polybutene-1, and modified polyolefin in a specific proportion, and when molded into a molded product with almost no surface roughness or color unevenness. It has an excellent balance of impact strength, rigidity, heat distortion temperature, surface hardness, moldability, etc., and is suitable for fields where surface appearance is important, such as household electrical appliances, OA equipment, automobile interior parts, etc. It is particularly suitable for

[Effects of the Invention] According to this invention, (1) it is possible to mold a molded product with excellent surface smoothness and no uneven color, (2) mechanical properties such as rigidity and body impact resistance, and heat resistance. It is possible to provide a glass TA fiber reinforced resin composition having excellent properties such as:

[Example] (Examples 1 to 17, Comparative Examples 1 to 9) Modified polyolefin A Modified polypropylene with a maleic acid addition amount of 5% by weight (Idemitsu Polytac H-1000F) Production of modified polyolefin B Equipped with a stirrer and a reflux device Polypropylene (MI = 8g 110 minutes,
Density = 0.90, Product name: Idemitsu Polypro J750
H) Terminal hydroxylation 1.2 per 100 parts by weight
- Polybutadiene (ll\average molecular weight = 2000, trade name: N 1ssoP B G -2000, manufactured by Nippon Soda Co., Ltd.) 5 parts by weight, acrylic acid 10 parts by weight, dicumyl peroxide 1.72 parts by weight, xylene 600 parts by weight 1 part, heated in an oil bath using an injection heater, stirred, reacted at 120°C for 1 hour, and then heated at 140°C.
The reaction was continued for 3 hours at °C.

After the reaction was completed, the mixture was cooled, precipitated with a large excess of a7ton, filtered under suction, and dried (at 70° C. for 50 hours) to obtain a white powdery polymer (modified polyolefin B). The amount of acrylic acid added to this polymer was 2.0% by weight.

Preparation of resin composition After blending other components except glass fiber with a Henschel mixer, it was fed to the hopper mouth of a twin-screw kneader with a quantitative feeder, while the glass fiber was side-fed with a quantitative feeder and heated at 220 ° C. The mixture was melt-kneaded to obtain pellets containing 0.5 parts by weight of carbon black.

The obtained pellets were dried at 100° C. for 3 hours and then molded into test pieces and disks with a diameter of 150 m using an injection molding machine, and their physical properties were measured. The results are shown in Table 1.

(Surface smoothness): Evaluated visually.

O: The surface is extremely smooth with almost no surface roughness.

O: The surface is slightly rough.

×--Surface roughness is noticeable.

××Φ・Surface roughness is noticeable.

(Color unevenness): Evaluated visually.

@116・There is no color unevenness at all.

O: Almost no color unevenness.

×: Color unevenness is noticeable.

×X: Color unevenness is extremely noticeable.

(Bending strength) - Fist - Conforms to JIS k 7203.

(Izotsu impact strength) +1+1・Compliant with JIS K 7110.

(Heat distortion temperature): Based on JIS K 7207.

Resin components in Table 1 and their symbols pp-i Mixture of propylene homopolymer and propylene-ethylene copolymer produced by two-stage polymerization, trade name "Idemitsu Polyprolene J 3050HJ, M"
I = 30 g/10 min, ethylene content: 6% by weight PP-2 Mixture of propylene homopolymer and propylene-ethylene copolymer produced by two-stage polymerization, trade name "Idemitsu Polypropylene J78 5 HJ, MI = 8g/10min, ethylene content: 5% by weight PP-3 Mixture of propylene homopolymer and propylene-ethylene copolymer produced by two-stage polymerization, trade name: “Idemitsu Polypropylene J450HJ, M I = 4g /10 min, ethylene content: 6% by weight PP-4 propylene homopolymer, MI = 8 g 710 min PB-1 polybutene-1, MI = leg/10 min FB-2 polybutene-1, MI = 2 g/10 Glass m fiber A Alkali-free glass, m fiber length: 3 am, RID diameter: 13 g, m, aminosilane surface treated glass! amB Alkali-free glass, fiber length: 3
Multilayer, -11 diameter: 9 m, aminosilane surface treated glass fiber C charred alkali glass, M & fiber length: 3 Peng, fiber diameter: 6 m, aminosilane surface treatment (hereinafter referred to as margin) From Table 1, polybutene - 1 is essential for achieving the object of the present invention, and it is clear that if the amount of polybutene-1 exceeds the range specified by the invention, the object of the invention cannot be achieved.

Furthermore, glass fiber reinforced resin compositions containing modified polyolefins have even better surface appearance and mechanical properties.

Claims (2)

[Claims] (1) 15-80% by weight of polypropylene, 20-60% by weight of polybutene-1, and 5-60% of glass fiber.
A glass fiber-reinforced polyolefin resin composition characterized in that the composition contains a glass fiber-reinforced polyolefin resin composition at a blending ratio of % by weight. (2) 15-80% by weight of polypropylene, 20-60% by weight of polybutene-1, and 5-60% of glass fiber.
1. A glass fiber-reinforced polyolefin resin composition, characterized in that it contains a resin composition in a blending ratio of % by weight, and a modified polyolefin in a blending ratio of 5 parts by weight or less based on 100 parts by weight of the resin composition.