JP2000109613A - High-strength thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which can give a product improved in impact resistance, rigidity, heat resistance, and strengths by mixing a partially or fully crosslinked rubbery polymer with a thermoplastic resin and an acicular or fibrous filler. SOLUTION: This composition comprises 100 pts.wt., in total, of 1-99 pts.wt. partially or fully rubbery polymer obtained by copolymerizing ethylene with 1-60 wt.% 3-20C α-olefin in the presence of a metallocene catalyst and having a density of 0.8-0.9 g/cm3, a melt index of 0.01-100 g/10 min, desirably, 0.2-20 g/10 min (at 190 deg.C under a load of 2.016 kg), and a melting point peak at room temperature or higher and 1-99 pts.wt., desirably, 5-95 pts.wt. thermoplastic resin, and 0.1-200 pts.wt., desirably, 1-150 pts.wt. acicular or fibrous filler having an average diameter of 0.01-1,000 μm, desirably, 0.1-500 μm, an average aspect ratio (length/diameter ratio) of 5-2,500, desirably, 10-1,000, and an average diameter of 0.01-1,000 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high mechanical strength thermoplastic resin composition reinforced with a fibrous or acicular filler and a partially or completely crosslinked rubbery polymer. . More specifically, the present invention relates to a high-strength flexible thermoplastic resin composition reinforced with a fibrous or acicular filler and a partially or completely crosslinked rubbery polymer, and a high impact resistance and high The present invention relates to a rigid thermoplastic resin composition having high rigidity and high heat resistance.

[0002]

2. Description of the Related Art A soft thermoplastic resin, that is, a thermoplastic elastomer, has not only excellent moldability but also impact resistance,
Because of its excellent flexibility, it is used in various fields including automotive materials, electrical materials, and housing materials.

In recent years, there has been a demand in such fields to improve the mechanical strength, particularly the tensile strength, of materials. For the purpose of this improvement, The Japan Rubber Association, Vol. 69, No. 9, 61
Page 5 (1996) discloses short fiber reinforcement of thermoplastic elastomers. However, although the fiber-reinforced elastomer has improved mechanical strength due to fiber reinforcement, it is inferior in abrasion resistance, durability, and the like, and there is a limit in using automotive materials and the like. Excellent wear resistance and durability,
Further, development of a high-strength thermoplastic elastomer composition is required.

On the other hand, as the hard thermoplastic resin, many resins such as a polypropylene resin, a styrene resin and a polyamide resin are generally known. These hard thermoplastic resins are required to have high mechanical strength depending on the use. For example, polypropylene resin and polyamide resin are sold as materials reinforced with glass fibers.
Of these, polyamide-based resins reinforced with glass fibers are used in automotive materials such as radiator tanks, tool housing materials such as electric drills, and office equipment such as office chairs. The polyamide resin reinforced with glass fiber has high strength because the polyamide resin as a base has relatively high strength. Therefore, the field of application is expanding. However, the polypropylene resin reinforced with glass fiber is limited in its use at present because the strength of the parent polypropylene resin is smaller than that of a polyamide resin or the like.

[0005] If a high-strength material made of a resin containing a polypropylene resin is used, not only will its use be expanded, but even if it is a polyamide resin, if the strength is further increased, it becomes possible to make it thinner and lighter. This leads to cost reduction and is more preferable. For this reason, there is a demand for the development of a harder thermoplastic resin material having higher strength.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, an object of the present invention is to provide a higher-performance soft thermoplastic resin and a higher-performance hard thermoplastic resin molded product. It is.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, in a region where the content of the thermoplastic resin is small, the thermoplastic resin is partially or completely contained. When co-existing a crosslinked rubber-like polymer and a specific shape of fibrous or acicular filler, surprisingly, a high-strength soft thermoplastic resin (heat (Plastic elastomer), and completed the present invention. Further, in the region where the content of the thermoplastic resin is large, when a rubber-like polymer partially or completely cross-linked to the thermoplastic resin and a fibrous or acicular filler of a specific shape coexist, it is surprising. In particular, they have found that it is a high-strength hard thermoplastic resin having excellent impact resistance, rigidity, and heat resistance, and have completed the present invention.

That is, the present invention relates to (A) 1 to 99 parts by weight of a partially or completely crosslinked rubbery polymer, (B) 1 to 99 parts by weight of a thermoplastic resin, and (A) a component (B) )
(C) The average diameter is 0.01 to 1000 μm with respect to 100 parts by weight of the total amount of the components, and the aspect ratio (length / length)
The present invention relates to a high-strength thermoplastic resin composition comprising 0.1 to 200 parts by weight of a fibrous or acicular filler having a diameter of 5 to 2500.

Hereinafter, the present invention will be described in detail.

First, each component of the present invention will be described in detail.

The partially or completely crosslinked rubbery polymer which is the component (A) of the thermoplastic resin molded article of the present invention will be described.

The rubbery polymer of the present invention is, for example, polystyrene, polyolefin, polyester, polyurethane, 1,2-polybutadiene, polyvinyl chloride or the like. Among these rubber polymers, a polyolefin-based rubber-like polymer (polyolefin-based thermoplastic elastomer) is preferable because of its excellent weather resistance and mechanical strength.

Among the polyolefin rubbery polymers, an ethylene / α-olefin copolymer rubber mainly comprising ethylene and α-olefin is most preferred.

The ethylene / α-olefin copolymer rubber will be described in more detail.
The ethylene / α-olefin copolymer mainly composed of α-olefin is more preferable. As the α-olefin having 3 to 20 carbon atoms, for example, propylene, butene-1,
Pentene-1, hexene-1, 4-methylpentene-
1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1 and the like.
These α-olefins may be used alone or
You may combine more than seeds. Further, a copolymer component may be included as the third component. Conjugated dienes such as 1,3-butadiene and isoprene as copolymerization components of the third component;
Non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, and ethylidene norbornene. Among them, especially ethylene / α-olefin copolymer rubber, especially ethylene / octene-1 copolymer rubber, is easy to crosslink and because it is a saturated rubber, the weather resistance of a thermoplastic resin molded product is also high. Excellent and most preferred.

The ethylene / α-olefin copolymer rubber suitably used as the component (A) is preferably produced using a metallocene catalyst.

In general, a metallocene-based catalyst is composed of a cyclopentadienyl derivative of a Group IV metal such as titanium or zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst but also has a higher activity than a Ziegler-based catalyst. The molecular weight distribution of the resulting polymer is narrow, and the distribution of the comonomer α-olefin having 3 to 20 carbon atoms in the co-weight is uniform. For this reason, the polymer obtained with the metallocene-based catalyst has a more uniform cross-linking and exhibits excellent rubber elasticity.

The ethylene / α-olefin copolymer rubber, which is the component (A) preferably used in the present invention, has an α-olefin copolymerization ratio of preferably 1 to 60% by weight, more preferably Is from 10 to 50% by weight, most preferably from 20 to 45% by weight. If the copolymerization ratio of the α-olefin exceeds 50% by weight, the molded article obtained from the composition of the present invention is unfavorably greatly reduced in tensile strength and the like.
On the other hand, if it is less than 1% by weight, the effect of improving the mechanical strength of the molded article obtained from the composition of the present invention is not obtained, which is not preferable.

The density of the ethylene / α-olefin copolymer rubber is preferably in the range of 0.8 to 0.9 g / cm ³ . By using a rubber-like polymer having a density in this range, a molded article having excellent flexibility can be obtained from a soft thermoplastic resin composition. In addition, a hard thermoplastic resin composition can provide a molded article having excellent impact resistance.

The ethylene / α-olefin copolymer rubber, which is the component (A) suitably used in the present invention, preferably has a long chain branch. Due to the presence of long-chain branching, the copolymerized α-
The density can be made smaller than the olefin ratio (% by weight), and a low-density, low-hardness, high-strength rubbery polymer can be obtained. The ethylene / α-olefin copolymer rubber having a long-chain branch is USP5
278272 and the like.

The ethylene / α-olefin copolymer rubber preferably has a DSC melting point peak at room temperature or higher. When it has a melting point peak, the form is stable in the temperature range below the melting point, the handleability is excellent, and the stickiness is small.

Further, the ethylene / α used in the present invention
-The melt index of the olefin copolymer rubber is
0.01 to 100 g / 10 minutes (190 ° C., 2.016 k
Those in the range of g) are preferably used, and more preferably 0.2 to 20 g / 10 min. If it exceeds 100 g / 10 minutes, the crosslinking property of the rubbery polymer is insufficient, and if it is less than 0.01 / 10 minutes, the fluidity of the composition is poor,
Undesirably, the workability is reduced.

The rubbery polymer as the component (A) of the composition of the present invention may be used as a mixture of a plurality of types. In such a case, it is possible to further improve the workability.

The rubbery polymer as the component (A) must be partially or completely crosslinked. The molded article obtained from the thermoplastic resin composition of the present invention, when cross-linked, when compared to the case without cross-linking, in the case of a soft system,
The durability, abrasion resistance and strength are greatly improved. In the case of a hard type, impact resistance, rigidity and heat resistance are greatly improved. Crosslinked rubbery polymer (rubbery polymer that does not dissolve in solvent) in all rubbery polymers in the thermoplastic resin composition of the present invention
Is defined by the degree of crosslinking, the degree of crosslinking is 30% or more,
Preferably, it is 50% or more.

Next, the thermoplastic resin as the component (B) in the thermoplastic resin composition of the present invention will be described.

The thermoplastic resin as the component (B) in the thermoplastic resin composition of the present invention is not particularly limited as long as it is compatible with or homogeneously dispersed with the component (A). For example, polystyrene-based, polyphenylene ether-based, polyolefin-based, polyvinyl chloride-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, and polymethacrylate-based resins may be used alone or in combination of two or more. it can. Among these, a polyolefin resin is particularly preferable as the thermoplastic resin of the component (B). This is because the thermoplastic resin composition of the present invention has high affinity and high strength with the ethylene / α-olefin copolymer rubber suitably used as the component (A) of the thermoplastic resin composition.

The polyolefin resin suitably used as the component (B) in the thermoplastic resin composition of the present invention can be roughly classified into a polyethylene resin, a polypropylene resin or a mixture of a polyethylene resin and a polypropylene resin.

As the polyethylene resin, high density polyethylene (HDPE), low density polyethylene (LDP)
E), linear low density polyethylene (LLDPE), copolymer of acrylic vinyl monomer and ethylene (EE
A, EMMA, etc.) or a copolymer of a vinyl acetate monomer and ethylene (EVA). However, among these, high density polyethylene (HD
PE), low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) are particularly preferred because of their high heat resistance and availability at low cost. These polyethylene resins may be used alone or in combination of two or more.

When high density polyethylene (HDPE) is used, its density generally ranges from 0.930 to 0.970.
g / cm ² , and the melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg is 0.0
It is preferably in the range of 5 to 100 g / 10 minutes. When low-density polyethylene (LDPE) or linear low-density polyethylene (LLDPE) is used, its density is generally in the range of 0.900 to 0.930 g / cm ² at 190 ° C. under a load of 2.16 kg. The measured melt flow rate (MFR) is 0.05 to 100 g / 1.
It is preferably in the range of 0 minutes. When the melt flow rate exceeds 100 g / 10 minutes, the mechanical strength and heat resistance of the molded article obtained from the thermoplastic resin composition of the present invention are insufficient. When molding the thermoplastic resin composition of (1), the fluidity is poor, and the molding processability is undesirably reduced.

As the polypropylene resin, homotactic polypropylene, isotactic copolymer resin of propylene with other α-olefins such as ethylene, butene-1, pentene-1, hexene-1 (including block and random) And the like.

230 ° C., 2.1 of polypropylene resin
Melt flow rate (MFR) measured at 6 kg load
Is preferably in the range of 0.1 to 100 g / 10 minutes. When the melt flow rate exceeds 100 g / 10 minutes, the mechanical strength and heat resistance of a molded article obtained from the thermoplastic resin composition of the present invention are insufficient, and 0.1 g / 1
If the time is less than 0 minutes, the fluidity is poor when molding the thermoplastic resin composition of the present invention, and the molding processability is undesirably reduced.

The polyolefin resin as the component (A) in the thermoplastic resin composition of the present invention comprises a polyethylene resin and / or a polypropylene resin as described above, but a homopolypropylene resin has high heat resistance. More preferred. However, homopolypropylene generally tends to be oxidatively decomposed and has a tendency to decrease in mechanical strength due to a decrease in molecular weight during long-term use. On the other hand, polyethylene resins generally have a tendency to crosslink without being oxidatively decomposed and maintain or improve mechanical strength. For this reason, when using a polypropylene-based resin, particularly when used for applications requiring durability, use a homopolypropylene and a polyethylene-based resin together or use a propylene-ethylene-based random or block polymer. Is preferred. In any case, the polypropylene resin has higher heat resistance than the polyethylene resin and is most preferable as the component (B) of the thermoplastic resin composition of the present invention.

The thermoplastic resin as the component (B) in the thermoplastic resin composition of the present invention may be a single kind or a combination of a plurality of kinds.

The thermoplastic resin, which is at least one component (B) selected from these resins, is used at a composition ratio of 1 to 99 parts by weight based on 100 parts by weight of the total of the components (A) and (B). Can be Preferably it is 5 to 95 parts by weight.
In the case of a soft thermoplastic resin composition, more preferably 2
0 to 80 parts by weight, most preferably 20 to 70 parts by weight. On the other hand, in the case of a hard thermoplastic resin composition, more preferably 30 to 90 parts by weight, and most preferably 60 to 90 parts by weight.
Parts by weight. If the amount is less than 1 part by weight, the fluidity and processability of the composition are undesirably reduced. If it exceeds 99 parts by weight, the effect of improving the strength of the composition is insufficient, which is not preferable.

Next, (C) of the thermoplastic resin composition of the present invention
The fibrous or acicular filler as a component will be described.

The fibrous or acicular filler has an average diameter of 0.01 to 1000 μm, preferably 0.1 to 1000 μm.
It is 1 to 500 μm, more preferably 1 to 100 μm, and most preferably 5 to 50 μm. The average aspect ratio (length / diameter) is 5 to 2500, preferably 1 to 5.
There is no particular limitation as long as it is 0 to 1000. If the average diameter is less than 0.01 μm, the reinforcing effect is small,
The effect of improving mechanical strength is not sufficient. If it exceeds 1000 μm, the dispersibility decreases, and similarly, the effect of improving the mechanical strength is not sufficient. If the average aspect ratio (length / diameter) is less than 5, the anisotropy is insufficient and the reinforcing effect is small,
On the other hand, if it exceeds 2,500, the fluidity during molding processing is not sufficient, causing problems in molding processing.

As the fibrous filler, for example, cotton,
Natural fiber such as silk, wool or hemp, regenerated fiber such as rayon or cupra, semi-synthetic fiber such as acetate or promix, synthetic fiber such as polyester, polyacrylonitrile, polyamide, aramid, polyolefin, carbon or vinyl chloride, glass or Examples thereof include inorganic fibers such as asbestos and metal fibers such as SUS, copper and brass.

As the needle-like filler, potassium titanate, magnesium oxysulfate, aluminum borate, wollastonite, sebiolite, zonotolite, phosphate fiber, dawsonite, gypsum fiber, MOS, needle-like calcium carbonate, tetrapot type oxide Whiskers made of zinc, silicon carbide or silicon nitride can be used.

The fibrous or acicular filler (C) in the thermoplastic resin composition of the present invention may be any one of the above materials and may be used alone or in combination of two or more. Among these materials, in the case of a soft thermoplastic resin composition, aramid fibers, polyacrylonitrile fibers, glass fibers, and the like are particularly preferable as fillers in terms of increasing strength. On the other hand, in the case of a hard thermoplastic resin composition, glass filler, carbon fiber, magnesium oxysulfate whisker, or the like is particularly preferable as a filler in terms of impact strength, rigidity, and heat resistance.

The above aramid fiber can be produced by dissolving isophthalamide or polyparaphenylene terephthalamide in an amide polar solvent or sulfuric acid and spinning the solution by a wet or dry method.

The polyacrylonitrile fiber is prepared by dissolving the polymer in a solvent such as dimethylformamide and dry spinning in a stream of air at 400 ° C. or by dissolving the polymer in a solvent such as nitric acid and wet spinning in water. It is manufactured by a wet spinning method or the like.

Commercially available glass fibers, carbon fibers or magnesium oxysulfate whiskers are used. These fibrous or needle-like fillers, which have been previously treated with maleic anhydride or a silane coupling agent, have a higher reinforcing effect and are more preferable.

The amount of the fibrous or acicular filler as the component (C) in the thermoplastic resin composition of the present invention is (A)
0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the total of the partially or completely crosslinked rubber polymer as the component and the thermoplastic resin as the component (B).
It is 150 parts by weight, more preferably 10 to 100 parts by weight, still more preferably 20 to 70 parts by weight.

As described above, the thermoplastic resin molded article of the present invention basically comprises at least (A) a partially or completely crosslinked rubbery polymer, (B) a thermoplastic resin and (C) a fiber. It is made of a filler in the shape of a needle or needle, but may contain other components as necessary, such as a polymer other than the above, a softener, a powdery inorganic filler, a plasticizer, and the like. As another polymer, one that improves interfacial adhesion between a filler and a thermoplastic resin is particularly effective for improving impact resistance, and is preferably contained as a fourth component. As such a material, it is preferable to coexist, for example, a modified maleic acid polymer or copolymer, a modified acrylic acid polymer or copolymer, a modified fumaric acid polymer or a copolymer, and the like. These materials are particularly effective when glass fiber is used as a filler. As the softener, process oils such as paraffinic and naphthenic can be used. When a softener is present, the hardness and flexibility of the soft thermoplastic resin composition can be adjusted. In the case of a hard thermoplastic resin composition, the rigidity tends to decrease slightly, but the impact resistance can be further improved. The blending of these softeners is particularly effective when a soft thermoplastic resin composition is used. In this case, (A)
5 to 100 parts by weight of the total amount of the component and the component (B)
250 parts by weight, preferably 10 to 150 parts by weight are used.
If the amount is less than 5 parts by weight, flexibility and workability are insufficient, and if it exceeds 250 parts by weight, bleed out of the softener becomes remarkable, which is not preferable.

Examples of the powdery inorganic filler include calcium carbonate, magnesium carbonate, silica, carbon black, titanium oxide, clay, mica, talc, magnesium hydroxide, and aluminum hydroxide. Examples of the plasticizer include phthalic acid esters such as polyethylene glycol and dioctyl phthalate (DOP). Also, other additives, for example,
Organic / inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, silicone oils, antiblocking agents, foaming agents, antistatic agents, antibacterial agents and the like are also suitably used.

Next, a method for producing the thermoplastic resin composition of the present invention will be described.

The thermoplastic resin composition of the present invention is preferably a crosslinked thermoplastic elastomer comprising a partially or completely crosslinked rubbery polymer as the component (A) and a thermoplastic resin as the component (B). In addition, a fibrous or acicular filler as the component (C) and, if necessary, a thermoplastic resin for adjusting the composition are produced. When obtaining molded products,
The mixture is previously melt-extruded and pelletized by a twin-screw extruder or the like, and the obtained pellets are processed into a molded product by injection molding, extrusion molding, compression molding, blow molding calender molding, foam molding or the like. However, in the method of preliminarily blending with a twin-screw extruder or the like, when the filler has a low strength, the filler is crushed when passing through the extruder, and the aspect ratio becomes small, so that a thermoplastic resin molded article having a desired mechanical strength is obtained. Sometimes it does not. in this case,
A crosslinked thermoplastic elastomer comprising a partially or completely crosslinked rubbery polymer as the component (A) and a thermoplastic resin as the component (B), and a filler or a thermoplastic resin solidified with the filler itself or a sizing agent or the like. The thermoplastic resin composition of the present invention is obtained by blending with a filler solidified by the above method, and a thermoplastic resin molded product is obtained by a method such as direct injection molding of the blended product. In this case, since the kneading only needs to be performed once at the time of injection molding, the aspect ratio in the molded article becomes closer to the aspect ratio of the raw material as compared with the method of blending with a twin-screw extruder and further performing injection molding. A thermoplastic resin molded article having mechanical strength is more preferable.

This method of blending the raw materials and obtaining a thermoplastic resin molded article having a large aspect ratio in only one kneading process is effective for fibrous fillers, particularly for glass fibers and carbon fibers. In the case of a fibrous filler, for example, it is preferable to specifically produce a high-strength molded article from the thermoplastic resin composition of the present invention by the following method. That is, first, a bundle (roving) of fibers such as glass fiber and carbon fiber.
The pellets are impregnated or extruded with a thermoplastic resin and pelletized to produce pellets containing fibers having the same length as the pellet length (referred to as long fiber pellets). More specifically,
For example, a method of immersing a roving of fibers such as glass fibers and carbon fibers in a molten thermoplastic resin and then pelletizing to a predetermined length or a method generally called a pultrusion method, such as glass fibers, carbon fibers, etc. A method of extruding a thermoplastic resin from the side with an extruder while aligning fiber rovings under tension, extruding the thermoplastic resin on the surface of the fibers and pelletizing, or tensioning the roving of fibers such as glass fiber and carbon fiber. There is a method of immersing in a convergence liquid such as latex, drying and pelletizing while aligning them below. The long fiber pellets produced by this method are usually 2 to 50 mm, preferably 3 to 2 mm.
Pellets having a length of 0 mm, more preferably 5 to 10 mm are preferable. The long fiber pellet and the partially or completely crosslinked rubbery polymer as the component (A) are combined with (B)
A crosslinked thermoplastic elastomer pellet comprising a thermoplastic resin as a component and, if necessary, a thermoplastic resin pellet for adjusting the composition are blended, and the pellet blend is injection molded to obtain a molded product.

The method for producing the thermoplastic resin composition of the present invention is as described above, and the partially or completely crosslinked rubbery polymer used as the component (A) and the component (B) used here are used. The crosslinked thermoplastic elastomer composed of a thermoplastic resin is produced, for example, as follows. That is, when the ethylene-α-olefin-based copolymer mainly composed of ethylene and α-olefin, which is the most preferred example of the present invention, is a rubber-like polymer, and the thermoplastic resin is a polyolefin-based resin, The ethylene-α-olefin-based copolymer is partially or completely cross-linked by heat-treating the state polymer and the polyolefin-based resin, the cross-linking agent and the cross-linking assistant with a twin-screw extruder, a Banbury mixer, or the like.
In this case, examples of the crosslinking agent include radical initiators such as organic peroxides and organic azo compounds. Specific examples of the radical initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,
3,5-trimethylcyclohexane, 1,1-bis (t
-Hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-
Bis (t-butylperoxy) octane, n-butyl-
Peroxy ketals such as 4,4-bis (t-butylperoxy) butane and n-butyl-4,4-bis (t-butylperoxy) valerate; di-t-butyl peroxide, dicumyl peroxide , T-butylcumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, α, α'-bis (t-
Butylperoxy) diisopropylbenzene, 2,5-
Dialkyl peroxides such as dimethyl-2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3; acetyl peroxide, isobutylene Luper oxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5
Diacyl peroxides such as trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioil peroxide; t-butylperoxyacetate, t-butylperoxyisobutyrate, t -Butyl peroxy-2-ethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, di-t-butyl peroxy isophthalate, 2,
Peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and cumylperoxyoctate; and t-butyl Hydroperoxides such as hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide Can be mentioned.

Among these compounds, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 are preferred.

These radical initiators are ethylene / α
-0.02 to 100 parts by weight of the olefin copolymer
It is used in an amount of 3 parts by weight, preferably 0.05 to 1 part by weight. The level of crosslinking is mainly determined by this amount. 0.
If the amount is less than 02 parts by weight, the crosslinking is insufficient, and if the amount exceeds 3 parts by weight, the crosslinking rate is not greatly improved, so that it is not a preferable direction.

Examples of the crosslinking assistant include divinylbenzene, triallyl isocyanurate, triallyl cyanurate,
Diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,
Trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, P-quinone dioxime, P, P'-dibenzoylquinone dioxime, phenylmaleimide, allyl methacrylate, N , N'-m-
Phenylene bismaleimide, diallyl phthalate, tetraallyloxyethane, 1,2-polybutadiene and the like are preferably used. These crosslinking aids may be used in combination of two or more.

The crosslinking aid is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer. If the amount is less than 0.1 part by weight, the crosslinking rate is low, which is not preferable. If the amount exceeds 5 parts by weight, the crosslinking ratio is not significantly improved, and an excessive amount of the crosslinking aid remains, which is not a preferable direction.

It is preferable to use a cross-linking agent and a cross-linking aid as described above as a cross-linking method. In addition, a phenol resin or bismaleimide may be used as a cross-linking agent.

In the production of the crosslinked thermoplastic elastomer, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder or the like can be used. In order to achieve particularly efficient crosslinking, a twin-screw extruder is preferably used. The twin-screw extruder uniformly and finely disperses the rubber-like polymer and the thermoplastic resin, and can also preferably carry out a cross-linking reaction by a cross-linking reaction with a cross-linking agent and a cross-linking aid, thereby continuously producing a cross-linked thermoplastic elastomer. Suitable to do. A specific manufacturing method can be manufactured through the following processing steps. That is, a rubbery polymer, preferably ethylene-α-
An olefin copolymer rubber and a thermoplastic resin, preferably a polyolefin-based resin, are thoroughly mixed and charged into a hopper of an extruder. The radical initiator and the crosslinking assistant may be added together with the rubbery polymer and the thermoplastic resin from the beginning, or may be added in the middle of the extruder. When oil is added as a softening agent, it may be added from the middle of the extruder, or may be added separately at the beginning and during the middle. A part of the rubbery polymer and the thermoplastic resin may be added in the middle of the extruder. When heated and melted and kneaded in the extruder, the rubber-like polymer and the radical initiator and the crosslinking assistant undergo a crosslinking reaction, and if necessary, an oil or the like is added and melt-kneaded, whereby the crosslinking reaction and kneading are performed. After sufficient dispersion, take out of the extruder. Pelletized to obtain pellets of crosslinked thermoplastic elastomer.

The thermoplastic resin composition of the present invention thus obtained can be used to produce various molded articles by any molding method. As the molding method, injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used.

[0056]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In these examples and comparative examples, the test methods used for evaluating various physical properties, and the production methods of the thermoplastic elastomer used for the raw materials and the blending are as follows.

1. Test method (1) Tensile strength Measured at 23 ° C. by a method according to JIS K6251.

(2) Tensile elongation Measured at 23 ° C. by a method according to JIS K6251.

(3) Flexural strength The flexural strength was measured at 23 ° C. in accordance with JIS K6758.

(4) Flexural modulus Measured at 23 ° C. by a method according to JIS K6758.

(5) Izod impact strength Measured at 23 ° C. by a method according to JIS K6758.

(V notch, 1/4 inch test piece) (6) Drop weight impact strength Using a drop weight impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.), the tip diameter of the drop weight: 13.6 mm, weight: 6.5 kg , Fall height: 1
00cm, holder diameter: 50mm, specimen thickness: 3m
m, temperature: 23 ° C., humidity 50%, total absorbed energy was measured. Larger values are more difficult to crack.

(7) Heat resistance (HDT) Measured in accordance with JIS K7207.

(8) Compression set Based on JIS K7207, at 70 ° C. for 22 hours
It was evaluated as an index of durability. The smaller the value, the better the durability.

(9) Filler Average Diameter and Aspect Ratio The number average particle diameter of the filler was determined by an electron microscope, while the length of the filler was determined by an optical microscope, and the aspect ratio was calculated from the length / diameter ratio. That is, the cross section of each filler is assumed to be a circle, and the arithmetic average of the major axis and the minor axis is defined as the average diameter of each filler. And number average particle diameter was calculated | required by arithmetic mean of the average diameter of 100 fillers. The average length of the above-mentioned filler was similarly obtained as the number average length.

(10) Degree of Crosslinking 0.5 g of the crosslinked thermoplastic elastomer was added to xylene 200
Reflux in ml for 4 hours. The solution was filtered with a filter paper for quantification, the residue on the filter paper was vacuum-dried, quantified, and calculated as the ratio (%) of the weight of the residue to the weight of the rubbery polymer in the crosslinked thermoplastic elastomer.

2. Raw materials (1) Rubbery polymer (a) Ethylene / octene-1 copolymer Produced by a method using a metallocene catalyst described in JP-A-3-1630088. The ethylene / octene-1 composition ratio of the copolymer was 72/28 (weight ratio) (referred to as TPE-1). (B) Ethylene / propylene / dicyclopentadiene copolymer It was produced by a method using a metallocene catalyst described in the gazette. The composition ratio of ethylene / propylene / dicyclopentadiene in the copolymer is 72/2.
4/4 (weight ratio) (referred to as TPE-2).

(2) Olefin resin (a) Polypropylene Isotactic homopolypropylene (trade name MA03) (referred to as PP) manufactured by Nippon Polychem Co., Ltd. (b) Ethylene (E) -propylene (PP) copolymer resin -1 Block E-PP resin manufactured by Japan Polyolefin Co., Ltd.
[E / PP = 6/94] (weight ratio) (trade name: PM97
0A)] (referred to as EP-1) (c) Ethylene (E) -propylene (PP) copolymer resin-2 Nippon Polyolefin Co., Ltd., random E-PP resin [E / PP = 7/93 (weight ratio) ) (Product name PM940
M] (referred to as EP-2) (d) Maleated polypropylene Maleated polypropylene (trade name Admer GF305) (referred to as M-PP) manufactured by Mitsui Chemicals, Inc. (3) High-density polyethylene manufactured by Asahi Chemical Industry Co., Ltd. , Suntech HD (product name B47
0) (referred to as HDPE) (4) Radical initiator 2,5-dimethyl-2,5-bis (t-manufactured by NOF Corporation)
Butylperoxy) hexane (trade name Perhexa 25)
B) (referred to as POX) (5) Cross-linking aid Wako Pure Chemical Industries, divinylbenzene (referred to as DVB) (6) Softener (paraffin oil) Idemitsu Kosan, Diana Process Oil (trade name PW-3)
80) (7) Filler (a) Glass fiber Aminosilane treated glass fiber roving made by Asahi Fiber (trade name: ER740) (thickness: 13 μm) (b) Carbon fiber Carbon fiber roving made by Toho Rayon (trade name: HTA-)
12K) (Thickness: 7μ) (c) Magnesium oxysulfate whisker Whisker made by Ube Materials (trade name: Moss Heidi A) (d) Polyacrylonitrile fiber (PAN fiber) Polyacrylonitrile (molecular weight 200,000) is dissolved in dimethylformamide And dry spinning in an air stream at 400 ° C. The average fiber diameter was controlled by the size of the spinneret, and the aspect ratio was controlled by the cutting speed.

3. Production Method of Crosslinked Thermoplastic Elastomer (1) TPV-1 A twin-screw extruder (40 mmφ, L / D = 47) having an injection port in the center of the barrel was used as an extruder. As the screw, a double screw having a kneading portion before and after the injection port was used. TPE-1 / PP / POX / DVB = 55.
6 / 44.4 / 0.38 / 0.74 (weight ratio) and melt-extruded at a cylinder temperature of 220 ° C. The degree of crosslinking of the obtained crosslinked thermoplastic elastomer was 82%.

(2) TPV-2 The ratio of TPE-1 / PP / POX / DVB was 55.6 /
A crosslinked thermoplastic elastomer was obtained in the same manner as in (1) except that the ratio was 44.4 / 0.19 / 0.37 (weight ratio).
The degree of crosslinking of this crosslinked thermoplastic elastomer was 55%.

(3) TPV-3 TPE-1 / PP / POX / DVB is converted to TPE-1 / EP
A crosslinked thermoplastic elastomer was obtained in the same manner as in (1) except that -1 / POX / DVB was used. The degree of crosslinking of this crosslinked thermoplastic elastomer was 81%.

(4) TPV-4 TPE-1 / PP / POX / DVB is converted to TPE-1 / PP
/ HDPE / POX / DVB and the ratio is 55.6
/33.3/11.1/0.19/0.37 (weight ratio)
A crosslinked thermoplastic elastomer was obtained in the same manner as in (1), except that The degree of crosslinking of this crosslinked thermoplastic elastomer was 85%.

(5) TPV-5 TPE-1 / PP / POX / DVB is converted to TPE-2 / PP
A crosslinked thermoplastic elastomer was obtained in the same manner as in (1) except that / POX / DVB was used. The degree of crosslinking of this crosslinked thermoplastic elastomer was almost 100%.

(6) TPV-6 The composition and ratio of TPE-1 / PP / POX / DVB
PE-1 / PP / POX / DVB = 70.0 / 30.0
/0.30/1.00, except for injecting 60 parts by weight of a softening agent (paraffin oil) with respect to 100 parts by weight of the total amount of TPE-1 and PP from the inlet at the center of the extruder. A crosslinked thermoplastic elastomer was obtained in the same manner as in (1). The degree of crosslinking of this crosslinked thermoplastic elastomer is 62%
Met.

(7) TPV-7 A crosslinked thermoplastic elastomer was obtained in the same manner as in (6) except that TPE-1 was changed to TPE-2. The degree of crosslinking of this crosslinked thermoplastic elastomer was 78%.

4. Method for Producing Non-Crosslinked Thermoplastic Elastomer (1) As a TPO-1 extruder, a twin-screw extruder (40 mmφ, L / D = 47) having an inlet at the center of the barrel was used. As the screw, a double screw having a kneading portion before and after the injection port was used. TPE-1 / PP = 55.6 / 44.4 (weight ratio) was mixed and melt-extruded at a cylinder temperature of 200 ° C.

(2) TPO-2 The ratio of TPE-1 / PP was 70/30, and a softening agent (paraffin oil) was added to 100 parts by weight of the total amount of TPE-1 and PP from the injection port at the center of the extruder. ) Was melt-extruded in the same manner as in (1) except that 60 parts by weight was injected.

Example 1 5% M-PP / 95% PP was extruded from a side while extruding a roving of 13 μm thick glass fiber under tension, and a polyolefin resin was extrusion-coated on the surface of the glass fiber. Then, it was cut into pellets having a length of 7 mm to produce long fiber pellets (referred to as GF-1). The aspect ratio of the glass fibers in the long fiber pellet is 538. The ratio of the long fiber pellet to glass / polyolefin resin was 56/44 (weight ratio). G
Each pellet of F-1, TPV-1, and PP was added to 53.6 / 3.
6.0 / 10.4 (weight ratio) and the molding temperature was 24
The temperature was set to 0 ° C., and the product was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 1 shows the characteristics of the molded product. In addition,
The ratio of polyolefin resin / rubber-like polymer (partially crosslinked) / glass fiber in the composition is 50.0 / 20.0 / 3
0.0 (weight ratio).

Example 2 A molded product was obtained in the same manner as in Example 1 except that TPV-1 was changed to TPV-2. Table 1 shows the characteristics of the molded product.
The ratio of polyolefin resin / rubber-like polymer (partially crosslinked) / glass fiber in the composition was 50.0 / 20.
0 / 30.0 (weight ratio).

Comparative Example 1 A molded product was obtained in the same manner as in Example 1 except that TPO-1 was changed to TPO-1. Table 1 shows the characteristics of the molded product.
The ratio of polyolefin resin / rubber-like polymer (non-crosslinked) / glass fiber in the composition was 50.0 / 20.0
/30.0 (weight ratio).

Example 3 Each pellet of GF-1, TPV-1, and PP was mixed with GF-1 /
A molded product was obtained in the same manner as in Example 1, except that TPV-1 / PP was mixed at 53.6 / 18.0 / 28.4 (weight ratio). Table 1 shows the characteristics of the molded product. The polyolefin resin / rubber polymer (partially crosslinked) in the composition
/ Glass fiber ratio is 60.0 / 10.0 / 30.0
(Weight ratio).

Example 4 Each pellet of GF-1, TPV-1, and PP was mixed with GF-1 /
A molded product was obtained in the same manner as in Example 1 except that TPV-1 / PP was mixed at 35.7 / 36.0 / 28.3 (weight ratio). Table 1 shows the characteristics of the molded product. The polyolefin resin / rubber polymer (partially crosslinked) in the composition
/ Glass fiber ratio is 60.0 / 20.0 / 20.0
(Weight ratio).

Example 5 A molded product was obtained in the same manner as in Example 1 except that TPV-1 was changed to TPV-5. Table 1 shows the characteristics of the molded product.
The ratio of polyolefin resin / rubber-like polymer (completely crosslinked) / glass fiber in the composition was 50.0 / 20.
0 / 30.0 (weight ratio).

Example 6 Material to be extrusion coated on glass fiber was 5% M-PP / 95%
A long fiber pellet (referred to as GF-2) was produced in the same manner as in Example 1, except that PP was changed to 5% M-PP / 95% EP-1. The ratio of the long fiber pellet to the glass / polyolefin resin was 56/44 (weight ratio). Each pellet of GF-2, TPV-3 and PP was
The mixture was mixed at 3.6 / 36.0 / 10.4 (weight ratio) and molded in the same manner as in Example 1 to obtain a molded product. Table 1 shows the characteristics of the molded product. The ratio of polyolefin-based resin / rubber-like polymer (partially crosslinked) / glass fiber in the composition is 50.
0 / 20.0 / 30.0 (weight ratio).

Example 7 The components and compositions of each pellet of GF-1, TPV-1, and PP were GF-1 / TPV-1 / EP-2 = 53.6 / 36.
A molded product was obtained in the same manner as in Example 1 except that mixing was performed at 0 / 10.4 (weight ratio). Table 1 shows the characteristics of the molded product. The ratio of polyolefin resin / rubber-like polymer (partially crosslinked) / glass fiber in the composition was 50.0 / 2.
0.0 / 30.0 (weight ratio).

Example 8 The material to be extrusion coated on glass fiber was 5% M-PP / 95%
5% M-PP / 71.3% PP / 23.7% H than PP
A long fiber pellet (referred to as GF-3) was produced in the same manner as in Example 1 except that DPE was used. The ratio of the long fiber pellet to the glass / polyolefin resin is 5
6/44 (weight ratio). GF-3, TPV-4,
Each pellet of PP and HDPE was added to 53.6 / 36.0 /
The mixture was mixed at 7.8 / 10.4 (weight ratio) and molded in the same manner as in Example 1 to obtain a molded product. Table 1 shows the characteristics of the molded product.
The ratio of polyolefin resin / rubber-like polymer (partially crosslinked) / glass fiber in the composition was 50.0 (PP:
40.0, HDPE: 10.0) /20.0/30.0
(Weight ratio).

Example 9 A molded product was obtained in the same manner as in Example 1 except that TPV-1 was changed to TPV-6. Table 1 shows the characteristics of the molded product.
The ratio of polyolefin resin / rubber-like polymer (partially crosslinked) / glass fiber / softening agent (paraffin oil) in the composition was 40.7 / 15.8 / 30.0 / 13.
5.0 (weight ratio).

[0088]

[Table 1]

Example 10 A roving of 13 μm thick glass fiber was cut into 7 mm pieces to make chops. This chop and TPV-1, P
Each pellet of P was mixed at 30.0 / 36.0 / 34.0 (weight ratio) and extruded at a resin temperature of 230 ° C. with a twin-screw extruder (Toshiba TEM-35B) to form pellets. The diameter of the glass fiber in the pellet was 13 μm and the length was 0.7 mm.
The aspect ratio of the glass fibers in the pellet is 54.
The pellets were used as a raw material at a molding temperature of 240 ° C. and molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product. The ratio of polyolefin resin / rubber-like polymer (partially crosslinked) / carbon fiber in the composition is 50.0 / 20.0 / 30.0 (weight ratio).

Comparative Example 2 A glass fiber roving having a thickness of 13 μm was cut into 7 mm pieces to obtain chops. The chop was further pulverized with a ball mill to obtain ultrashort fibers having an average length of about 100 μm. This ultra-short fiber and each pellet of TPV-1 and PP were added to 30.0
/36.0/34.0 (weight ratio), and extruded into a pellet at a resin temperature of 230 ° C with a twin-screw extruder (Toshiba TEM-35B). The diameter of the glass fiber in the pellet is 13μ
m, and the average length was 42 μm. The aspect ratio of the glass fibers in the pellet is 3.2. Using these pellets as raw materials, an injection molding machine (Toshiba IS
45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product. The ratio of polyolefin resin / rubber-like polymer (partially crosslinked) / carbon fiber in the composition is 5%.
0.0 / 20.0 / 30.0 (weight ratio).

Example 11 5% M-PP / 95% PP was extruded from the side with an extruder while roving a carbon fiber having a thickness of 7 μm under tension, and a polyolefin resin was extrusion-coated on the surface of the glass fiber. Then, it was cut into pellets having a length of 7 mm to produce long fiber pellets (referred to as CF-1). The aspect ratio of the glass fibers in the long fiber pellet is 1,000.
The ratio of the long fiber pellets to glass / polyolefin resin was 50/50 (weight ratio). CF-1,
Each pellet of TPV-1, PP was added to 30.0 / 36.0 /
The mixture was mixed at 34.0 (weight ratio), the molding temperature was set to 240 ° C., and the mixture was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product. The polyolefin resin / rubber-like polymer (partially crosslinked) /
The ratio of carbon fibers is 50.0 / 20.0 / 30.0
(Weight ratio).

Example 12 Each of pellets of magnesium oxysulfate whisker (Mosh Heidi), TPV-1, and PP was mixed with 30.0 / 3.
The mixture was mixed at a weight ratio of 6.0 / 34.0, and extruded at a resin temperature of 230 ° C. into a pellet using a twin-screw extruder (Toshiba TEM-35B). The average diameter of the whiskers in the pellets is 0.6,
The average length was 8 μm. The aspect ratio of the glass fibers in the pellet is 13. Using these pellets as raw materials, the molding temperature was set to 240 ° C and an injection molding machine (Toshiba IS45PN)
V) to obtain a molded product. Table 2 shows the characteristics of molded products
Shown in The ratio of polyolefin resin / rubber-like polymer (partially crosslinked) / magnesium oxysulfate whisker in the composition article was 50.0 / 20.0 / 30.
0 (weight ratio).

[0093]

[Table 2]

Examples 13 to 18, Comparative Examples 3 to 5 Mixing, kneading and extruding PAN fibers at the ratios shown in Table 3 during the production of crosslinked thermoplastic elastomer (TPV-7) and non-crosslinked thermoplastic elastomer (TPO-2). Was. A sheet having a thickness of 2 mm was formed from the obtained composition by compression molding at 200 ° C., and the mechanical strength was measured. Table 3 shows the results.

[0095]

[Table 3]

[0096]

When the thermoplastic resin composition of the present invention is of a soft type, it becomes a material having high durability, abrasion resistance and strength. In the case of a hard material, the material is excellent in impact resistance, rigidity, and heat resistance. Soft thermoplastic resin compositions include automotive parts, automotive interior and exterior materials, airbag covers, mechanical parts, electrical parts,
It can be widely used for soft applications such as cables, hoses, belts, toys, miscellaneous goods, daily necessities, building materials, sheets, films, especially electric wire coating materials or home wallpaper. On the other hand, in the case of hard type, radiator tanks, power tools, automobile parts such as office chairs, office parts, electric parts,
It can be used for hard applications such as tools, daily necessities, building materials, etc., and plays a large role in the industrial world.

Claims (4)

[Claims] (A) 1 to 99 parts by weight of a rubbery polymer partially or completely crosslinked, (B) a thermoplastic resin
To 99 parts by weight, and the total amount of component (A) and component (B) 1
(C) average diameter of 0.01 to 10 parts by weight per 100 parts by weight
00 μm and an aspect ratio (length / diameter) of 5-2
500 fibrous or acicular fillers 0.1-20
A high-strength thermoplastic resin composition comprising 0 parts by weight. 2. The (A) partially or completely crosslinked rubbery polymer is an ethylene / α-olefin copolymer mainly composed of ethylene and α-olefin having 3 to 20 carbon atoms. 2. The high-strength thermoplastic resin composition according to 1. 3. The high-strength thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (B) is a polyolefin resin. 4. The high-strength thermoplastic resin composition according to claim 3, wherein the polyolefin resin is mainly composed of a polypropylene resin.