JP2001294760A - Thermoplastic resin composition having high strength and high rigidity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin having high strength. SOLUTION: The thermoplastic resin composition having high strength and high rigidity comprises 1-50 pts.wt. of a hydrogenated block copolymer of an aromatic vinyl monomer with a conjugated diene monomer, (B) 50-99 pts.wt. of a thermoplastic resin and (C) 0.1-200 pts.wt., based on 100 pts.wt. of the total of the components (A) and (B), of a filler having an average diameter of 0.01-1,000 μm and an average aspect ratio (length/diameter) of 5-2,500.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a filler, particularly a fibrous or acicular filler, preferably a fibrous filler and a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer. The present invention relates to a reinforced high-strength and high-rigidity thermoplastic resin composition.

[0002]

2. Description of the Related Art Many thermoplastic resins are generally known, such as polypropylene resins, styrene resins and polyamide resins. These thermoplastic resins are required to have high mechanical strength depending on the use. For example, polypropylene-based resins and polyamide-based resins are sold with glass fiber reinforced materials. Among these, polyamide resin reinforced with glass fiber is used for automotive materials such as radiator tanks, tool housing materials such as electric drills,
It is used for 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,
At present, the use of the polypropylene resin reinforced with glass fibers is limited because the strength of the parent polypropylene resin is smaller than that of the polyamide resin or the like.

[0003] If a resin containing a polypropylene-based resin is used as a high-strength material, not only will its use be expanded, but even if it is a polyamide-based resin, if the strength is further increased, the thickness can be reduced, and the weight can be reduced. This leads to cost reduction and is more preferable. For this reason, there is a demand for the development of even higher strength materials for these thermoplastic resins.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-strength thermoplastic resin in view of such circumstances.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a filler having a specific shape, specifically a fibrous or a specific shape, has been added to a thermoplastic resin. When present with a needle-like filler, impact resistance and rigidity can be improved. However, for example, when a composition comprising a thermoplastic resin and a filler is formed by using glass fiber or carbon fiber as the filler, the filler is oriented in a certain direction by the flow of the resin.

Therefore, the strength differs between the vertical and horizontal directions of the molded product,
Practical strength such as strength at impact is not enough as expected. Therefore, there is a problem that the molded article is damaged when dropped, hits an object, or hits an object such as a stone. However, when a rubbery polymer consisting of a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer coexists here, even higher impact resistance is obtained, even if the filler is oriented. The present inventors have found that a thermoplastic resin molded article having practical strength and little decrease in rigidity, and having high strength and high rigidity, has led to the completion of the present invention.

Further, when a polyolefin resin is used as a thermoplastic resin, a molded article obtained by molding this composition is whitened by impact. However, when the rubbery weight% of a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer is used as a reinforcing material, surprisingly, this whitening is also significantly improved. This led to the completion of the present invention.

That is, the present invention relates to (A) a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer.
To 50 parts by weight, (B) a thermoplastic resin, preferably 50 to 99 parts by weight of a polyolefin resin, and (C) an average diameter of 0.1 part by weight based on 100 parts by weight of the total amount of the components (A) and (B). Filler having an aspect ratio (length / diameter) of 5 to 2500
The present invention relates to a high-strength and high-rigidity thermoplastic resin composition comprising 100 parts by weight.

In the present invention, the mechanical strength, particularly the impact strength, can be significantly improved by coexisting a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer. When a simple rubber-like polymer such as ethylene-propylene copolymer (EPR) is used as a reinforcing agent for the purpose of increasing mechanical strength such as impact resistance, when the composition is molded, glass fiber is used. Alternatively, the rubber-like polymer is oriented in a certain direction by the flow of the resin similarly to the filler such as the carbon fiber.

Therefore, even if a rubber-like polymer is used in combination, the strength of the rubber-like polymer cannot be greatly improved. However,
In particular, by coexisting a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer as a rubbery polymer, it is possible to specifically and significantly improve mechanical strength, particularly impact strength. it can. The reason for this is that the hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer is not pseudo-crosslinked, that is, it is not crosslinked, but it appears to be crosslinked, and the thermoplastic resin It is presumed that the rubbery polymer dispersed therein behaves as if it were crosslinked, and is difficult to orient along with the flow of the resin.

Crosslinking of the rubbery polymer also makes it possible to suppress orientation in the molding flow direction when molding the composition. However, the cost can be reduced by using a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer. In addition,
A molded article obtained by molding a composition in which a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer coexists is hardly whitened is that a rubber-like polymer dispersed in a thermoplastic resin is hardly whitened. It is estimated that the coalesced particles are specifically finely dispersed.

Hereinafter, the present invention will be described in detail. First, each component of the present invention will be described in detail. The hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer as the component (A) will be described. The hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer is obtained by partially or partially converting the conjugated diene monomer portion of a block copolymer of an aromatic vinyl monomer and a conjugated diene monomer. It is a completely hydrogenated block copolymer.

The aromatic vinyl monomer constituting the block copolymer is styrene, α-methylstyrene, p-methylstyrene,
Examples of monomers such as chlorostyrene, p-bromostyrene, and 2,4,5-tribromostyrene include
Of these, styrene monomers are the least expensive and are most preferred. Further, examples of the main conjugated diene monomer constituting the block copolymer include 1,3-butadiene and isoprene.

The block structure of the block copolymer is as follows:
When a polymer block composed of an aromatic vinyl monomer is represented by S, and a polymer block composed of a conjugated diene and / or a partially or completely hydrogenated unit thereof is represented by B, SB, S (BS ) n, (where n is an integer of 1 to 3), S (BSB) m, (where m is an integer of 1 to 2) linear block copolymer, or (SB) pX (where p is 3 X is an integer of up to 6. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, or a polyepoxy compound.) .

Of these, SB type 2 and SBS type 3
SBSB type 4 linear block copolymers are preferred. The number average molecular weight of the hydrogenated block copolymer of these aromatic vinyl monomer / conjugated diene monomer is generally 2
It is preferable to use those of up to 200,000. An aromatic vinyl content of 10 to 70% by weight can be used.

The preferred range of the content of the aromatic vinyl varies depending on the thermoplastic resin used, and cannot be specified without limitation. For example, when the thermoplastic resin is a polyolefin resin, 50% by weight is used. The following is preferred. When the thermoplastic resin is a styrene resin, the content is preferably 50% by weight or more. The conjugated diene may enter the main chain in the same molecule (1-4 bond) or enter in a branched structure (1-2 bond), and the compatibility with the thermoplastic resin varies depending on the amount thereof, and the conjugated diene of the present invention may be different. The characteristics of the molded article obtained by molding the plastic tree composition also differ slightly, but this ratio is not particularly limited. Generally, the rigidity of a molded product obtained by molding the composition of the present invention is slightly lower as the amount that can enter in a branched structure is larger,
Blushing tends to be slightly better.

The hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer as the component (A) of the present invention has a basic composition of the above composition. Block copolymer of aromatic vinyl monomer / conjugated diene monomer to which polar group is provided with hydrogenated block copolymer of isomer / conjugated diene monomer as a basic structure, for example, maleic anhydride product, epoxy Includes chemical products. When using these, they may be used alone,
Further, it may be used in combination with a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer having no polar group, which is a basic composition.

This hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer having a polar group also has rubber-like properties, and is a molded article obtained by molding the composition of the present invention. In addition to the effect of imparting impact resistance, when used as a thermoplastic resin other than a polyolefin-based resin or a styrene-based resin as described below, this thermoplastic resin and an aromatic vinyl monomer / In some cases, the hydrogenated block copolymer of the conjugated diene monomer is difficult to be compatible, but it may be used as a compatibilizer for imparting compatibility at this time. The hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer having a polar group may be used alone when the aromatic vinyl monomer / hydrogenated block copolymer is used alone.
When used together with a hydrogenated block copolymer of a conjugated diene monomer, it is counted as the component (A).

As described above, by adding a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer, a composition which becomes a high-strength and high-rigid molded article excellent in impact resistance can be obtained. It is possible to use another rubbery polymer in addition to the aromatic vinyl monomer / conjugated diene monomer hydrogenated block copolymer as a material for imparting impact resistance. Is also possible.

Examples of other rubbery polymers include polybutadiene polymer rubber, styrene-butadiene random or block copolymer rubber, hydrogenated random copolymer rubber of styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer. Acrylic rubbers such as coalesced rubber, isoprene rubber, chloroprene rubber, and butyl acrylate rubber, and ethylene / α-olefin copolymer rubbers can be mentioned.

Of these, ethylene and carbon atoms 3
Most preferred are ethylene / α-olefin copolymer rubbers having α-olefins of up to 20. 3-20 carbon atoms
Examples of the α-olefin include 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. Further, a terpolymer such as an ethylene / propylene / diene copolymer (EPDM) is also included. Among these, an ethylene / α-olefin copolymer rubber in which heptene-1 or octene-1 is an α-olefin is used in combination with a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer. Thereby, the effect of imparting impact resistance is enhanced. The ethylene / α-olefin copolymer rubber may be crosslinked.

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, polyolefin-based, polystyrene-based, polyphenylene ether-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 preferred. The reason for this is that the thermoplastic resin composition of the present invention has a strong affinity with the hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer, which is the component (A), and obtains a high strength resin. Depends on Further, polypropylene-based resins tend to be mainly used for automobiles, and polyolefin-based resins are becoming main resins in the world.

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.

Examples of the polypropylene resin include a homopolypropylene, an isotactic copolymer resin of propylene and other α-olefins such as ethylene, butene-1, pentene-1 and hexene-1 (including block and random). And the like. The melt flow rate (MFR) of the polypropylene resin measured at 230 ° C. under a load of 2.16 kg is preferably in the range of 0.1 to 100 g / 10 minutes. Melt flow rate is 100g
If it exceeds / 10 minutes, the mechanical strength and heat resistance of the molded article obtained from the thermoplastic resin composition of the present invention are insufficient,
If it is less than 0.1 g / 10 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 preferably used as the component (B) 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 heat resistance. Higher and 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. When the thermoplastic resin is a polyolefin resin or a styrene resin such as polystyrene, the aromatic vinyl monomer /
If the hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer is well compatible with the hydrogenated block copolymer of the conjugated diene monomer and the appropriate hydrogenated block copolymer is selected, the two components are not separated. In the case of other resins, there is no compatibility between the hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer and the thermoplastic resin and phase separation occurs, and the phenomenon that the molded product is delaminated is caused. May occur.

In this case, in order to help the compatibility between the two,
A compatibilizer may be added as an auxiliary. For example, when the thermoplastic resin is a polyamide resin, a material having a polar group, such as a maleic anhydride or epoxidized aromatic vinyl monomer / conjugated diene monomer hydrogenated block copolymer or maleic anhydride A polypropylene or polyethylene resin or the like can be used in combination.

The ratio of component (A) to component (B) is
Component (A) is 1 to 50 parts by weight, component (B) is 50 to 99.
It must be parts by weight. Preferably, the component (A) is 5 to 40 parts by weight, and the component (B) is 60 to 95 parts by weight. Particularly preferably, the component (A) is 10 to 40 parts by weight, and the component (B) is 60 to 90 parts by weight. When the amount of the component (A) is less than 1 part by weight, the effect of improving the strength such as impact strength of a molded article molded from the thermoplastic resin composition of the present invention is not sufficient, which is not preferable. If the amount of the component (A) exceeds 50 parts by weight, the rigidity of the molded article formed from the thermoplastic of the present invention is undesirably too low.

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 5 μm.
00 μm, more preferably 1 to 100 μm, most preferably 5 to 50 μm. The average aspect ratio (length / diameter) is 5 to 2500, preferably 10 to 1
There is no particular limitation as long as it is 500. If the average diameter is less than 0.01 μm, the reinforcing effect is small and 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. The average aspect ratio (length / diameter) is 5
If it is less than anisotropy, the anisotropy is insufficient and the reinforcing effect is small. On the other hand, if it exceeds 2,500, the fluidity at the time of molding is not sufficient, causing problems in molding.

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. In addition, as a needle-like filler,
Potassium titanate, magnesium oxysulfate,
Aluminum borate, wollastonite, sebiolite,
Examples include zonotolite, phosphate fiber, dawsonite, gypsum fiber, MOS, acicular calcium carbonate, tetrapot type zinc oxide, whisker made of silicon carbide or silicon nitride, and the like.

As the fibrous or acicular filler (C) in the thermoplastic resin composition of the present invention, any one of the above-mentioned materials can be arbitrarily selected and used alone or in combination. Among these materials, glass fiber, carbon fiber, and magnesium oxysulfate whisker are preferable as fillers in terms of impact strength, rigidity, and heat resistance. Of these, glass fibers and carbon fibers are particularly preferred. The reason is that these materials exhibit particularly high rigidity. Glass fibers and carbon fibers can be used alone or in combination. Carbon fibers have a higher effect of increasing the rigidity of a molded article formed from the thermoplastic resin composition of the present invention than glass fibers. However, it is expensive. By using a mixture of glass fiber and carbon fiber, it is possible to provide a thermoplastic resin composition which is relatively inexpensive and can be formed into a molded article having high strength and high rigidity.

As glass fibers or carbon fibers, commercially available ones are used. It is more preferable that the filler is previously treated with maleic anhydride or a silane coupling agent, a urethane resin, an epoxy resin, or the like because of its high reinforcing effect. The amount of the fibrous or acicular filler as the component (C) in the thermoplastic resin composition of the present invention depends on the amount of the hydrogenated block of the aromatic vinyl monomer / conjugated diene monomer as the component (A). The total amount of the polymer and the thermoplastic resin as the component (B) is 10
0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 10 to 100 parts by weight with respect to 0 parts by weight.
Parts by weight, more preferably 10 to 70 parts by weight.

When the amount is less than 0.1 parts by weight, the effect of imparting rigidity is low. If the amount exceeds 200 parts by weight, the thermoplastic resin composition of the present invention has low fluidity and is inferior in molding processability when molded. In the case where another rubber-like polymer is used in addition to the hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer as the component (A), the fibrous or The amount of the needle-like filler is such that the rubbery polymer used in combination is also regarded as the component (A), and the component (A) is a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer and 0.1 parts by weight based on 100 parts by weight of the total amount of the other combined rubbery polymer and the thermoplastic resin as the component (B).
To 200 parts by weight.

As described above, the thermoplastic resin molded article of the present invention basically comprises at least (A) a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer,
It consists of (B) a thermoplastic resin and (C) a fibrous or acicular filler, but if necessary, other components such as a special polymer other than a general thermoplastic resin, a softener, a powdered inorganic filler and a plastic. Agents and the like can be contained. As the special polymer, one that improves the interfacial adhesion between the filler and the thermoplastic resin is particularly effective for improving the impact resistance, and is preferably contained as the fourth component.

Examples of such a material include a polymer having a polar group in the molecule such as a maleic acid-modified polymer or copolymer, an acrylic acid-modified polymer or copolymer, a fumaric acid-modified polymer or copolymer. It is preferable that molecular materials coexist. 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 rigidity tends to decrease slightly, but the impact resistance can be further improved.

Further, whitening can be further improved. When adding these softeners, the mixing ratio is 5 to 250 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B).
Parts by weight, preferably 10 to 150 parts by weight. If the amount is less than 5 parts by weight, the improvement effect is not remarkable, and if it exceeds 250 parts by weight, bleed out of the softener becomes remarkable, which is not preferable. When a rubbery polymer other than the hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer is used in combination, the amount of the softener is not limited to the aromatic vinyl monomer as the component (A). 5 to 250 parts by weight based on 100 parts by weight of the total of the hydrogenated block copolymer of the monomer / conjugated diene monomer and the other combined rubbery polymer and the thermoplastic resin (B). .

Examples of the powdery inorganic filler include talc, magnesium hydroxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, silica, carbon black, titanium oxide, clay, and mica. Of these, talc, magnesium hydroxide and aluminum hydroxide are preferred. Talc has the effect of improving heat resistance. Magnesium hydroxide and aluminum hydroxide have the effect of imparting flame retardancy.

When these talc, magnesium hydroxide and aluminum hydroxide are added, a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer (A) and a component (B) are added. Total amount of a certain thermoplastic resin 1
5 to 250 parts by weight per 100 parts by weight is preferred. If the amount is less than 5 parts by weight, the effect of the addition is not remarkable. 2
If it exceeds 50 parts by weight, the rigidity is reduced. When a rubber-like polymer other than the hydrogenated block copolymer of the aromatic vinyl monomer / conjugated diene monomer is used in combination, the amount of the powdery inorganic filler added is the aromatic component (A). 5 to 250 parts by weight based on 100 parts by weight of the total of the hydrogenated block copolymer of the vinyl monomer / conjugated diene monomer and the other combined rubbery polymer and the thermoplastic resin as the component (B) And

Examples of the plasticizer include phthalic acid esters such as polyethylene glycol and dioctyl phthalate (DOP). Also, other additives such as organic / inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, silicone oils, antiblocking agents, foaming agents, antistatic agents, antibacterial agents, etc. Are also preferably 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 basically comprises a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer as the component (A) and a hydrogenated block copolymer as the component (B). It is manufactured by mixing a fibrous or needle-like filler as the component (C) with a plastic resin. The mixing method is generally to melt-knead the above components using an extruder or the like to obtain the thermoplastic resin composition of the present invention. When a molded article is obtained, this composition can be used as a raw material and processed by injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding, or the like to form a molded article.

However, in such a method of preliminarily melting and kneading with an extruder or the like, when the filler has a low strength, the filler is crushed when passing through the extruder, the aspect ratio becomes small, and the thermoplastic resin having the desired mechanical strength is obtained. It may not be a molded product. In this case, the component (A) is a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer and a filler itself or a filler solidified with a sizing agent or the like, or a filler solidified with a thermoplastic resin or the like. If necessary, a thermoplastic resin for adjusting the composition is blended to form the thermoplastic resin composition of the present invention, and a thermoplastic resin molded product is obtained by a method such as direct injection molding of the blend.

At this time, a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer as the component (A),
The filler hardened with a sizing agent or a thermoplastic resin, and the thermoplastic resin for adjusting the composition are preferably pellets. In this case, since the kneading only needs to be performed once during the injection molding, the aspect ratio in the molded product becomes closer to the aspect ratio of the raw material as compared with the method of blending with an extruder and further performing injection molding. It becomes a strong thermoplastic resin molded product.

This method, in which a thermoplastic resin molded article having a large aspect ratio can be obtained by blending raw materials and kneading only once, is particularly effective when a fibrous filler such as glass fiber or carbon fiber is used as the filler. Can be used. In the case of a fibrous filler, 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 (fiber) of glass fiber, carbon fiber, or the like is impregnated with a thermoplastic resin or extruded to form a pellet, or a bundle of fiber such as glass fiber, carbon fiber, or the like is thermoplastic resin emulsion. A pellet containing fibers having the same length as the pellet length (referred to as long fiber pellets) is manufactured by a method such as continuous immersion in (latex), coating with a thermoplastic resin and pelletizing. More specifically, a method of immersing a roving of fiber such as glass fiber or carbon fiber in a molten thermoplastic resin and then pelletizing to a predetermined length or a method generally called a pultrusion method is used. A method of extruding a thermoplastic resin from the side with an extruder while aligning rovings of fibers such as fibers under tension, extruding the thermoplastic resin on the surface of the fibers, and pelletizing or a method of forming fibers such as glass fibers and carbon fibers. There is a method in which the roving is immersed in a convergence liquid such as a thermoplastic resin emulsion (latex) while being aligned under tension, dried, and pelletized.

The long fiber pellets produced by this method usually have a pellet length of 2 to 50 mm, preferably 3 to 20 mm, more preferably 5 to 10 mm. This long fiber pellet, a hydrogenated block copolymer pellet of an aromatic vinyl monomer / conjugated diene monomer as the component (A), and a thermoplastic resin pellet for adjusting the composition, if necessary, are blended. Then, this blended product is injection molded to obtain a molded product.

The length of the filler in the molded article obtained by molding the thermoplastic resin composition of the present invention is preferably 0.1 when glass fiber or carbon fiber is used as the fibrous filler.
90 to 10% for 5 mm or less, 10 to 9 for 0.5 to 2 mm
It is preferable that 0% and 0.2 mm or more are 0 to 30%. More preferably, 80 to 20% of glass fibers having a length of 0.5 mm or less, 20 to 80% of glass fibers having a length of 0.5 to 2 mm, and 5 to 5% of glass fibers having a length of 2 mm or more.
25%, more preferably 60 to 25% of glass fibers having a length of 0.5 mm or less, 40 to 75% of glass fibers having a length of 0.5 to 2 mm, and 5 to 5% of glass fibers having a length of 2 mm or more.
~ 20%.

By having such a fiber length distribution, it is possible to obtain a molded article having excellent appearance, high strength and high rigidity. When the length of the glass fiber or carbon fiber filler in the molded article is 0.5 mm or less and more than 90% (when 0.5 mm to 2 mm is less than 10%), the molded article obtained from the thermoplastic resin composition of the present invention The effect of increasing the strength and rigidity of the steel is reduced. When 0.5 mm or less is less than 10% (0.5 mm to 2 mm is 90% or more), the appearance of a molded article obtained from the thermoplastic resin composition of the present invention is not good. The reason is that if there are too many long fibers in the molded article, fiber aggregates and the like are contained in the molded article and the appearance is deteriorated. 0.2m
When the length of the fibers having a length of m or more exceeds 30%, the appearance of the molded article tends to be poor.

The thermoplastic resin composition of the present invention can produce various molded articles by any molding method. Molding methods include injection molding, extrusion molding, compression molding, blow molding,
Calender molding, foam molding and the like are preferably used. The molded article obtained by molding the thermoplastic resin composition of the present invention has high strength and high rigidity, and can be used for various applications. For example, antifreeze system automotive parts such as radiator tanks,
It can also be used for tool parts such as power tool housings, office chair parts or other daily necessities, building materials and the like. Among these, it can be effectively used especially for antifreeze liquid automobile parts, tool parts, office chair parts and the like.

[0050]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In these examples and comparative examples, test methods and raw materials used for evaluating various physical properties are as follows.

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

(2) Flexural strength The flexural strength was measured at 23 ° C. in accordance with JIS K6758. (3) Flexural modulus Measured at 23 ° C. by a method according to JIS K6758. (4) Izod impact strength Measured at 23 ° C. by a method according to JIS K6758.

(V notch, 1/4 inch test piece)

(5) Drop Weight Impact Strength Using a drop weight impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.), tip diameter of drop weight: 13.6 mm Weight: 6.5 kg, drop height: 10
0cm, holder diameter: 50mm, specimen thickness: 3m
m, temperature: 23 ° C., humidity 50%, total absorbed energy was measured. Larger values are more difficult to crack.

(6) Filler Average Diameter and Aspect Ratio The number average particle diameter of the filler was determined by an electron microscope, while the filler length 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. Then, the number average particle diameter was determined by arithmetic mean of the average diameter of 100 fillers. The average length of the above-mentioned filler was also determined as the number average length. (7) Fiber length in molded article The molded article was baked, and the distribution of fiber length was measured by image analysis using an optical microscope.

2. Raw Materials (1) Hydrogenated block copolymer of aromatic vinyl monomer / conjugated diene monomer (a) Styrene / butadiene hydrogenated block copolymer (trade name: Tuftek H1062, manufactured by Asahi Kasei Corporation)
(B) Kuraray Co., Ltd., styrene / isoprene hydrogenated block copolymer (Septon 2002, styrene content: 30% by weight) (HTR-) 2)

(C) Styrene / butadiene hydrogenated block copolymer (trade name: Tuftec H1081 styrene content: 60% by weight) manufactured by Asahi Kasei Corporation (HTR)
(D) Manufactured by Asahi Kasei Kogyo Co., Ltd., maleic anhydride styrene / butadiene hydrogenated block copolymer (trade name: Tuftec M1943, styrene content: 20% by weight) (M-
(E) Daicel Chemical Industries, Ltd., Epoxidized styrene / butadiene hydrogenated block copolymer (trade name Epofriend A1005 Styrene content: 40% by weight) (E
-HTR)

(2) Thermoplastic 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 Nippon Polyolefin Co., Ltd., block E-PP resin [E / PP = 6/94] (weight ratio) (trade name: PM97
0A)] (referred to as EP-1)

(C) Ethylene (E) -propylene (PP) copolymer resin-2 Random E-PP resin [E / PP = 7/93 (weight ratio) (trade name: PM940), manufactured by Japan Polyolefin Co., Ltd.]
M] (referred to as EP-2) (d) Maleated polypropylene Maleated polypropylene (trade name Admer GF305) manufactured by Mitsui Chemicals, Inc. (referred to as M-PP)

(E) High-density polyethylene Suntech HD (trade name: B47, manufactured by Asahi Kasei Corporation)
0) (referred to as HDPE) (f) Polystyrene Polystyrene manufactured by Asahi Kasei Corporation (trade name: GP68)
5) (referred to as PS) (g) Polyamide (6 nylon) 6 nylon (trade name: Amilan CM10) manufactured by Toray Industries, Inc.
07) (referred to as PA)

(E) Polycarbonate Novalex (7022A) (referred to as PC) manufactured by Mitsubishi Engineering-Plastics Corporation (f) Polyester PET bottle pulverized product (referred to as PET)

(3) Filler (a) Glass fiber Roving made of Asahi Fiber aminosilane-treated glass 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 manufactured by Ube Materials (trade name: Moss Heidi A)

(4) Others (a) Ethylene / octene-1 copolymer Produced by a method using a metallocene catalyst described in JP-A-3-16388. The composition ratio of ethylene / octene-1 in the copolymer was 72/28 (weight ratio) (referred to as EO-1). (B) EPR Ethylene / propylene copolymer rubber manufactured by Mitsui Chemicals (trade name: EPM0045) ) (Referred to as EPR)

[0064]

Example 1 5% M-PP / 95% PP was extruded from the side with an extruder while a roving of 13 μm thick glass fiber was aligned under tension, and the surface of the glass fiber was extrusion-coated with a polyolefin resin. And 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. In addition, the glass fiber /
The ratio with the polyolefin resin was 56/44 (weight ratio). The pellets of GF-1, HTR-1, and PP were mixed at the compounding ratio shown in Table 1, 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 1 shows the composition of the molded article, the fiber length in the molded article, and the properties.

[0065]

Examples 2 to 11 Tables 1 and 2 also show the results obtained in various formulations in the same manner as in Example 1.

[0066]

Comparative Examples 1 and 2 Example 1 without adding a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer
The results obtained in the same manner as in the above were repeated, and E was replaced with a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer.
Table 1 also shows the results obtained by using PR in the same manner as in Example 1. The whitened state of the damaged portion in the drop weight impact strength test was significantly whitened over the periphery in Comparative Examples 1 and 2, but was not whitened at all in Example 1.

[0067]

Example 12 A roving of 13 μm thick glass fiber was cut into 7 mm pieces to make chops. This chop and each pellet of HTR-1 and PP were added to 30.0 / 20.0 /
50.0 (weight ratio), and a twin screw extruder (Toshiba TEM
At -35B), the mixture was extruded and pelletized at a resin temperature of 230 ° C. The diameter of the glass fiber in the pellet is 13 μm and the length is 0.1 mm.
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.

[0068]

Comparative Example 3 A roving of glass fiber having a thickness of 13 μm was cut into 7 mm and chopped. The chop was further pulverized with a ball mill to obtain ultrashort fibers having an average length of about 100 μm. The ultrashort fibers and the pellets of HTR-1 and PP were mixed at 30.0 / 20.0 / 50.0 (weight ratio), and the resin temperature was adjusted to 23 with a twin-screw extruder (Toshiba TEM-35B).
Extruded and pelletized at 0 ° C. The diameter of the glass fiber in the pellet was 13 μm, and the average length was 40 μm. The aspect ratio of the glass fibers in the pellet is 3.1. 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.

[0069]

Example 13 5% M-PP / 95% PP was extruded from the side while extruding a roving of carbon fiber having a thickness of 7 μm under tension with an extruder, and the surface of the carbon fiber was extrusion-coated with a polyolefin resin. And cut into 7 mm long pellets to produce long fiber pellets (referred to as CF-1). Aspect ratio of glass fiber in long fiber pellet is 1
000. The ratio of carbon fiber / polyolefin-based resin in the long fiber pellet was 30/70 (weight ratio). Table 2 shows each pellet of CF-1, HTR-1, and PP.
And the mixture was molded at an injection molding machine (Toshiba IS45PNV) at a molding temperature of 240 ° C. to obtain a molded product.
Table 2 shows the composition of the molded article, the fiber length in the molded article, and the properties.

[0070]

Example 14 Each of magnesium oxysulfate whisker (Mosh Heidi), HTR-1 and PP pellets was mixed at 30.0 / 20.0 / 50.0 (weight ratio),
The mixture was extruded and pelletized at a resin temperature of 230 ° C. using a screw extruder (Toshiba TEM-35B). The average diameter of the whiskers in the pellets was 0.6, and the average length was 8 μm. The aspect ratio of the glass fibers in the pellet is 13. 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.

[0071]

Example 15 An AS emulsion (acrylonitrile-styrene latex; acrylonitrile 2) was prepared while a roving of glass fiber having a thickness of 13 μm was aligned under tension.
(5%, solid content concentration: 50% by weight) Glass fiber is immersed in the bath layer, AS resin is adhered, dried, cut into a 5.5 mm long pellet, and a long fiber pellet (referred to as GF-2) Was manufactured. The aspect ratio of the glass fiber in the long fiber pellet is 423. The ratio of the long fiber pellet to glass / AS resin is 80/20 (dry weight ratio).
Met. Each pellet of GF-2, HTR-3, and PS was mixed at the compounding ratio shown in Table 3 and molded in the same manner as in Example 1 to obtain a molded product. Table 3 shows the composition of the molded article, the fiber length in the molded article, and the properties.

[0072]

Example 16 A molded product was obtained in the same manner as in Example 16 except that PS was changed to PA. Table 3 shows the composition of the molded article, the fiber length in the molded article, and the properties.

[0073]

Example 17 A molded product was obtained in the same manner as in Example 16 except that PS was changed to PC. Table 3 shows the composition of the molded article, the fiber length in the molded article, and the properties.

[0074]

Embodiment 18 Embodiment 16 except that PS is made of PET
A molded article was obtained in the same manner as described above. Table 3 shows the composition of the molded article, the fiber length in the molded article, and the properties.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

According to the thermoplastic resin composition of the present invention,
It is possible to improve impact resistance and rigidity. Therefore, it can be used for applications such as automobile parts such as radiator tanks, tool parts, office chair parts, office parts, electric parts, daily necessities, building materials, etc., and plays a large role in the industrial world.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/40 C08K 3/40 7/00 7/00 7/06 7/06 7/14 7/14 9 / 04 9/04 C08L 23/00 C08L 23/00 23/10 23/10 // (C08L 101/00 (C08L 101/00 53:00) 53:00) (72) Inventor Shigekatsu Yoshida Kawasaki City, Kanagawa Prefecture Asahi Kasei Kogyo Co., Ltd. 1-3-1 Asahi Kasei Kogyo Co., Ltd. F-term (reference) BD043 BD051 BG051 BG133 BP012 BP021 BP031 CF001 CF003 CG001 CH071 CL001 CL003 CL063 CN021 DA016 DA076 DC006 DE106 DE186 DE236 DJ006 DJ026 DK006 DL006 EV256 EW046 FA043 FA046 FA066 FA073 FA076 FD013 FD016 FD020 GC00GN

Claims (9)

[Claims] (A) 1 to 50 parts by weight of a hydrogenated block copolymer of an aromatic vinyl monomer / conjugated diene monomer,
The average diameter of (C) is 0.01 to 1000 μm with respect to 50 to 99 parts by weight of the thermoplastic resin (B) and 100 parts by weight of the total amount of the components (A) and (B), and the aspect ratio (length) Filler with a thickness / diameter of 5 to 2500 0.1 to
A high-strength and high-rigidity thermoplastic resin composition comprising 200 parts by weight. 2. The high-strength and high-rigidity thermoplastic resin composition according to claim 1, wherein the thermoplastic resin as the component (B) is a polyolefin resin. 3. The high-strength polyolefin resin according to claim 3, wherein the polyolefin resin is mainly a polypropylene resin.
High rigidity thermoplastic resin composition. 4. The high-strength and high-rigidity thermoplastic resin composition according to claim 1, wherein the filler as the component (C) is a glass fiber and / or a carbon fiber. 5. A glass fiber or carbon fiber raw bead is coated with a thermoplastic resin and further has an average length of 1 to 25 mm.
Thermoplastic resin pellets containing glass fibers or carbon fibers cut to a hydrogenated block copolymer pellet of aromatic vinyl monomer / conjugated diene monomer or aromatic vinyl monomer / conjugated diene monomer The high-strength and high-rigidity thermoplastic resin composition according to claim 4, wherein a pellet comprising a melt-kneaded mixture of a hydrogenated block copolymer and a thermoplastic resin, and a thermoplastic resin pellet as required. Production method. 6. A high-strength, high-rigidity thermoplastic resin molded article obtained by molding the composition according to claim 1. 7. An antifreeze-resistant automobile part obtained by molding the composition according to claim 1. 8. A tool part obtained by molding the composition according to claim 1. 9. An office chair part obtained by molding the composition according to claim 1.