CN1175052C - High-stiffness high-strength thermoplastic resin molded article - Google Patents

Abstract

A thermoplastic resin molded article comprising glass fibers and a thermoplastic resin, wherein the glass fibers are contained in an amount of 1 to 60% by weight, and the glass fibers having a length of not more than 0.5mm among the fibers are contained in an amount of 90 to 10%, the glass fibers having a length of 0.5 to 2mm are contained in an amount of 10 to 90%, and the glass fibers having a length of not less than 2mm are contained in an amount of 0 to 30%.

Description

High-stiffness and high-strength thermoplastic resin moldings

technical field

The present invention relates to a high stiffness and high strength glass fiber reinforced thermoplastic resin molded article and its production method.

Background technique

As the thermoplastic resin, many resins such as polyethylene-based resins, polypropylene-based resins, polystyrene-based resins, polyamide-based resins, and the like are known. These thermoplastic resins are required to have high stiffness and high strength according to their end use. The most preferred method of providing these properties is glass fiber reinforcement, such as glass fiber reinforced polypropylene based resins, glass fiber reinforced polyamide based resins, and the like. Among them, glass fiber-reinforced polyamide resins are widely used as materials for automobiles such as radiator tanks, for tools such as casing materials for electric drills, and for office machinery such as office chairs. Even by mixing polyamide resin and glass fiber, this glass fiber-reinforced polyamide resin can exhibit high stiffness and high strength, and since the polyamide resin as a base has high strength, its application fields are wide wide. On the other hand, compared with glass fiber-reinforced polyamide resin, the strength of glass fiber-reinforced polypropylene-based resin is not enough, and since the strength of the polypropylene-based resin itself is lower than that of polyamide-based resin, its use is currently limited. .

When general-purpose resins such as polypropylene resins that are mild to the environment (this is almost a general trend in the world) become high-stiffness and high-strength materials, their uses will be wider. When polyamide-based resin is also a high-stiffness and high-strength material, it can be processed at a very thin thickness, which contributes to its weight reduction and cost reduction. Therefore, among various thermoplastic resins, materials with higher stiffness and high strength are required.

Summary of the invention

In view of the above circumstances, an object of the present invention is to provide thermoplastic resin molded articles having higher stiffness and higher strength.

The present inventors conducted intensive studies mainly using polyolefin-based resins, particularly polypropylene-based resins to achieve the above objects. Initially, polypropylene-based resins alone did not satisfy the required functions at all for applications requiring high stiffness and strength, such as materials for automobiles such as radiator tanks, materials for housings for tools such as electric drills, and materials for office machinery such as office chairs. Thus, a method called "short fiber method" in the industry, which is the same as the method commonly used in glass fiber-reinforced polyamides, has been studied, in which glass fibers (chopped glass fibers) are mixed with polypropylene-based resins, Kneading out of the machine, and injection molding of the obtained pellets to form molded products. However, considering the above-mentioned application, the resulting molded article did not achieve practical strength at all, but the stiffness and mechanical strength of the article were improved compared with polypropylene-based resins containing no glass fiber therein.

JP-A-3-188131, JP-A-3-243308 and JP-A-8-336832 etc. disclose a kind of method called "long fiber method", wherein make the fiber with length 7-12mm covered with polypropylene Polypropylene resin pellets of glass fibers and polypropylene resin pellets are blended for direct molding.

In the above short fiber method, glass fibers (chopped glass fibers) are mixed with a polypropylene-based resin, kneaded with an extruder, and then injection molded to form a molded article.

Therefore, two passes of kneading (extrusion kneading and screw kneading at the time of injection molding) are performed, and as a result, the glass fibers are broken and their length becomes extremely short. On the contrary, in the long fiber method, since a molded article is produced only by kneading with a screw at the time of injection molding, the length of the glass fiber may remain long. The research results of this long-fiber method show that although the length of glass fibers varies depending on the molding conditions, too short a length does not exhibit sufficient stiffness and strength, and too long a length does not express sufficient surface condition.

However, unexpectedly, the present inventors have found that when the length distribution of the glass fibers is within the specified range, the molded articles become excellent in surface condition, stiffness, and mechanical strength, and the molded articles become practical in the above-mentioned applications. Strength of. Further, although higher mechanical strength is required depending on the application, the present inventors found that when a rubber-like polymer of some shape is made to coexist with a molded article comprising a polypropylene-based resin and glass fibers having a length distribution in a prescribed range, the mold The article becomes a higher level of surface condition, stiffness and mechanical strength. Meanwhile, the present inventors found that the above facts are applicable to resins other than polypropylene-based resins.

Based on the above knowledge, the present invention has been accomplished.

In this regard, the reason why a molded article of higher level of mechanical strength can be obtained when a rubber-like polymer is allowed to coexist is as follows: Generally, when a raw material of a molded article is processed by molding such as injection molding, glass fibers are oriented, and the article in its The longitudinal and transverse directions exhibit different mechanical strengths, resulting in directional (anisotropic) mechanical strength, whereby mechanical strength such as impact resistance becomes high in one direction and becomes low in the other direction. However, the rubber-like polymer alleviates the directionality (anisotropy).

The present invention relates to a high-stiffness and high-strength thermoplastic resin molded product and a production method thereof, said molded product comprising glass fiber and a thermoplastic resin, wherein the content of said glass fiber is 1 to 60% by weight, said fiber The content of glass fibers with a length not greater than 0.5 mm is 90 to 10%, the content of glass fibers with a length of 0.5 to 2 mm is 10 to 90%, and the content of glass fibers with a length not less than 0.5 mm is 0 to 30%.

More specifically, the present invention relates to a high-stiffness, high-strength, especially excellent impact-resistant thermoplastic resin molded article, comprising glass fibers, thermoplastic resins and rubber-like polymers, wherein the content of the glass fibers is 1 to 60 % (weight), the glass fibers with a length of not more than 0.5mm contain 90 to 10%, those with a length of 0.5 to 2mm are 10 to 90%, and those with a length of not less than 2mm are 0 to 30%, so The content of the rubber-like polymer is 1 to 40% by weight.

The molded article of the present invention can remarkably improve mechanical strength, particularly impact strength, by allowing the rubber-like polymer to coexist with glass fibers. When making the rubber-like polymer coexist, it is more preferable to partially or completely crosslink the rubber-like polymer. When cross-linked, the improvement is greater than when it is not cross-linked. The reason is as follows: in the case where the rubber-like polymer is not cross-linked, when the raw material of the molded article is molded to provide the molded article of the present invention, the material is extended in the flow direction thereof, and thus the rubber-like polymer is mixed with the glass fiber same way orientation. In contrast, in the case where the rubber-like polymer is cross-linked, the material does not extend in the direction of its flow and thus retains the shape of the rubber-like polymer in the molded article even if the glass fibers are oriented and the rubber-like polymer Things are not oriented either. As a result, the mechanical strength, in particular the impact strength, is significantly improved.

best practice

First, each component of the present invention is explained in detail.

The glass fibers in the thermoplastic resin molded article of the present invention have an average diameter of 0.01 to 1000 μm, preferably 0.1 to 500 μm, more preferably 1 to 100 μm, most preferably 5 to 50 μm. Its average length is 0.2 to 3 mm, preferably 0.5 to 2 mm. When the average diameter thereof is less than 0.01 μm, its reinforcement effect is low and its mechanical strength improvement effect is insufficient. When the average diameter thereof is larger than 1000 µm, its dispersibility is lowered, and its effect of improving mechanical strength is also insufficient. When the average length thereof is less than 0.2 mm, the reinforcement effect is low and the mechanical strength improvement effect is insufficient. On the other hand, when the average length thereof is greater than 3 mm, the surface condition of the molded article is poor. The glass fiber content of the thermoplastic resin molded article of the present invention is 1 to 60% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight, most preferably 20 to 40% by weight. When the glass fiber content is less than 1% by weight, the effect of improving the mechanical strength is insufficient. On the other hand, when the glass fiber content is higher than 60% by weight, not only the surface condition of the molded article becomes poor, but also its mechanical strength decreases due to the decreased content of thermoplastic resin for maintaining mechanical strength.

Although the mechanical strength of the molded article is influenced by the average diameter and average length of the glass fibers (as described above), it is most predominantly influenced by the length distribution of the glass fibers. In other words, the presence of many short fibers in the molding does not necessarily lead to a significant improvement in mechanical strength. The presence of longer fibers therein improves the mechanical strength, but the length of the glass fibers in the molded article is not necessarily as long as possible.

For example, JP-A-3-243308 discloses a molded article in which at least 50% by weight of glass fibers having a length of at least 2 mm is present. However, moldings of this fiber length cannot be produced without the use of very low molecular weight thermoplastic resins. Even when long fibers are contained in the molded article, the thermoplastic resin itself exhibits low mechanical strength, so that a molded article with high stiffness and high strength cannot be obtained. Even if it can be molded with a commercially available thermoplastic resin, the resulting molded article has a poor appearance and is not worthy of being a commercial product.

Requirements for the glass fiber in the molded article of the present invention: the content of glass fiber with a length not greater than 0.5 mm is 90 to 10%, the content of glass fiber with a length of 0.5 to 2 mm is 10 to 90%, and the content of glass fiber with a length not less than 2 mm is 0 to 30%; Preferably the glass fiber content is 80 to 20% with a length of not more than 0.5mm, 20 to 80% for a length of 0.5 to 2mm, and 5 to 25% for a length of not less than 2mm; more preferably glass fibers with a length of not more than 0.5mm The fiber content is 60 to 25%, the content of 0.5 to 2mm in length is 40 to 75%, and the content of not less than 2mm in length is 5 to 20%. With the above length distribution of the glass fibers, for the first time, a molded article with good appearance and high stiffness and high mechanical strength can be provided.

When the content of glass fibers having a length of not more than 0.5 mm is more than 90%, the effect of improving the mechanical strength is insufficient. Furthermore, the length of the glass fibers in the molded article significantly affects the surface condition. The reason is as follows: It is not easy to apply shear when molding processing is employed with long glass fibers remaining in the molded article. As a result, the glass fiber tends to be hardly dispersed in the thermoplastic resin, and the dispersion state of the glass fiber in the resin becomes uneven, causing variability (localization), and the surface condition deteriorates due to fuzzing or unevenness due to glass fiber bonding , while reducing the mechanical strength. For this reason, when long glass fibers are retained, the surface condition deteriorates and the mechanical strength tends to decrease. When the content of glass fibers having a length of not more than 0.5 mm is less than 10%, the appearance of the molded article is poor and the mechanical strength is lowered.

When the content of glass fibers having a length of 0.5 to 2 mm is less than 10%, the content of glass fibers having a length of not more than 0.5 mm becomes large, and the effect of improving mechanical strength is insufficient. When the content of glass fibers having a length of 0.5 to 2 mm is more than 90%, the appearance of the molded article is poor, and the mechanical strength tends to decrease.

When the content of glass fibers with a length of not less than 2mm is more than 30%, it is the same as the above case.

The length of the glass fibers in the molded article varies depending on the molding conditions for molding the material of the molded article of the present invention. Generally, under the condition that the melt viscosity of the molded product material is high and shear is applied, the glass fibers are broken during kneading and the length becomes short. Thus, molding at high temperature maintains the original long length of the glass fibers. Keep the original long length of the glass fiber when molding while keeping the screw speed low. In addition, the length of glass fibers in molded articles varies with the design of the molding machine. For example, molding with a deeply grooved screw maintains the original long length of the glass fibers. Optimum molding conditions are preferably selected in order to obtain a molded product having an appropriate length of glass fibers and thus an excellent appearance.

As the glass fiber in the molded article of the present invention, E glass, S glass, C glass, AR glass and the like can be used. In this regard, it is preferable to use glass fibers pretreated with a coupling agent such as a silane coupling agent in order to improve the adhesion to the resin. In the molded article of the present invention, glass fiber is an essential component, but other fibers such as natural fibers such as cotton, silk, wool, hemp, etc., regenerated fibers such as rayon, cupro, etc., semi-synthetic fibers such as acetate fiber, promix etc., synthetic fibers such as polyester, polyacrylonitrile, polyamide, aramid, polyolefin, carbon fiber, polyvinyl chloride, etc., inorganic fibers such as glass, asbestos, etc., metal fibers such as SUS, copper, brass, etc., also can be used together. Among them, carbon fiber has a significant effect on improving stiffness, so it can be used together with glass fiber to further improve stiffness.

Next, the rubber-like polymer, which is a component preferably contained in the thermoplastic resin molded article of the present invention, is described.

The preferred component in the moldings of the invention, the rubber-like polymer, has a glass transition temperature (Tg) preferably not higher than -30°C. The rubber-like polymer includes, for example, diene rubbers such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), etc., saturated rubbers obtained by hydrogenating the above-mentioned diene rubbers, iso Pentadiene rubber, neoprene rubber, acrylic rubber such as polybutylacrylate, etc., and ethylene-α-olefin copolymer rubber, etc. Among them, especially ethylene-α-olefin copolymer rubber mainly containing ethylene and α-olefin and polymers having a similar structure are excellent in weather resistance and mechanical strength and are therefore particularly preferred. The polymer having a similar structure therein means, for example, a rubber obtained by hydrogenating polybutadiene, which is a rubber similar in structure to an ethylene-butene-1 copolymer.

Among the ethylene-α-olefin copolymer rubbers, ethylene-α-olefin copolymer rubbers mainly containing ethylene and an α-olefin having a carbon number of 3 to 20 are more preferred. Examples of α-olefins having 3 to 20 carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, and octene-1 , Nonene-1, Decene-1, Undecene-1, Dodecene-1, etc. These α-olefins may be used alone or in combination of at least two kinds.

Furthermore, as a third component, a component copolymerizable therewith may be contained. As the third copolymerizable component, conjugated dienes such as 1,3-butadiene, isoprene, etc., non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene , cyclooctadiene, methyl norbornene, ethylidene norbornene, etc. As the ethylene-α-olefin copolymer rubber containing the third copolymerizable component, ethylene-propylene-conjugated or non-conjugated diene terpolymer rubber (EPDM) can be cited.

However, with respect to one of the uses of the molded article of the present invention—the housing of an electric tool, which is usually used outdoors, it is required to have weather resistance. Disadvantageously, ethylene-α-olefin copolymer rubbers containing conjugated or non-conjugated dienes have poorer weather resistance than ethylene-α-olefin copolymer rubbers containing no conjugated or non-conjugated dienes.

The present invention does not exclude ethylene-α-olefin copolymer rubbers containing conjugated or non-conjugated dienes, but ethylene-α-olefin copolymer rubbers containing no conjugated or non-conjugated dienes are preferred. Examples thereof include copolymer rubbers of ethylene and at least one selected from hexene-1, 4-methylpentene-1, and octene-1. Among them, copolymer rubbers of ethylene and octene-1 are particularly preferable. The reason is that it has excellent weather resistance and rubber elasticity. In addition, the reason is that in the case of using a polyolefin-based resin as the thermoplastic resin in the molded article of the present invention and the molded article is used as a housing of an electric tool, rubber having a high degree of branching, that is, rubber having long-chain branching is used. There is almost no phenomenon of white streaks at the time, but generally when the tool is dropped, white streaks appear on the molded product due to impact.

Copolymer rubbers of ethylene and octene-1 suitable for use as the rubber-like polymers of the present invention are preferably produced using metallocene catalysts. The melt index of the ethylene-α-olefin copolymer rubber used as a raw material for obtaining the molded article of the present invention is preferably in the range of 0.01 to 100 g/10 min (190°C, 2.16 kg), more preferably in the range of 0.2 to 20 g/10 min . Above 100 g/10 min, the rubber-like polymer does not sufficiently exhibit rubber elasticity. When it is less than 0.01 g/10 min, flowability becomes poor when molding to obtain the molded article of the present invention, resulting in a decrease in workability, which is disadvantageous.

The preferred component of the invention, the rubber-like polymer, is preferably partially or completely crosslinked. The reason is as follows: As described above, when molding the material of the molded article to provide the molded article of the present invention, the resin generally extends in its flow direction, thereby orienting the resin. However, in the case where the rubber-like polymer is cross-linked, the material does not extend toward its flow direction, thereby maintaining the shape of the rubber-like polymer even in a molded article, and thus the rubber-like polymer lightens its Directional, but fiberglass oriented.

In the case of cross-linking the rubber-like polymer, the degree of cross-linking is defined by the ratio of the amount of the cross-linked rubber-like polymer (solvent-insoluble rubber-like polymer) to the total amount of the rubber-like polymer in the thermoplastic resin molding , the degree of crosslinking is preferably not lower than 20%, more preferably not lower than 50%.

As a preferred component of the present invention, the rubber-like polymer is used as a component in an amount of 1 to 30% by weight, preferably 5 to 30% by weight, more preferably 10 to 30% by weight, most preferably 15 to 25% by weight is preferred. Mechanical strength, particularly impact resistance, is greatly influenced by the shape of the rubber-like polymer, that is, its morphology. Regarding the shape, the number average particle diameter (in circles) measured on a surface cut at right angles to the flow direction upon molding is preferably 0.1 to 1.5 μm, more preferably 0.2 to 1.2 μm. In the case where the rubber-like polymer is not cross-linked, it is molded to extend toward the flow direction, so that when the shape of the rubber-like polymer in the molded article is observed through an electron microscope, parallel to the flow direction and perpendicular to the flow direction different shapes on the surface. In addition, the shape of the surface portion and the inside of the molded article are slightly different, and the shapes of the inlet end portion and the end portion are also slightly different. Accordingly, the shape of the rubber-like polymer in the molded article of the present invention is defined as the number-average particle diameter in circles measured at the central portion and inside of the molded article on a surface cut at right angles to the flow direction upon molding. In this regard, the number average particle diameter in terms of circles is defined as follows: Regardless of whether it is cross-linked or not, the shape of the rubber-like polymer in the molded article does not have to be spherical, and image analysis of photographs observed by an electron microscope was performed using Expressed as number average particle diameter in circles. When the number-average particle diameter in terms of circles is not more than 0.1 μm, the effect of improving the mechanical strength is insufficient. On the other hand, when it is not less than 1.5 µm, the effect of improving the mechanical strength is insufficient.

When the rubber-like polymer in the molded article of the present invention is used as one component, it can be used in admixture of plural kinds. In this case, processability can be further improved.

The thermoplastic resin in the thermoplastic resin molded article of the present invention is explained below.

The thermoplastic resin in the thermoplastic resin molded article of the present invention is not limited as long as the rubber-like polymer preferably used is compatible therewith or uniformly dispersed therein, or is compatible therewith or uniformly dispersed therein by using a compatibilizer . For example, resins such as polystyrene type (polystyrene), polyphenylene ether type (polyphenylene ether type), polyolefin type (polyolefin type), polyvinyl chloride type, polyamide type (polyamide type), poly Ester type (polyester type), polyphenylene sulfide type (polyphenylene sulfide type), polycarbonate type, polymethacrylate type resins may be used alone or in admixture of at least two types. Among them, polyolefin-based resins are preferably used as the thermoplastic resin. The reason is as follows: When a rubber-like polymer is present in the thermoplastic resin molded article of the present invention, the resin is highly compatible with ethylene-α-olefin copolymer rubber or a polymer of similar structure suitable as the rubber-like polymer. properties, high-strength moldings can be obtained.

Polyolefin-based resins suitable for use in the present invention are simply classified into three categories: polyethylene-based resins, polypropylene-based resins, and mixtures of polyethylene-based resins and polypropylene-based resins.

The polyethylene resins include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), copolymers of acrylic vinyl monomers and ethylene (EEA, EMMA, etc.), Copolymer of vinyl acetate monomer and ethylene (EVA), etc. Among them, high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE) are particularly preferable because they have high heat resistance and are available at low cost. These polyethylene-based resins may be used alone or in combination of at least two kinds.

When high-density polyethylene (HDPE) is used as the raw material of the molded article of the present invention, its density is generally in the range of 0.930 to 0.970 g/cm ² , and the melt flow rate (MFR) measured at 190 ° C and 2.16 kg load is preferably In the range of 0.05 to 100 g/10 min. 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/ ^cm2 , and the melt flow rate (MFR) measured at 190 ° C and 2.16 kg load ) is preferably in the range of 0.05 to 100 g/10 min. When its melt flow rate (MFR) is higher than 100 g/10 min, the mechanical strength and heat resistance of the molded article of the present invention are insufficient. On the other hand, when the melt flow rate (MFR) thereof is lower than 0.05 g/10 min, when the molded article of the present invention is molded, the fluidity becomes poor and the workability decreases, which is disadvantageous.

The polypropylene-based resins include polypropylene (homopolymer), copolymers of propylene and another α-olefin such as ethylene, butene-1, pentene-1, hexene-1, etc. (including block copolymers and random copolymer) resins.

The melt flow rate (MFR) of the polypropylene-based resin used to obtain the molded article of the present invention as measured at 230° C. under a load of 2.16 kg is preferably in the range of 0.1 to 100 g/10 min. When its melt flow rate (MFR) is higher than 100 g/10 min, the mechanical strength and heat resistance of the molded article of the present invention are insufficient. On the other hand, when the melt flow rate (MFR) thereof is lower than 0.1 g/10 min, when the molded article of the present invention is molded, the fluidity becomes poor and the processability is lowered, which is disadvantageous.

As described above, the polyolefin-based resins preferably used to obtain the molded article of the present invention include polyethylene-based and/or polypropylene-based resins. When the molded article of the present invention is used as a housing of an electric tool, the housing thereof rises to a high temperature due to heat generated by a motor provided therein, and thus heat resistance is required. For this reason, polypropylene-based resin is more preferable because of its heat resistance. In addition, when the molded article is used for a radiator tank in contact with a high-temperature coolant liquid, the polypropylene-based resin is more preferable because heat resistance is required. However, polypropylene homopolymers are generally prone to oxidative decomposition, and their molecular weight decreases during long-term use, so their mechanical strength tends to decrease. On the other hand, polyethylene is generally not easily oxidatively decomposed, and tends to maintain mechanical strength or improve through its crosslinking. Therefore, when using polypropylene resin, in applications requiring heat resistance, it is sometimes preferred to use polypropylene homopolymer in combination with polyethylene-based resins, or random or block copolymers of propylene monomers and vinyl monomers alone or in combination.

In this regard, the thermoplastic resin in the thermoplastic resin molded article of the present invention is preferably a polyolefin-based resin because the resin has a high affinity with ethylene-α-olefin copolymer rubber or a structurally similar polymer suitable as a rubber-like polymer. Compatibility, high strength moldings can be obtained. However, as described above, thermoplastic resins other than the polyolefin-based resins such as polystyrene-based resins, polyphenylene ether-based resins, and the like may also be used.

When thermoplastic resins other than polyolefin-based resins are used, the resins generally do not necessarily have good compatibility with ethylene-α-olefin copolymer rubbers suitable as rubber-like polymers. In this case, a compatibilizer is used. As the compatibilizer, there may be mentioned polymer materials, etc., whose molecules contain the polyolefin-based component and the component of the thermoplastic resin used or a component compatible with the thermoplastic resin. Examples thereof include hydrogenated styrene-butadiene block copolymer resin, styrene-grafted polyethylene, and the like when polystyrene-based resin is used as the resin. When a thermoplastic resin other than polystyrene-based resin is used as the resin, the material of the compatibilizer is selected as above.

As described above, the thermoplastic resin molded article of the present invention includes a thermoplastic resin containing at least glass fibers and preferably further containing a rubber-like polymer. Other components such as thermoplasticity-providing polymers (modifiers), softeners, powdery inorganic fillers, whiskers, plasticizers other than the thermoplastic resin as a matrix may be contained as needed. As the polymer (modifier) other than the above-mentioned thermoplastic resin as a matrix, thermoplastic resins capable of interfacially bonding glass fibers and the thermoplastic resin of the present invention are exemplified. For example, in the case of a polyolefin-based resin suitable for use as the thermoplastic resin of the present invention, as a material for improving interfacial adhesion between glass fibers and a thermoplastic resin as a matrix, maleic acid-modified polyolefin or a maleic acid-modified polyolefin can be cited. Polyolefins copolymerized with acid, polyolefins modified with acrylic acid or polyolefins copolymerized with acrylic acid, polyolefins modified with fumaric acid or polyolefins copolymerized with fumaric acid, etc. The presence of the above modifiers is effective to improve impact resistance.

As the softener, processing oils such as paraffin oil, naphthenic oil and the like can be used. In the presence of a softener, although the stiffness is slightly lowered, it can exhibit the effect of further improving the impact resistance. It also exhibits a flow-improving effect. Generally, when a molded product is dropped, its peripheral portion is seen to be whitened by the impact, which lowers the value of the product. But the softening agent has the effect of improving the whitening.

The powdery inorganic fillers include talc, mica, clay, calcium carbonate, magnesium carbonate, silicon oxide, carbon black, titanium oxide, magnesium hydroxide, aluminum hydroxide and the like. Among them, talc is particularly preferable because it increases the stiffness of the polyolefin-based resin suitable for use as the thermoplastic resin component of the molded article of the present invention. When talc is added, its amount is in the range of 1 to 50% by weight, preferably in the range of 5 to 40% by weight, more preferably in the range of 5 to 30% by weight, particularly preferably in the range of 10 to 50% by weight. 20% (weight) range. Talc, when present, may be present in combination with a mixture of glass fibers and a thermoplastic resin, or preferably with a mixture of glass fibers, a thermoplastic resin and a rubber-like polymer.

The plasticizer includes polyethylene glycol, phthalates such as dioctyl phthalate (DOP), and the like. Other additives such as organic or inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, silicone oils, antiblocking agents, foaming agents, antistatic agents, antifungal agents may be suitably used.

A preferable production method of the thermoplastic resin molded article of the present invention is described below.

The molded article of the present invention can be obtained by direct molding a blended material obtained by blending glass fiber itself or glass fiber hardened with latex or thermoplastic resin or the like with a thermoplastic resin. Preferably, glass fiber itself or glass fiber hardened with latex or a thermoplastic resin, etc., and a thermoplastic resin containing a rubber-like polymer (preferably a partially or completely crosslinked rubber-like polymer) (hereinafter referred to as " The thermoplastic elastomer") and, if necessary, a thermoplastic resin are blended to obtain the resulting blended material to obtain the molded article of the present invention. With this method, only one kneading is done and the length of the fibers in the molded article can be kept very long, resulting in a molded article of high stiffness compared to the short-fiber method which requires blending with a twin-screw extruder followed by injection molding . A more preferred method is as follows: soak a bundle of glass fibers (rovings) in latex, impregnate the rovings with a thermoplastic resin, or extrude a thermoplastic resin so that the rovings are covered with the resin to prepare a fiberglass containing the same length as the pellets. Thermoplastic resin pellets of glass fibers (hereinafter referred to as "long fiber pellets"). The pellets are then blended with thermoplastic resin pellets and the blend is injection molded. When a rubber-like polymer is contained as a component in a molded article, the above-mentioned long fiber pellets and thermoplastic resin pellets (hereinafter referred to as "thermoplastic polymers") containing a rubber-like polymer (preferably a partially or completely cross-linked rubber-like polymer) are pelletized. Elastomer pellets") and thermoplastic resin pellets are blended when necessary, and the blend is injection molded. When talc is contained as a component in a molded article, the above-mentioned long fiber pellets and thermoplastic resin pellets containing talc and thermoplastic resin pellets as needed are blended, and the blend thereof is injection molded. When a polyolefin-based resin is used as the thermoplastic resin, polymers other than the thermoplastic resin as a matrix that are preferably added to improve the adhesion between the resin and the glass fibers may be used in any manner in the thermoplastic resin covering the glass fibers, thermoplastic In elastomers, in thermoplastic resins, or in combinations thereof.

Here, a method for producing a crosslinked rubber-containing thermoplastic elastomer preferably used including a thermoplastic resin containing a partially or completely crosslinked rubber-like polymer is explained taking a polyolefin-based resin as an example of a thermoplastic resin.

Preferably, the ethylene-α-olefin copolymer mainly comprising ethylene and α-olefin and/or a polymer of similar structure, polyolefin resin, crosslinking agent and The auxiliary agent is heat treated. As the crosslinking agent preferably used herein, radical initiators such as organic peroxides, organic azo compounds and the like can be cited. Examples of the free radical initiator include peroxyketals such as 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy) Oxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane , 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)octane, n-butyl-4,4-bis(tert-butylperoxy) ) butane, n-butyl-4,4-bis(tert-butyl peroxy)valerate, etc.; dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxide Cumyl, α, α'-bis(tert-butylperoxy-m-isopropyl)benzene, α,α'-bis(tert-butylperoxy)diisopropylbenzene, 2,5-di Methyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, etc.; diacyl peroxide Substances such as acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, m-toluoyl peroxide, etc.; peroxyesters such as tert-butyl peracetate, tert-butyl perisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl perlaurate, tert-butyl perbenzoate, di-tert-butyl perisophthalate, 2,5-dimethyl-2,5-di(tert-benzoylperoxy)hexane, per tert-butyl maleate, tert-butyl peroxyisopropyl carbonate, cumyl peroctoate, etc.; hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, dicumyl hydroperoxide, 2,5-dimethylhexane-2,5-diperoxide, 1,1,3,3-tetramethylbutyl peroxide, etc.

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

The free radical initiator is used in an amount in the range of 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the ethylene-α-olefin copolymer and the polyolefin resin. The degree of crosslinking is mainly determined by this amount. When the amount is less than 0.02 parts by weight, the crosslinking is insufficient, and even when the amount is more than 3 parts by weight, the crosslinking ratio is not necessarily greatly improved.

As crosslinking aids, preferably divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethyl Acrylate, 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, etc. These crosslinking aids can be used in combination of various types.

The amount of the crosslinking aid is in the range 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 and the polyolefin resin. When the amount is less than 0.1 parts by weight, the degree of crosslinking is low, and even when the amount is more than 5 parts by weight, the degree of crosslinking is not necessarily greatly improved.

As a crosslinking method, it is preferable to use a crosslinking agent and a crosslinking auxiliary agent as described above, but in addition, a phenolic resin, bismaleimide, or the like can also be used.

The production method of the long fiber pellets is described below.

The method comprises: immersing glass fiber roving in molten thermoplastic resin, and then making pellets of predetermined length; making the glass fiber roving uniform under stretching, and extruding thermoplastic resin laterally from it with an extruder, Thereby, extruding the thermoplastic resin on the surface of the glass fiber, and then performing pelletizing (generally called "extrusion method"); and immersing the glass fiber roving in an emulsion (latex), and then drying to make pellets of a predetermined length, etc. method. The thermoplastic resin covering the glass fiber can be appropriately selected from the above-mentioned resins, but is preferably the same kind as the thermoplastic resin as the matrix. The emulsion is also preferably the same kind as the thermoplastic resin as the matrix or a kind compatible therewith. As an example of the emulsion, when the thermoplastic resin is polyolefin resin, ethylene-vinyl acetate emulsion can be used; when the thermoplastic resin is polystyrene resin or modified polyphenylene ether resin, benzene can be used. Ethylene-butadiene emulsion; the thermoplastic resin is polyacrylonitrile-styrene resin (AS), polyacrylonitrile-butadiene-styrene resin (ABS), polycarbonate resin (PC), polyester When the resin (PET, PBT, etc.) is used, an acrylonitrile-styrene emulsion can be used; when the thermoplastic resin is a polyamide-based resin, a polyurethane-based emulsion can be used.

The length of the long fiber pellets obtained above is usually 2 to 100 mm, preferably 3 to 50 mm, more preferably 5 to 20 mm. The long fiber pellets contain glass fibers of the same length as the pellets. Mixing long fiber pellets with pellets of thermoplastic resin, injection molding under suitable molding conditions; or preferably long fiber pellets with rubber-like polymers (preferably partially or fully cross-linked rubber-like polymers) and/or Or thermoplastic resin pellets of talc and thermoplastic resin pellets mixed when necessary, injection molding under suitable molding conditions.

In order to obtain the molded article of the present invention, molding methods such as extrusion molding, compression molding, etc. can be used in addition to injection molding.

The molded articles of the invention thus produced have excellent appearance, high stiffness and strength, and also excellent heat resistance.

Depending on its use, it is desirable for the molded article of the invention to soften on its surface. For example, regarding the housing of an electric tool, the grip part can be softened to provide a feeling of warmth without fatigue during use. Softening is carried out on the surface of the molded article of the present invention to produce a laminated article, for example, preferably using the following method: two-color molding of the material of the molded article of the present invention and a thermoplastic elastomer; placing the molded article of the present invention in a mold, and then Insert molding of the body; co-extrusion molding of the material of the molded article of the present invention with a thermoplastic elastomer; and the like. As the thermoplastic elastomer, a thermoplastic elastomer containing the aforementioned rubber-like polymer (preferably a partially or completely crosslinked rubber-like polymer) is preferable. The thermoplastic resin and the rubber-like polymer preferably present in the molded article of the present invention, and the thermoplastic resin and the rubber-like polymer in the thermoplastic elastomer laminated on the surface thereof may be the same or different, respectively. But preferably the same. The reason is as follows: when they are all the same, the molded article and the thermoplastic elastomer laminated thereon have good adhesion. When the material is recycled, it is not necessary to strip the thermoplastic elastomer from the molded article, it is only necessary to grind to the extent that the strength is reduced, add glass fibers, and then these materials can be recycled to produce the molded article of the present invention.

The present invention is explained in detail below in conjunction with examples and comparative examples, but should not be construed as limiting the present invention.

In this regard, the test methods for evaluating the respective properties, the raw materials, and the production methods of the thermoplastic elastomers used in the blending in these Examples and Comparative Examples are as follows.

1. Test method

(1) Tensile strength: Measured at 23°C according to the method of JIS K6251.

(2) Bending strength: Measured at 23°C according to the method of JIS K6758.

(3) Flexural strength: measured at 23°C according to the method of JIS K6758.

(4) Izod impact strength: Measured at 23°C according to the method of JIS K6758 (V-notch, 1/4 inch test piece).

(5) Impact strength of falling ball:

Using a falling ball tester (manufactured by Toyoseikiseisaku-syo Ltd.), the total energy absorbed was measured under the following conditions: falling ball tip diameter: 13.6 mm, weight: 6.5 kg, drop height: 100 cm, jig diameter: 5 mm, test piece thickness: 3 mm , temperature: 23° C., humidity: 50%; the higher the value, the harder it is for the molded article to break.

(6) Heat resistance (HDT): Measured according to the method of JIS K7207.

(7) Length of glass fibers in molded article: The molded article was fired, and the fiber length distribution was measured by image analysis using an optical microscope.

(8) Average particle diameter of the rubber-like polymer: The molded article was cut at right angles to the flow direction at the time of molding with a slicer. Observed by electron microscope. The number average particle diameter in circles was determined by image analysis.

(9) Degree of crosslinking: 0.5 g of crosslinked thermoplastic elastomer was refluxed in 200 ml of xylene for 4 hours. The solution was filtered through filter paper to measure its amount. The residue on the paper was vacuum-dried, the amount thereof was measured, and the ratio (%) of the weight of the residue to the weight of the rubber-like polymer in the crosslinked thermoplastic elastomer was calculated.

2. Raw material

(1) rubber-like polymer

(a) Ethylene-octene-1 copolymer:

Produced using a metallocene catalyst method as described in JP-A-3-163088. The composition ratio of ethylene/octene-1 in the copolymer was 72/28 (weight ratio) (referred to as "TPE-1").

(b) Ethylene-propylene-dicyclopentadiene copolymer:

Produced by the metallocene catalyst method as described in JP-A-3-163088. The composition ratio of ethylene/propylene/dicyclopentadiene in the copolymer was 72/24/4 (weight ratio) (referred to as "TPE-2").

(2) Thermoplastic resin

(a) Polypropylene:

Isotactic propylene homopolymer (MAO3) (called "PP") produced by Japan Polychem Co.

(b) Ethylene (E)-propylene (PP) copolymer resin-1:

Block E-PP resin [E/P=6/94 (weight ratio) (PM 970A)] produced by Japan Polyolefin Co. (called "EP-1")

(c) Ethylene (E)-propylene (PP) copolymer resin-2:

Atactic E-PP resin [E/P=7/93 (weight ratio) (PM 940M)] produced by Japan Polyolefin Co. (called "EP-2")

(d) Maleated polypropylene:

ADMER(F305) manufactured by Mitsui Chemical Co. (called "M-PP")

(e) Maleated polyethylene:

ADMER(HB030) manufactured by Mitsui Chemical Co. (called "M-PE")

(f) High-density polyethylene:

SUNTEC HD (B470) manufactured by Asahi Chemical Industry Co. Ltd. (called "HDPE")

(g) polystyrene:

STYRON PS(683) manufactured by Asahi Chemical Industry Co.Ltd. (referred to as "PS")

STYRON HIPS (403) manufactured by Asahi Chemical Industry Co.Ltd. (referred to as "HIPS")

(h) Polyacrylonitrile-styrene:

STYRAC AS(769) manufactured by Asahi Chemical Industry Co.Ltd. (referred to as "AS")

(i) Polyacrylonitrile-butadiene-styrene:

STYRAC ABS (100) manufactured by Asahi Chemical Industry Co. Ltd. (referred to as "ABS")

(j) polycarbonate:

NOVALEX (702A) manufactured by Mitsubishi Engineering Plastics Co. (referred to as "PC")

(k) Polycarbonate/polyacrylonitrile-butadiene-styrene:

PC/ABS manufactured by Asahi Chemical Industry Co.Ltd. (referred to as "PC/ABS")

(l) Polyester:

Regrind material for PET bottles (known as "PET")

(3) Free radical initiator

2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane (PERHEXA 25B) produced by NOF CORPORATION (referred to as "POX")

(4) Cross-linking aids

Divinylbenzene (known as "DVB") produced by Wako Pure Chemical Ltd.

(5) Softener (paraffin oil)

DIANA processing oil (called "PW-380") produced by Idemitsu Kosan Co.

(6) Glass fiber

Aminosilane-treated glass fiber roving (ER 740) produced by Asahi Fiber Co. (thickness: 13 μm)

(7) Talc

Generic commodity (called "talc") manufactured by Japan Talc Co.

3. Production method of cross-linked thermoplastic elastomer

(1)TPV-1

A twin-screw extruder (40mmφ, L/D=47) having a feeding port at the center of the barrel was used as the extruder. A twin-flight screw with a kneading portion adjacent to the feed port was used as the screw. TPE-1, PP, POX, and DVB were mixed at a ratio of TPE-1/PP/POX/DVB of 55.6/44.4/0.38/0.74 (weight ratio), and melted and extruded at a cylinder temperature of 220°C. The degree of crosslinking of the obtained crosslinked thermoplastic elastomer was 82%.

(2)TPV-2

Perform the same steps as (1) to obtain a cross-linked thermoplastic elastomer, but the ratio of TPE-1/PP/POX/DVB is changed to 55.6/44.4/0.19/0.37 (weight ratio). The degree of crosslinking of the resulting crosslinked thermoplastic elastomer was 55%.

(3)TPV-3

Perform the same steps as (1) to obtain a crosslinked thermoplastic elastomer, but TPE-1, PP, POX and DVB are changed to TPE-1, EP-1, POX and DVB. The degree of crosslinking of the obtained crosslinked thermoplastic elastomer was 81%.

(4)TPV-4

Perform the same steps as (1) to obtain a cross-linked thermoplastic elastomer, but TPE-1, PP, POX and DVB are changed to TPE-1, PP, HDPE, POX and DVB, and the ratio is changed to 55.6/33.3/11.1/0.19 /0.37 (weight ratio). The degree of crosslinking of the obtained crosslinked thermoplastic elastomer was 85%.

(5)TPV-5

Perform the same steps as (1) to obtain a crosslinked thermoplastic elastomer, but TPE-1, PP, POX and DVB are changed to TPE-2, PP, POX and DVB. The degree of crosslinking of the obtained crosslinked thermoplastic elastomer is approximately 100%.

(6)TPV-6

The same procedure as (1) was carried out to obtain a crosslinked thermoplastic elastomer, but based on 100 parts by weight of the total amount of TPE-1 and PP, 33 parts by weight of a softener (paraffin oil) was fed from the feed port at the center of the barrel. The degree of crosslinking of the obtained crosslinked thermoplastic elastomer was 82%.

(7)TPV-7

Carry out the same steps as (1) to obtain a cross-linked thermoplastic elastomer, but the ratio of TPE-1/PP/POX/DVB is changed to 70.0/30.0/0.48/0.93 (weight ratio), based on 100 parts by weight of TPE-1 and PP For the total amount, 20 parts by weight of softening agent (paraffin oil) is supplied from the feed port at the central part of the machine barrel. The degree of crosslinking of the obtained crosslinked thermoplastic elastomer was 81%.

4. Production method of non-crosslinked thermoplastic elastomer

(1) TPO-1

A twin-screw extruder (40mmφ, L/D=47) having a feeding port at the center of the barrel was used as the extruder. A twin-flight screw with a kneading portion adjacent to the feed port was used as the screw. TPE-1 and PP were mixed at a ratio of TPE-1/PP of 55.6/44.4 (weight ratio), and melt-extruded at a cylinder temperature of 200°C.

Example 1

In the case of stretching, the glass fiber roving with a thickness of 13 μm is made uniform, and M-PP and PP with a ratio of 5%/95% are extruded sideways from it with an extruder, thereby extruding the polyolefin resin on the glass. on and cover the surface of the fiber. Pellets were then cut into 7 mm long pellets to produce long fiber pellets (termed "GF-1"). The ratio of the long-fiber-cut glass fiber/polyolefin resin is 56/44 (weight ratio). The pellets of GF-1 and PP were mixed at a ratio of 53.6/46.4 (weight ratio), molded with an injection molding machine (Toshiba IS45PNV) at a molding temperature of 240°C, and other conditions were set at general conditions to obtain molded products. The composition of the moldings (including the distribution of glass fibers) and their properties are shown in Table 1.

Comparative example 1

A glass fiber roving having a thickness of 13 μm was cut to a length of 7 mm to obtain chopped fibers. The chopped fibers and PP were mixed in a ratio of 30/70 (weight ratio), extruded with a twin-screw extruder (Toshiba TEM-35B) at a resin temperature of 230° C., and pelletized to obtain pellets. Molding was carried out with an injection molding machine (Toshiba IS45PNV) at a molding temperature of 230°C using the pellets as a raw material to obtain molded articles. The compositions of the moldings and their properties are shown in Table 1.

Comparative example 2

According to Example 1, the pellets of GF-1 and PP are mixed in the ratio of 53.6/46.4 (weight ratio), and molded under the following conditions: the molding temperature is set at 290 ° C, the back pressure and the screw speed during molding And the injection rate was set extremely low, and it was difficult to apply shear, unlike Example 1. In the obtained molded article, the glass fiber content of not more than 0.5 mm in length was 0%, the content of glass fiber having a length of 0.5 to 2 mm was 49%, and the content of glass fiber not less than 0.5 mm in length was 51%. The surface condition of the molded article was extremely poor. On the other hand, the surface condition of the molded article obtained in Example 1 was good. The compositions of the moldings and their properties are shown in Table 1.

Example 2

Using long fiber pellets (GF-1) as obtained in Example 1, the pellets of GF-1, TPV-1 and PP are mixed in the ratio of 53.6/36.0/10.4 (weight ratio), using the same method as in Example 1 The injection molding machine was used for molding at a molding temperature of 240° C. to obtain molded articles. Its composition and properties are shown in Table 1.

Comparative example 3

A glass fiber roving having a thickness of 13 μm was cut to a length of 7 mm to obtain chopped fibers. The chopped fibers, TPV-1 and PP were mixed in a ratio of 53.6/36.0/10.4 (weight ratio), extruded at a resin temperature of 230°C with the same twin-screw extruder as in Comparative Example 1, and pelletized , to obtain pellets. Molding was carried out with the same injection molding machine as in Example 1 at a molding temperature of 230° C. using the pellets as a raw material to obtain molded articles. The compositions of the moldings and their properties are shown in Table 1.

Comparative example 4

The pellets of GF-1, TPV-1 and PP were mixed at a ratio of 53.6/36.0/10.4 (weight ratio) as in Example 2, and molded under the same conditions as in Comparative Example 2. In the obtained molded article, the content of glass fibers with a length of not more than 0.5 mm was 0%, the content of those with a length of 0.5 to 2 mm was 56%, and the content of those with a length of not less than 0.5 mm was 44%. Similar to Comparative Example 2, due to the Bonding was not uniform and the surface condition of the moldings was extremely poor. On the other hand, the surface condition of the molded article obtained in Example 2 was good. The compositions of the moldings and their properties are shown in Table 1.

Example 3

The same procedure as in Example 2 was carried out to obtain a molded article, but the molding temperature was set at 225°C. The compositions of the moldings and their properties are shown in Table 1.

Example 4

The same procedure as in Example 2 was carried out to obtain a molded article, except that TPV-2 was used instead of TPV-1. The compositions of the moldings and their properties are shown in Table 1.

Example 5

The same procedure as in Example 1 was carried out to obtain a molded article, except that TPO-1 was used instead of TPV-1. The compositions of the moldings and their properties are shown in Table 1.

Example 6

The same procedure as in Example 2 was carried out to obtain a molded article, but the pellets of GF-1, TPV-1 and PP were mixed in a ratio of 53.6/18.0/28.4 (weight ratio). The compositions of the moldings and their properties are shown in Table 1.

Example 7

The same procedure as in Example 2 was carried out to obtain a molded article, but the pellets of GF-1, TPV-1 and PP were mixed in a ratio of 35.7/36.0/28.3 (weight ratio). The compositions of the moldings and their properties are shown in Table 1.

Example 8

The same procedure as in Example 1 was carried out to obtain a molded article, except that TPV-5 was used instead of TPV-1. The compositions of the moldings and their properties are shown in Table 2.

Example 9

The same procedure as Example 1 was followed to produce long fiber pellets (designated "GF-2"), but the material to be extruded onto the glass fiber surface and covering said surface consisted of M-PP in the ratio 5%/95% and PP into M-PP and EP-1 with a ratio of 5%/95%. The ratio of the long-fiber-cut glass fiber/polyolefin resin is 56/44 (weight ratio). The pellets of GF-2, TPV-3 and EP-1 were mixed in a ratio of 53.6/36.0/10.4 (weight ratio), and molded in the same manner as in Example 2 to obtain molded articles. The compositions of the moldings and their properties are shown in Table 2.

Example 10

The same procedure as in Example 2 was carried out to obtain a molded article, but pellets of GF-1, TPV-1 and EP-2 were mixed in a ratio of 53.6/36.0/10.4 (weight ratio). Its composition and properties are shown in Table 2.

Example 11

The same procedure as in Example 1 was followed to produce long fiber pellets (designated "GF-3"), but the material to be extruded onto the glass fiber surface and covering said surface consisted of M-PP in the ratio 5%/95% and PP into M-PP, PP and HDEP with a ratio of 5%/71.3%/23.7%. The ratio of the long-fiber-cut glass fiber/polyolefin resin is 56/44 (weight ratio). The pellets of GF-3, TPV-4 and PP were mixed at a ratio of 53.6/36.0/10.4 (weight ratio), and molded in the same manner as in Example 2 to obtain molded articles. The compositions of the moldings and their properties are shown in Table 2.

Example 12

The same procedure as in Example 2 was carried out to obtain a molded article, but pellets of GF-1 and TPV-1 were mixed in a ratio of 53.6/46.4 (weight ratio). The compositions of the moldings and their properties are shown in Table 2. Regarding the test pieces used in the falling ball impact strength test, the molded article of Example 2 was slightly whitish, while the molded article of Example 12 was not whitish at all.

Example 13

Mix TPV-1, PP and talc at a ratio of 56.0/28.5/15.5 (weight ratio), extrude with a twin-screw extruder (Toshiba TEM-35B) at a resin temperature of 230°C, and pelletize to obtain pelletized . This pellet was mixed with the pellet of GF-1 at a ratio of 64.3/35.7 (weight ratio), and molded in the same manner as in Example 2 to obtain a molded article. The compositions of the moldings and their properties are shown in Table 3.

Examples 14 and 15

The same procedure as in Example 1 was carried out to obtain a molded article, except that TPV-6 was used instead of TPV-1. The granulation of GF-1, TPV-6 and PP is mixed in the ratio of 53.6/36.0/10.4 in embodiment 14, in the ratio of 53.6/46.4/0 (weight ratio) in embodiment 15, to be mixed with embodiment 15 2 Molding was carried out in the same manner to obtain a molded article. The compositions of the moldings and their properties are shown in Table 3.

Example 16

A glass fiber roving with a thickness of 13 μm is homogenized under tension, immersed in a bath containing AS emulsion (acrylonitrile-styrene latex; acrylonitrile 25%, solid concentration: 50% by weight), thereby being covered with AS resin, and then dried . Pellets cut to a length of 5.5 mm yielded long fiber pellets (designated "GF-4"). The ratio of the long-fiber-cut glass fiber/AS resin is 80/20 (dry weight ratio). Pellets of GF-4 and PS were mixed at a ratio of 25.0/75.0 (weight ratio), and molded in the same manner as in Example 2 to obtain molded articles. The compositions of the moldings and their properties are shown in Table 4.

Example 17

The same procedure as in Example 16 was carried out to obtain a molded article, except that PS was replaced by HIPS. The compositions of the moldings and their properties are shown in Table 4.

Example 18

A molded article was obtained by carrying out the same procedure as in Example 16, but substituting AS for PS. The compositions of the moldings and their properties are shown in Table 4.

Example 19

The same procedure as in Example 16 was carried out to obtain a molded article, but ABS was used instead of PS. The compositions of the moldings and their properties are shown in Table 4.

Example 20

A molded article was obtained by carrying out the same procedure as in Example 16, but using PC instead of PS. The compositions of the moldings and their properties are shown in Table 4.

Example 21

A molded article was obtained by carrying out the same procedure as in Example 16, but using PC/ABS instead of PS. The compositions of the moldings and their properties are shown in Table 4.

Example 22

A molded article was obtained by carrying out the same procedure as in Example 16, but using PET instead of PS. The compositions of the moldings and their properties are shown in Table 4.

Example 23

The same procedure as Example 1 was followed to produce long fiber pellets (designated "GF-5"), but the material to be extruded onto the glass fiber surface and covering said surface consisted of M-PP in the ratio 5%/95% And PP is changed to M-PE and HDPE with a ratio of 5%/95%. The ratio of the long-fiber-cut glass fiber/polyolefin resin is 56/44 (weight ratio). The pellets of GF-5 and HDPE were mixed at a ratio of 53.6/46.4 (weight ratio), and molded in the same manner as in Example 1 to obtain molded articles. The compositions of the moldings and their properties are shown in Table 4.

Example 24

Using the same molding machine as in Example 1, the molded articles obtained in Examples 1 and 2 were placed in a metal mold set at 40°C, and insert molding was performed with TPV-7 at a cylinder temperature of 240°C . The resulting laminate has an extremely high adhesiveness, so that the two layers of the laminate cannot be peeled off at their interface. The surface hardness (A hardness) of the thermoplastic elastomer was 78, and the soft feeling of the molded article was excellent.

Industrial Applicability

The thermoplastic resin molded article of the present invention can be used in applications requiring high stiffness and high strength, including not only automotive parts such as radiator tanks, etc., industrial parts such as housing materials for electric tools, office parts such as office chairs, etc. , but also includes electronic components, daily necessities, building materials, etc., which play an important role in industry.

Table 1 Composition and physical properties of compounds and moldings Example 1 Comparative example 1 Comparative example 2 Example 2 Comparative example 3 Comparative example 4 Example 3 Example 4 Example 5 Example 6 Example 7 compound PPEP-1EP-2 46.4 70.0 46.4 10.4 34.0 10.4 10.4 10.4 10.4 28.4 28.3 TPV-1TPV-2TPV-3TPV-4TPV-5TPV-6TPO-1 36.0 36.0 36.0 36.0 36.0 36.0 18.0 36.0 GF-1GF-2GF-3 short fiber 53.6 30.0 53.6 53.6 30.0 53.6 53.6 53.6 53.6 53.6 35.7 Composition of moldings Thermoplastic Resins Polypropylene Resins Polyethylene Resins Glass Fibers Rubber Polymers 70.030.0 70.030.0 70.030.0 50.030.020.0 50.030.020.0 50.030.020.0 50.030.020.0 50.030.020.0 50.030.020.0 60.030.010.0 60.020.020.0 Proportion of glass fibers with a length of not more than 0.5 mm Proportion of glass fibers with a length of 0.5 to 2 mm Proportion of glass fibers with a length of not less than 2 mm 275815 10000 04951 49518 10000 05644 82180 355411 255916 345412 256015 The average particle size of the rubber-like polymer in circles (μm) 0.53 0.56 1.08 0.42 0.68 0.83 0.58 0.72 Physical properties of moldings Tensile strength (kg/cm ² ) flexural strength (kg/cm ² ) flexural modulus (kg/cm ² ) HDT (°C) under high load (18.5kg) Izod impact strength (kg*cm/cm ) Falling ball impact strength (J) total energy absorbed 113017007030016014.25.9 820980490001506.33.1 7301120520001547.13.3 89012405120015728.912.8 6508203900014810.14.6 7209304100015310.94.7 78011204920015621.29.3 87012105020015627.712.3 85011404830015517.88.0 107014205120015723.710.6 87011803500015324.210.8

Table 2 Composition and physical properties of compounds and moldings Example 8 Example 9 Example 10 Example 11 Example 12 compound PPEP-1EP-2 10.4 10.4 10.4 10.4 TPV-1TPV-2TPV-3TPV-4TPV-5TPV-6TPO-1 36.0 36.0 36.0 36.0 46.4 GF-1GF-2GF-3 short fiber 53.6 53.6 53.6 536. 53.6 Composition of moldings Thermoplastic Resins Polypropylene Resins Polyethylene Resins Glass Fibers Rubber Polymers 50.030.020.0 50.030.020.0 50.030.020.0 40.49.630.020.0 46.130.025.8 Proportion of glass fibers with a length of not more than 0.5 mm Proportion of glass fibers with a length of 0.5 to 2 mm Proportion of glass fibers with a length of not less than 2 mm 454510 45469 45478 275815 50437 The average particle size of the rubber-like polymer in circles (μm) 0.51 0.54 0.53 0.62 0.49 Physical properties of moldings Tensile strength (kg/cm ² ) flexural strength (kg/cm ² ) flexural modulus (kg/cm ² ) HDT (°C) under high load (18.5kg) Izod impact strength (kg*cm/cm ) Falling ball impact strength (J) total energy absorbed 86011805220015825.811.5 88012105080015529.713.2 9 1012205140015628.812.7 87012105060015329.512.9 6909003980014741.118.0

table 3 Composition and physical properties of compounds and moldings Example 13 Example 14 Example 15 compound PP 18.3 10.4 TPV-1TPV-6 36.0 36.0 46.4 GF-1 35.7 53.6 53.6 talc 10.0 Composition of moldings Thermoplastic Resin Polypropylene Resin Glass Fiber Rubber Polymer Softener (Paraffin Oil) Talc 50.020.020.010.0 46.130.015.08.9 39.130.019.411.5 Proportion of glass fibers with a length of not more than 0.5 mm Proportion of glass fibers with a length of 0.5 to 2 mm Proportion of glass fibers with a length of not less than 2 mm 405010 414811 305614 The average particle size of the rubber-like polymer in circles (μm) 0.38 0.54 0.68 Physical properties of moldings Tensile strength (kg/cm ² ) flexural strength (kg/cm ² ) flexural modulus (kg/cm ² ) HDT (°C) under high load (18.5kg) Izod impact strength (kg*cm/cm ) Falling ball impact strength (J) total energy absorbed 90012304500015525.111.1 76011404940015029.312.9 6307403810014441.714.8

Table 4 Composition and physical properties of compounds and moldings Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 compound PPHIPSASASABSPCPC/ABSPETHDPE 75.0 75.0 75.0 75.0 75.0 75.0 75.0 46.4 GF-4GF-5 25.0 25.0 25.0 25.0 25.0 25.0 25.0 53.6 Composition of moldings Thermoplastic Resins Polystyrene Resins AS Resins PC Resins PET Resins PE Resins Glass Fibers Rubber Polymers 75.05.020.0 69.05.020.06.0 80.020.0 60.020.020.0 5.075.020.0 35.037.520.07.5 5.075.020.0 70.030.0 Proportion of glass fibers with a length of not more than 0.5 mm Proportion of glass fibers with a length of 0.5 to 2 mm Proportion of glass fibers with a length of not less than 2 mm 375211 405010 45478 414811 53425 414910 405010 355411 The average particle size of the rubber-like polymer in circles (μm) 1.03 0.32 0.32 Physical properties of moldings Tensile Strength (kg/cm ² ) Flexural Strength (kg/cm ² ) Flexural Modulus (kg/cm ² ) Izod Impact Strength (kg*cm/cm) Falling Ball Impact Strength (J) Total Energy Absorbed 7601290635308.24.0 68010804800013.16.0 121018808723014.16.3 75011904850028.213.0 125019306500010.04.8 79012504800032.814.5 106015807488015.57.0 6609305640017.78.0

Claims (11)

1. A thermoplastic resin molded article comprising glass fibers and a thermoplastic resin, wherein the content of the glass fibers is 1 to 40% of the total weight of the thermoplastic resin molded article, and the glass fibers having a length of not more than 0.5 mm in the fibers contain 90 to 10% of the fiber weight, 10 to 90% of the length of 0.5 to 2mm, and 0 to 30% of the length of not less than 2mm, the thermoplastic resin is selected from polystyrene type resin, polyphenylene ether type resin , polyolefin-type resins, polyvinyl chloride-type resins, polyamide-type resins, polyester-type resins, polyphenylene sulfide-type resins, polycarbonate-type resins, polymethacrylate-type resins or more than one of the above polymers mixture of substances. 2. The thermoplastic resin molded article of claim 1, further comprising 1 to 30% of the total weight of the thermoplastic resin molded article constituted by an ethylene-α-olefin copolymer containing an ethylene unit and an α-olefin unit having a carbon number of 3 to 20 of rubbery polymers. 3. The thermoplastic resin molded article according to claim 1 or 2, further comprising 1 to 50% of talc based on the total weight of the thermoplastic resin molded article. 4. The thermoplastic resin molded article according to claim 1 or 2, wherein the thermoplastic resin is a polyolefin-based resin. 5. The thermoplastic resin molded article according to claim 4, wherein said polyolefin-based resin contains a polypropylene-based resin. 6. The thermoplastic resin molded article of claim 2, wherein the rubbery polymer is partially or completely crosslinked. 7. The production method of the thermoplastic resin molded article of claim 1, comprising the steps of mixing and injection molding: (i) mixing (a) glass fiber-containing thermoplastic resin pellets obtained by covering glass fiber rovings having an average diameter of 1 to 50 μm with a thermoplastic resin and then cutting them to an average length of 1 to 25 mm, and (b) At least one resinous pellet selected from thermoplastic resin pellets, rubbery polymer-containing thermoplastic resin pellets, talc-containing thermoplastic resin pellets, and rubbery polymer- and talc-containing thermoplastic resin pellets ,as well as (ii) Injection molding the mixed pellets of (a) and (b) obtained in step (i). 8. The method for producing a thermoplastic resin molded article according to claim 7, further comprising 1 to 30% by weight of ethylene-α, which is composed of an ethylene unit and an α-olefin unit having a carbon number of 3 to 20, based on the total weight of the thermoplastic resin molded article. -Rubber polymers composed of olefin copolymers. 9. A laminated molded article comprising a thermoplastic elastomer and a molded article of a thermoplastic resin according to claim 1, wherein said thermoplastic resin molded article is covered with said thermoplastic elastomer, said thermoplastic resin being selected from polystyrene type Resin, polyphenylene ether type resin, polyolefin type resin, polyvinyl chloride type resin, polyamide type resin, polyester type resin, polyphenylene sulfide type resin, polycarbonate type resin, polymethacrylate type resin or a mixture of more than one of the above polymers. 10. The laminated molded article according to claim 9, further comprising 1 to 30% by weight of a rubbery polymer consisting of an ethylene-α-olefin copolymer containing an ethylene unit and an α-olefin unit having a carbon number of 3 to 20 . 11. The laminated molded article of claim 9, wherein the thermoplastic elastomer is a polyolefin-based thermoplastic elastomer.