WO2001059009A1

WO2001059009A1 - Thermoplastic resin formed article having high rigidity and high strength

Info

Publication number: WO2001059009A1
Application number: PCT/JP2000/000794
Authority: WO
Inventors: Hideo Kinoshita; Ikuji Ohtani; Yoshikazu Suda
Original assignee: Asahi Kasei Kabushiki Kaisha
Priority date: 2000-02-14
Filing date: 2000-02-14
Publication date: 2001-08-16
Also published as: CN1175052C; DE10084451T1; CN1347437A

Abstract

A thermoplastic resin formed article comprising a glass fiber and a thermoplastic resin, wherein the glass fiber is incorporated in an amount of 1 to 60 wt % and is comprised of 90 to 10 % of a glass fiber having a length of 0.5 mm or less, 10 to 90 % of a glass fiber having a length of 0.5 to 2 mm and 0 to 30 % of a glass fiber having a length of 2 mm or more.

Description

Description High rigidity and high strength thermoplastic resin moldings Technical field

The present invention relates to a high-rigidity / high-strength thermoplastic resin molded article reinforced with glass fiber and a method for producing the same.

Background art

Many resins are known as thermoplastic resins, such as polyethylene resins, polypropylene resins, styrene resins, and polyamide resins. These thermoplastic resins are required to have high rigidity and high strength depending on the application. The most preferable method for imparting this performance is reinforcement by glass fiber. For example, glass fiber reinforced polypropylene resin, glass fiber reinforced polyamide resin and the like are sold. Among them, glass fiber reinforced polyamide resins are widely used as materials for automobiles such as radiator tanks, materials for tool housings such as electric drills, and materials for office equipment such as office chairs. In this glass fiber reinforced polyamide resin, since the polyamide resin serving as the matrix has relatively high strength, high rigidity and high strength can be exhibited simply by combining the polyamide resin and glass fiber. Therefore, its use field is expanding. On the other hand, glass fiber reinforced polypropylene resin does not have sufficient strength compared to glass fiber reinforced polyamide because the strength of the polypropylene resin itself, which is the matrix, is smaller than that of polyamide resin. At present, usable applications are limited.

If general-purpose resins, such as environmentally friendly polypropylene-based resins, which are becoming mainstream in the world, become high-rigidity and high-strength materials, their applications will not only expand, but even polyamide-based resins will have even higher rigidity. In addition, if the strength is high, the thickness can be reduced, which leads to a reduction in weight and cost, which is more preferable. For this reason, materials having higher rigidity and higher strength are required for various thermoplastic resins.

Disclosure of the invention

In view of this situation, the present invention has been developed to provide a thermoplastic resin having higher rigidity and higher strength. It is intended to provide a molded article.

In order to achieve the above-mentioned object, the present inventors have first studied intensively mainly using a polyolefin-based resin, particularly a polypropylene-based resin. First, polypropylene resin alone is required for applications requiring high rigidity and high strength, such as materials for automobiles such as radiator tanks, materials for tool housings such as electric drills, and materials for office equipment such as office chairs. Not satisfy the performance. For this reason, a method called the short fiber method in the same industry as the method usually used for glass fiber reinforced polyamide, that is, a glass fiber (chopped glass) is mixed with a propylene-based resin and kneaded with an extruder, and the obtained product is obtained. We examined a method of injection molding the pellets into a molded product.The obtained molded product has improved rigidity and mechanical strength compared to a mere polypropylene resin containing no glass fiber, but the above applications were considered. Did not reach practical strength at all. JP-A-3-188131, JP-A-3-24833, and JP-A-3-33638, etc., a method called a long fiber method, that is, For example, a method is disclosed in which a polypropylene resin pellet containing glass fibers of 7 to 12 mm in length coated with a polypropylene resin and a polypropylene resin pellet are blended and directly molded. In the short fiber method described above, glass fiber (Chipop glass) is mixed with a polypropylene resin, kneaded with an extruder, and then injection molded to form a molded product. Therefore, extrusion kneading and screw kneading during injection molding are performed twice. Therefore, the glass fiber is broken during the kneading, and the fiber length becomes extremely short. In contrast, in the long fiber method, the glass fiber in the molded article can be kept long because the molded article is produced only by screw kneading during injection molding. As a result of the study using the long fiber method, the length of the glass fiber in the molded product differs depending on the molding conditions, but the rigidity and strength are not sufficient even if it is short, and the surface appearance is not enough even if it is long.

However, surprisingly, if the length distribution of the glass fibers in the molded article is limited to a certain range, the molded article has excellent surface appearance, rigidity and mechanical strength, and has practical strength in the above-mentioned applications. The present inventors have found that Furthermore, a higher level of mechanical strength is required for some applications, but a rubber-like polymer with a certain shape is further added to a molded product made of glass fiber and polypropylene resin having a certain length distribution. When coexisting, it has a higher level of surface appearance, and The present inventors have found that a molded article having excellent rigidity and mechanical strength can be obtained. At the same time, they have found that they can be applied not only to polypropylene resins but also to other resins.

Based on these findings, the present invention has been completed.

When a rubber-like polymer coexists, a molded article with a higher level of mechanical strength can be obtained because the glass fibers are oriented when the molding material is molded by injection molding or the like. Since the mechanical strength differs in the vertical and horizontal directions with respect to the molding direction, directional (anisotropic) is generated in the mechanical strength. Therefore, the mechanical strength such as impact resistance is high in one direction, and Although the result is low in the direction, the rubbery polymer relaxes this directionality (anisotropic).

The present invention relates to a thermoplastic resin molded article containing glass fiber and a thermoplastic resin, wherein the glass fiber is contained at a content of 1 to 60% by weight and has a length of 0.5 mm or less. 90 to 90% fiber, 0.5 to 2 mm long glass fiber is 10 to 90%, 2 mm or more glass fiber is 0 to 30% high rigidity. The present invention relates to a molded article and a method for producing the same.

More preferably, the present invention is a thermoplastic green resin molded article containing glass fiber, a thermoplastic resin, and further a rubbery polymer, wherein the glass fiber is contained at a content of 1 to 60% by weight. Glass with a length of less than 0.5 mm, glass with 90 to 10%, glass with a length of 0.5 to 2 mm with 10 to 90%, glass with a length of 2 mm or more The fiber content is 0 to 30% and the rubbery polymer is 1 to 30% by weight ⁰ /. The present invention relates to a thermoplastic resin molded article having high rigidity and high strength, particularly excellent in impact resistance.

In the molded article of the present invention, mechanical strength, particularly impact resistance, can be significantly improved by coexisting a rubbery polymer with glass fiber. Rubbery polymers are preferred over their ability to partially or completely crosslink. When cross-linking is performed, the improvement effect is even greater than when no cross-linking is performed. The reason for this is that when the rubber-like polymer is not crosslinked, the material for the molded article of the present invention is stretched in the flow direction of the material and molded like the glass fiber when molding the material for the molded article of the present invention. The coalesce is also oriented, but when the rubber-like polymer is cross-linked, the shape of the rubber-like polymer in the molding material is not stretched in the flow direction. It is estimated that even if the glass fibers are oriented, the rubber-like polymer does not orient even if the glass fiber is oriented, which leads to a significant improvement in mechanical strength, especially a significant improvement in impact resistance. are doing.

BEST MODE FOR CARRYING OUT THE INVENTION

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

The glass fiber in the thermoplastic resin molded article of the present invention has an average diameter of 0.01 to 1000 m, preferably 0.1 to 500 / ζπι, more preferably 1 to: 100 / zm, and most preferably. 5 to 50 μπι. The average length is 0.2 to 3 mm, preferably 0.5 to 2 mm. If the average diameter is less than 0.01 m, 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. On the other hand, if the average length is less than 0.2 mm, the effect of capturing is small and the effect of improving mechanical strength is not sufficient. On the other hand, if it exceeds 3 mm, the appearance of the molded product is poor. The glass fiber content of the 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, and 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 not sufficient. If the content exceeds 60% by weight, the appearance of the molded product will deteriorate, and at the same time, the mechanical strength tends to decrease due to the decrease in the amount of the thermoplastic resin that maintains the mechanical strength.

Although the mechanical strength of a molded article is also affected by the average diameter and average length of the glass fiber as described above, the length distribution of the glass fiber is the most dominant factor. That is, the presence of many short fibers in a molded article does not lead to a large improvement in mechanical strength. The presence of longer fibers increases the mechanical strength, but the longer the glass fibers in the molded article, the better.

For example, Japanese Patent Application Laid-Open No. 3-243308 discloses a molded article in which fibers of at least 50% by weight and having a length of at least 2 mm or more are present in the molded article. However, unless a very low molecular weight thermoplastic resin is used, it is not possible to produce a molded article with such a fiber length. High rigidity and high strength due to low mechanical strength of resin itself Cannot be obtained. Even if it is possible to mold with a commercially available thermoplastic resin, the molded product will have poor appearance and no commercial value. The glass fiber in the molded article of the present invention is 90 to 90% of glass fiber having a length of 0.5 mm or less, 10 to 90% of glass fiber having a length of 0.5 to 2 mm, and 2 mm or more. Glass fiber with a length of 0 to 30%, preferably glass fiber with a length of 0.5 mm or less 80 to 20%, glass fiber with a length of 0.5 to 2 mm 20 to 80%, 2 mm or more 5 to 25% glass fiber of length, more preferably 60 to 25% glass fiber of 0.5 mm or less length, 40 to 75% of glass fiber of 0.5 to 2 mm length, 2 It is necessary that 5 to 20% of glass fiber with a length of at least mm is used. By having such a glass fiber length distribution, it is possible to obtain a molded product having excellent appearance, high rigidity and high mechanical strength for the first time.

If the glass fiber length of 0.5 mm or less exceeds 90%, the effect of improving the mechanical strength is not sufficient. In addition, the length of the glass fiber in the molded article has a great influence on the surface appearance of the molded article. The reason for this is that if you try to adopt a molding process that can leave long glass fibers during molding, you tend to avoid using the largest share, and as a result, the glass fibers are made of thermoplastic resin. It becomes difficult to disperse in the glass, the dispersion state of the glass fiber becomes uneven in the resin, and the liquid becomes uneven (localization), and unevenness due to fuzzing and agglomeration of the glass fiber occurs, and the surface condition becomes poor. It is considered that the mechanical strength is lowered at the same time. For this reason, if a long glass fiber is to be left, the surface appearance becomes poor and the mechanical strength tends to decrease. If the glass fiber having a length of 0.5 mm or less is less than 10%, the appearance of the molded product is not good and the mechanical strength is reduced.

In addition, when the glass fiber length of 0.5 to 2 mm is less than 10%, the amount of glass fiber of 0.5 mm or less in the molded product increases, and the effect of improving the mechanical strength is not sufficient. If it exceeds 90%, the appearance of the molded article tends to be poor and the mechanical strength tends to be low.

The same is true when the glass fiber length of 2 mm or more exceeds 30%.

The length of the glass fiber in the molded article is determined by the molding of the material for the molded article of the present invention. Depends on conditions. In general, under conditions where the melt viscosity of the molded article material is high and the share is high, the glass fiber breaks during kneading and becomes shorter, so that molding at a high temperature keeps the glass fiber long. In addition, if the molding is performed with the screw rotation speed set at a low value during molding, the glass fiber can be kept long. Furthermore, the length varies depending on the design of the molding machine. For example, molding using a deep groove screw can keep the glass fiber long. In order to obtain a molded article of the present invention having an appropriate fiber length and excellent appearance, it is preferable to select optimal molding conditions.

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. The glass fiber used is preferably pretreated with, for example, a silane coupling agent or the like in order to increase the adhesion to the resin. In the molded article of the present invention, glass fiber is an essential component, but other fibers, for example, natural fibers such as cotton, silk, wool or hemp, recycled fibers such as rayon or cuvula, acetate or promix, etc. Semi-synthetic fiber, polyester, polyacrylonitrile, polyamide, alamide, polyolefin, synthetic fiber composed of carbon or vinyl chloride, inorganic fiber composed of glass or asbestos, or metal fiber composed of SUs, copper or brass It is also possible to use them in combination. Among these, carbon fiber has a remarkable effect of increasing rigidity, so that it is possible to further improve rigidity by using it together with glass fiber.

Next, the rubbery polymer which is a component preferably contained in the thermoplastic resin molded article of the present invention will be described.

The rubbery polymer, which is a preferable component of the molded article of the present invention, preferably has a glass transition temperature (T g) of −30 ° C. or lower. Examples of such a rubbery polymer include polybutadiene, Gen-based rubbers such as poly (styrene-butadiene) and poly (acrylonitrile-butadiene) and acrylic rubbers such as hydrogenated saturated rubber, isoprene rubber, chloroprene rubber, polybutyl acrylate, etc. — Olefin copolymer rubbers and the like. Among these, ethylene-a-olefin copolymer rubber mainly composed of ethylene and _α -olefin or a polymer having a structure similar thereto has excellent weather resistance, mechanical strength, etc. Particularly preferred. Here, the polymer having a similar structure is, for example, a rubber obtained by adding hydrogen to polybutadiene, becomes a rubber having a structure similar to an ethylene / butene-11 copolymer by weight, and refers to such a polymer.

Among these ethylene-ct-olefin copolymer rubbers, an ethylene-α-olefin copolymer mainly comprising ethylene and a-olefin having 3 to 20 carbon atoms is more preferable. Examples of the haloolefins having 3 to 20 carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methinolepentene1, heptene-1, octene1, nonene-1, decene-1. 1, undesen-1 and dodecene 1-1. These phosphores may be used alone or in combination of two or more.

Further, a copolymer component may be included as the third component. Examples of the third component are non-conjugated components such as 1,3-butadiene and isoprene; conjugated pentagens; Conjugated Gens and the like. Examples of the ethylene 'α-olefin copolymer rubber containing the third component copolymer component include, for example, ethylene-propylene-conjugated or non-conjugated gen terpolymer rubber (EPDM) and the like. .

However, in the electric tool housing which is one application of the molded article of the present invention, the tool is often used outdoors, and weather resistance is required. Therefore, the ethylene / α-olefin copolymer rubber containing no conjugated or non-conjugated gen has better weather resistance than the ethylene / α-olefin copolymer rubber containing no conjugated or non-conjugated gen. Inferior and not preferred.

The present invention does not exclude an ethylene / α-olefin copolymer rubber containing a conjugated or non-conjugated diene, but does not exclude an ethylene / α-olefin-based copolymer rubber containing no conjugated or non-conjugated diene. Is more preferred. Examples thereof include copolymer rubbers of ethylene and hexene-11,4-methylpentene-11 or otaten-11. Among these, a copolymer rubber of ethylene and otaten-11 is particularly preferred. The reason is that it has excellent weather resistance and rubber elasticity. Further, in the molded article of the present invention, the thermoplastic resin is a polyolefin resin, and the molded article is It has been pointed out that when used in a power tool housing, etc., when the tool is dropped, the impact will cause the molded product to whiten.It is better to use rubber with a high degree of branching, that is, rubber with long chain branches. Difficult to convert, it depends.

The ethylene octene-1 copolymer rubber suitably used as the rubbery polymer of the present invention is preferably one produced using a meta-mouth catalyst. 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 from 0.01 to: 100 g / 10 min (190.C, 2.16 kg )), And more preferably 0.2 to 20 gZlO. If it exceeds 100 gZl 0 minutes, the rubber elasticity of the rubbery polymer is insufficient, and if it is less than 0.01 / 10 minutes, the flowability is poor at the time of molding to obtain the molded article of the present invention, and the processability is poor. It is undesirably reduced.

The rubbery polymer, which is a preferred component of the molded article of the present invention, is more preferably partially or completely crosslinked. The reason for this is that, as described above, when molding a material for a molded article to obtain the molded article of the present invention, the resin is stretched and oriented in the flow direction, but the rubber-like polymer is crosslinked. Therefore, the shape of the rubber-like polymer of the raw material can be maintained in the molded article without being stretched in the flow direction, so that even if the glass fiber is oriented, the rubber-like polymer relaxes the directionality. It is.

In the case of crosslinking, the ratio of the crosslinked rubbery polymer (rubbery polymer that does not dissolve in the solvent) in the total rubbery polymer present in the thermoplastic resin molded product is defined as the degree of crosslinking, The degree is preferably at least 20%, more preferably at least 50%.

When the rubbery polymer which is a preferable component in the molded article of the present invention is used as one component, its content is 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. The mechanical strength, especially the impact resistance, of a molded article largely depends on the shape of the rubbery polymer in the molded article, that is, the morphology. The shape is preferably such that the number average particle diameter in terms of a circle from a cut surface in a direction perpendicular to the flow direction during molding is 0.1 to 1.5 / xm. More preferably, it is 0.2 to 1.2ππ. Here, if the rubber-like polymer is not crosslinked, it is stretched in the flow direction at the time of molding, so that the rubber-like polymer in the molded article is When the shape is observed with an electron microscope, the shape differs between the plane parallel to the flow direction and the plane perpendicular to the flow direction. In addition, the shapes are slightly different between the surface layer and the inside of the molded product, and between the gate and the terminal. For this reason, the shape of the rubber-like polymer of the molded article of the present invention is defined by the number-average particle diameter in terms of a circle from the center of the molded article and a cross section perpendicular to the flow direction at the time of molding at the center. The average particle size in terms of circle means that the shape of the rubbery polymer present in the molded product is not necessarily spherical regardless of whether it is crosslinked or not. It is converted into a circle and expressed as the number average of its diameter. When the number average particle diameter in circle is less than 0.1 μm, the effect of improving mechanical strength is not sufficient. On the other hand, when the thickness is 1.5 μm or more, the effect of improving mechanical strength is not sufficient.

When the rubber-like polymer in the molded article of the present invention is used as one component, a plurality of types may be mixed and used. In this case, the workability can be further improved.

Next, the thermoplastic resin in the thermoplastic resin molded article of the present invention will be described.

The thermoplastic resin in the thermoplastic resin molded article of the present invention is one that is compatible or uniformly dispersed with the rubbery polymer preferably used, or one that is compatible or uniformly dispersed with a compatibilizer. If there are any restrictions, For example, polystyrene, polyphenylene ether, polyolefin, polyvinyl chloride, polyamide, polyester, polyphenylene sulfide, polycarbonate, polymethacrylate resins, etc., or a mixture of two or more resins Can be used. Among these, a polyolefin-based resin is preferable as the thermoplastic resin. The reason is that, when a rubber-like polymer is allowed to coexist with the thermoplastic resin molded article of the present invention, an ethylene-diol copolymer rubber preferably used as the rubber-like polymer or a polymer having a structure similar thereto This is because it has a high affinity and high strength. The polyolefin-based resin suitably used in the present invention is roughly classified into a polyethylene-based resin, a polypropylene-based resin, or a mixture of a polyethylene-based resin and a polypropylene-based resin.

Examples of polyethylene resins include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), copolymers of acrylic-based monomer and ethylene (EEA, EMMA, etc.) or Bull acetate Copolymers of monomers and ethylene (EVA) and the like can be mentioned. Among these, high-density polyethylene (HDPE), low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) 1 are particularly preferable because they have high heat resistance and can be obtained at low cost. These polyethylene resins may be used alone or in combination of two or more.

When high-density polyethylene (HDPE) is used as the material for the molded article of the present invention, its density generally ranges from 0.930 to 0.970.

The melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg is preferably in the range of 0.05 to 100 g / l 0 min. When using low density polyethylene (LDP E) or linear low density polyethylene (LLDPE), its density is generally a 0.900 to 0. Of 930 g / cm ² range, 190 ° C, 2. The melt flow rate (MFR) measured at a load of 16 kg is preferably in the range of 0.05 to: 100 gZ for 10 minutes. If the melt flow rate exceeds 100 g / 10 minutes, the molded article of the present invention has insufficient mechanical strength and heat resistance, and if the melt flow rate is less than 05 g Z10 minutes, it is used to obtain the molded article of the present invention. When molding a material, the flowability is poor and the molding processability is undesirably reduced.

Examples of the polypropylene resin include polypropylene (homopolymer) and copolymer resin (block, random copolymer) of propylene and other α-olefins such as ethylene, butene-11, pentene-11, hexene-11. (Including coalescence).

The melt flow rate (MFR) of the polypropylene resin used to obtain the molded article of the present invention measured at 230 ° C and under a load of 2.16 kg is 0.1 to :! It is preferably in the range of O O g / 10 min. If the melt flow rate exceeds 100 g / 10 minutes, the mechanical strength and heat resistance of the molded article of the present invention are insufficient, and if the melt flow rate is less than 0.1 lg / 10 minutes, molding is performed to obtain the molded article of the present invention. In this case, the flowability is poor and the molding processability is undesirably reduced.

The polyolefin resin preferably used for obtaining the molded article of the present invention is composed of a polyethylene resin and / or a polypropylene resin as described above. For example, when the molded article of the present invention is used for a power tool housing, the Motor Since the housing itself becomes high temperature due to heat generation and heat resistance is required, a polypropylene resin is more preferable because of its high heat resistance. Furthermore, when used in applications such as radiator tanks, they come in contact with high-temperature coolant liquids, and therefore also require heat resistance in this case, and polypropylene resins are more preferable. However, polypropylene homopolymers are generally susceptible to oxidative degradation, and their mechanical strength tends to decrease due to molecular weight reduction during long-term use. On the other hand, polyethylene generally does not decompose with acid and tends to maintain or improve mechanical strength by crosslinking. Therefore, when using a polypropylene resin, especially in applications where durability is required, a homopolymer of polypropylene and a polyethylene resin are used in combination, or a random or block polymer of a propylene monomer and an ethylene monomer is used. It may be preferable to use or use together.

The thermoplastic resin in the thermoplastic resin molded article of the present invention has a high affinity for an ethylene-α-olefin copolymer rubber suitably used as a rubber-like polymer or a polymer having a structure similar thereto, It is preferable to use a polyolefin resin because a high-strength resin can be obtained, but it is also possible to use a thermoplastic resin other than a polyolefin resin such as a polystyrene resin and a polyphenylene ether resin as described above. it can.

When a thermoplastic resin other than a polyolefin-based resin is used, the compatibility with the ethylene-polyolefin copolymer rubber preferably used as the rubber-like polymer is often not necessarily good. In that case, a compatibilizer is used. Examples of the compatibilizer include a polymer material having both a polyolefin-based component and a thermoplastic resin component to be used in the molecule or a component compatible with the thermoplastic resin. Examples of the polystyrene resin include hydrogenated styrene-butadiene block resin and styrene-grafted polyethylene. When using a thermoplastic resin other than a polystyrene resin, the compatibilizer should be selected in a similar way.

The thermoplastic resin molded article of the present invention is composed of a thermoplastic resin containing at least glass fiber and preferably a rubber-like polymer as described above, and other components, if necessary, a matrix for imparting thermoplasticity. Polymers other than thermoplastic resins (modifiers), It can contain softeners, powdered inorganic fillers, whiskers and plasticizers. Examples of the polymer (modifier) other than the thermoplastic resin serving as the matrix include a thermoplastic resin capable of interfacially bonding the glass fiber and the thermoplastic resin of the present invention. For example, in the case of a polyolefin resin suitably used as the thermoplastic resin of the present invention, as a material for improving the interfacial adhesion between the glass fiber and the thermoplastic resin as a matrix, for example, a copolymer of maleic acid-modified polyolefin or maleic acid is used. Examples thereof include polymerized polyolefin, acrylic acid-modified polyolefin or copolymerized polyolefin with acrylic acid, fumaric acid-modified polyolefin, and copolymerized polyolefin with fumaric acid. The coexistence of such a modifier is effective for improving the impact resistance.

As the softener, a process oil such as a paraffinic or naphthenic oil can be used. When a softener is present, the stiffness tends to decrease slightly, but it has the effect of further improving the impact resistance. In addition, when processing is performed to obtain the molded article of the present invention, there is an effect that fluidity can be improved, and when the molded article is dropped, the peripheral part may be whitened due to impact. . The softening agent has the effect of improving the whitening.

Examples of the powdery inorganic filler include talc, myric, clay, calcium carbonate, magnesium carbonate, silica, carbon black, titanium oxide, magnesium hydroxide, magnesium hydroxide, aluminum hydroxide, and the like. Among them, talc is particularly preferable because it can increase the rigidity of a polyolefin-based resin suitably used as a thermoplastic resin which is a component of the molded article of the present invention. When talc is added, its amount is 1 to 50% by weight, preferably 5 to 40% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 20% by weight. When talc is made to coexist, it may be made to coexist in a combination of a thermoplastic resin and glass fiber, or preferably in a combination of a thermoplastic resin, glass fiber and a rubbery polymer. .

Examples of the plasticizer include phthalate esters such as polyethylene glycol and octyl phthalate (DOP). Also, other additives, such as organic and inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, Silicone oil, antiblocking agents, foaming agents, antistatic agents, antibacterial agents and the like are also suitably used.

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

The molded article of the present invention can be obtained by blending glass fiber itself or glass fiber hardened with latex or a thermoplastic resin with a thermoplastic resin, and directly molding this blended article. Preferably, a thermoplastic resin containing a glassy fiber or a rubbery polymer (preferably a partially or completely crosslinked rubbery polymer) and a glass fiber or the like hardened with a latex or a thermoplastic resin (hereinafter referred to as “thermoplastic”). The thermoplastic resin is blended with a thermoplastic resin if necessary, and the molded product of the present invention is obtained by a method of directly injection-molding the blended product. When this method is carried out, kneading is performed only once at the time of injection molding, so that the fiber length in the molded product is maintained longer than the short fiber method which requires blending with a twin-screw extruder and injection molding. Therefore, a molded product having high rigidity can be obtained. A more preferable method is to impregnate a thermoplastic resin into a force for dipping a bundle of glass fibers (or a bing) into a latex or a roving, or to extrude a thermoplastic resin and coat the roving with a resin, thereby forming a pellet length. This is a method in which thermoplastic resin pellets containing glass fibers of the same length as above (hereinafter referred to as long fiber pellets) are prepared, and this is pellet-blended with the thermoplastic resin pellets, and this blended product is injection-molded. . When the molded article contains a rubber-like polymer as one component, thermoplastic resin pellets containing the above-mentioned long-fiber pellets and a rubber-like weight (preferably a partially or completely crosslinked rubber-like polymer) (hereinafter referred to as “thermoplastic pellets”). This is called thermoplastic elastomer pellets.) If necessary, blend the thermoplastic resin pellets with pellets and injection-mold this blend. When talc is contained as one component in the molded article, the above-mentioned long fiber pellets and thermoplastic resin pellets containing talc, preferably thermoplastic elastomer pellets, and if necessary, thermoplastic resin pellets are blended by pellet blending. The product is injection molded. When a polyolefin resin is used as the thermoplastic resin, a polymer other than the thermoplastic resin, which is a matrix preferably added to increase the adhesiveness between the resin and the glass fiber, is a thermoplastic resin that coats the glass fiber. Medium, thermoplastic elastomer or thermoplastic resin added with caro, or a combination thereof. Here, a method for producing a thermoplastic elastomer containing a crosslinked rubber, which is composed of a thermoplastic resin containing a partially or completely crosslinked rubbery polymer, which is most preferably used, is exemplified by a polyolefin resin as the thermoplastic resin. A description is given below.

Preferably, an ethylene / α-olefin copolymer mainly composed of ethylene and α-olefin and a polymer having a structure similar to Ζ or a similar polymer, a polyolefin resin, a cross-linking agent and a cross-linking aid are used in a twin-screw extruder. Heat treatment with a Panbury mixer. In this case, the crosslinking agent preferably used includes a radical initiator such as an organic peroxide and an organic azo compound. Specific examples of the radical initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyloxy) -1,3,3 , 5-Trimethylcyclohexane, 1,1-bis (t-hexylpropoxy) cyclohexane, 1,1-bis (t-butylinoxy) Dodecane, 1,1-bis (t-butyl) (Norepoxy) Cyclic hexane, 2,2-bis (t-butynoleveroxy) octane, n-butyl-4,4 Mono-bis (t-ptinoleperoxy) butane, n-butyl-4,4 Peroxyketals such as mono-bis (t-butyl peroxy) valerate; and di-t-butyl baroxyside, dicuminoleno. 1-oxide, t-ptinoleminoleopoxide, α, '-bis (t-ptinoleperoxy-1 m-isopropyl) benzene, a, a, -bis (t-petit ^^ peroxy) diisopropylbenzene, Dialkyl peroxides such as 2,5-dimethyl-2,5_bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne_3; acetyl peroxide, isoacetate Butyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioiloperoxide and other diacyl peroxides; t-butyl peroxyacetate, t_butyl peroxyi Soptylate, t-butyl peroxy-1-ethylhexanoate, t-butyl peroxylaurylate, t-butyl peroxybenzoate, g-t-butyl peroxyisophthalate, 2,5-dimethynolate 2,5-di (Benzoylperoxy) hexane, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, and Peroxy esters such as ruperoxy octoxide; t-butyl hydroperoxide, tamen hydroperoxide, diisopropinolebenzene hydroperoxide, 2,5-dimethylhexane-1,2,5-dihydro Hydroperoxides such as peroxide and 1,1,3,3-tetramethylbutyl peroxide can be mentioned.

Among these compounds, 1,1-bis (t-butylperoxy) -13,3,5-trimethylcyclohexane, di-t-butylperoxide, dicumyl peroxide, 2,5-dimethyl-2,5- Bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexine-13 are preferred.

These radical initiators are used in an amount 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-olefin copolymer and the polyolefin resin. Used in The level of crosslinking is primarily determined by this amount. If the amount is less than 0.02 parts by weight, the crosslinking is insufficient, and if it exceeds 3 parts by weight, the crosslinking ratio is not significantly improved.

Cross-linking aids include dibutylbenzene, triarinoleisocyanurate, triaryl cyanurate, diacetone diacrylamide, polyethylene dalicol diatalylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolpropane triatalylate, ethylene glycol dimethacrylate, triethylene glycol resmethacrylate, methylen glycolone resmethacrylate, disopropininolebenzene, p-quinone dixime, p, p 'dibenzoinolequinone dioxime, fu Ninole maleimide, aryl metathalylate, N, N'-m-phenylene bismaleimide, diaryl phthalate, tetraaryl oxetane, 1,2-polybutadiene, etc. are preferred. It is needed. These crosslinking aids may be used in combination of two or more.

The crosslinking aid is used in an amount of 0.1 to 5 parts by weight, and preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the ethylene 'olefin copolymer and the polyolefin resin. If the amount is less than 0.1 part by weight, the crosslinking rate is low, which is not preferable. If the amount exceeds 5 parts by weight, the crosslinking ratio is not significantly improved and is not preferable. It is preferable to use a cross-linking agent and a cross-linking assistant as described above as a cross-linking method. In addition, a phenol resin or bismaleimide may be used as the cross-linking agent. .

Next, a method for producing a long fiber pellet will be described.

The manufacturing method is a method of dipping a glass fiber roving in a molten thermoplastic resin and then pelletizing it to a predetermined length.The extruder extrudes the thermoplastic resin while aligning the glass fiber roving under tension. Extrusion from the side, extruding thermoplastic resin on the surface of glass fiber and pelletizing (general method called pultrusion method), or dipping glass fiber rovings in emulsion (latex) and then drying There is a method of pelletizing to a predetermined length. As the thermoplastic resin to be coated on the glass fiber, any of the above-mentioned resins can be appropriately selected and used, but is preferably the same as the thermoplastic resin to be a matrix. Also, it is preferable that the emulsion be the same as or compatible with the thermoplastic resin as the matrix. Examples of emanolions include, for example, ethylene-vinyl acetate emulsion when the thermoplastic resin is a polyolefin resin, and styrene-butadiene emulsion when the thermoplastic resin is a polystyrene resin or a modified polyphenylene ether resin. The thermoplastic resin is polyacrylonitrile-styrene resin (AS), polyacrylonitrile-butadiene-styrene resin (ABS), polycarbonate resin (PC), polyester resin (PET, PBT, etc.) In the case of), it is possible to use atari lonitrile-styrene emulsion, and when the thermoplastic resin is a polyamide, a urethane-based emulsion may be used.

The long fiber pellets thus obtained are usually 2 to 100 mm, preferably 3 to 50 mm, more preferably 5 to 20 mm in length. This long fiber pellet contains glass fibers of the same length as the pellet length. This long fiber pellet is mixed with a thermoplastic resin pellet and injection-molded under appropriate molding conditions, or preferably, the long fiber pellet is mixed with a rubber-like polymer (preferably partially or completely cross-linked). A pellet of a thermoplastic elastomer containing a (rubber-like polymer), a thermoplastic resin containing z or a torque, and, if necessary, a pellet of a thermoplastic resin are mixed and injection-molded under appropriate molding conditions. In order to obtain the molded article of the present invention, it is possible to perform molding by extrusion molding, compression molding, or the like, in addition to injection molding.

The molded article of the present invention thus produced is a product having excellent appearance, high rigidity, high strength, and excellent heat resistance.

The molded article of the present invention is desired to soften the surface of the molded article depending on the use. For example, in the housing of a power tool, by softening a portion for gripping the power tool, it is possible to impart effects such as not to be tired during use and to feel warmth. The soft molding of the surface of the molded article of the present invention is preferably performed, for example, by molding the molded article material of the present invention and a thermoplastic elastomer in two colors, and loading the molded article of the present invention in a mold. This is carried out by insert molding of a thermoplastic elastomer, or by co-extrusion of the molded article material of the present invention and a thermoplastic elastomer to produce a laminate. As the thermoplastic elastomer, a thermoplastic elastomer containing the above-mentioned rubbery polymer (preferably, a partially or completely crosslinked rubbery polymer) is preferable. The thermoplastic resin and the rubbery polymer preferably coexisting in the molded article of the present invention and the thermoplastic resin and the rubbery polymer in the thermoplastic elastomer laminated on this surface may be different from each other or the same. It may be. However, it is preferable that they be the same. The reason is that the same component has better adhesion between the molded product and the thermoplastic elastomer laminated on it, and at the same time, when this material is recycled, the molded product and the thermoplastic elastomer are peeled off Even if this is not done, the laminated product itself is powder-framed, glass fibers are added to the extent that the strength is reduced, and this can be reused as a raw material in the production of the molded article of the present invention.

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, the test methods used for evaluating various physical properties, and the production methods of the thermoplastic elastomer used for the raw materials and the blending are as follows.

1. Test method

(1) Tensile strength

The measurement was performed at 23 ° C. by a method according to JISK 6251.

(2) Bending strength It was measured at 23 ° C by a method in accordance with JIS K6758.

(3) Flexural modulus

The measurement was performed at 23 ° C according to a method according to JIS K 6758.

(4) Izod impact strength

The measurement was performed at 23 ° C according to a method according to JIS K6758.

(V notch, 1/4 inch specimen)

(5) Drop weight impact strength

Using a falling weight impact tester (manufactured by Toyo Seiki Seisakusho), tip diameter of falling weight: 13.6 mm, weight: 6.5 kg, falling height 100 cm, holder diameter: 5 mm, test thickness: 3 mm The total absorbed energy was measured at a temperature of 23 ° C and a humidity of 50%. Larger values are more difficult to crack.

(6) Heat resistance (HDT)

It was measured by a method according to JIS K7207.

(7) Length of glass fiber in molded product

The molded product was fired, and the distribution of fiber length was measured by image analysis using an optical microscope.

(8) Average particle size of rubbery polymer

The molded product was cut by a microtome at right angles to the flow during molding. This was observed with an electron microscope. The number average particle diameter in terms of yen was measured by image analysis.

(8) Degree of crosslinking

0.5 g of the crosslinked thermoplastic elastomer is refluxed for 4 hours in 20 ml of xylene. The solution was filtered with a filter paper for quantification, the residue on the filter paper was dried in vacuo, quantified, and calculated as the ratio (%) of the weight of the residue to the weight of the rubbery polymer in the crosslinked thermoplastic elastomer.

2. Raw materials

(1) Rubbery polymer

(a) Ethylene / otaten-1 copolymer

A method using a meta-mouth catalyst described in JP-A-3-163088 Made from The composition ratio of ethylene Z-otaten-11 in the copolymer was 72/28 (weight ratio) (referred to as TPE-1)

(b) Ethylene / propylene / dicyclopentene copolymer

It was produced by a method using a meta-mouth catalyst described in JP-A-3-163088. The composition ratio of ethylene / propylene Z-dicyclopentagen of the copolymer was 72/24/4 (weight ratio). (Referred to as TPE-2)

(2) Thermoplastic resin

(a) Polypropylene

Nippon Polychem Co., Ltd., isotactic homopolypropylene (MA0

3) (referred to as PP)

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

Nippon Polyolefin Co., Ltd., block E-PP resin [EZPP = 6Z

94] (weight ratio) (PM97 OA)] (referred to as EP-1)

(c) Ethylene (E) -propylene (PP) copolymer resin 1

Nippon Polyolefin Co., Ltd., random E-PP resin [E / PP = 7 /

93 (weight ratio) (PM940M) (referred to as EP-2)

(d) Maleated polypropylene

Admir (F 305) (M-PP) manufactured by Mitsui Chemicals, Inc. (e) Maleated polyethylene

Admar (HB030) (M-PE) manufactured by Mitsui Chemicals, Inc. (f) High density polyethylene

Suntech HD (B470) manufactured by Asahi Kasei Corporation (HDPE)

(g) Polystyrene

Asahi Kasei Kogyo Co., Ltd., Stylon PS (683) (referred to as PS) Asahi Kasei Kogyo Co., Ltd., Stylon HI PS (403) (referred to as HI PS) (h) Poly (acrylonitrile-styrene)

Styrac AS (769) (AS) manufactured by Asahi Kasei Corporation (i) Poly (acrylonitrile-butadiene-styrene)

Styrac AB S (100) (ABS) manufactured by Asahi Kasei Corporation

(j) Polycarbonate

Novalex (702, manufactured by Mitsubishi Engineering-Plastics Corporation)

A) (referred to as PC)

(k) Polycarbonate Z-poly (acrylonitrile-butadiene-styrene PCZABS (PC / ABS) manufactured by Asahi Kasei Corporation)

(1) Polyester

Ground PET bottle (referred to as PET)

(3) Radical initiator

Nippon Oil & Fats Co., Ltd., 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane (Perhexa 25B) (referred to as POX)

(4) Crosslinking aid

Manufactured by Wako Pure Chemical, divinylbenzene (referred to as DVB)

(5) Softener (paraffin oil)

Idemitsu Kosan, Diana Process Oil (PW-380)

(6) Glass fiber

Aminosilane treated glass fiber roving (ER 740) manufactured by Asahi Fiber Co., Ltd. (thickness: 13 μm)

(7) Talc

General product made by Nippon Talc Co., Ltd. (referred to as talc)

Method for producing crosslinked thermoplastic elastomer

(1) TPV-1

As an extruder, a twin screw extruder (4 Omm0,

L / D = 47) was used. As the screw, a double screw having a kneading part before and after the injection port was used. TPE-1 / PP / POX / DVB = 55. 6 / 44.4 / 0. 38 / 0.74 (weight ratio) were mixed and melt-extruded at a cylinder temperature of 220 ° C. Degree of crosslinking of the obtained crosslinked thermoplastic elastomer Was 82%.

(2) TPV— 2

A crosslinked thermoplastic elastomer was obtained in the same manner as in (1) except that the ratio of TPE-lZPPZPOXZDVB was 55.6 / 44. 4 / 0.19 / 0.37 (weight ratio). The degree of crosslinking of this crosslinked thermoplastic elastomer was 55%.

(3) TP V-3

A crosslinked thermoplastic elastomer was obtained in the same manner as (1) except that TPE-1 / P PZPOXZDVB was changed to TPE_1 / EP-1 / POX / DVB. The degree of crosslinking of this crosslinked thermoplastic elastomer was 81%.

(4) TPV-4

TPE-1 / P PZPOX / DVB is TPE-1ZP P / HDPE / PO XZDVB, and the ratio is 55.6 / 33. 3/1 1.1 / 0. 19 / 0.37 (weight ratio) Except for this, a crosslinked thermoplastic elastomer was obtained in the same manner as in (1). The degree of crosslinking of this crosslinked thermoplastic elastomer was 85%.

(5) A crosslinked thermoplastic elastomer was obtained in the same manner as in (1) except that TPV-5 was used. Degree of crosslinking of the crosslinked thermoplastic I ¹ production Erasutoma is Atsuta almost 100%.

(6) TPV-6

Crosslinking heat is applied in the same manner as (1) except that 33 parts by weight of softener (paraffin oil) is injected from the injection port in the center of the extruder to 100 parts by weight of the total amount of TPE-1 and PP. A plastic elastomer was obtained. The degree of crosslinking of this crosslinked thermoplastic elastomer was 82%.

(7) TPV-7

TPE-1ZP The ratio of P / POX / DVB is 70.0 / 30.0 / 0.4.8 / 0.93, and the total amount of TPE-1 and PP is 100 parts by weight from the injection port at the center of the extruder. 20 parts by weight of softener (paraffin oil) A crosslinked thermoplastic elastomer was obtained in the same manner as in (1) except that it was added. The degree of crosslinking of this crosslinked thermoplastic elastomer was 81%.

4. Manufacturing method of non-crosslinked thermoplastic elastomer

(1) TPO-1

As an extruder, a twin screw extruder (4 Omm0,

L / D = 47) was used. A screw with a kneading section before and after the injection port was used as the screw. TP E-1 / P P = 5 5.6 / 44.4 (weight ratio) was mixed and melt-extruded at a cylinder temperature of 200 ° C.

Example 1

1 3 // M 5% M—PP / 95% PP is extruded from the side while extruding a roving of glass fiber of m thickness under tension, and the polyolefin resin is extrusion coated on the surface of the glass fiber. Then, it was cut into pellets having a length of 7 mm to produce long fiber pellets (referred to as GF_1). The ratio of the long fiber pellet to the glass Z polyolefin resin was 56/44 (weight ratio). The pellets of GF-1 and PP were mixed at 53.6 / 46.4 (weight ratio), the molding temperature was 240 ° C, and the other molding conditions were general conditions. The injection molding machine (Toshiba Molding was performed by IS 45 PNV) to obtain a molded product. Table 1 shows the composition (including the distribution of glass fibers) in the molded product and its properties.

Comparative Example 1

A roving of 13 μπι thick glass fiber was cut into 7 mm and chopped. This chop and PP were mixed at a ratio of 30/70 (weight ratio), and the resin temperature was 230 using a twin-screw extruder (Toshiba TEM-35B). C. Extruded and pelletized. Using this pellet as a raw material, molding was performed at an injection molding machine (Toshiba IS 45 PNV) at a molding temperature of 230 ° C to obtain a molded product. Table 1 shows the composition of the molded article and its properties. Comparative Example 2

A material obtained by mixing each pellet of GF-1 and PP in Example 1 at 53.6 / 46.4 (weight ratio), the molding temperature was 290 ° C, the back pressure during molding, and the screw rotation speed. However, the firing speed was also reduced to an extreme state, and unlike Example 1, molding was carried out under conditions where it was extremely difficult to obtain the largest share. The glass fiber of 2 mm or more in the obtained molded product is 0. 5% or less was 0%, 0.5 to 2.Omm was 49%, and 0.5mm or more was 51%, but the surface appearance of the molded product was extremely bad due to unevenness due to glass fiber aggregation. I got it. On the other hand, the appearance of the molded product obtained in Example 1 was good. Table 1 shows the composition of the molded article and its properties.

Example 2

Using the long fiber pellet (GF-1) obtained in Example 1, each pellet of GF-1, TPV-11 and PP was mixed at 53.6 / 36.0 / 10.4 (weight ratio). Then, the molding temperature was set to 240 ° C., and molding was performed using the same injection molding machine as in Example 1 to obtain a molded product. Table 1 shows the composition of the molded article and its properties.

Comparative Example 3

A 13〃m thick glass fiber roving was cut to 7 mm and made into a chop. This chop, TPV_1,? ? Were mixed at a ratio of 53.6 / 36. 0 / 10.4 (weight ratio), and were extruded and pelletized at a resin temperature of 230 ° C using the same twin-screw extruder as in Comparative Example 1. Using the pellets as a raw material, molding was performed at the molding temperature of 230 ° C. using the same injection molding machine as in Example 1 to obtain a molded product. Table 1 shows the composition of the molded article and its characteristics.

Comparative Example 4

Molding was carried out under the same conditions as in Comparative Example 2 using a material obtained by mixing the pellets of GF-1, TPV-1, and PP of Example 2 at a ratio of 53.6 / 36.0 / 10.4 (weight ratio). . The glass fiber of 2 mm or more in the obtained molded product was 0% for 0.5 mm or less, 56% for 0.5 to 2.Omm, and 44% for 0.5 mm or more. As in Comparative Example 2, the surface appearance was extremely poor due to unevenness due to the aggregation of glass fibers. On the other hand, the appearance of the molded product obtained in Example 2 was good. Table 1 shows the composition of the molded article and its properties.

Example 3

Molding was performed in the same manner as in Example 2 except that the molding temperature was set to 225 ° C to obtain a molded product. Table 1 shows the composition of the molded article and its properties.

Example 4

Molding was performed in the same manner as in Example 2 except that TPV-1 was changed to TPV-2. Product was obtained. Table 1 shows the composition of the molded article and its properties.

Example 5

Molding was performed in the same manner as in Example 1 except that TPO-1 was changed to TPO-1 to obtain a molded article. Table 1 shows the composition of the molded article and its properties.

Example 6

Same as Example 2 except that each pellet of GF-1, TPV-1, PP is mixed at GF-1 / TPV-1 / PP = 5 3.6 / 18. 0 / 28.4 (weight ratio). Molding was performed to obtain a molded product. Table 1 shows the composition of the molded article and its properties.

Example 7

Same as Example 2 except that GF-1, TPV-1, and PP pellets are mixed at GF-1 / TPV-1 / PP = 35.7 / 36.0 / 28.3 (weight ratio). Molding was performed to obtain a molded product. Table 1 shows the composition of the molded article and its properties.

Example 8

Molding was performed in the same manner as in Example 1 except that TPV-1 was changed to TPV-5 to obtain a molded article. Table 2 shows the composition of the molded article and its properties.

Example 9

Except that the material to be extruded and coated on glass fiber is 5% M-P PZ 95% PP and 5% M-PP Z95% EP-1 In the same manner as in Example 1, long fiber pellets (referred to as GF_2) Was manufactured. The ratio of the long fiber pellets to the glassy polyolefin resin was 56/44 (weight ratio). Each pellet of GF-2, TPV-3 and EP-1 was mixed at 53.6 / 36.0 / 10.4 (weight ratio), and molding was performed in the same manner as in Example 2 to obtain a molded product . Table 2 shows the composition of the molded article and its properties.

Example 10

Example 2 except that the components and compositions of GF-1, TPV_1, and PP pellets were mixed at GF-1ZTPV-1 / ΕΡ-2 = 53.6 / 36. 0 / 10.4 (weight ratio). Molding was performed in the same manner to obtain a molded product. Table 2 shows the composition of the molded article and its properties.

Example 11 Except that the material to be extruded on the glass fiber is changed from 5% M-PPZ95% PP to 5% M-PP / 71.3% PP / 23.7% HDPE, a long fiber pellet (GF —3). The ratio of the long fiber pellets to the glass polyolefin resin was 56/44 (weight ratio). The pellets of GF-3, TPV-4 and PP were mixed at 53.6 / 36.0 / 10.4 (weight ratio) and molded in the same manner as in Example 2 to obtain a molded product . Table 2 shows the composition of the molded article and its properties.

Example 12

Molding was performed in the same manner as in Example 2 except that the composition of each pellet of GF_1 and TPV-1 was mixed at 53.6 / 46.4 (weight ratio). Table 2 shows the composition of the molded product and its properties.The test piece during the drop weight impact test was slightly whitened in the molded product of Example 2 but completely whitened in the molded product of Example 12. I didn't. Example 13

TPV-1, PP and talc were mixed at a ratio of 56.0 / 28.5 / 5 / 15.5 and extruded into a pellet at a resin temperature of 230 ° C with a twin-screw extruder (Toshiba TEM-35B). . This pellet and each pellet of GF_1 were mixed at a ratio (weight ratio) of 64.3 / 35.7, and molding was performed in the same manner as in Example 2 to obtain a molded product. Table 3 shows the composition of the molded article and its properties.

Examples 14 and 15

Molding was performed in the same manner as in Example 1 except that TPV-1 was changed to TPV-6 to obtain a molded article. For each pellet of GF-1, TPV-6 and PP, 53.6 / 36. 0 / 10.4 in Example 14 and 53.6 / 46.4 / 0/0 in Example 15 (weight ratio) And molded in the same manner as in Example 2 to obtain a molded product. Table 3 shows the composition of the molded article and its properties.

Example 16

AS emulsion (acrylonitrile-styrene latex; acrylonitrile 25%, solids concentration 50% by weight) while rubbing glass fiber roving of 13 μπι thickness under tension, dipped the glass fiber in the bath layer, AS resin is adhered, dried, cut into a 5.5 mm long pellet, and a long fiber pellet (GF-4) ) Was manufactured. The ratio of the long fiber pellet to the glass ZAS resin was 80Z20 (dry weight ratio). The 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 a molded product. Table 4 shows the composition of the molded article and its properties.

Example 17

Molding was performed in the same manner as in Example 16 except that PS was changed to HIPS to obtain a molded product. Table 4 shows the composition of the molded article and its properties.

Example 18

Molding was performed in the same manner as in Example 16 except that PS was set to AS to obtain a molded product. Table 4 shows the composition of the molded article and its properties.

Example 19

Molding was performed in the same manner as in Example 16 except that P S was changed to A B S to obtain a molded product. Table 4 shows the composition of the molded article and its properties.

Example 20

Molding was performed in the same manner as in Example 16 except that PS was changed to PC to obtain a molded product. Table 4 shows the composition of the molded article and its properties.

Example 21

Molding was performed in the same manner as in Example 16 except that PS was PCZABS to obtain a molded product. Table 4 shows the composition of the molded article and its properties.

Example 22

Molding was performed in the same manner as in Example 16 except that PS was PET, and a molded article was obtained. Table 4 shows the composition of the molded article and its properties.

Example 23

A long fiber pellet (referred to as GF-5) was prepared in the same manner as in Example 1 except that the material to be extrusion-coated on the glass fiber was changed from 5% M-P PZ 95% PP to 5% M-PE Z 95% HDPE. Manufactured. The ratio of the long fiber pellets to the glass / polyolefin resin was 56Z44 (weight ratio). Each pellet of GF-5 and HDPE was mixed at 53.6 / 46.4 (weight ratio) and molded in the same manner as in Example 1 to obtain a molded product. Table 4 shows the composition of the molded article and its properties. Example 2 4

Using the same molding machine as in Example 1, the molded articles obtained in Example 1 and Example ² were loaded into a mold set at 40 ° C. Insert-molded ¥ -7. The obtained laminate had extremely high adhesion, and the interface between the two could not be peeled off. The surface hardness (A hardness) of the thermoplastic elastomer was 78, and the softness of the molded product was extremely excellent.

Industrial applicability

The thermoplastic resin molded article of the present invention has high rigidity and high rigidity, such as automobile parts such as radiator tanks, industrial parts such as power tool housings, office parts such as office chairs, electric parts, daily necessities, and building materials. It can be used for applications that require strength, and plays a major role in the industrial world.

table 1

Table 2

Table 3

Table 4

Claims

The scope of the claims

1. A thermoplastic resin molded article comprising a glass fiber and a thermoplastic resin, the glass fibers are contained in a content of 1-6 0 weight ^_0/0, and 0. 5 mm or less in length 90 to 90% of glass fiber, 10 to 90% of glass fiber of 0.5 to 2 mm length, and 0 to 30% of glass fiber of 2 mm or more length Resin molded products.

2. The thermoplastic resin molded article according to claim 1, further comprising a rubbery polymer in a content of 1 to 40% by weight.

3. The thermoplastic resin molded article according to claim 1, further comprising talc in a content of 1 to 50% by weight.

4. The thermoplastic resin is a polyolefin resin. The thermoplastic resin molded product according to any one of claims 1 to 3.

5. The thermoplastic resin molded article according to claim 4, wherein the polyolefin-based resin mainly contains a polypropylene-based resin.

6. The thermoplastic resin according to any one of claims 2 to 5, wherein the rubbery polymer is an ethylene-α-olefin copolymer containing mainly ethylene and _α -olefin having 3 to 20 carbon atoms. Molding.

7. The thermoplastic resin molded article according to any one of claims 2 to 6, wherein the rubbery polymer is partially or completely crosslinked.

8. Average diameter:! A thermoplastic resin pellet containing glass fiber obtained by coating a glass fiber roving of ~ 50 m with a thermoplastic resin and further cutting it to an average length of 1 to 25 mm;

At least one selected from the group consisting of thermoplastic resin pellets, thermoplastic resin pellets containing a rubbery polymer, thermoplastic resin pellets containing talc, and thermoplastic resin pellets containing a rubbery polymer and talc. The method for producing a thermoplastic resin molded article according to any one of claims 1 to 7, comprising a step of mixing and molding the resin pellet of (1).

9. A laminated molded article of a thermoplastic elastomer and a thermoplastic resin, wherein the molded article of the thermoplastic resin according to any one of claims 1 to 7 is coated with a thermoplastic elastomer.

10. The laminated molded product according to claim 8, wherein the thermoplastic elastomer is a polyolefin-based thermoplastic elastomer.