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WO2001059009A1 - Article forme de resine thermoplastique presentant une rigidite et une resistance elevees - Google Patents

Article forme de resine thermoplastique presentant une rigidite et une resistance elevees Download PDF

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Publication number
WO2001059009A1
WO2001059009A1 PCT/JP2000/000794 JP0000794W WO0159009A1 WO 2001059009 A1 WO2001059009 A1 WO 2001059009A1 JP 0000794 W JP0000794 W JP 0000794W WO 0159009 A1 WO0159009 A1 WO 0159009A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
molded article
glass fiber
resin
molding
Prior art date
Application number
PCT/JP2000/000794
Other languages
English (en)
Japanese (ja)
Inventor
Hideo Kinoshita
Ikuji Ohtani
Yoshikazu Suda
Original Assignee
Asahi Kasei Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Kabushiki Kaisha filed Critical Asahi Kasei Kabushiki Kaisha
Priority to CNB008061831A priority Critical patent/CN1175052C/zh
Priority to PCT/JP2000/000794 priority patent/WO2001059009A1/fr
Priority to DE10084451T priority patent/DE10084451T1/de
Publication of WO2001059009A1 publication Critical patent/WO2001059009A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • 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.
  • 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.
  • glass fiber reinforced polypropylene resin, glass fiber reinforced polyamide resin and the like are sold.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present inventors have first studied intensively mainly using a polyolefin-based resin, particularly a polypropylene-based resin.
  • 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.
  • 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.
  • glass fiber Chopop glass
  • 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.
  • the glass fiber in the molded article can be kept long because the molded article is produced only by screw kneading during injection molding.
  • 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.
  • 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.
  • 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.
  • 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.
  • mechanical strength can be significantly improved by coexisting a rubbery polymer with glass fiber.
  • Rubbery polymers are preferred over their ability to partially or completely crosslink.
  • 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.
  • 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 / ⁇ , more preferably 1 to: 100 / zm, and most preferably. 5 to 50 ⁇ .
  • 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 ⁇ m, 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • It is necessary that 5 to 20% of glass fiber with a length of at least mm is used.
  • the glass fiber length of 0.5 mm or less exceeds 90%, the effect of improving the mechanical strength is not sufficient.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • T g glass transition temperature
  • 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.
  • ethylene-a-olefin copolymer rubber mainly composed of ethylene and ⁇ -olefin or a polymer having a structure similar thereto has excellent weather resistance, mechanical strength, etc.
  • 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.
  • an ethylene- ⁇ -olefin copolymer mainly comprising ethylene and a-olefin having 3 to 20 carbon atoms is more preferable.
  • 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.
  • a copolymer component may be included as the third component.
  • the third component are non-conjugated components such as 1,3-butadiene and isoprene; conjugated pentagens; Conjugated Gens and the like.
  • the ethylene ' ⁇ -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.
  • EPDM non-conjugated gen terpolymer rubber
  • the ethylene / ⁇ -olefin copolymer rubber containing no conjugated or non-conjugated gen has better weather resistance than the ethylene / ⁇ -olefin copolymer rubber containing no conjugated or non-conjugated gen. Inferior and not preferred.
  • the present invention does not exclude an ethylene / ⁇ -olefin copolymer rubber containing a conjugated or non-conjugated diene, but does not exclude an ethylene / ⁇ -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.
  • the thermoplastic resin is a polyolefin resin
  • 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 / ⁇ -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.
  • 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%.
  • the rubbery polymer which is a preferable component in the molded article of the present invention When 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 1.2 ⁇ .
  • 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
  • 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.
  • the shapes are slightly different between the surface layer and the inside of the molded product, and between the gate and the terminal.
  • 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 ⁇ m, the effect of improving mechanical strength is not sufficient. On the other hand, when the thickness is 1.5 ⁇ m or more, the effect of improving mechanical strength is not sufficient.
  • 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.
  • thermoplastic resin in the thermoplastic resin molded article of the present invention will be described.
  • 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.
  • polyethylene resins examples 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.
  • 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.
  • 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.
  • LDP E low density polyethylene
  • LLDPE linear low density polyethylene
  • 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.
  • 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.
  • the flowability is poor and the molding processability is undesirably reduced.
  • polypropylene resin examples include polypropylene (homopolymer) and copolymer resin (block, random copolymer) of propylene and other ⁇ -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.
  • a polypropylene resin is more preferable because of its high heat resistance.
  • polypropylene resins are more preferable.
  • polypropylene homopolymers are generally susceptible to oxidative degradation, and their mechanical strength tends to decrease due to molecular weight reduction during long-term use.
  • 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.
  • thermoplastic resin in the thermoplastic resin molded article of the present invention has a high affinity for an ethylene- ⁇ -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.
  • the compatibility with the ethylene-polyolefin copolymer rubber preferably used as the rubber-like polymer is often not necessarily good.
  • a compatibilizer is used.
  • 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.
  • the polystyrene resin include hydrogenated styrene-butadiene block resin and styrene-grafted polyethylene.
  • 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.
  • a copolymer of maleic acid-modified polyolefin or maleic acid is used as a material for improving the interfacial adhesion between the glass fiber and the thermoplastic resin as a matrix.
  • a copolymer of maleic acid-modified polyolefin or maleic acid is used as a material for improving the interfacial adhesion between the glass fiber and the thermoplastic resin as a matrix.
  • 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.
  • a process oil such as a paraffinic or naphthenic oil can be used.
  • a softener When a softener is present, the stiffness tends to decrease slightly, but it has the effect of further improving the impact resistance.
  • the softening agent has the effect of improving the whitening.
  • the powdery inorganic filler examples include talc, myric, clay, calcium carbonate, magnesium carbonate, silica, carbon black, titanium oxide, magnesium hydroxide, magnesium hydroxide, aluminum hydroxide, and the like.
  • 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.
  • talc 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.
  • talc 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. .
  • plasticizer examples include phthalate esters such as polyethylene glycol and octyl phthalate (DOP).
  • phthalate esters such as polyethylene glycol and octyl phthalate (DOP).
  • 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.
  • thermoplastic resin molded article of the present invention 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 is a thermoplastic resin that coats the glass fiber.
  • 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 polyolefin resin as the thermoplastic resin.
  • an ethylene / ⁇ -olefin copolymer mainly composed of ethylene and ⁇ -olefin and a polymer having a structure similar to ⁇ or a similar polymer, a polyolefin resin, a cross-linking agent and a cross-linking aid are used in a twin-screw extruder.
  • the crosslinking agent preferably used includes a radical initiator such as an organic peroxide and an organic azo compound.
  • radical initiator examples 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.
  • 1,1-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.
  • 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. .
  • 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.
  • 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.
  • the emulsion be the same as or compatible with the thermoplastic resin as the matrix.
  • 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.
  • thermoplastic resin is polyacrylonitrile-styrene resin (AS), polyacrylonitrile-butadiene-styrene resin (ABS), polycarbonate resin (PC), polyester resin (PET, PBT, etc.)
  • AS polyacrylonitrile-styrene resin
  • ABS polyacrylonitrile-butadiene-styrene resin
  • PC polycarbonate resin
  • PET polyester resin
  • PBT PBT, etc.
  • 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.
  • 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.
  • 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 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.
  • the measurement was performed at 23 ° C. by a method according to JISK 6251.
  • the measurement was performed at 23 ° C according to a method according to JIS K 6758.
  • the measurement was performed at 23 ° C according to a method according to JIS K6758.
  • the molded product was fired, and the distribution of fiber length was measured by image analysis using an optical microscope.
  • 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.
  • 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.
  • TPE-1 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)
  • Admar (HB030) (M-PE) manufactured by Mitsui Chemicals, Inc. (f) High density polyethylene
  • PET Ground PET bottle
  • Aminosilane treated glass fiber roving (ER 740) manufactured by Asahi Fiber Co., Ltd. (thickness: 13 ⁇ m)
  • 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%.
  • 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%.
  • 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%.
  • 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%.
  • 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%.
  • 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)
  • 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%.
  • a roving of 13 ⁇ 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
  • Example 1 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.
  • 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.
  • 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.
  • 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.
  • the surface appearance was extremely poor due to unevenness due to the aggregation of glass fibers.
  • the appearance of the molded product obtained in Example 2 was good. Table 1 shows the composition of the molded article and its properties.
  • 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.
  • 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.
  • 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 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 13 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.
  • Example 2 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.
  • TPV-1 was changed to TPV-6 to obtain a molded article.
  • 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)
  • Table 3 shows the composition of the molded article and its properties.
  • AS emulsion (acrylonitrile-styrene latex; acrylonitrile 25%, solids concentration 50% by weight) while rubbing glass fiber roving of 13 ⁇ 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 shows the composition of the molded article and its properties.
  • Example 2 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.
  • 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.

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Abstract

L'invention concerne un article formé de résine thermoplastique comprenant une fibre de verre ainsi qu'une résine thermoplastique, cette fibre de verre étant comprise dans une proportion de 1 à 60 % en poids et constituée de 90 à 10 % par une fibre de verre présentant une longueur égale ou inférieure à 0,5 mm, de 10 à 90 % par une fibre de verre présentant une longueur de 0,5 à 2 mm, et de 0 à 30 % par une fibre de verre présentant une longueur supérieure ou égale à 2 mm.
PCT/JP2000/000794 2000-02-14 2000-02-14 Article forme de resine thermoplastique presentant une rigidite et une resistance elevees WO2001059009A1 (fr)

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Application Number Priority Date Filing Date Title
CNB008061831A CN1175052C (zh) 2000-02-14 2000-02-14 高劲度高强度的热塑性树脂模制品
PCT/JP2000/000794 WO2001059009A1 (fr) 2000-02-14 2000-02-14 Article forme de resine thermoplastique presentant une rigidite et une resistance elevees
DE10084451T DE10084451T1 (de) 2000-02-14 2000-02-14 Formkörper aus thermoplastischem Harz mit hoher Steifigkeit und hoher Festigkeit

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005036521A1 (fr) * 2003-10-14 2005-04-21 Kabushiki Kaisha Kawai Gakki Seisakusho Levier superieur de piano a queue
JP2005255733A (ja) * 2004-03-09 2005-09-22 Asahi Kasei Chemicals Corp 自動車アンダーフード構造部成形品
JP2008202013A (ja) * 2007-02-23 2008-09-04 Daicel Polymer Ltd 自動車用樹脂外装部品
JP2009185150A (ja) * 2008-02-05 2009-08-20 Idemitsu Kosan Co Ltd 伝熱性樹脂組成物及びその樹脂成形体
KR101476286B1 (ko) * 2013-03-26 2014-12-24 동국실업 주식회사 폴리프로필렌 수지 조성물
US20150259511A1 (en) * 2013-09-27 2015-09-17 Sumitomo Riko Company Limited Glass-fiber-reinforced thermoplastic resin molding product, and production method therefor
JP2015203049A (ja) * 2014-04-11 2015-11-16 テクノポリマー株式会社 鏡胴用筒状体及び鏡胴
WO2016152560A1 (fr) * 2015-03-26 2016-09-29 住友理工株式会社 Article moulé en résine thermoplastique renforcée par fibres de verre et son procédé de fabrication
US10472475B2 (en) 2017-03-31 2019-11-12 Sumitomo Riko Company Limited Method of producing glass-fiber-reinforced thermoplastic resin molded object and glass-fiber-reinforced thermoplastic resin molded object obtained by the method
WO2020091051A1 (fr) * 2018-11-02 2020-05-07 株式会社プライムポリマー Composition de résine à base de propylène renforcée de fibres longues et corps moulé renforcé de fibres longues

Families Citing this family (4)

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CN104672625B (zh) * 2013-11-29 2018-09-21 住友化学株式会社 树脂组合物
KR20170006683A (ko) * 2015-07-09 2017-01-18 한국파렛트풀주식회사 재생재를 포함하는 2종 이상의 혼합 수지, 유리장섬유 및 올레핀계 고무수지를 포함하는 조성물
WO2016013819A1 (fr) * 2014-07-25 2016-01-28 한국컨테이너풀 주식회사 Composition comprenant au moins deux résines, des fibres de verre et une résine de caoutchouc à base d'oléfine
CN112266615A (zh) * 2020-11-19 2021-01-26 南京特塑复合材料有限公司 一种高尺寸稳定性聚苯硫醚复合材料制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0234665A (ja) * 1988-07-22 1990-02-05 Tokai Rubber Ind Ltd 導電性樹脂組成物
JPH0292952A (ja) * 1988-09-29 1990-04-03 Unitika Ltd フエノール樹脂成形材料組成物
EP0446752A1 (fr) * 1990-03-13 1991-09-18 Mitsubishi Petrochemical Co., Ltd. Composition de résine de polypropylène pour moulage par soufflage
WO1998021281A1 (fr) * 1996-11-14 1998-05-22 Kawasaki Steel Corporation Moulage en resine thermoplastique electroconductrice armee de fibre de verre longue et procede d'elaboration
JPH10219027A (ja) * 1997-02-06 1998-08-18 Nitto Boseki Co Ltd ガラス繊維パウダ−強化樹脂組成物
JPH10298364A (ja) * 1997-04-24 1998-11-10 Calp Corp 強化ポリオレフィン系樹脂組成物及びそれからなる成形品
JPH11129246A (ja) * 1997-10-28 1999-05-18 Idemitsu Petrochem Co Ltd ガラス繊維強化熱可塑性樹脂ペレット

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0234665A (ja) * 1988-07-22 1990-02-05 Tokai Rubber Ind Ltd 導電性樹脂組成物
JPH0292952A (ja) * 1988-09-29 1990-04-03 Unitika Ltd フエノール樹脂成形材料組成物
EP0446752A1 (fr) * 1990-03-13 1991-09-18 Mitsubishi Petrochemical Co., Ltd. Composition de résine de polypropylène pour moulage par soufflage
WO1998021281A1 (fr) * 1996-11-14 1998-05-22 Kawasaki Steel Corporation Moulage en resine thermoplastique electroconductrice armee de fibre de verre longue et procede d'elaboration
JPH10219027A (ja) * 1997-02-06 1998-08-18 Nitto Boseki Co Ltd ガラス繊維パウダ−強化樹脂組成物
JPH10298364A (ja) * 1997-04-24 1998-11-10 Calp Corp 強化ポリオレフィン系樹脂組成物及びそれからなる成形品
JPH11129246A (ja) * 1997-10-28 1999-05-18 Idemitsu Petrochem Co Ltd ガラス繊維強化熱可塑性樹脂ペレット

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7678977B2 (en) 2003-10-14 2010-03-16 Kabushiki Kaisha Kawai Gakki Seisakusho Repetition lever of grand piano
WO2005036521A1 (fr) * 2003-10-14 2005-04-21 Kabushiki Kaisha Kawai Gakki Seisakusho Levier superieur de piano a queue
JP2005255733A (ja) * 2004-03-09 2005-09-22 Asahi Kasei Chemicals Corp 自動車アンダーフード構造部成形品
JP2008202013A (ja) * 2007-02-23 2008-09-04 Daicel Polymer Ltd 自動車用樹脂外装部品
JP2009185150A (ja) * 2008-02-05 2009-08-20 Idemitsu Kosan Co Ltd 伝熱性樹脂組成物及びその樹脂成形体
KR101476286B1 (ko) * 2013-03-26 2014-12-24 동국실업 주식회사 폴리프로필렌 수지 조성물
US10351693B2 (en) 2013-09-27 2019-07-16 Sumitomo Riko Company Limited Glass-fiber-reinforced thermoplastic resin molding product, and production method therefor
US20150259511A1 (en) * 2013-09-27 2015-09-17 Sumitomo Riko Company Limited Glass-fiber-reinforced thermoplastic resin molding product, and production method therefor
JP2015203049A (ja) * 2014-04-11 2015-11-16 テクノポリマー株式会社 鏡胴用筒状体及び鏡胴
WO2016152560A1 (fr) * 2015-03-26 2016-09-29 住友理工株式会社 Article moulé en résine thermoplastique renforcée par fibres de verre et son procédé de fabrication
CN106661241A (zh) * 2015-03-26 2017-05-10 住友理工株式会社 玻璃纤维强化热塑性树脂成型体和其制法
CN106661241B (zh) * 2015-03-26 2018-01-02 住友理工株式会社 玻璃纤维强化热塑性树脂成型体和其制法
US10279517B2 (en) 2015-03-26 2019-05-07 Sumitomo Riko Company Limited Glass-fiber-reinforced thermoplastic resin molding product, and production method therefor
JP2016183297A (ja) * 2015-03-26 2016-10-20 住友理工株式会社 ガラス繊維強化熱可塑性樹脂成形体およびその製法
US10472475B2 (en) 2017-03-31 2019-11-12 Sumitomo Riko Company Limited Method of producing glass-fiber-reinforced thermoplastic resin molded object and glass-fiber-reinforced thermoplastic resin molded object obtained by the method
WO2020091051A1 (fr) * 2018-11-02 2020-05-07 株式会社プライムポリマー Composition de résine à base de propylène renforcée de fibres longues et corps moulé renforcé de fibres longues

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