JP5339577B2 - Long fiber reinforced resin pellets - Google Patents

Abstract

Disclosed is a resin pellet reinforced with a long-fiber filler. The pellet comprises a long-fiber filler and a thermoplastic resin mixture, wherein the long-fiber filler is arranged in the pellet spirally around the lengthwise direction of the pellet (the direction of the center axis). The pellet has a skin layer having a small long-fiber filler content and a core having a large long-fiber filler content. The cross-sectional area of the core accounts for 30 to 70% of the cross-sectional area of the pellet. The thermoplastic resin mixture comprises a polyphenylene ether and a thermoplastic resin other than the polyphenylene ether.

Description

  The present invention relates to a long fiber filler reinforced resin pellet. The present invention also relates to a resin pellet mixture containing long fiber filler reinforced resin pellets, a molded product obtained by melt-molding long fiber filler reinforced resin pellets, a method for producing long fiber filler reinforced resin pellets, and the like.

  Thermoplastic resins have excellent formability and are widely used in automobiles, machinery, building materials, housing equipment parts, and the like. In particular, a reinforced thermoplastic resin composition blended with glass fiber is very useful for substituting a metal material and reducing the weight of components and the number of components because of its excellent mechanical properties and moldability. In addition, since the reinforced thermoplastic resin composition has excellent impact resistance (particularly surface impact resistance) and rigidity, it is widely used for members that are heavily loaded, members that are repeatedly loaded, and the like.

In Patent Document 1, as a means for achieving a long fiber filler reinforcing composition, pellets having the same reinforcing fiber length and pellet length are obtained by impregnating the resin while drawing the resin strand from the glass fiber roving. A pultrusion method is disclosed as a production method. This method is the most commonly used method to date.
However, the long fiber reinforced resin composition has a shorter contact time between the resin and the fiber than a normal short fiber reinforced resin composition in which short fibers such as chopped strands are melt-kneaded with an extruder. There is a problem in wettability, and studies have been made to improve it.

For example, Patent Document 2 discloses that a thermoplastic resin having a considerably low melt viscosity is selected and used as one of the methods by which a continuous aligned filament can be wetted with a thermoplastic resin satisfactorily.
Further, Patent Document 3 discloses a technique for improving the flexibility and buckling resistance of a strand by twisting the long fiber strand, and Patent Document 4 is excellent by applying twist similarly. There is a disclosure of a manufacturing method having high productivity.

Japanese Patent Publication No.52-3985 Japanese Patent Publication No.63-37694 JP-A-5-169445 JP 2003-175512 A

However, in the technique disclosed in Patent Document 2, the interfacial strength between the resin and the fiber is not sufficient, and the resulting pellet causes vertical cracking during transportation, or the long fiber filler is detached from the pellet, and the detached long fiber The phenomenon that the filler adheres to, for example, a product bag or a molding machine hopper has occurred, and improvement has been demanded from the market. Further, since the interfacial strength between the resin and the fiber is not sufficient and the surface of the pellet is not glossy, there is a problem that the friction resistance between the pellets is increased and a biting failure into the molding machine occurs.
In addition, when a strong twist is applied based on the techniques disclosed in Patent Documents 3 and 4, when processing with a molding machine or the like, for example, when polypropylene or polyamide is used as a resin, the melt viscosity is There is a problem in that the applied long fibers cannot be sufficiently defibrated and the development of characteristics such as high heat resistance and impact resistance is insufficient.

  In the present invention, the long fiber filler and the thermoplastic resin have excellent wettability, and vertical cracking during pellet transportation and detachment of the long fiber filler from the pellet are extremely suppressed, and the appearance of the pellet is improved. An object of the present invention is to provide a long fiber filler reinforced resin pellet capable of forming a molded article having extremely high heat resistance and impact resistance because it is excellent and further has excellent fibrillation properties during molding. .

As a result of intensive studies to solve the above problems, the present inventors have arranged the long fiber filler in the long fiber filler reinforced resin pellet in a spiral shape in the pellet with the length direction of the pellet as the central axis direction. As a result, it was found that the above problems could be solved, and the present invention was completed.
That is, the present invention is as follows.

(1) A pellet composed of a long fiber filler and a thermoplastic resin mixture,
The long fiber filler is disposed in the pellet in a spiral shape with the length direction of the pellet as the central axis direction in the pellet, and the spiral lead is 20 mm to 80 mm ,
The pellet has a skin layer portion with a low long fiber filler content and a core portion with a high long fiber filler content, and is cut in the thickness direction of the pellet with a microtome to form a smooth cross section, using an optical microscope The cross-sectional area of the core part obtained by observing, photographing with reflected light, and calculating by image analysis is in the range of 30% to 70% of the cross-sectional area of the pellet,
Long fiber filler reinforced resin pellets, wherein the thermoplastic resin mixture comprises polyphenylene ether and a thermoplastic resin other than polyphenylene ether.
(2) The long fiber filler reinforced resin pellet according to 1 above, wherein a ratio of an average fiber length of the long fiber filler to a length of the long fiber filler reinforced resin pellet exceeds 1.0.
(3) The long fiber filler reinforced resin pellet according to 1 or 2 above, wherein a ratio of the long fiber filler in the long fiber filler reinforced resin pellet is 30 to 70% by mass.
(4) The long fiber filler reinforced resin pellet according to any one of the above 1 to 3, wherein the long fiber filler is a glass fiber.
(5) The reduced viscosity (0.5 g / dl concentration chloroform solution at 30 ° C.) of the polyphenylene ether is in the range of 0.30 to 0.55 dl / g, The long fiber filler reinforced resin pellet as described.
(6) The polyphenylene ether is a copolymer containing 2,3,6-trimethylphenol, and the proportion of 2,3,6-trimethylphenol units in the polyphenylene ether is 10 to 30% by mass. 6. The long fiber filler reinforced resin pellet according to any one of 1 to 5 above.
(7) The thermoplastic resin other than the polyphenylene ether is selected from the group consisting of styrene resin, olefin resin, polyester, polyamide, polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone, polysulfone and polyarylketone. The long fiber filler reinforced resin pellet according to any one of 1 to 6 above, which is one or more selected.
(8) The thermoplastic resin other than the polyphenylene ether is at least one selected from the group consisting of homopolystyrene, rubber-modified polystyrene, acrylonitrile-styrene copolymer, and a copolymer of N-phenylmaleimide and styrene. The long fiber filler reinforced resin pellet of any one of 1-7.
(9) The long fiber filler reinforced resin pellet as described in 8 above, wherein the proportion of polyphenylene ether in the thermoplastic resin mixture is 10 to 90% by mass.
(10) The thermoplastic resin other than the polyphenylene ether is one or more selected from the group consisting of polypropylene, liquid crystal polyester, polyamide, polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone, polysulfone and polyarylketone. The long fiber filler reinforced resin pellet according to any one of 1 to 7 above.
(11) The long fiber filler reinforced resin pellet as described in 10 above, wherein the proportion of polyphenylene ether in the thermoplastic resin mixture is 1 to 50% by mass.
(12) The long fiber filler reinforced resin pellet according to any one of the above 1 to 11, further comprising a compatibilizing agent.
(13) The long fiber as described in 12 above, wherein the compatibilizer is a compound having one or more functional groups selected from the group consisting of an epoxy group, an oxazolyl group, an imide group, a carboxylic acid group, and an acid anhydride group. Filler reinforced resin pellet.
(14) The long fiber filler reinforced resin pellet according to any one of 1 to 13 above, further containing 0.1 to 5 parts by mass of a sterically hindered phenol-based antioxidant with respect to 100 parts by mass of the thermoplastic resin mixture. .
(15) The long fiber filler reinforced resin pellet according to any one of 1 to 14, further comprising 5 to 50 parts by mass of a halogen-free flame retardant with respect to 100 parts by mass of the thermoplastic resin mixture.
(16) The long fiber filler reinforced resin pellet according to any one of the above 1 to 15, further comprising a filler other than the long fiber filler.
(17) A resin pellet mixture containing 100 parts by mass of the long fiber filler reinforced resin pellets according to any one of 1 to 16 above and 0.5 to 150 parts by mass of resin pellets not including the long fiber filler.
(18) The resin pellet mixture according to 17 above, wherein the ratio of the long fiber filler in the resin pellet mixture is 10 to 60% by mass. (19) The resin pellet not including the long fiber filler is a long fiber. 19. The resin pellet mixture as described in 17 or 18 above, which contains a filler other than the filler.
(20) The filler other than the long fiber filler is an hydroxide of an element selected from magnesium and calcium, an oxide of an element selected from the group consisting of magnesium, titanium, iron, copper, zinc, and aluminum, zinc sulfide, and boron. It is at least one filler selected from the group consisting of zinc acid, calcium carbonate, talc, wollastonite, glass, carbon black, carbon nanotubes and silica, and the average particle diameter of fillers other than the long fiber filler is 1 mm. 20. The resin pellet mixture as described in 19 above, which is:
( 21 ) A pellet composed of a long fiber filler and a thermoplastic resin mixture,
The long fiber filler is disposed in the pellet in a spiral shape with the length direction of the pellet as the central axis direction in the pellet, and the spiral lead is 20 mm to 80 mm ,
The pellet has a skin layer portion with a low long fiber filler content and a core portion with a high long fiber filler content, and is cut in the thickness direction of the pellet with a microtome to form a smooth cross section, using an optical microscope The cross-sectional area of the core part obtained by observing, photographing with reflected light, and calculating by image analysis is in the range of 30% to 70% of the cross-sectional area of the pellet,
The thermoplastic resin mixture is made of polyphenylene ether and a thermoplastic resin other than polyphenylene ether, and is a method for producing long fiber filler reinforced resin pellets,
(1) A step of producing the molten thermoplastic resin mixture using an extruder,
(2) a step of impregnating the long fiber filler into the molten thermoplastic mixture;
(3) A process of taking a twisted strand to form a resin strand,
(4) A step of cutting the resin strand into a pellet shape,
A method for producing a long fiber filler reinforced resin pellet.
( 22 ) It is a manufacturing method of the long fiber filler reinforced resin pellet as described in said ( 21 ), Comprising: Here, the length as described in said ( 21 ) including process (1)-(4) continuously in this order Manufacturing method of fiber filler reinforced resin pellet.
(23) in the step (1), and the polyphenylene ether, further comprising a polyphenylene thermoplastic resin other than ether, the step of mixing to the production of the thermoplastic resin mixture in a molten state, above (21) or The manufacturing method of the long fiber filler reinforced resin pellet as described in ( 22 ).
( 24 ) The set temperature of the immersion bath for impregnating the long fiber filler in the molten state in the thermoplastic resin mixture in the step (2) is 20 ° C or higher than the set temperature of the extruder in the step (1). The manufacturing method of the long fiber filler reinforced resin pellet of any one of ( 21 )-( 23 ) which is high temperature.
( 25 ) The method for producing a long fiber filler reinforced resin pellet according to any one of ( 21 ) to ( 24 ), wherein the take-up speed in the step (3) is in the range of 10 to 150 m / min.

  According to the present invention, the long fiber filler and the thermoplastic resin have excellent wettability, and vertical cracks during pellet transportation and detachment of the long fiber filler from the pellet are extremely suppressed, and the pellet It is possible to provide a long fiber filler reinforced resin pellet capable of molding a molded article having extremely high heat resistance and impact resistance because it has an excellent appearance and also has excellent fibrillation properties during molding. it can.

Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
The long fiber filler reinforced resin pellet of the present embodiment (hereinafter sometimes simply referred to as “pellet”) is composed of a long fiber filler and a thermoplastic resin composition containing a thermoplastic resin mixture. Pellet.
The long fiber filler is arranged in the pellet in a spiral shape with the length direction of the pellet as the central axis direction, the spiral lead is 20 mm to 80 mm, and the pellet is a skin with a low long fiber filler content. It has a layer part and a core part with much long fiber filler content, The cross-sectional area of this core part is the range of 30 to 70% of this pellet cross-sectional area.
The thermoplastic resin mixture (hereinafter sometimes simply referred to as “resin”) is composed of polyphenylene ether and a thermoplastic resin other than polyphenylene ether.

(Long fiber filler)
In the present embodiment, the long fiber filler used in the long fiber filler reinforced resin pellet is arranged in a spiral shape with the length direction of the pellet as the central axis direction in the pellet, and the spiral lead is 20 mm to 80 mm. And the pellet has a skin layer portion having a low long fiber filler content and a core portion having a high long fiber filler content, and the cross-sectional area of the core portion is 30 to 70% of the cross-sectional area of the pellet. It is a range.

In the present embodiment, the long fiber filler is arranged in a spiral shape in the pellet with the length direction of the pellet as the central axis, and the length direction of the pellet means the extension direction of the long fiber filler And when the pellet shape is a cylindrical pellet, it means its height direction.
In the present embodiment, being arranged in a spiral means that the long fiber filler is present in the pellet in a twisted state.
In the present embodiment, the long fiber filler is disposed in the pellet in a spiral shape with the length direction of the pellet as the central axis direction, thereby causing vertical cracks during pellet transportation and from the pellet of the long fiber filler. Desorption can be suppressed.

In the present embodiment, the long fiber filler is present as a bundle of fibers in the pellet in a spiral shape, thereby suppressing the detachment of the long fiber filler from the pellet and making the pellet excellent in the appearance of the pellet. it can. In the pellet, the bundle of long fiber filler fibers is more preferably a single bundle.
In the present embodiment, the fact that the long fiber filler is not arranged in a spiral means that the long fiber filler is not present in a twisted state but in a pellet, and is arranged in a spiral. Examples of the non-pellet include the pellets disclosed in Patent Document 1 and Patent Document 2.

In the present embodiment, the spiral lead has the same meaning as the lead used in the screw. Specifically, when the long fiber filler arranged in a spiral shape makes one rotation (360 °) around the outer periphery of the strand. This means the distance in the length direction of the surface of the traveling strand.
In this embodiment, since the spiral lead is 20 mm or more, it is possible to prevent the resin and the long fiber filler from being peeled at the interface, thereby deteriorating the appearance of the pellet and degrading the defibration during molding. can do. Further, when the spiral lead is 80 mm or less, it is possible to suppress vertical cracking during pellet transportation, detachment of the long fiber filler from the pellet, and poor biting into the molding machine during molding.

  In the present embodiment, the spiral lead is preferably 25 mm or more, more preferably 27 mm or more, and further preferably 30 mm or more. The spiral lead is preferably 75 mm or less, more preferably 60 mm or less, and even more preferably 55 mm or less.

In the present embodiment, the pellet has a skin layer portion with a low long fiber filler content and a core portion with a high long fiber filler content, and the cross-sectional area of the core portion is 30 to 70 of the pellet cross-sectional area. % Range.
The skin layer portion with a low long fiber filler content is a continuous region from the surface of the pellet made of resin, and the long fiber filler filled is filled with the entire length of the pellet. When the filling amount of the filler is less than half of the filler, for example, when the filling amount of the long fiber filler in the pellet is 40% by mass, it means a region where the filling amount of the long fiber filler is less than 20% by mass. In the present embodiment, the long fiber filler exists in a twisted state even in a region that is less than half the amount of the long fiber filler in the pellet. The region surrounded by the region having the long fiber filler corresponding to (i.e., the region not continuous from the pellet surface) is taken as the core portion and excluded from the skin layer portion.
In the present embodiment, the core portion having a high long fiber filler content means a portion excluding the skin layer portion having a low long fiber filler content in the cross-sectional area of the pellet. In this embodiment, since the long fiber filler is arranged in the pellet in a twisted state, the long fiber filler exists in an aggregated form in the pellet. The skin layer portion and the core portion can be easily distinguished.

In the present embodiment, when the cross-sectional area of the core part is 30 to 70% of the cross-sectional area of the pellet, it is possible to greatly improve the appearance of the pellet, and the effect of improving the biting into the molding machine is achieved. Can be obtained. Moreover, it is possible to obtain a glossy appearance as the pellet appearance, and it is possible to obtain a pellet having a high-grade appearance.
In the present embodiment, the cross-sectional area of the core portion is preferably 35% or more of the pellet cross-sectional area, more preferably 40% or more, and further preferably 45% or more. The cross-sectional area of the core portion is preferably 65% or less of the pellet cross-sectional area, and more preferably 60% or less.
In the present embodiment, the cross-sectional area of the core portion is measured as an average value of the cross-sectional area of the core portion by observing at least 10 cross-sections of the pellet as described in the examples described in detail below. Can do.

  In the present embodiment, the length (fiber length) of the long fiber filler is a molded body obtained by melt molding a long fiber filler reinforced resin pellet or the like (hereinafter sometimes simply referred to as “molded body”). In order to sufficiently increase the heat resistance and impact resistance, the thickness is preferably 3 mm or more, more preferably 4 mm or more, and further preferably 5 mm or more. In addition, the length of the long fiber filler is preferably 50 mm or less, more preferably 30 mm or less, and further preferably 20 mm or less from the viewpoint of handleability in molding or the like.

In the present embodiment, the fiber length of the long fiber filler is excellent in appearance, and in order to obtain a pellet with less vertical cracks, the fiber of the long fiber filler that is included is included rather than the length of the pellet containing the long fiber filler. It is preferable that the length is long, and it is more preferable that the ratio of the average fiber length of the long fiber filler to the length of the pellet exceeds 1.0.
The ratio of the average fiber length of the long fiber filler to the length of the pellet is more preferably in the range of 1.01 to 1.2, still more preferably 1.02 or more, and 1.03 or more. It is particularly preferred. The ratio of the average fiber length of the long fiber filler to the length of the pellet is more preferably 1.15 or less, still more preferably 1.1 or less, and particularly preferably 1.08 or less. preferable.
In this Embodiment, the length of a pellet means the length of the length direction of a pellet, for example, in the case of a cylindrical pellet, it means the height.

In this Embodiment, it is preferable that content of the long fiber filler in a pellet is 30-70 mass%.
By setting the content of the long fiber filler in the pellet to 30% by mass or more, the take-up property at the time of producing the pellet can be improved, and the viscosity of the strand at the time of producing the pellet can be maintained at an appropriate viscosity. Further, by setting the content of the long fiber filler in the pellet to 70% by mass or less, the penetration of the resin into the long fiber filler can be improved and the wettability can be improved. The speed can be controlled well.
The content of the long fiber filler in the pellet is more preferably 40% by mass or more, and further preferably 45% by mass or more. Further, the content of the long fiber filler in the pellet is more preferably 60% by mass or less, and further preferably 55% by mass or less.

In the present embodiment, the long fiber filler used in the long fiber filler reinforced resin pellet is, for example, one or more long fiber fillers selected from the group consisting of carbon fiber, glass fiber, metal fiber, aramid fiber, and the like. Is mentioned.
In the present embodiment, the long fiber filler is preferably at least one selected from carbon fibers and glass fibers from the viewpoint of increasing the strength and rigidity of the molded body composed of the long fiber reinforced pellets of the present embodiment. More preferably, it is a glass fiber.

  In the present embodiment, the diameter of the long fiber filler is not particularly limited, but is preferably 5 μm or more, more preferably 8 μm or more, and further preferably 10 μm or more. Moreover, it is preferable that the diameter of a long fiber filler is 25 micrometers or less, It is more preferable that it is 20 micrometers or less, It is further more preferable that it is 17 micrometers or less.

In the present embodiment, for the purpose of improving the wettability of the resin and improving the handleability, the surface of the long fiber filler may be appropriately attached with a coupling agent or a sizing agent.
Examples of the coupling agent include amino-based, epoxy-based, chloro-based, mercapto-based, and cationic-based silane coupling agents, and amino-based silane coupling agents can be suitably used.

Examples of the sizing agent include a sizing agent containing at least one selected from maleic anhydride compounds, urethane compounds, acrylic compounds, epoxy compounds, and copolymers of these compounds, and urethane compounds. A sizing agent containing can be preferably used.
The content of the sizing agent in the long fiber filler is preferably 0.1 to 0.5% by mass. By attaching the sizing agent content to 0.1% by mass or more and adhering to the surface of the long fiber filler, the vertical cracking of the pellet can be prevented, and the sizing agent content being 0.5% by mass or less By adhering to the surface of the filler, in the step of impregnating the long fiber filler into the resin, the fibrillation property of the long fiber filler is not impaired, so that deterioration in productivity can be suppressed. Content of sizing agent Is more preferably 0.15% by mass or more, further preferably 0.2% by mass, and still more preferably 0.25% by mass or more. Further, the content of the sizing agent is more preferably 0.45% by mass or less, further preferably 0.4% by mass or less, and further preferably 0.35% by mass or less.

(Thermoplastic resin mixture)
In the present embodiment, the thermoplastic resin mixture used for the long fiber filler reinforced resin pellets is composed of polyphenylene ether and a thermoplastic resin other than polyphenylene ether.
(Polyphenylene ether)
In the present embodiment, polyphenylene ether is present in the thermoplastic resin mixture, so that the melt viscosity in the resin is appropriately improved, and the twisted long fiber filler is very easily defibrated at the time of molding. Is possible.
By increasing the fibrillation property of the long fiber filler at the time of molding, it becomes possible to maximize the strength and rigidity of the resin molded body, that is, the characteristics by blending the long fiber filler.
In the present embodiment, the polyphenylene ether is a homopolymer and / or copolymer having a repeating structural unit represented by the following formula (1).

(Wherein O is an oxygen atom, R _{1 to} R ₄ are each independently hydrogen, halogen, primary or secondary C1-C7 alkyl group, phenyl group, C1-C7 haloalkyl group, C1-C7. Represents an aminoalkyl group, a C1-C7 hydrocarbyloxy group, or a halohydrocarbyloxy group (provided that at least two carbon atoms separate the halogen atom from the oxygen atom).

  In this Embodiment, the manufacturing method of polyphenylene ether will not be specifically limited if it is a well-known method. For example, U.S. Pat. No. 3,306,874, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-A-50-51197, JP-B-52-17880. And a manufacturing method disclosed in Japanese Patent Publication No. 63-152628.

Examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6-phenyl). -1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like.
Examples of the copolymer of polyphenylene ether include copolymers of 2,6-dimethylphenol and other phenols, such as copolymers of 2,3,6-trimethylphenol and 2-methyl. And a copolymer with -6-butylphenol.

  As polyphenylene ether, from the viewpoint of commercial availability, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol A coalescence or a mixture thereof is preferred. Further, when using a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, the ratio of each monomer unit is 10 to 30% by mass of 2,30% by weight in the polyphenylene ether copolymer. A copolymer containing 3,6-trimethylphenol as a structural unit is preferable, more preferably 15 to 25% by mass, and still more preferably 20 to 25% by mass.

In this embodiment, the reduced viscosity of polyphenylene ether (ηsp / c: dl / g, 0.5 g / dl concentration chloroform solution, measured at 30 ° C.) is in the range of 0.30 to 0.55 dl / g. Is preferred. The reduced viscosity of the polyphenylene ether is more preferably 0.53 dl / g or less, further preferably 0.45 dl / g or less, and further preferably 0.36 dl / g or less.
When the reduced viscosity of the polyphenylene ether is 0.30 dl / g or more, it is possible to obtain pellets that are excellent in the defibration properties of the long fiber filler at the time of molding, and when the reduced viscosity is 0.55 dl / g or less, Can be improved.

In the present embodiment, a mixture of two or more polyphenylene ethers having different reduced viscosities can be used without particular limitation. For example, a mixture of a polyphenylene ether having a reduced viscosity of about 0.40 dl / g and a polyphenylene ether having a reduced viscosity of about 0.50 dl / g, a low molecular weight polyphenylene ether having a reduced viscosity of about 0.08 to 0.12 dl / g, and a reduced viscosity. Examples thereof include a mixture with polyphenylene ether of about 0.50 dl / g.
When a mixture of two or more polyphenylene ethers having different reduced viscosities is used, the reduced viscosity of the mixed polyphenylene ether is preferably in the range of 0.30 to 0.55 dl / g.

In the present embodiment, the polyphenylene ether may be one modified with a modifier, and examples of the modifier include saturated or saturated maleic anhydride, N-phenylmaleimide, malic acid, citric acid, fumaric acid, and the like. Examples include unsaturated dicarboxylic acids and derivatives thereof, vinyl compounds such as styrene, acrylic acid esters, and methacrylic acid esters.
In this case, it may be modified in advance, and a modifier may be added at the same time when a resin is produced by melt extrusion.
In the case of using a modified polyphenylene ether as the polyphenylene ether, it may be modified in advance, or it may be modified at the same time by adding a modifier when the resin is produced by melt extrusion.

(Thermoplastic resin other than polyphenylene ether)
The thermoplastic resin other than polyphenylene ether is not particularly limited. For example, styrene resin, olefin resin, polyester, polyamide, polyphenylene sulfide, polyarylate, polyetherimide, polyethersulfone, polysulfone, Examples thereof include at least one selected from the group consisting of polyaryl ketones and mixtures thereof.

  The thermoplastic resin other than polyphenylene ether is preferably polypropylene, liquid crystal polyester, polyamide, polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone, polysulfone, polyarylketone, homopolystyrene, rubber-modified polystyrene, acrylonitrile. -At least 1 sort (s) chosen from the group which consists of a styrene copolymer, a copolymer of N-phenylmaleimide and styrene, and these mixtures is mentioned.

As thermoplastic resins other than polyphenylene ether, olefin-based resins such as polypropylene, which are thermoplastic resins having relatively low affinity with polyphenylene ether, polyesters such as liquid crystal polyester, polyamide, polyarylene sulfide, polyarylate, polyetherimide, poly When using 1 type chosen from the group which consists of ether sulfone, polysulfone, polyaryl ketone, and these mixtures, it is preferable that content of polyphenylene ether in resin is the range of 1-50 mass%. The content of polyphenylene ether in the resin is more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 15% by mass. Further, the content of polyphenylene ether in the resin is more preferably 45% by mass or less, further preferably 40% by mass or less, and further preferably 35% by mass.
When the content of polyphenylene ether is 1% by mass or more, the heat resistance of the obtained resin can be increased, which is preferable. Moreover, it is preferable that content of polyphenylene ether is 50 mass% or less from a viewpoint of suppressing the deterioration of wettability with a long fiber filler.

  As thermoplastic resins other than polyphenylene ether, homopolystyrene, rubber-modified polystyrene, acrylonitrile-styrene copolymer, copolymer of N-phenylmaleimide and styrene, which are thermoplastic resins having relatively high affinity with polyphenylene ether, and these In the case of using one or more polystyrene resins selected from the group consisting of these mixtures, the content of polyphenylene ether in the resin is preferably in the range of 10 to 90% by mass. The content of polyphenylene ether in the resin is more preferably 20% by mass or more, and further preferably 30% by mass. Further, the content of polyphenylene ether in the resin is more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 60% by mass or less.

(Styrene resin)
In the present embodiment, examples of the styrenic resin include homopolystyrene, rubber-modified polystyrene (generally referred to as high impact polystyrene), styrene-butadiene block copolymer and / or a hydrogenated product thereof, styrene- Examples include isoprene block copolymers and / or hydrogenated products thereof, and copolymers of styrene and vinyl monomers capable of radical copolymerization.

Specific examples of vinyl monomers capable of radical copolymerization with styrene include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl such as acrylic acid, butyl acrylate, methacrylic acid, methyl methacrylate, and ethylhexyl methacrylate. Examples thereof include unsaturated carboxylic acid anhydrides and derivatives thereof such as carboxylic acid and esters thereof, maleic anhydride and N-phenylmaleimide, and diene compounds such as butadiene and isoprene. Is possible.
Styrene resins are preferably homopolystyrene, rubber-modified polystyrene, acrylonitrile-styrene copolymers, copolymers of N-phenylmaleimide and styrene, and mixtures thereof from the viewpoint of commercial availability. It is done.

  Homopolystyrene and rubber-modified polystyrene have a reduced viscosity (measured at a concentration of 0.5 g / 100 ml in a 30 ° C. toluene solution) from the viewpoint of maintaining the balance between fluidity and mechanical strength of the resulting thermoplastic resin mixture. Homopolystyrene and rubber-modified polystyrene in the range of 0.5 to 2.0 dl / g are preferred. The reduced viscosity of homopolystyrene and rubber-modified polystyrene is more preferably 0.7 dl / g or more, and further preferably 0.8 dl / g or more. The reduced viscosity of homopolystyrene and rubber-modified polystyrene is preferably 1.5 dl / g or less, more preferably 1.2 dl / g or less.

As the acrylonitrile-styrene copolymer, a copolymer containing 3 to 30% by mass of acrylonitrile as a structural unit in the acrylonitrile-styrene copolymer from the viewpoint of chemical resistance and heat resistance of the resulting thermoplastic resin mixture. Is preferred.
The content of acrylonitrile is more preferably 5% by mass or more, and further preferably 7% by mass or more. Further, the content of acrylonitrile is more preferably 20% by mass or less, further preferably 15% by mass or less, and further preferably 10% by mass or less.
The acrylonitrile-styrene copolymer may be a copolymer obtained by further copolymerizing 30 parts by mass or less of butadiene with respect to 100 parts by mass of the acrylonitrile-styrene copolymer.

The copolymer of N-phenylmaleimide and styrene is 15 to 70% by mass in the copolymer of N-phenylmaleimide and styrene from the viewpoint of heat resistance of the resulting thermoplastic resin mixture and affinity for polyphenylene ether. A copolymer containing N-phenylmaleimide as a structural unit is preferred. The content of N-phenylmaleimide is more preferably 20% by mass or more, and further preferably 25% by mass or more. Further, the content of N-phenylmaleimide is more preferably 65% by mass or less, and further preferably 60% by mass or less.
The copolymer of N-phenylmaleimide and styrene may be a copolymer obtained by further copolymerizing 30 parts by mass or less of acrylonitrile with respect to 100 parts by mass of the N-phenylmaleimide and styrene copolymer.
The glass transition temperature of the copolymer of N-phenylmaleimide and styrene is preferably in the range of 140 ° C. to 220 ° C. from the viewpoint of maintaining the heat resistance of the resulting thermoplastic resin mixture.
The glass transition temperature in the present embodiment is, for example, a glass transition temperature that can be observed when measured with a DSC measurement apparatus at a temperature increase rate of 20 ° C./min.

(Olefin resin)
In the present embodiment, examples of the olefin resin include polyethylene, polypropylene, a copolymer of ethylene and α-olefin, a copolymer of ethylene and acrylate, and the like (hereinafter simply referred to as “PP”). Is sometimes abbreviated as ")".

  In the present embodiment, polypropylene includes a crystalline propylene homopolymer, a crystalline propylene homopolymer portion obtained in the first step of polymerization, and propylene, ethylene and / or at least one other type of polymer after the second step of polymerization. Examples thereof include crystalline propylene-ethylene block copolymers having a propylene-ethylene random copolymer portion obtained by copolymerizing an α-olefin (for example, 1-butene, 1-hexene and the like). Polypropylene may be a mixture of a crystalline propylene homopolymer and a crystalline propylene-ethylene block copolymer.

  Polypropylene is usually in the range of a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of 3 to 100 atm in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound. It can be obtained by polymerization. At this time, a chain transfer agent such as hydrogen can be added in order to adjust the molecular weight of the polymer. As the polymerization method, either batch type or continuous type can be used. Methods such as solution polymerization in a solvent such as butane, pentane, hexane, heptane, octane, and slurry polymerization can be selected. The bulk polymerization in the inside, the gas phase polymerization method in the gaseous monomer, etc. can be applied.

  In order to increase the isotacticity and polymerization activity of polypropylene, an electron donating compound can be used as an internal donor component or an external donor component as a third component. As these electron-donating compounds, known compounds can be used, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, methyl toluate, triphenyl phosphite, tributyl phosphite and the like. Phosphoric acid esters, phosphoric acid derivatives such as hexamethylphosphoric triamide, alkoxy ester compounds, aromatic monocarboxylic acid esters and / or aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, and various alcohols And / or various phenols.

In this embodiment, the density of the propylene polymer portion of the polypropylene is usually in 0.90 g / cm ³ or more, preferably 0.90~0.93g / cm ^3, 0.90~0. More preferably, it is 92 g / cm ³ .
The method for measuring the density of the propylene polymer portion can be easily determined by the JIS K-7112 underwater substitution method. Further, when polypropylene is a copolymer with α-olefin mainly composed of propylene, the copolymer component is extracted from the polypropylene using a solvent such as hexane, and the density of the remaining propylene polymer portion is determined as described above. It can be easily determined by the JIS K-7112 underwater substitution method.

  In the present embodiment, it is also effective to add a known crystal nucleating agent to increase the density of polypropylene. The crystal nucleating agent is not particularly limited as long as it improves the crystallinity of polypropylene. For example, an organic system such as an aromatic carboxylic acid metal salt, a sorbitol derivative, an organic phosphate, an aromatic amide compound, etc. Examples thereof include nucleating agents and inorganic nucleating agents such as talc.

  In the present embodiment, the MFR of polypropylene (conforming to JIS K-6758: 230 ° C., 21.2 N load) is 10 g / 10 min or more from the viewpoint of improving the wettability of the long fiber filler to the thermoplastic resin mixture. It is preferably 20 to 50 g / 10 minutes, more preferably 25 to 40 g / 10 minutes, and even more preferably 30 to 40 g / 10 minutes.

(polyester)
In the present embodiment, examples of the polyester include polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate, and liquid crystal polyesters. Among these, liquid crystal polyesters Is preferred.

In the present embodiment, the liquid crystal polyester is a polyester called a thermotropic liquid crystal polymer. The thermotropic liquid crystal polymer is not particularly limited, and examples thereof include thermotropic liquid crystal polyesters having p-hydroxybenzoic acid, alkylene glycol, and terephthalic acid as main structural units, p-hydroxybenzoic acid, and 2-hydroxy. Examples include thermotropic liquid crystal polyesters having -6-naphthoic acid as the main structural unit, p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, and thermotropic liquid crystal polyesters having terephthalic acid as the main structural unit.
As the liquid crystalline polyester used in the present embodiment, those composed of the following structural units (a), (b), and (c) and / or (d) as necessary are preferably used.

The structural units (a) and (b) are respectively a structural unit of polyester formed from p-hydroxybenzoic acid and a structural unit generated from 2-hydroxy-6-naphthoic acid.
By using the structural units (a) and (b), it is possible to obtain a resin having an excellent balance of mechanical properties such as excellent heat resistance, fluidity and rigidity.
X in the structural units (c) and (d) is a group arbitrarily selected from the following group.

The structural unit (c) is preferably a structural unit formed from ethylene glycol, hydroquinone, 4,4′-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, bisphenol A, etc., and ethylene glycol, 4,4′- A structural unit generated from dihydroxybiphenyl and hydroquinone is more preferable, and a structural unit generated from ethylene glycol and 4,4′-dihydroxybiphenyl is more preferable.
The structural unit (d) is preferably a structural unit formed from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, etc., and is a structural unit generated from 2,6-naphthalenedicarboxylic acid and terephthalic acid. More preferably.

  As the structural unit (c) and the structural unit (d), at least one or two or more of the structural units described above can be used in combination. When two or more types are used in combination, for example, in the structural unit (c), the structural unit generated from ethylene glycol and the structural unit generated from hydroquinone, the structural unit generated from ethylene glycol, and 4,4′-dihydroxybiphenyl are generated. And structural units generated from hydroquinone and 4,4′-dihydroxybiphenyl. Moreover, in the structural unit (d), a structural unit generated from terephthalic acid / a structural unit generated from isophthalic acid, a structural unit generated from terephthalic acid / 2, a structural unit generated from 2,6-naphthalenedicarboxylic acid, and the like can be given. .

The proportion of the structural units (a), (b), (c) and (d) used in the liquid crystal polyester is not particularly limited, but the structural units (c) and (d) are basically equimolar amounts. It is preferable.
The following structural unit (e) composed of the structural units (c) and (d) can also be used as the structural unit in the liquid crystal polyester.

In the structural unit (e), X is as described above.
As the structural unit (e), specifically, a structural unit generated from ethylene glycol and a structural unit generated from terephthalic acid, a structural unit generated from hydroquinone and a structural unit generated from terephthalic acid, 4,4′-dihydroxy Structural units produced from biphenyl and structural units produced from terephthalic acid, structural units produced from 4,4′-dihydroxybiphenyl and structural units produced from isophthalic acid, structural units produced from bisphenol A and structures produced from terephthalic acid Examples thereof include structural units generated from hydroquinone and 2,6-naphthalenedicarboxylic acid.

In the present embodiment, the liquid crystal polyester may contain other aromatic dicarboxylic acid, aromatic diol, aromatic hydroxycarboxylic acid as necessary within a small amount of range that does not impair the characteristics and effects of the present embodiment. Structural units generated from can be introduced.
In the present embodiment, the temperature at which the liquid crystal polyester starts to show a liquid crystal state at the time of melting (hereinafter referred to as liquid crystal start temperature) is preferably 150 to 350 ° C, and more preferably 180 to 320 ° C. By setting the liquid crystal starting temperature within this range, the obtained resin can have a favorable balance of color tone, heat resistance and moldability.
As a method for measuring the liquid crystal starting temperature in the present embodiment, specifically, using a polarizing microscope having a heating stage, the liquid crystalline polyester is observed under polarized light while being heated at a heating rate of 1 ° C./min. Thus, the temperature at which the anisotropic melt phase is observed.

In the present embodiment, the dielectric loss tangent (tan δ) at 25 ° C. and 1 MHz of the liquid crystal polyester is preferably 0.03 or less, and more preferably 0.025 or less.
In the present embodiment, the dielectric loss tangent is a value determined by a test method based on JIS-K6911. The smaller the value of the dielectric loss tangent, the smaller the dielectric loss, which is preferable because the electric noise generated when the resin is used as a raw material for electric / electronic parts is suppressed. In particular, at 25 ° C. in the high frequency region, that is, in the 1 to 10 GHz region, the dielectric loss tangent (tan δ) is preferably 0.03 or less, and more preferably 0.025 or less.

In the present embodiment, the apparent melt viscosity (liquid crystal starting temperature + 30 ° C. and shear rate of 100 / sec) of the liquid crystal polyester is preferably 10 to 3,000 Pa · s, and more preferably 10 to 2,000 Pa · s. More preferably, it is more preferably 10 to 1,000 Pa · s. By making the apparent melt viscosity within this range, the fluidity of the resin can be made preferable.
Specific examples of the method for measuring the apparent melt viscosity in the present embodiment include a method for measuring the viscosity at a shear rate using a capillary rheometer. The melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ can be measured with a capillary rheometer. For example, a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used. The temperature can be measured at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ .

(polyamide)
In this embodiment, the polyamide is not particularly limited as long as it has an amide bond {—NH—C (═O) —} in the repeating structure of the polymer.
The method for producing the polyamide is not particularly limited, and examples thereof include ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, and polycondensation of aminocarboxylic acid.
In the present embodiment, examples of the diamine include aliphatic diamines, alicyclic diamines, and aromatic diamines.
Examples of the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 1,9-nonane diamine, 2-methyl-1,8-octane diamine, 2,2,4. -Trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p-phenylene Examples include diamine, m-xylylenediamine, and p-xylylenediamine.

In the present embodiment, examples of the dicarboxylic acid include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.
Examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. , And dimer acid.
In the present embodiment, examples of lactams include ε-caprolactam, enantolactam, and ω-laurolactam.
In the present embodiment, examples of the aminocarboxylic acid include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13 -Aminotridecanoic acid etc. are mentioned.

  In the present embodiment, as the polyamide, copolymer polyamides obtained by polycondensation of lactams, diamines, dicarboxylic acids, and / or ω-aminocarboxylic acids, alone or in a mixture of two or more, are used. can do. In addition, copolymerized polyamides obtained by polymerizing lactams, diamines, dicarboxylic acids, and / or ω-aminocarboxylic acids to a low molecular weight oligomer stage in a polymerization reactor and then increasing the molecular weight in an extruder or the like are also preferably used. can do.

  In the present embodiment, as the polyamide, polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612, polyamide MXD (m-xylylenediamine) 6, polyamide 6T, polyamide 6I, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 6T / 6I, polyamide 6 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 6 / 12 / 6T, polyamide 66/12 / 6T, polyamide 6/12 / 6I, polyamide 66/12 / 6I, polyamide 9T, and the like can be suitably used (for example, polyamide 6I is hexamethylenediamine). And isophthal It means polymerization polyamide resin acids, polyamide 6 / 6T means ε- aminocaproic acid, hexamethylenediamine, and the polyamide copolymer resin terephthalic acid.). Polyamides obtained by further copolymerizing with two or more of these polyamide resins using an extruder or the like can also be used.

  In the present embodiment, the polyamide is preferably a polyamide having an aromatic ring in a repetitive structural unit from the viewpoint of improving the heat resistance of a molded article made of the obtained long fiber filler reinforced pellets. Specifically, polyamide MXD (m-xylylenediamine) · 6, polyamide 6T, polyamide 6I, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 6T / 6I, polyamide 6 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 6/12 / 6T, polyamide 66/12 / 6T, polyamide 6/12 / 6I, polyamide 66/12 / 6I, polyamide 9T, etc., and polyamide 6T / 6I, polyamide 66 / 6T / 6I, and polyamide 9T are more preferable, and polyamide 9T is more preferable. It may be a mixture of the above preferred polyamides.

In the present embodiment, the viscosity of the polyamide is preferably in the range of 70 to 160 ml / g, more preferably in the range of 80 to 150 ml / g, as measured in 96% sulfuric acid according to ISO307.
When the viscosity of the polyamide is 70 ml / g or more, the take-up property of the strands during pellet production can be well controlled, and when it is 160 ml / g or less, the wettability of the long fiber filler and the resin is improved. It can be controlled well.

In the present embodiment, as the polyamide, a mixture of two or more polyamides having the same type of polyamide but different viscosity numbers can be used. Examples of the polyamide mixture include a mixture of a polyamide having a viscosity number of 170 ml / g and a polyamide having a viscosity number of 80 ml / g, a mixture of a polyamide having a viscosity number of 120 ml / g and a polyamide having a viscosity number of 115 ml / g, and the like.
The viscosity of the polyamide mixture can be measured in accordance with ISO 307 by dissolving the polyamide mixture in 96% sulfuric acid, and is preferably in the above-mentioned range.

  In the present embodiment, in order to improve the compatibility between polyamide and polyphenylene ether, the terminal amino group concentration of the polyamide is preferably 5 μmol / g or more, more preferably 10 μmol / g or more, and 12 μmol / g. g or more is more preferable, and 15 μmol / g or more is even more preferable. In order to satisfactorily control the wettability between the long fiber filler and the resin, the terminal amino group concentration of the polyamide is preferably 45 μmol / g or less, more preferably 40 μmol / g or less, and 35 μmol / g or less. More preferably, it is more preferably 30 μmol / g or less.

  In the present embodiment, the terminal carboxyl group concentration of the polyamide is preferably 20 μmol / g or more, more preferably 30 μmol / g or more, and 150 μmol from the viewpoint of mechanical properties such as resin fluidity and rigidity. / G or less, more preferably 100 μmol / g or less, and even more preferably 80 μmol / g or less.

  In the present embodiment, the ratio of the terminal amino group concentration to the terminal carboxyl group concentration (terminal amino group concentration / terminal carboxyl group concentration) of the polyamide is not particularly limited, but is 1.0 or less from the viewpoint of mechanical properties. Preferably, it is 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less. Moreover, a pellet can be stably obtained by setting the ratio of the terminal amino group concentration and the terminal carboxyl group concentration of the polyamide to 0.1 or more.

  In the present embodiment, a known method can be used as a method for adjusting the terminal amino group concentration and the terminal carboxyl group concentration of the polyamide. For example, a diamine compound is used so that a predetermined terminal concentration is obtained during polymerization of the polyamide resin. , Monoamine compounds, dicarboxylic acid compounds, monocarboxylic acid compounds, acid anhydrides, monoisocyanates, monoacid halides, monoesters, and methods of adding terminal adjusters such as monoalcohols.

  Examples of the terminal adjusting agent that reacts with the terminal amino group include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isopropanol. Aliphatic monocarboxylic acids such as butyric acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and aromatics such as phenylacetic acid Group monocarboxylic acid, and a plurality of mixtures arbitrarily selected from these. These monocarboxylic acid compounds include acetic acid, propionic acid, butyric acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid from the viewpoints of reactivity, stability of the sealing end, price, etc. Acid, stearic acid, and benzoic acid are preferred, and benzoic acid is more preferred.

  Examples of terminal modifiers that react with terminal carboxyl groups include fats such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Alicyclic monoamines such as aromatic monoamine, cyclohexylamine, and dicyclohexylamine, aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine, and a plurality of mixtures arbitrarily selected from these. As these monoamine compounds, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, stability of the sealing end, price, and the like.

In the present embodiment, the concentration of the terminal amino group and the terminal carboxyl group of the polyamide is preferably determined from ¹ H-NMR from the integral value of the characteristic signal corresponding to each terminal group in terms of accuracy and simplicity. The method disclosed in JP-A-7-228775 can be followed. As the measurement solvent, heavy trifluoroacetic acid is preferably used. ^The number of ¹ H-NMR integrations is preferably at least 300 scans even when measured with an instrument having sufficient resolution.
As a method for measuring the concentration of the terminal amino group and the terminal carboxyl group of the polyamide, it can be carried out according to a measurement method by titration as disclosed in JP-A-2003-055549.
In order to eliminate the influence of mixed additives and lubricants, it is more preferable to quantify by ¹ H-NMR.

In this Embodiment, when a terminal amino group and / or a terminal carboxyl group are adjusted using a terminal blocker, it will be in the state by which the active terminal was sealed. When, for example, benzoic acid, which is a monocarboxylic acid, is used as the end capping agent, an end group capped with a phenyl group end is generated.
In the present embodiment, the concentration of the polyamide-capped end groups is preferably 20% or more, more preferably 40% or more, further preferably 45% or more, and 50%. More preferably, it is more than the above. Further, the concentration of the end group sealed with polyamide is preferably 85% or less, more preferably 80% or less, and further preferably 75%.

In the present embodiment, the end capping rate of polyamide is determined by measuring the number of terminal carboxyl groups, terminal amino groups, and end groups blocked with a terminal capping agent present in the polyamide, respectively, and calculating according to the following calculation formula: Terminal sealing rate (%) = [(α−β) / α] × 100
(Wherein α represents the total number of terminal groups of the molecular chain (this is usually equal to twice the number of polyamide molecules), β is the total number of terminal carboxyl groups and terminal amino groups remaining unblocked) Represents.)

In the present embodiment, the moisture content of the polyamide is preferably in the range of 500 to 3000 ppm, more preferably in the range of 500 to 2000 ppm.
By setting the moisture content of the polyamide to 500 ppm or more, pellets with good color tone can be obtained, and by setting the water content to 3000 ppm or less, a significant decrease in viscosity of the resin can be suppressed.
Specifically, the moisture content measurement method in the present embodiment is a moisture vaporization method based on the ISO15512 method B.

(Polyarylene sulfide)
In the present embodiment, the polyarylene sulfide is a polymer containing an arylene sulfide repeating unit represented by the following formula in an amount of usually 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more.
[-Ar-S-]
(In the formula, Ar represents an arylene group.)
In the present embodiment, the arylene group includes p-phenylene group, m-phenylene group, substituted phenylene group, p, p′-diphenylenesulfone group, p, p′-biphenylene group, p, p′-diphenylene. A carbonyl group, a naphthylene group, etc. are mentioned, As a substituent, a C1-C10 alkyl group and a phenyl group are mentioned.

  In the present embodiment, the polyarylene sulfide may be a homopolymer having one type of arylene group as a structural unit. From the viewpoint of processability and heat resistance, two or more different arylene groups may be mixed. The copolymer obtained by using may be used. The polyarylene sulfide is preferably a polyphenylene sulfide in which the arylene group is a phenylene group, and a polyphenylene sulfide having a repeating unit of p-phenylene sulfide as a main constituent element (hereinafter sometimes simply referred to as “PPS”). ) Is more preferable because it is excellent in processability and heat resistance and is easily available industrially.

In the present embodiment, the polyarylene sulfide is produced by a method in which a halogen-substituted aromatic compound, for example, p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrogen sulfide in a polar solvent. And a method of polymerizing in the presence of sodium hydroxide and hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, a method such as self-condensation of p-chlorothiophenol, and amides such as N-methylpyrrolidone and dimethylacetamide A method of reacting sodium sulfide and p-dichlorobenzene in a sulfone solvent such as a system solvent or sulfolane is preferably used.
In the present embodiment, trichlorobenzene can also be used as a branching agent as necessary in order to bring a branched structure to the molecular chain of polyarylene sulfide.

In the present embodiment, the method for producing polyarylene sulfide is not particularly limited as long as it is a known method. For example, US Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671, Japanese Patent Publication No. 45-3368, Japanese Patent Publication No. 52-12240, Japanese Patent Publication No. Sho 61-225217, US Pat. No. 3,274,165, Examples thereof include the methods disclosed in Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, and Japanese Patent Laid-Open No. 5-222196, and the prior art methods exemplified in these patents.
In the present embodiment, the PPS obtained by the above known polymerization method is usually a linear PPS.

In the present embodiment, after polymerizing linear PPS, heat treatment is further performed in the presence of oxygen at a temperature not higher than the melting point of PPS (for example, 200 to 250 ° C.) to promote oxidative crosslinking, so that the molecular weight and viscosity of the polymer are moderate. The cross-linked PPS can be obtained by increasing the thickness of the PPS. Cross-linked PPS also includes semi-cross-linked PPS with a slight degree of cross-linking.
PPS can be used in combination of one or two of linear PPS and cross-linked PPS. It is preferable to use the linear PPS and the cross-linked PPS in combination since the effect that the particle size of the polyphenylene ether dispersed phase can be reduced is exhibited.

In the present embodiment, in order to reduce whitening of the pellets and mold deposit during molding due to PPS, the content of the oligomer contained in PPS in PPS is preferably 0.7% by mass or less.
In the present embodiment, the oligomer contained in PPS means a substance that is extracted into a methylene chloride solution when PPS is extracted with methylene chloride. In general, an oligomer contained in PPS is a substance known as an impurity of PPS, and the content of the oligomer can be specifically measured by the following method.
Add 5 g of PPS powder to 80 ml of methylene chloride, perform Soxhlet extraction for 6 hours, cool to room temperature, and transfer the extracted methylene chloride solution to a weighing bottle. Subsequently, the container used for the extraction is washed in three portions with a total of 60 ml of methylene chloride, and the washing solution is collected in the weighing bottle. Next, the methylene chloride in the weighing bottle is evaporated and removed by heating to about 80 ° C., the residue is weighed, and the amount extracted from the methylene chloride from the amount of the residue, that is, the proportion of the oligomer present in the PPS. Can be requested.

In the present embodiment, the polyarylene sulfide has a melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ of preferably 10 to 150 Pa · s, more preferably 10 to 100 Pa · s, and more preferably 10 to 80 Pa · s. More preferably, it is s.
When the melt viscosity at 300 ° C. at a shear rate of 100 sec ⁻¹ of the polyarylene sulfide is 10 Pa · s or more, excellent mechanical properties are given to the resin, and when it is 150 Pa · s or less, Impregnation of resin is improved.

In the present embodiment, the melt viscosity of polyarylene sulfide at 300 ° C. at a shear rate of 100 sec ⁻¹ can be measured with a capillary rheometer. Using length = 10 mm and capillary diameter = 1 mm, the measurement can be performed at a temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ .

(Polyarylate)
In the present embodiment, the polyarylate is a polymer including an aromatic ring and an ester bond in a structural unit, and is also referred to as a polyaryl ester. As the polyarylate, for example, a polyarylate having a repeating unit represented by the following formula (2) composed of bisphenol A and terephthalic acid and / or isophthalic acid is preferably used.
In the present embodiment, polyarylate having a molar ratio of terephthalic acid to isophthalic acid of about 1: 1 is preferable from the viewpoints of heat resistance in the molded body and toughness of the resin.

In the present embodiment, as the polyarylate, a commercially available product can be used. For example, a trade name “U polymer” manufactured by Unitika Ltd. can be used.
As the molecular weight of polyarylate, the polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC) is preferably 5,000 to 300,000, more preferably 10,000 to 300,000, and 10,000 to 100,000. More preferably. When the number average molecular weight of the polyarylate is 5,000 or more, the heat resistance of the molded article tends to be good and the mechanical strength of the resin tends to be high. In addition, the dispersed phase of the polyether phenol tends to be more finely dispersed.
As a method for measuring the polystyrene-equivalent number average molecular weight in the present embodiment, specifically, GPC is used, chloroform is used as a solvent, column temperature is 40 ° C., and the standard polystyrene is measured in advance under the same conditions. It is a method from a curve of detection time-molecular weight. At this time, the concentration of the polyarylate chloroform solution is 1 g / liter. The detector is preferably measured at about 280 nm using an ultraviolet absorption detector.

(Polyethersulfone, Polyetherimide, Polysulfone)
Polyethersulfone, polyetherimide, and polysulfone that can be used in the present embodiment can be appropriately used from the group of known amorphous super engineering plastics.
Specific products of polyethersulfone include, for example, Radel A (registered trademark), Radel R (registered trademark) manufactured by Solvay Advanced Polymers, MITSUI PES manufactured by Mitsui Chemicals, and Ultra Zone E (manufactured by BASF Japan). Registered trademark) and the like.
Specific examples of the polyetherimide include Ultem (registered trademark) manufactured by SABIC Innovative Plastics.
Specific examples of polysulfone include Udel (registered trademark) manufactured by Solvay Advanced Polymers, Mindel (registered trademark), Ultra Zone S (registered trademark) manufactured by BASF Japan, and the like.

(Polyaryl ketone)
In the present embodiment, the polyaryl ketone is a thermoplastic resin containing an aromatic ring, an ether bond and a ketone bond in its structural unit. For example, polyether ketone, polyether ether ketone, polyether ketone Examples include ketones.
In this Embodiment, the polyether ether ketone which has a repeating unit represented by following formula (3) is used suitably.

In the present embodiment, a commercially available product can be used as the polyether ether ketone. Trade name), trade name “Ultrapek” (PEKEKK) (registered trademark) manufactured by BASF, and the like, and trade name “PEEK” (registered trademark) manufactured by VICTREX are preferably used.
Polyaryl ketones may be used alone or in combination of two or more.

In the present embodiment, the molecular weight of the polyaryl ketone can be determined by using melt viscosity as an index, and the melt viscosity is preferably in the range of 50 to 5000 Pa · s (500 to 50000 Poise), preferably 70 to 3000 Pa · s. It is more preferable that it is 100 to 2500 Pa · s, more preferably 200 to 1000 Pa · s.
If the melt viscosity of the polyaryl ketone is 50 Pa · s or more, the mechanical strength of the resin tends to be good, and if it is 5000 Pa · s or less, the moldability of the resin tends to be good.
In the present embodiment, the melt viscosity of polyaryl ketone is an apparent melt viscosity measured when extruding polyaryl ketone heated to 400 ° C. from a nozzle having an inner diameter of 1 mm and a length of 10 mm with a load of 100 kg. is there.

(Compatibilizer)
In this embodiment, as a thermoplastic resin other than polyphenylene ether, an olefin resin, polyester, polyamide, polyarylene sulfide, polyetherimide, polyethersulfone, polysulfone, which is a resin having relatively low affinity with polyphenylene ether, When using 1 type chosen from the group which consists of a polyaryl ketone and these mixtures, it is preferable that the compatibilizer of thermoplastic resins other than polyphenylene ether and polyphenylene ether is included.

  When the thermoplastic resin other than polyphenylene ether is an olefin resin, it is preferable to use a compatibilizing agent because the polyphenylene ether and the olefin resin are essentially incompatible. A thermoplastic resin mixture composed of olefin resin and polyphenylene ether shows a structure in which polyphenylene ether is dispersed in an olefin resin continuous phase. Polyphenylene ether has a heat resistance above the glass transition temperature of the amorphous part of olefin resin. It shows an important role in reinforcing sex.

In order to improve the compatibility between the two, a copolymer having a segment chain highly compatible with the olefin resin and a segment chain highly compatible with polyphenylene ether can be used as a compatibilizing agent. Examples of the compatible copolymer include a copolymer having a polystyrene chain-polyolefin chain.
In the present embodiment, as a compatibilizing agent for olefin resin and polyphenylene ether, a copolymer having a polyphenylene ether chain-polyolefin chain, at least two polymer blocks A mainly composed of an aromatic vinyl compound, and a conjugated diene are used. Examples thereof include a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one polymer block B mainly composed of a compound, and a hydrogenated block copolymer is preferred.

Examples of the hydrogenated block copolymer as a compatibilizing agent for an olefin resin and polyphenylene ether include ABA, ABAB, (ABB) ₄ -Si, A- Examples thereof include a hydrogenated block copolymer obtained by hydrogenating a block copolymer having a structure such as B-A-B-A. A means a polymer block mainly composed of an aromatic vinyl compound, and B means a polymer block mainly composed of a conjugated diene compound.
The content of the aromatic vinyl compound in the polymer block A and the content of the conjugated diene compound in the polymer block B are each preferably at least 70% by mass.
The hydrogenated block copolymer is an olefinic unsaturated bond derived from a conjugated diene compound in a block copolymer composed of an aromatic vinyl compound-conjugated diene compound, 50% or less, preferably 30% or less, more preferably 10 It is preferable that the block copolymer is reduced by hydrogenation reaction up to% or less.

  In this embodiment, the block copolymer useful as a compatibilizer for the olefin resin and polyphenylene ether is the same as the block copolymer as an impact modifier described later, and is used as a thermoplastic resin other than polyphenylene ether. When an olefin resin is used, the block copolymer has both a function as a compatibilizing agent and a function as an impact modifier. Among block copolymers as impact modifiers to be described later, those that can be more suitably used as compatibilizers for polyphenylene ether and PP are conjugated diene compounds, and the 1,2-vinyl bond amount of the polybutadiene portion is, A so-called high vinyl type block copolymer of 50% to 90% can be suitably used.

When the thermoplastic resin other than polyphenylene ether is polyamide, examples of the compatibilizer include compatibilizers disclosed in detail in JP-A-8-48869 and JP-A-9-124926. . All of these known compatibilizers can be used and can be used in combination.
In the present embodiment, among the compatibilizers, for example, maleic acid or a derivative thereof, citric acid or a derivative thereof, and fumaric acid or a derivative thereof are preferable.

The content of the compatibilizing agent in the present embodiment is preferably 0.01 to 25 parts by mass and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the mixture of polyamide and polyphenylene ether. Preferably, it is 0.1-5 mass parts.
In the present embodiment, the polyphenylene ether particles are preferably present as a dispersed phase having an average particle size of 0.1 to 5 μm in the polyamide continuous phase, and the average particle size is more preferably in the range of 0.3 to 3 μm. Preferably, it is in the range of 0.5-2 μm.
In the present embodiment, it is preferable that the impact modifier described later be present in the polyphenylene ether dispersed phase.

When the thermoplastic resin other than polyphenylene ether is polyarylene sulfide, the thermoplastic resin mixture composed of polyarylene sulfide and polyphenylene ether preferably exhibits a structure in which polyphenylene ether is dispersed in a polyarylene sulfide matrix. Taking advantage of its high glass transition temperature, it plays an important role in reinforcing the heat resistance above the glass transition temperature of the amorphous part of polyarylene sulfide.
Polyarylene sulfide and polyphenylene ether are incompatible, and a copolymer of a compound containing an epoxy group and / or an oxazolyl group is useful for improving the compatibility.
In the present embodiment, by using a compatibilizing agent, there is an effect of remarkably reducing the occurrence of burrs in the molded body when molded with pellets.
However, if these effects are not expected, a compatibilizer may not be required.

In this embodiment, as a compatibilizing agent for polyarylene sulfide and polyphenylene ether, a copolymer of an unsaturated monomer having an epoxy group and / or an oxazolyl group and a monomer having styrene as a main component is preferably used. be able to.
The monomer having styrene as a main component is a monomer containing a monomer copolymerizable with styrene containing 65% by mass or more, more preferably 75 to 95% by mass of styrene. For example, an unsaturated monomer having an epoxy group and / or Or an unsaturated monomer having an oxazolyl group, a copolymer of styrene, an unsaturated monomer having an epoxy group and / or an unsaturated monomer having an oxazolyl group, and styrene / acrylonitrile = 90 to 75% by mass / 10 to 25% by mass And the like.

Examples of the unsaturated monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, and glycidyl itaconate. Glycidyl methacrylate is preferred.
Examples of the unsaturated monomer having an oxazolyl group include vinyl oxazoline compounds. For example, 2-isopropenyl-2-oxazoline is industrially available and can be suitably used.

Other monomers that copolymerize with an unsaturated monomer having an epoxy group and / or an oxazolyl group include, in addition to styrene, vinyl cyanide monomers such as acrylonitrile as copolymerization components, vinyl acetate, (meth) acrylic acid esters, etc. Is mentioned.
The copolymer preferably contains 0.3 to 20% by mass, more preferably 1 to 15% by mass of the structural unit of an unsaturated monomer having an epoxy group and / or an unsaturated monomer having an oxazolyl group. It is more preferable to contain 3-10 mass%.
By using an unsaturated monomer having an epoxy group and / or an unsaturated monomer having an oxazolyl group in the range of 0.3 to 20% by mass, the compatibility between PPS and polyphenylene ether can be maintained high. In addition to greatly suppressing the occurrence of burrs in the molded body molded using the pellets obtained in this way, it has an excellent effect on the balance between heat resistance and toughness (impact strength) and mechanical strength. .

  Examples of the copolymer include styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, styrene-glycidyl methacrylate-acrylonitrile copolymer, styrene-vinyl oxazoline copolymer, styrene-vinyl oxazoline. -An acrylonitrile copolymer etc. are mentioned.

In this Embodiment, it is preferable that it is 0.5-5 mass parts with respect to a total of 100 mass parts of polyphenylene ether and polyarylene sulfide, and, as for the preferable compounding quantity of a compatibilizing agent, it is 1-5 mass parts. It is more preferable, and it is still more preferable that it is 1-3 mass parts.
If the compounding amount of the compatibilizer is 0.5 parts by mass or more, the compatibility between the polyarylene sulfide and the polyphenylene ether is improved, and if it is 5 parts by mass or less, the average particle diameter of the polyphenylene ether forming the dispersed phase Is 10 μm or less, and it is possible to greatly suppress the occurrence of burrs in the molded body formed using the obtained pellets, and to bring about an excellent effect in heat resistance (impact strength) and balance between toughness and mechanical strength. When no compatibilizer is used, a molded article having high heat resistance and impact resistance is provided.

  At this time, the polyphenylene ether particles are preferably present in the polyarylene sulfide continuous phase as a dispersed phase having an average particle diameter of 10 μm or less, more preferably 8 μm or less, and even more preferably 5 μm or less. In order to prevent deterioration of the appearance of the pellets obtained and peeling phenomenon, it is effective that the dispersion average particle diameter does not exceed 10 μm. At this time, it is desirable that the impact modifier described later be present in the polyphenylene ether dispersed phase.

When the thermoplastic resin other than polyphenylene ether is polyester, the compatibilizer is preferably a compound having an epoxy group, an oxazolyl group, an imide group, a carboxylic acid group, or an acid anhydride group, and more preferably a compound having an epoxy group. .
Specific examples include glycidyl methacrylate / styrene copolymer, glycidyl methacrylate / styrene / methyl methacrylate copolymer, glycidyl methacrylate / styrene / methyl methacrylate / methacrylate copolymer, glycidyl methacrylate / styrene / acrylonitrile copolymer, vinyl oxazoline / Examples thereof include styrene copolymers, N-phenylmaleimide / styrene copolymers, N-phenylmaleimide / styrene / maleic anhydride copolymers, styrene / maleic anhydride copolymers, and the like. Also, a graft copolymer such as an ethylene / glycidyl methacrylate copolymer and a polystyrene graft copolymer may be used.

In this embodiment, the compatibilizer of polyester and polyphenylene ether includes glycidyl methacrylate / styrene copolymer, vinyl oxazoline / styrene copolymer, N-phenylmaleimide / styrene copolymer, N-phenylmaleimide / styrene. / Maleic anhydride copolymer is preferred, and glycidyl methacrylate / styrene copolymer is more preferred.
The ratio of the compound having one or more functional groups selected from an epoxy group, an oxazolyl group, an imide group, a carboxylic acid group, and an acid anhydride group, which are monomers in these copolymers, and the styrene compound is particularly limited. Although it is not a thing, it has 1 or more types of functional groups chosen from an epoxy group, an oxazolyl group, an imide group, a carboxylic acid group, and an acid anhydride group from a viewpoint of generation | occurrence | production of silver at the time of injection molding, and the time of extrusion. It is preferable that a compound is 50 mass% or less.

In the present embodiment, the addition amount of the compatibilizer of polyester and polyphenylene ether is 0.1 parts by mass or more from the viewpoint of the tensile strength of the pellets with respect to 100 parts by mass of the total of polyphenylene ether and polyester. Preferably, it is preferably 10 parts by mass or less, more preferably 1 to 7 parts by mass, and further preferably 3.5 to 6 parts by mass from the viewpoint of flame retardancy of the pellets.
The method of adding the compatibilizer is not particularly limited, but there is a method in which a masterbatch is prepared by adding it together with polyphenylene ether or melt-kneading polyester in advance, and then adding this masterbatch to polyphenylene ether. preferable.

At this time, it is necessary that polyphenylene ether forms a dispersed phase and polyester forms a continuous phase. When the polyester forms a continuous phase, the pellets are excellent in chemical resistance and resin rigidity. These dispersion forms can be easily determined by observing with a transmission microscope, for example. A preferable dispersed particle size of polyphenylene ether is 40 μm or less. More preferably, it is 20 μm or less.
In the present embodiment, when an impact modifier described later is blended, the impact modifier is preferably present in the polyphenylene ether dispersed phase. It is also useful for the thermoplastic resin composition in the present embodiment to adopt a sea-island lake structure in which polyester is further present in the polyphenylene ether phase, which is a dispersed phase, by the production method. An example of a specific method for forming a sea-island lake structure is as follows. Using an extruder having one or more supply ports in the middle of the extruder, a part of polyphenylene ether and polyester and necessary from the extruder supply port There is a method in which both compatibilizers are supplied and the remaining polyester is supplied from a supply port in the middle of the extruder.

When the thermoplastic resin other than polyphenylene ether is a thermosetting resin that is polyarylate, polyetherimide, polyethersulfone, polysulfone, or polyarylketone, as a compatibilizer, polypropylene, polyamide, PPS, and liquid crystal All of the above-described compatibilizers for polymers and polyphenylene ethers can be used. Since these resins generally have high processing temperatures, the terminal functional groups are often inactivated by the reaction, causing some kind of reaction (such as heat or breakage of molecular chains by peroxides). After that, it is preferable to select and use the above-mentioned compatibilizer as appropriate.
Compatibilization can be achieved without causing such a reaction. Specifically, it is very useful to add a small amount of polyarylate as a compatibilizing agent for polyphenylene ether and polyaryl ketone in order to enhance the compatibility of both.
In the present embodiment, as a compatibilizing agent for polyphenylene ether and a thermoplastic resin other than polyphenylene ether, an inorganic metal oxide can also be used, for example, from the group consisting of zinc, titanium, calcium, magnesium, and silicon. Examples of the oxide include one or more selected metal oxides. Among these, zinc oxide is preferable.

(Stabilizer)
In the present embodiment, various known stabilizers can also be suitably used for stabilizing a thermoplastic resin other than polyphenylene ether and / or polyphenylene ether.
Stabilizers include, for example, metal stabilizers such as zinc oxide and zinc sulfide, sterically hindered phenol antioxidants, phosphorous heat stabilizers, antioxidants such as sulfur heat stabilizers, and sterically hindered amine light stabilizers. And organic stabilizers such as benzotriazole-based UV absorbers.
It is preferable that the preferable compounding quantity of these various stabilizers is 0.1-5 mass parts with respect to 100 mass parts of resin mixtures.
In the present embodiment, the stabilizer is preferably a sterically hindered phenolic antioxidant.
Specific examples include Irganox (registered trademark) 1098 or Irganox (registered trademark) 1076 available from Ciba Specialty Chemicals.

In the present embodiment, in the step of impregnating the long-fiber filler into the thermoplastic resin mixture, there is a high possibility of being exposed to oxygen in the atmosphere. It is possible to prevent discoloration of the pellets that are produced.
In this Embodiment, it is preferable that content of a sterically hindered phenolic antioxidant is 0.1 mass part or more with respect to 100 mass parts of thermoplastic resin mixtures, and it is 0.2 mass part or more. Is more preferable, and it is still more preferable that it is 0.3 mass part or more. In addition, the content of the sterically hindered phenolic antioxidant is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 2 parts by mass or less.

(Flame retardants)
In the present embodiment, an organic or inorganic flame retardant can be contained for the purpose of imparting flame retardancy. Examples of the flame retardant include halogen-containing compounds, antimony compounds, phosphorus flame retardants, cyclic nitrogen compounds, silicon compounds, metal hydroxides, and the like. Among these, a phosphorus flame retardant, a cyclic nitrogen compound, and a silicon compound are preferable from the viewpoint of imparting low specific gravity simultaneously with flame retardancy.
Examples of phosphorus-based flame retardants include red phosphorus, organophosphate compounds, phosphazene compounds, phosphinates, phosphonates, phosphoramide compounds, and the like.
Examples of the organic phosphate compound include triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl bis (3,5,5′-trimethylhexyl phosphate), ethyl diphenyl phosphate, 2-ethylhexyl di (p -Tolyl) phosphate, bis (2-ethylhexyl) p-tolyl phosphate, tolyl phosphate, bis (2-ethylhexyl) phenyl phosphate, tris (nonylphenyl) phosphate, di (dodecyl) p-tolyl phosphate, tricresyl phosphate, Dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate Fate, bisphenol A bis (diphenyl phosphate), diphenyl (3-hydroxyphenyl) phosphate, bisphenol A bis (dicresyl phosphate), resorcin bis (diphenyl phosphate), resorcin bis (dixylenyl phosphate), 2- Examples include naphthyl diphenyl phosphate, 1-naphthyl diphenyl phosphate, di (2-naphthyl) phenyl phosphate, and the like.
Examples of the organic phosphate compound include aromatic condensed phosphate compounds represented by the following formula (4) or formula (5).

(In the formula, Q1, Q2, Q3, and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms, R1 and R2 represent a methyl group, and R3 and R4 each independently represent hydrogen. Represents an atom or a methyl group, n represents an integer of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, and m1, m2, m3 and m4 each independently represents 1 to Represents an integer of 3.)

The aromatic condensed phosphate ester compound is generally a mixture of 90% or more of compounds in which n represents an integer of 1 to 3, and can be obtained as a mixture of multimers and other by-products in which n is 4 or more. .
For example, a phosphoric acid ester compound mainly composed of bisphenol A-bis (diphenyl phosphate) (manufactured by Daihachi Chemical Co., Ltd., CR741) or a phosphoric acid ester compound mainly composed of bisphenol A-bis (dixylenyl phosphate) Aromatic condensed phosphate esters of bisphenol A, such as phosphate ester compounds (PX200) manufactured by Daihachi Chemical Co., Ltd. and resorcin-bis (diphenyl phosphate) ), An aromatic condensed phosphate ester of resorcins such as a phosphate ester compound (manufactured by Daihachi Chemical Co., Ltd., CR-733S). Aromatic phosphoric acid ester compounds of resorcins and bisphenol A are preferable in terms of volatility and heat resistance, and are aromatic of resorcins and bisphenol A having an acid value of 0.5 or less, preferably 0.1 or less. A condensed phosphate ester compound is more preferable in terms of water resistance and electrical characteristics, and an aromatic condensed phosphate ester compound of bisphenol A is more preferable.

  Examples of the phosphazene compound include compounds having a cyclic structure and a linear structure represented by the following formula (6), and compounds having a cyclic structure are preferable, and n = 3 and 4 6-membered and 8-membered rings. The phenoxyphosphazene compound is more preferable.

(In the formula, each R independently represents an aliphatic or aromatic group having 1 to 20 carbon atoms, and n represents an integer of 3 or more.)
The compound may be cross-linked by a cross-linking group selected from the group consisting of a phenylene group, a biphenylene group and a group represented by the following formula (7).

（式中、Ｘは、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−又は−Ｏ−を表す。）

(In the formula, X represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—).

  The phosphazene compound represented by the above formula (6) is a known compound, for example, “Inorganic Polymers” Pretice-Hall International, Inc., 1992, p61−, by James E. Mark, Harry R. Allcock, Robert West. It is described in p140. Synthesis examples for obtaining these phosphazene compounds are disclosed in JP-B-3-73590, JP-A-9-71708, JP-A-9-183864, JP-A-11-181429, and the like. For example, in the synthesis of non-crosslinked cyclic phenoxyphosphazene compounds, R. According to the method described by Allcock, “Phosphorus Nitrogen Compounds”, Academic Press, (1972), 1.0 unit mole (115. dichlorophosphazene oligomer (mixture of 62% trimer and 38% tetramer)). After adding a toluene solution of sodium phenolate to 580 g of 20% chlorobenzene solution containing 9 g) under stirring, the mixture is reacted at 110 ° C. for 4 hours, and after purification, an uncrosslinked cyclic phenoxyphosphazene compound is obtained.

  Since the phosphazene compound has a higher phosphorus content in the compound than a normal phosphate ester compound, it can secure sufficient flame retardancy even with a small amount of addition, and is excellent in hydrolyzability and thermal decomposability. Since deterioration of physical properties of the thermosetting resin composition can be suppressed, it is a preferable compound as a phosphorus-based flame retardant, and a phosphazene compound having an acid value of 0.5 or less is more preferable in terms of flame retardancy, water resistance and electrical properties. preferable.

  As phosphinates, phosphinates and / or diphosphinates represented by the following formula (8) or formula (9) and / or their condensates (hereinafter simply referred to as “phosphinates”): There is.)

Wherein R ¹ and R ² are the same or different and represent a linear or branched C1-C6 alkyl and / or aryl or phenyl, and R ³ represents a linear or branched C1-C1 C10 alkylene, C6 to C10 arylene, C6 to C10 alkylarylene or C6 to C10 arylalkylene, and M is calcium (ion), magnesium (ion), aluminum (ion), zinc (ion), bismuth ( Ion), manganese (ion), sodium (ion), potassium (ion) and one or more selected from protonated nitrogen bases, m is 2 or 3, and n is an integer of 1 to 3 And x is 1 or 2.)

  The phosphinic acid salts in the present embodiment can be produced by a known method as disclosed in European Patent Application Publication No. 699708 and Japanese Patent Laid-Open No. 8-73720. For example, the phosphinic acid salt can be produced by reacting phosphinic acid with a metal carbonate, metal hydroxide or metal oxide in an aqueous solution, but is not limited to this method. Etc. can also be produced. Phosphinates are generally monomeric compounds, but depending on the reaction conditions, polymeric phosphinates that are condensates having a degree of condensation of 1 to 3 are also included depending on the environment.

  In the present embodiment, examples of phosphinic acid include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphine). Acid), methylphenylphosphinic acid, diphenylphosphinic acid, and mixtures thereof.

  Examples of the metal component include one or more selected from calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and / or protonated nitrogen base, and calcium It is preferably at least one selected from ions, magnesium ions, aluminum ions, and zinc ions.

  Examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethylmethylphosphinic acid. Zinc, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinate, methyl -Zinc n-propylphosphinate, methandi (methylphosphinic acid) calcium, methandi (methylphosphine) Acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, benzene-1 , 4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, diphenylphosphinic acid Examples include calcium, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

  In the present embodiment, as the phosphinic acid salts, from the viewpoint of flame retardancy and suppression of mold deposit, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate Zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are preferred.

In the present embodiment, from the viewpoint of the mechanical strength of the molded product obtained by molding the pellets and the appearance of the molded product, the average particle diameter (d50%) of the phosphinates is preferably 0.5 μm or more, The thickness is more preferably 1.0 μm or more, and further preferably 2 μm or more. The average particle size of the phosphinic acid salts is preferably 40 μm or less, more preferably 20 μm, further preferably 15 μm or less, and still more preferably 10 μm or less.
In the present embodiment, when the number average particle diameter of the phosphinates is 0.5 μm or more, handling property and biting into an extruder and the like are improved during processing such as melt kneading to obtain a preferable resin. be able to. Moreover, when the average particle diameter of the phosphinic acid salts is 40 μm or less, the mechanical strength of the molded body is easily developed, and the effect of improving the good surface appearance of the molded body is obtained.

  As the particle size distribution of these phosphinates, the ratio (d75% / d25%) of 25% particle size (d25%) to 75% particle size (d75%) from the smaller particle size exceeds 1.0. It is preferably 5.0 or less. It is more preferable that it is 1.2-4.0, and it is further more preferable that it is 1.5-3.0. By using phosphinates having a d75% / d25% value of more than 1.0 and 5.0 or less, the surface impact strength of the resin composition can be remarkably improved.

  In the present embodiment, the average particle size (d50%) and the particle size distribution are based on a volume-based particle size measured using a laser diffraction / scattering particle size distribution measuring apparatus. Moreover, it is a value measured using 3% isopropanol aqueous solution as a dispersion medium of phosphinates. Specifically, using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 (manufactured by Horiba, Ltd.), blank measurement was performed with a dispersion medium of 3% isopropanol aqueous solution, and then the measurement sample was passed through the specified transmission. It can be determined by putting it at a rate (95% to 70%) and measuring. The sample is dispersed in the dispersion medium by irradiating with ultrasonic waves for 1 minute.

In the phosphinates in the present embodiment, unreacted products or by-products may remain as long as the effects of the present embodiment are not impaired.
In the present embodiment, two or more phosphorus flame retardants may be used in combination.
In this Embodiment, it is preferable that it is 1-50 mass parts with respect to 100 mass parts of thermoplastic resin mixtures, and, as for content of phosphorus flame retardant, it is more preferable that it is 1-40 mass parts. More preferably, it is -30 mass parts, More preferably, it is 3-25 mass parts.
When the content of the phosphorus-based flame retardant is 3 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin mixture, the flame retardancy of the pellets is good. Moreover, by being 40 mass parts or less, the mechanical strength and heat deformation resistance of a molded object are favorable.

Examples of the silicon compound include silicone, caged silsesquioxane or a partial cleavage structure thereof, and silica.
Silicone is an organosiloxane polymer, which may have a linear structure, a crosslinked structure, or a structure constituted by a certain ratio thereof, and may be a single substance or a mixture thereof. In view of the above, a linear structure is preferable. From the viewpoint of flame retardancy and impact resistance, those having a functional group as a terminal group or side chain group in the molecule are preferred. As a functional group, an epoxy group and an amino group are preferable.
Specifically, silicone oil, modified silicone oil, silicone powder manufactured by Toray Dow Corning Silicone Co., Ltd., straight silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., reactive silicone oil, non-reactive silicone oil, silicone powder KMP Series or the like can be used. Either liquid or solid can be used.

Those of the liquid form, a viscosity at 25 ° C., is preferably 10~10,000mm ² / s, more preferably 100~8,000mm ² / s, at 500~3,000mm ² / s More preferably it is.
The solid particles preferably have an average particle size of 0.1 to 100 μm, more preferably 0.5 to 30 μm, and even more preferably 0.5 to 5 μm.

  In this Embodiment, it is preferable to add 0.1 mass part or more of silicone from the point of a flame-retardant effect with respect to 100 mass parts of thermoplastic resin mixtures. In order to suppress the decrease in rigidity, it is preferable to add 10 parts by mass or less. A more preferred lower limit is 0.3 parts by mass, and even more preferred is 0.5 parts by mass. A more preferable upper limit is 5 parts by mass, and further preferably 2 parts by mass.

A cyclic nitrogen compound is a cyclic organic compound containing a nitrogen element. Specifically, melamine derivatives such as melamine, melem, and melon are preferably used, and melem and melon are preferable from the viewpoint of volatility.
The cyclic nitrogen compound is preferably added in an amount of 0.1 part by mass or more with respect to 100 parts by mass of the thermoplastic resin mixture from the viewpoint of flame retardancy. In order to suppress the decrease in rigidity, it is preferable to add 10 parts by mass or less. A more preferred lower limit is 0.3 parts by mass, and even more preferred is 0.5 parts by mass. A more preferable upper limit is 5 parts by mass, and further preferably 2 parts by mass.

(Fillers other than long fiber filler)
In this Embodiment, fillers other than a long fiber filler may be included if needed, for example, the fibrous filler whose fiber length is 3 mm or less, and the granular filler whose particle diameter is 1 mm or less are mentioned. Examples of the fibrous filler having a fiber length of 3 mm or less include one or more selected from carbon fiber, glass fiber, metal fiber, aramid fiber, etc., and preferably one or more selected from carbon fiber and glass fiber. Is more preferable.
In addition, the fiber length of the fibrous filler whose fiber length here is less than 3 mm is not included in calculation of the average fiber length of the long fiber filler of this Embodiment.

  Examples of the particulate filler having a particle diameter of 1 mm or less include hydroxides of elements selected from magnesium and calcium, oxides of elements selected from the group consisting of magnesium, titanium, iron, copper, zinc and aluminum, zinc sulfide, Examples thereof include at least one filler selected from the group consisting of zinc borate, calcium carbonate, talc, wollastonite, glass, carbon black, carbon nanotube, and silica. Among these, hydroxides of elements selected from magnesium or calcium, oxides of elements selected from magnesium, titanium and zinc, zinc sulfide, zinc borate, calcium carbonate, talc, wollastonite, glass, carbon black, Carbon nanotubes are preferred, and oxides of elements selected from calcium hydroxide, titanium and zinc, zinc sulfide, calcium carbonate, talc, wollastonite, and carbon black are more preferred.

  As addition amount of fillers other than long fiber filler, it is preferable to add so that it may be 20 mass% or less in a long fiber filler reinforced resin pellet, it is preferable that it is 15 mass% or less, and it is 10 mass% or less. It is preferable. The lower limit of the amount of filler other than the long fiber filler is not particularly limited, but may be the minimum amount necessary for the intended effect when added, and when a nucleating effect is expected Is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. In order to expect the effect of dimensional stability, the minimum amount is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more.

  In the present embodiment, wollastonite is obtained by purifying, pulverizing and classifying a natural mineral containing calcium silicate as a component. Artificially synthesized materials can also be used. The size of wollastonite is preferably one having an average particle diameter of 2 to 9 μm and an aspect ratio of 5 or more, more preferably an average particle diameter of 3 to 7 μm and an aspect ratio of 5 or more, and further preferably an average particle diameter of 3 to 3. 7 μm, aspect ratio 8 to 30.

In the present embodiment, as the talc, a refined, pulverized and classified natural mineral containing magnesium silicate as a component can be preferably used, and the crystal of the (0 0 2) diffraction plane of talc by wide-angle X-ray diffraction. The child diameter is preferably 570 mm or more.
The (0 0 2) diffractive surface of talc is a (0 0 2) diffractive surface in which the presence of talc Mg ₃ Si ₄ O ₁₀ (OH) ₂ is identified using a wide-angle X-ray diffractometer and the interlayer distance is talc. This can be confirmed by matching with the lattice plane spacing of about 9.39 mm. The crystallite diameter of the (0 0 2) diffraction plane of talc is calculated from the half width of the peak.
As the shape of talc, the average particle diameter is preferably in the range of 1 to 20 μm, and the ratio of 25% particle diameter (d25%) to 75% particle diameter (d75%) (d75) from the smaller particle diameter. % / D25%) having a particle size distribution in the range of 1.0 to 2.5 is preferable. (D75% / d25%) is more preferably 1.5 to 2.2, and the average particle size is more preferably 1 to 16 μm, and further preferably 3 to 9 μm.

  In the present embodiment, the average particle size and particle size distribution of talc are volume-based particle sizes measured using a laser diffraction / scattering particle size distribution measuring device. Moreover, it is a value measured using ethanol as a dispersion solvent of talc.

In the present embodiment, examples of the oxide of an element selected from titanium and zinc include titanium dioxide and zinc oxide, and titanium dioxide is preferable.
The titanium dioxide may be a treated titanium dioxide surface-treated with an alumina / silicon compound and / or polysiloxane, and the content as titanium dioxide is preferably in the range of 90 to 99% by mass. More preferably, it is the range of 93-98 mass%. In this case, the surface treatment agent is not included as the amount of titanium dioxide.
The average particle diameter of titanium dioxide is preferably in the range of 0.05 to 1 μm, more preferably in the range of 0.1 μm to 0.5 μm, and still more preferably in the range of 0.2 μm to 0.4 μm. .

  In the present embodiment, the average particle diameter is a measured value obtained by a centrifugal sedimentation method and refers to a weight median diameter. The solvent for dispersing the particulate filler at this time should be appropriately selected depending on the type of the particulate filler. For example, in the case of titanium dioxide, it is preferable to use a sodium hexametaphosphate solution.

  In this Embodiment, you may add various additives other than what was mentioned above as needed. An additive will not be specifically limited if it is generally mix | blended with compounding, such as a plastics and a rubber-like polymer. Examples of the additive include additives described in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.). Specific examples include plasticizers such as naphthenic, paraffinic and aromatic process oils and fatty acid esters, aliphatic dibasic acid esters, phthalic acid esters, and epoxidized soybean oil used as rubber softeners, Pigments such as iron oxide, lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearyl amide, mold release agents, organic polysiloxane, flame retardant aids, antistatic agents, colorants Etc. These additives may be used in combination of two or more.

(Long fiber filler reinforced resin pellets)
The long fiber filler reinforced resin pellet of the present embodiment is a pellet composed of the long fiber filler and the thermoplastic resin mixture.
In the present embodiment, the average length of the long fiber filler reinforced resin pellet is preferably 3 mm or more, more preferably 5 mm or more, and further preferably 8 mm or more. Moreover, it is preferable that the average length of a long fiber filler reinforced resin pellet is 50 mm or less, More preferably, it is 40 mm or less, More preferably, it is 15 mm or less.
In order not to deteriorate the impact strength of the molded product formed by molding the long fiber filler reinforced resin pellet of the present embodiment, the average length is preferably 3 mm or more, and the biting property to the molding machine is improved. In order not to deteriorate, the average length is preferably 50 mm or less.
In the present embodiment, the average pellet length is a value calculated by taking out 50 arbitrary pellets, measuring the length of each pellet with calipers, and taking the average value of the lengths of all pellets. .

In this Embodiment, it is preferable that the average diameter of a long fiber filler reinforced resin pellet is 0.5 mm or more, It is more preferable that it is 1 mm or more, It is further more preferable that it is 2 mm or more. The average diameter of the long fiber filler reinforced resin pellet is preferably 8 mm or less, more preferably 5 mm or less, and further preferably 4 mm or less.
The average diameter of the pellets is taken out of 50 arbitrary pellets, the maximum diameter (long diameter in the case of an ellipse) and the minimum diameter (short diameter in the case of an ellipse) of each pellet are measured with a caliper, and the average value is taken. It is a value calculated by taking the average value of the diameters of the pellets.

(Resin pellet mixture)
In the present embodiment, the long fiber filler reinforced resin pellet is a resin obtained by adding 0.1 to 150 parts by mass of resin pellets that do not include the long fiber filler to 100 parts by mass of the long fiber filler reinforced resin pellet. It can also be used as a pellet mixture.
Content of the resin pellet which does not contain a long fiber filler is 0.5 mass part or more with respect to 100 mass parts of long fiber filler reinforced resin pellets, Preferably it is 1 mass part or more, More preferably, it is 2 mass parts or more. It is. Moreover, content of the resin pellet which does not contain a long fiber filler is 120 mass parts or less, Preferably it is 100 mass parts or less, More preferably, it is 80 mass parts or less.
In order not to lower the impact resistance of the molded article made of the resin pellet mixture, it is preferable not to exceed the upper limit amount, and in the case of using a colorant masterbatch as a resin pellet not containing long fiber filler, it is easy to color In order to maintain the properties, it is preferable not to fall below the lower limit.

In this Embodiment, it is preferable that content of the long fiber filler in a resin pellet mixture is 10 mass% or more in the resin pellet mixture whole quantity, More preferably, it is 15 mass% or more, More preferably, 20 mass % Or more, more preferably 25% by mass or more. Moreover, it is preferable that content of the long fiber filler in a resin pellet mixture is 60 mass% or less, More preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less.
In order not to reduce the impact strength of the molded product obtained by molding the resin pellet mixture, it is preferably 10% by mass or more, and from the viewpoint of suppressing the resin temperature during molding, it is 60% by mass or less. preferable.

In this Embodiment, the resin pellet which does not contain a long fiber filler may contain fillers other than a long fiber, and a granular filler is mentioned as fillers other than a long fiber.
Examples of the particulate filler include hydroxides of elements selected from magnesium and calcium, oxides of elements selected from the group consisting of magnesium, titanium, iron, copper, zinc and aluminum, zinc sulfide, zinc borate, calcium carbonate, talc. , At least one filler selected from wollastonite, glass, carbon black, carbon nanotubes and silica.
It is preferable that the average particle diameter of a granular filler is 1 mm or less, and can specifically mention the granular filler which may be included in a long fiber filler reinforced resin pellet.

  The amount of the granular filler added to the resin pellet not including the long fiber filler is preferably 50% by mass or less, more preferably 40% by mass or less in the resin pellet not including the long fiber filler. Preferably it is 30 mass% or less. Although it does not specifically limit regarding the minimum of the addition amount of a granular filler, What is necessary is just the minimum amount required for expression of the effect intended when it adds. As a guideline, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more.

Examples of the resin component constituting the resin pellet that does not include long fibers in the present embodiment include styrene resin, olefin resin, polyester, polyamide, polyarylene sulfide, polyetherimide, polyethersulfone, polysulfone, and polyaryl ketone. And one selected from the group consisting of these, and a more preferred component is that it further contains polyphenylene ether.
In this Embodiment, as a resin component which comprises the resin pellet which does not contain a long fiber, the thermoplastic resin mixture mentioned above about the long fiber filler reinforced resin pellet can be used conveniently.

  The long fiber filler reinforced resin pellet of this embodiment and the resin pellet not containing long fiber may contain an impact modifier if necessary. There are no particular limitations on the impact modifier that can be used here, but those that can be preferably used include mainly a polymer block A mainly composed of at least one aromatic vinyl compound and at least one conjugated diene compound. At least one selected from a block copolymer comprising the polymer block B (hereinafter sometimes simply referred to as a block copolymer) and an ethylene / α-olefin copolymer according to the purpose. It is a seed.

“Mainly” in a polymer block mainly composed of an aromatic vinyl compound refers to a block in which at least 50% by mass or more of the block is an aromatic vinyl compound. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.
The same applies to “mainly” in a polymer block mainly composed of a conjugated diene compound, and refers to a block in which at least 50% by mass or more is a conjugated diene compound. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.

In the present embodiment, in the block copolymer, the polymer block may be a copolymer block, and the aromatic vinyl compound in the random copolymer portion may be uniformly distributed or tapered. It may be distributed.
In the copolymer block, a portion where the aromatic vinyl compound is uniformly distributed and / or a portion where the aromatic vinyl compound is distributed in a tapered shape may coexist. A plurality of portions having different aromatic vinyl compound contents may coexist. In this case, for example, even in the case of a block in which a small amount of a conjugated diene compound or other compound is randomly bonded in the aromatic vinyl compound block, 50% by mass of the block is formed from the aromatic vinyl compound. Thus, it is regarded as a block copolymer mainly composed of an aromatic vinyl compound. The same applies to the case of a conjugated diene compound.

As the block copolymer comprising the polymer block A mainly composed of the aromatic vinyl compound and the polymer block B mainly composed of the conjugated diene compound, block copolymers having the following structures are generally exemplified.
(AB) _n , A- (BA) _n- B, B- (AB) _{n + 1} , [(AB) k] _{m + 1-} Z, [(AB) _k- A] _{m + 1} -Z, [(BA) _k ] _{m + 1} -Z, [(BA) _k -B] _{m + 1} -Z
(In the above formula, Z represents a residue of a coupling agent or a residue of an initiator of a polyfunctional organolithium compound. N, k and m are integers of 1 or more, generally 1 to 5)

  Among these, a preferable bond type of the block copolymer is a block copolymer having a bond type selected from AB type, ABA type, and ABAB type. It is preferable that it is an ABA type and an ABBA type, and it is more preferable that it is an ABA type. Of course, these may be a mixture.

In the present embodiment, examples of the aromatic vinyl compound used in the aromatic vinyl compound-conjugated diene compound block copolymer include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and diphenylethylene. One or more can be selected from among them, and styrene is preferred. The content of the aromatic vinyl compound in the aromatic vinyl compound-conjugated diene compound block copolymer can usually be suitably selected from 1 to 70% by mass, preferably 5 to 55% by mass. More preferably, it is 10-55 mass%.
Aromatic vinyl compound-conjugated diene compound block copolymer As the conjugated diene compound used for the block copolymer, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. 1 type or 2 types or more are selected from butadiene, isoprene, and combinations thereof.

  In the present embodiment, the block copolymer may be a hydrogenated block copolymer. A hydrogenated block copolymer is an aliphatic double bond of a polymer block mainly composed of a conjugated diene compound by hydrogenating the block copolymer of the aromatic vinyl compound and the conjugated diene compound described above. In which the amount of hydrogen (ie, hydrogenation rate) is controlled in the range of more than 0 to 100%. A preferable hydrogenation rate of the hydrogenated block copolymer is 50% or more, more preferably 80% or more, and further preferably 98% or more.

  As an example of a specific hydrogenation method, an olefin derived from a conjugated diene compound existing in a block copolymer is obtained by adding a hydrogenation catalyst and hydrogen gas in a hydrocarbon solvent and performing a hydrogenation reaction. By reducing the polyunsaturated bond, a hydrogenated block copolymer can be obtained. The hydrogenation reaction is not particularly limited in its production method as long as the olefinic unsaturated bond derived from the conjugated diene compound present in the block copolymer can be reduced.

In the present embodiment, these block copolymers further have aromatic functional groups obtained by reacting them with unsaturated compounds having functional groups (for example, carboxylic acid groups, acid anhydride groups, ester groups, hydroxyl groups, etc.). A vinyl compound-conjugated diene compound block copolymer and a hydrogenated block copolymer having a functional group which is a hydrogenated product thereof can also be used.
In this embodiment, the block copolymer can be used without any problem as a mixture of a non-hydrogenated block copolymer and a hydrogenated block copolymer.
In the present embodiment, a block copolymer modified in whole or in part or a block copolymer preliminarily mixed with oil as described in WO 02/094936 is also suitable. Can be used.

In the present embodiment, the ethylene / α-olefin copolymer is a copolymer of ethylene and at least one kind of α-olefin having 3 to 20 carbon atoms, and the above α having 3 to 20 carbon atoms. Specific examples of the olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and 1-tridecene. 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1 -Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-d -1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof. Among these α-olefins, a copolymer using an α-olefin having 3 to 12 carbon atoms is preferable.
The ethylene / α-olefin copolymer preferably has an α-olefin content of 1 to 30 mol%, more preferably 2 to 25 mol%, and even more preferably 3 to 20 mol%.

  In the present embodiment, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidenenorbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene At least one of non-conjugated dienes such as may be copolymerized.

  An ethylene / α-olefin copolymer generally reacts with an unsaturated compound further having a functional group (for example, a carboxylic acid group, an acid anhydride group, an ester group, a hydroxyl group, etc.). Ethylene / α-olefin copolymer having a functional group, or a copolymer of ethylene and a functional group-containing monomer (for example, epoxy group, carboxylic acid group, acid anhydride group, ester group, hydroxyl group, etc.) And a copolymer of ethylene / α-olefin / functional group-containing monomer.

In this Embodiment, preferable content at the time of mix | blending an impact modifier is 1-15 mass parts with respect to a total of 100 mass parts of thermoplastic resins other than polyphenylene ether and polyphenylene ether, More preferably, 3 ˜12 parts by mass.
When the content is 1 part by mass or more, the toughness of a molded body formed by molding the long fiber filler reinforced pellets is improved, and when the content is 15 parts by mass or less, the mechanical strength and heat resistance are excellent.

In the long fiber filler reinforced resin pellet of this embodiment, the resin pellet which does not contain a long fiber, or the resin pellet mixture, a carbon filler for electric conduction may further be included.
Examples of the conductive carbon-based filler include conductive carbon black, carbon nanotube, and carbon fiber.
Examples of the conductive carbon black include ketjen black (EC, EC-600JD) available from ketjen black international.
Examples of carbon nanotubes include carbon fibrils (BN fibrils) available from Hyperion Catalysis International. Among the carbon fibrils, carbon fibrils as disclosed in International Publication No. 94/23433 are particularly preferable.

In this Embodiment, there is no restriction | limiting in particular regarding the addition method of the carbon filler for electroconductivity, The following method is mentioned.
(1) A method of previously mixing a conductive carbon-based filler with a thermoplastic resin mixture when producing a long fiber filler reinforced resin pellet.
(2) A method of previously mixing a conductive carbon-based filler with a resin component when producing resin pellets that do not contain long fiber filler.
(3) When producing a resin pellet mixture, a master batch in which long fiber filler reinforced resin pellets, resin pellets that do not contain long fibers as necessary, and conductive carbon-based fillers are blended in a thermoplastic resin other than polyphenylene ether in advance. How to add.

  Also in the methods (1) and (2) described above, the conductive carbon filler is preferably added in the form of a masterbatch previously blended in a thermoplastic resin other than polyphenylene ether. When the conductive carbon-based filler is conductive carbon black in the master batch, the content is preferably 5 to 15% by mass. When the conductive carbon-based filler is another conductive carbon-based filler, the content is 10 to 30%. It is preferable that it is mass%. More preferably, when the conductive carbon-based filler is conductive carbon black, the content is 7 to 12% by mass, and when the conductive carbon-based filler is another conductive carbon-based filler, the content is 15 to 25% by mass. is there.

As a master batch in which a conductive carbon-based filler is preliminarily blended in a thermoplastic resin other than polyphenylene ether, for example, a technique in the case of polyamide as the thermoplastic resin is disclosed in JP-A-2-201811. As described above, conductive carbon black is preliminarily dispersed in polyamide in a master batch, or conductive carbon as described in US Pat. No. 6,942,823 filed by the present applicant. Masterbatch in which black is moderately non-uniformly dispersed in polyamide, or polyamide 66 / carbon fibril masterbatch available from Hyperion Catalyst International (trade name: Polyamide 66 with Fiber ™ Nanotubes RM 4620-00: carbon fibrils of 20%) carbon fibril master batch or the like, and the like. The same master batch can be mentioned also in thermoplastic resins other than polyamide.
In the present embodiment, the master batch is preferably a master batch in which the conductive carbon black is moderately non-uniformly dispersed in the thermoplastic resin.

More specifically, the appropriate non-uniform dispersion means that when a continuous 3 mm ² surface is observed using an optical microscope, at least a part of the conductive carbon black is agglomerated particles having a major axis of 20 to 100 μm. A master batch of ~ 100 is preferred. More preferably, it is a master batch in which 2 to 30 aggregated particles of conductive conductive carbon black having a major axis of 20 to 100 μm are present when a continuous 3 mm ² surface is observed using an optical microscope.
The method disclosed in US Pat. No. 6,942,823 can be used for observation of aggregated particles of conductive carbon black in the masterbatch.

(Manufacturing method of long fiber filler reinforced resin pellets)
As a manufacturing method of the long fiber filler reinforced resin pellet of this Embodiment, (1) The process which manufactures a thermoplastic resin mixture of a molten state using an extruder, (2) The heat of a molten state of a long fiber filler It is a method including a step of impregnating a plastic resin mixture, (3) a step of taking a twisted strand to form a resin strand, and (4) a step of cutting the resin strand into a pellet shape.
In this Embodiment, it is preferable to include process (1)-(4) continuously in this order.
In the present embodiment, as preferable equipment, as disclosed in Japanese Patent Application Laid-Open No. 2003-175512, an extruder for melting and kneading a resin, and then a resin to a long fiber reinforcing material installed downstream thereof It is preferable to use equipment including a bath for immersion for impregnation and a twist roller for twisting a resin strand impregnated with resin.

In the present embodiment, by twisting the long fiber filler, an effect of easily impregnating the resin into the long fiber filler can be obtained. In addition, this step also has an effect of expelling bubbles existing between the fibers of the long fiber filler to the outside of the strand cross section.
Examples of the method for imparting twist include a method of rotating the exit of the impregnation die around the axis of the strand with a motor, and a method of using a twisting machine for rotating the strand around the take-up direction of the strand when taking up the strand.

  In the present embodiment, the twister has, for example, a rotating roller arranged so as to be opposed to each other while shifting the angle of each roller shaft, and a long fiber filler impregnated with a resin in the roller of the twister. Twist can be given by making it pass. Moreover, it is preferable to arrange | position a twist machine between a water bath and a pelletizer.

As the extruder used for the melt kneading of the resin in the step (1), any of a single screw extruder, a twin screw extruder, and a kneader may be used, but a twin screw extruder is preferable.
As a specific method for producing a thermoplastic resin mixture in a molten state, (1A) a thermoplastic resin mixture prepared by melting and kneading a thermoplastic resin other than polyphenylene ether and polyphenylene ether in advance is supplied to an extruder. A method of melting again, (1B) a method in which thermoplastic resins other than polyphenylene ether and polyphenylene ether are simultaneously fed from the supply port of the same extruder and melt kneaded, and (1C) heat other than polyphenylene ether and polyphenylene ether Although the method etc. which melt-knead by supplying a plastic resin from a different supply port are mentioned, any method may be used. Among these, the method (1B) or (1C) is more preferable.

  Which of the production methods (1B) and (1C) is preferred depends on what is used as the thermoplastic resin other than polyphenylene ether, but the preferred production method is different. For example, as a thermoplastic resin other than polyphenylene ether, When using a resin highly compatible with polyphenylene ether, the production method (1B) may be generally used. On the other hand, in the case of a resin having low compatibility with polyphenylene ether, the production method (1C) is generally preferable. Specifically, polyphenylene ether and a compatibilizing agent are introduced from the supply port of the extruder, and after a functionalization step of polyphenylene ether, a thermoplastic resin other than polyphenylene ether is added from another supply port at the subsequent stage. , A method of kneading, a method of charging a mixture of a part of a thermoplastic resin other than polyphenylene ether and polyphenylene ether from the supply port of the extruder, and a method of charging the remaining thermoplastic resin other than polyphenylene ether from the subsequent supply port Etc. In any case, when a thermoplastic resin having low compatibility with polyphenylene ether is used, a known production method effective for compatibilization can be employed.

In the present embodiment, in the step of producing a molten thermoplastic resin using an extruder, a step of producing a thermosetting resin mixture by mixing polyphenylene ether and a thermoplastic resin other than polyphenylene ether (5 ) Is preferably included.
In the case of including a filler other than the long fiber filler in the long fiber filler reinforced resin pellet of the present embodiment, the supply position of the filler is not particularly limited, and is located on the most upstream side like the resin. You may supply from a feed port, and you may supply from the supply port located after resin reaches | attains a molten state. An extruder having a plurality of supply ports in the latter stage of the extruder can be suitably used.

In the present embodiment, the setting temperature of the bath for impregnation in the step (2) is preferably set to a temperature at which the melt viscosity at a shear rate of 1000 sec ^{−1 is} in the range of 10 to 200 Pa · s. The melt viscosity of the thermoplastic resin mixture is more preferably 20 Pa · s or more, further preferably 30 Pa · s or more, and further preferably 40 Pa · s or more. The melt viscosity of the thermoplastic resin mixture is more preferably 180 Pa · s or less, further preferably 150 Pa · s or less, and still more preferably 100 Pa · s.
The melt viscosity of the thermoplastic resin mixture varies depending on the type of thermoplastic resin other than polyphenylene ether, the viscosity of each resin component, the presence / absence of the compatibilizer, and the amount. The method of adjusting the melt viscosity of a desired resin is very effective.

The set temperature of the impregnation bath in the step of impregnating the long fiber filler into the molten thermoplastic resin mixture is 20 ° C. or more higher than the set temperature of the extruder in the step of manufacturing the molten thermoplastic resin mixture It is preferable to set to. This temperature is also a useful method for bringing the viscosity of the molten resin within the above-described viscosity range. More preferably, the set temperature of the bath for impregnation is a temperature that is 30 ° C. or more higher than the set temperature of the extruder in the step of producing the molten thermoplastic resin mixture. The upper limit of the set temperature of the impregnation bath is not particularly limited, but 50 ° C. can be set as one standard in order to avoid decomposition of the resin.
The temperature at which the melt viscosity at a shear rate of 1000 sec ⁻¹ of the thermoplastic resin mixture is 10 to 200 Pa · s is 280 to 350 ° C., for example, when the thermoplastic resin other than polyphenylene ether is PPS. As a guideline, it is desirable to prepare a thermoplastic resin mixture having a melt viscosity at 310 ° C. and a shear rate of 1000 sec ⁻¹ of 10 to 200 Pa · s.
In the present embodiment, it is preferable to install several rollers in the impregnation bath for the purpose of defibrating the long fiber filler and promoting the impregnation.

In the method for producing pellets of the present embodiment, the take-up speed of the resin strand in the step (3) is preferably 10 to 150 m / min, more preferably 20 m / min or more, and 35 m / min. More preferably. The take-up speed of the resin strand is more preferably 100 m / min or less, and further preferably 80 m / min.
In the step (3), the non-Newtonian property of viscosity can be effectively utilized by increasing the take-up rate of the resin strands from 10 to 150 m / min from the general rate, and impregnating the resin into the long fiber filler. The effect of improving can be obtained.

The production method of the resin pellet that does not include the long fiber filler that can constitute the resin pellet mixture in the present embodiment is not particularly limited as long as it is a known production method, but a single screw extruder, a twin screw extruder, Either a Brabender or a kneader can be used.
The production method of the resin pellet mixture including the long fiber filler reinforced resin pellet of the present embodiment is not particularly limited, but a desired amount of the long fiber filler reinforced resin pellet and the resin pellet not including the long fiber filler are tumbler and screw blender. A production method using a mixing and stirring device such as a Henschel mixer is preferred.

(Molded body)
The molded body of the present embodiment is a molded body obtained by melt molding the long fiber filler reinforced resin pellets, and a molded body obtained by melt molding the resin pellet mixture.
The molded body in the present embodiment includes a bulk molded body manufactured by injection molding, a film / sheet molded body molded by extrusion molding or inflation molding, and a molded body molded by profile extrusion.

The molded body obtained by melt molding the pellet and / or the resin pellet mixture can be industrially used as various parts. For example, IC tray materials, chassis of various disc players, electrical / electronic parts such as cabinets, OA parts and machine parts such as various computers and peripherals, motorcycle cowls, and automobile fenders, door panels, fronts Panel, rear panel, rocker panel, rear bumper panel, back door garnish, emblem garnish, fuel inlet panel, over fender, outer door handle, door mirror housing, bonnette air intake, bumper, bumper guard, roof rail, roof rail leg, pillar, Various aero parts such as pillar covers, wheel covers, spoilers, exterior parts such as various malls, emblems, instrument panels, console boxes, It can be suitably used for interior parts typified by the rim or the like.
In the present embodiment, the molded body including the conductive carbon-based filler can be suitably used as a mechanical part that needs to be prevented from malfunctioning due to static electricity, and an interior / exterior part that requires electrical conductivity.

  In this embodiment, when injection molding long fiber filler reinforced resin pellets, etc., it is carried out with an injection molding machine equipped with a screw for long fiber filler to keep the fibrous filler fiber length in the molded body long. More preferable from the viewpoint. The weight average fiber length of the fibrous filler in the molded body is preferably in the range of 1 mm to 7 mm. A more preferred lower limit is 1.2 mm. Moreover, a more preferable upper limit is 5 mm. The lower limit is preferably 1 mm from the viewpoint of suppressing anisotropy and improving the surface impact property of the obtained molded body, and the upper limit is preferably 7 mm from the viewpoint of suppressing deterioration of the appearance of the molded body.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to only these examples. Note that the evaluation method and measurement method used in this embodiment are as follows.

[Resin used]
Polyphenylene ether Polyphenylene ether (PPE-1):
Reduced viscosity ηsp / c: 0.51 dl / g
Polymer composed of 2,6-dimethylphenol Polyphenylene ether (PPE-2):
Reduced viscosity ηsp / c: 0.42 dl / g
Polymer composed of 2,6-dimethylphenol Polyphenylene ether (PPE-3): polyphenylene ether polymerized according to Japanese Patent Publication No. 60-34571
Reduced viscosity ηsp / c: 0.32 dl / g
Polymer composed of 2,6-dimethylphenol Polyphenylene ether copolymer (PPE-4): polyphenylene ether copolymer polymerized according to JP-A 64-33131
Reduced viscosity ηsp / c: 0.53 dl / g
Polymer composed of 2,6-dimethylphenol (75%) and 2,3,6-trimethylphenol (25%)

Resins other than polyphenylene ether Styrenic resin Homopolystyrene (PS-1): Polystyrene 680 obtained from PS Japan Co., Ltd.
Homopolystyrene (PS-2): Stylon (registered trademark) 685 obtained from Dow Chemical Company (USA)
High impact polystyrene (PS-3): High impact polystyrene obtained from PS Japan Co., Ltd. Rubber content: 8%

Olefin resin Polypropylene (PP-1): Homopolypropylene Density = 0.90 g / cm ³ , MFR = 35 g / 10 min (230 ° C., 21.2 N load)
Polypropylene (PP-2): Homopolypropylene Density = 0.91 g / cm ³ , MFR = 40 g / 10 min (230 ° C., 21.2 N load)
Polypropylene (PP-3): Homopolypropylene
Density = 0.90 g / cm ³ , MFR = 1.2 g / 10 min (230 ° C., 21.2 N load)

Polyester Liquid crystalline polyester (LCP): Liquid crystalline polyester prepared according to Preparation Example 1 Melting point (DSC method): 319 ° C.
Melt viscosity (330 ° C., shear rate 100 sec ⁻¹ ): 18 Pa · s
Polyamide Polyamide 6,6 (PA66): Vidyne (registered trademark) 48BX obtained from Solusia Inc. (USA)
Polyamide 9, T (PA9T): Polyamide 9T prepared according to Preparation Example 2
Terminal amino group concentration: 20 μmol / g
Terminal carboxyl group concentration: 65 μmol / g

Polyarylene sulfide Polyphenylene sulfide (PPS-1): Cross-linked poly (p-phenylene sulfide)
Melt viscosity: 130 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.6% by mass
Polyphenylene sulfide (PPS-2): Semi-crosslinked poly (p-phenylene sulfide)
Melt viscosity: 140 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.5 mass%
Polyphenylene sulfide (PPS-3): Linear type poly (p-phenylene sulfide)
Melt viscosity: 110 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.3 mass%
Polyphenylene sulfide (PPS-4): Linear type poly (p-phenylene sulfide)
Melt viscosity: 75 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.3 mass%
Polyphenylene sulfide (PPS-5): Linear type poly (p-phenylene sulfide)
Melt viscosity: 38 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.5 mass%
Polyphenylene sulfide (PPS-6): Linear type poly (p-phenylene sulfide)
Melt viscosity: 14 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.5 mass%
Polyphenylene sulfide (PPS-7): Semi-crosslinked type poly (p-phenylene sulfide)
Melt viscosity: 180 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.5 mass%
Polyphenylene sulfide (PPS-8): cross-linked poly (p-phenylene sulfide)
Melt viscosity: 240 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.5 mass%
Polyphenylene sulfide (PPS-9): Semi-crosslinked type poly (p-phenylene sulfide)
Melt viscosity: 310 Pa · s (shear rate 100 sec ⁻¹ , 300 ° C.), oligomer amount: 0.4 mass%

Polyarylate Polyarylate (PAR): U-polymer (registered trademark) U-100 obtained from Unitika Ltd.
Polyaryl ketone Polyetheretherketone (PEEK): VICTREX PEEK (registered trademark) 151G obtained from Victrex

Impact modifier (when used in PP, it also functions as a compatibilizer)
Polystyrene block-hydrogenated polybutadiene-polystyrene block (SEBS-1)
Bonded styrene content: 43%, 1,2-vinyl bond content of polybutadiene part: 75%,
Number average molecular weight of polystyrene chain: 15000, polybutadiene part hydrogenation rate is 99.8%
Polystyrene block-hydrogenated polybutadiene-polystyrene block (SEBS-2)
Bonded styrene content: 60%, 1,2-vinyl bond content of polybutadiene part: 80%,
Number average molecular weight of polystyrene chain: 24,000, hydrogenation rate of polybutadiene part is 99.2%
Polystyrene block-hydrogenated polybutadiene-polystyrene block (SEBS-3)
Bonded styrene content: 33%, 1,2-vinyl bond content of polybutadiene part: 47%
Number average molecular weight of polystyrene chain: 29000, hydrogenation rate of polybutadiene part: 99.8%
Polystyrene block-hydrogenated polybutadiene-polystyrene block (SEBS-4)
Bonded styrene content: 60%, 1,2-vinyl bond content of polybutadiene part: 55%
Number average molecular weight of polystyrene chain: 24000, hydrogenation rate of polybutadiene part: 99.2%

Flame retardant Phosphoric ester flame retardant (FR-1): CR-741 obtained from Daihachi Chemical Co., Ltd.
Aluminum phosphinate (FR-2): Exolit OP930 obtained from Clariant

Long fiber filler Glass fiber roving (LGF): ER2400T-448N obtained from Nippon Electric Glass Co., Ltd.
2400 TEX roving-like glass fiber bundle filament with a fiber diameter of 17 μm

Compatibilizer Maleic anhydride (MAH): Crystal MAN-AB manufactured by NOF Corporation
Styrene / glycidyl methacrylate copolymer (SG-C)
Containing 5% by mass of glycidyl methacrylate Weight average molecular weight: 110,000
Styrene-2-isopropenyl-2-oxazoline copolymer (SO-C)
Contains 5% by mass of 2-isopropenyl-2-oxazoline Weight average molecular weight: 146,000
Stabilizer Steric hindrance phenolic antioxidant (Irg1098)
Irganox 1098 obtained from Ciba Specialty Chemicals

[Preparation Example 1] <Production of LCP>
P-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, hydroquinone, 2,6-naphthalenedicarboxylic acid, and acetic anhydride are charged into a 2 liter polymerization vessel equipped with a stirring blade and a distillation tube. Deacetic acid polycondensation was performed. The temperature of the reaction vessel charged with the raw materials was raised from 40 ° C. to 190 ° C. over 3 hours in a nitrogen gas atmosphere, kept at 190 ° C. for 1 hour, then further heated to 325 ° C. over 2 hours and reacted for 10 minutes. I let you. Next, the pressure was reduced to 20 mmHg at 325 ° C. for 20 minutes, and the reaction was further continued for 5 minutes to complete the polycondensation. As a result of the polymerization, a theoretical amount of acetic acid was distilled off to obtain a liquid crystal polyester having a theoretical structural formula represented by the following formula (7).
The melting point by DSC was 319 ° C. As a result of measuring the melt viscosity using a capillary rheometer, it was 18 Pa · s at a shear rate of 1000 seconds ^{−1 at} 330 ° C. In addition, the component ratio of a composition represents molar ratio.

[Preparation Example 2] <Production of aromatic polyamide (polyamide 9T)>
According to the method described in Examples of JP-A-2000-103847, terephthalic acid as a dicarboxylic acid component, 1,9-nonamethylenediamine and 2-methyl-1,8-octamethylenediamine as a diamine component, end-capping Octylamine or benzoic acid as a stopper, sodium hypophosphite monohydrate and distilled water as a polymerization catalyst were placed in an autoclave and sealed (water content in reaction system: 25% by mass). After sufficiently substituting the autoclave with nitrogen, the internal temperature was raised to 260 ° C. over 2 hours with stirring, and the reaction was carried out as it was. The internal pressure at this time was 46 atmospheres.
Next, with the temperature of the reaction vessel maintained at 260 ° C. and the water content at 25% by mass, the reaction product was kept at room temperature under a nitrogen atmosphere for 3 minutes from a nozzle (6 mm diameter) at the bottom of the reaction vessel. After taking out to the container of a normal pressure, it dried at 120 degreeC and obtained the primary polycondensate of the non-foaming powder form.
Subsequently, this powdery primary polycondensate was heated to 250 ° C. over 2 hours with stirring under a nitrogen atmosphere, and further subjected to solid phase polymerization for a predetermined time.
The end-capping rate and end-group concentration of the obtained aromatic polyamide were measured in accordance with the end-capping rate measurement described in Examples of JP-A-7-228689. Phosphorus element was quantified by Thermo Jarrel Ash. It was carried out at a wavelength of 213.618 (nm) by high frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by IRIS / IP. The terminal amino group concentration was 20 μmol / g, the terminal carboxyl group concentration was 65 μmol / g, and the terminal blocking rate was 55%.
The evaluation items shown below were carried out using the obtained resin pellets and strands. The results are shown in Table 1.

[Evaluation item]
(Melt viscosity of resin)
Using a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), using two capillaries with a capillary length of 10 mm and a capillary diameter of 1 mm, two shear rates sandwiching a shear rate of 1000 s ⁻¹ at the temperatures described individually. The apparent melt viscosity was measured by and extrapolated to 1000 seconds ⁻¹ .
(Spiral lead of fibrous filler)
About 30 cm of the strand during extrusion of the long fiber filler reinforced composition was sampled, and the length required for the pattern of the glass fiber strands contained therein to float around the strand surface was measured. .

(Length ratio of long fiber filler to pellet length)
After measuring the average length of the pellets, the resin components were incinerated in an electric furnace set to 650 ° C., and only the lengths of the obtained glass fibers exceeding 3 mm were imaged. The weight average fiber length was measured according to the following formula using an analyzer. In addition, the measurement was performed on at least 500 or more.
Lw = Σ (Li ² × Ni) / Σ (Li × Ni)
Here, Lw represents the weight average fiber length, Li represents the representative fiber length of each group, and Ni represents the number of long fiber fillers in each group. Here, the fibers were grouped in increments of 0.1 mm, and the middle fiber length in the fiber length range was set as the representative fiber length of the group. As a specific example, long fiber fillers (glass fibers) having a fiber length of more than 3 mm and not more than 3.1 mm are set as one group, and the representative fiber length is set to 3.05 mm.
(Long fiber filler content)
The resin component was incinerated in an electric furnace in which the resin pellets were set at 650 ° C., and the contained long fiber filler content was measured from the residue weight.

(Impregnability of resin into long fiber filler)
Methyl red propyl alcohol solution is color changing indicator (hydrochloric acid 1 cm ³ in propyl alcohol saturated solution 50 cm ³ of methyl red was added to pH prepared, which has improved color development of the methyl red) was prepared, optionally The 10 strands selected in the above were immersed in the solution from the fracture surface to a 1 cm portion for about 30 minutes. Then, it pick_out | removed and the penetration condition of the color indicator in the length direction of a strand was confirmed. The impregnation property of the resin into the long fiber filler was evaluated based on the state of penetration of the color indicator from the fracture surface of the strand. The penetration distances of 10 strands were averaged, and those having an average penetration length of 5 mm or less were evaluated as “B”, those having penetration from 5 mm to 10 mm were Δ, and those having penetration of 10 mm or more were determined as “X”.

(Cross sectional area ratio of core part of pellet cross section)
The pellet was cut with a microtome in the thickness direction of the pellet to obtain a smooth cross section, observed with reflected light using an optical microscope, photographed, and the cross-sectional area ratio of the core portion of the pellet cross section was calculated by image analysis.
(Pellet surface appearance)
The surface appearance of the pellet was visually observed. A sample having a sufficient gloss was evaluated as A, a portion of the pellet having no gloss was evaluated as B, and a portion of the pellet having no gloss was evaluated as C.
(Vertical cracking of pellets)
100 pellets were selected at random, sealed in a metal container with a capacity of 50 cm ³ , shaken at an amplitude of 50 mm and a vibration frequency of 60 reciprocations / minute, and then the internal pellets were taken out, causing vertical cracks. The number of pellets was measured.
(Elimination of long fiber filler)
When evaluating the vertical cracks of the pellets, the amount of glass fibers attached to the wall surface of the metal container was visually determined.

(Fiber disintegration of long fiber filler)
Using the obtained long fiber reinforced pellets, IS100GN (manufactured by Toshiba Machine Co., Ltd.) equipped with a screw suitable for forming long fiber filler reinforced pellets with a small compression ratio, a multipurpose 4 mm thick material conforming to ISO294-1 A test piece was molded. The obtained multipurpose test piece was incinerated with resin components at 650 ° C. in an electric furnace, slowly removed, and then gently removed, and the shape retention of the ash content (the shape of the multipurpose test piece was measured with a net fiber of long fiber filler. Whether or not it is held). In addition, if the fibrillation property of the long fiber filler is good, it becomes easier for the long fiber filler to form a network at the time of molding, and shape retention is increased. On the other hand, if the defibration property at the time of molding is poor, the network molding will be insufficient and the shape retention will be greatly inferior. Therefore, the fibrillation property of the long fiber filler was evaluated based on the shape retention.
The evaluation criteria for shape retention are shown below.
AA: The shape of the multipurpose test piece is substantially maintained.
A: The shape is maintained except near the gate.
B: Only the flow end portion holds the shape.
C: The shape is not maintained.

(Surface impact strength of molded piece)
The IS100GN (manufactured by Toshiba Machine Co., Ltd.) equipped with a screw suitable for molding the long fiber filler reinforced resin pellets obtained in the examples with a small compression ratio was used to produce 50 × 90 × 2. A 5 mm flat test piece was molded. Using the obtained test piece, using a graphic impact tester (manufactured by Toyo Seiki Co., Ltd.), using a holder diameter of 40 mm, a striker diameter of 12.7 mm, and a striker mass of 6.5 kg, an impact test is performed from a height of 128 cm. Total absorbed energy was measured at 23 ° C temperature.

(DTUL of molded piece)
A multi-purpose test piece having a thickness of 4 mm conforming to ISO294-1 was molded using the same molding machine as that used to mold the test piece for measuring the surface impact strength.
Using the obtained multi-purpose test piece, the deflection temperature under load was measured with a load of 0.45 MPa and / or 1.8 MPa in accordance with ISO75.
(Charpy impact strength of the molded piece)
Using the same molding machine as that used for molding the test piece for measuring the surface impact strength, a multi-purpose test piece having a thickness of 4 mm in conformity with ISO294-1 was formed, and the obtained test piece was used in accordance with ISO179. The Charpy impact strength with a notch below ℃ was measured.
(Bending strength of molded piece)
Using a multipurpose test piece obtained in the same manner as the Charpy impact strength test piece, the bending strength was measured in accordance with ISO178.

<Manufacturing of PS / PPE1>
The maximum cylinder temperature of L / D = 42 co-rotating twin screw extruder [ZSK25: manufactured by Coperion Co.] with one supply port on the upstream side and one supply port on the downstream side is set to 320 ° C. 20 parts by mass of PPE-1 and 20 parts by mass of PS-1 are supplied to the extruder from the side supply port, and 60 parts by mass of PS-1 is supplied from the downstream side supply port. PS / PPE1 was obtained by melting and kneading while devolatilizing under reduced pressure from a vent port provided later, and cooling and taking off the strand with water. In addition, the screw rotation speed at this time was 300 rpm. As a result of measuring the melt viscosity of the obtained PS / PPE1 using a capillary rheometer, the temperature at 20 to 100 Pa · s at a shear rate of 1000 seconds ⁻¹ was about 300 ° C.

<Manufacturing of PS / PPE2>
Except for supplying 50 parts by mass of PPE-1 and 20 parts by mass of PS-1 to the extruder from the upstream supply port, and supplying 30 parts by mass of PS-2 from the downstream supply port, respectively. It implemented like manufacture of PS / PPE1, and manufactured PS / PPE2. As a result of measuring the melt viscosity of the obtained PS / PPE2 using a capillary rheometer, the temperature at which a viscosity of 200 Pa · s at a shear rate of 1000 sec ⁻¹ was over 320 ° C.

<Manufacturing of PS / PPE3>
Except for supplying 40 parts by mass of PPE-2 and 10 parts by mass of PS-1 to the extruder from the upstream supply port, and supplying 50 parts by mass of PS-1 from the downstream supply port, all PS This was carried out in the same manner as in the production of / PPE1 to obtain PS / PPE3. As a result of measuring the melt viscosity of the obtained PS / PPE3 using a capillary rheometer, the temperature at 20 to 100 Pa · s at a shear rate of 1000 seconds ⁻¹ was about 310 ° C.

<Manufacturing of PS / PPE4>
Except having changed PPE supplied from an upstream supply port into PPE-3, it implemented in all the same way as PS / PPE1, and PS / PPE4 was obtained. As a result of measuring the melt viscosity of the obtained PS / PPE4 using a capillary rheometer, the temperature at 20 to 100 Pa · s at a shear rate of 1000 seconds ⁻¹ was about 280 ° C.

<Manufacturing of PS / PPE5>
Except that the PPE supplied from the upstream supply port was changed to PPE-4, everything was carried out in the same manner as PS / PPE1 to obtain PS / PPE5. As a result of measuring the melt viscosity of the obtained PS / PPE5 using a capillary rheometer, the temperature at 20 to 100 Pa · s at a shear rate of 1000 seconds ⁻¹ was about 330 ° C.

<Manufacturing of PS / PPE6>
Except that 55 parts by mass of PPE-1 and 45 parts by mass of PS-2 were supplied to the extruder from the upstream supply port, respectively, except that nothing was added from the downstream supply port. This was carried out in the same manner as in the production of / PPE1 to obtain PS / PPE6.
This PS / PPE6 was mixed with long fiber filler reinforced pellets and used when measuring the properties of the molded product.

<Manufacture of PA / PPE1>
L / D = 48 co-rotating twin screw extruder [ZSK40MC: manufactured by Coperion, 12 temperature control blocks (L / D per block) 4) and an auto screen changer block, upstream supply port: first block, downstream supply port: sixth block, vent port for removing volatile components by vacuum suction: fifth block and tenth block ] Is set to 320 ° C., and 35 parts by mass of PPE-1, 0.1 part by mass of MAH, 10 parts by mass of SEBS, and 5 parts by mass of PS-3 from the upstream supply port. Then, the mixture was supplied to an extruder, melted and kneaded, and subsequently 50 parts by mass of PA66 was supplied from the downstream supply port, followed by melt-kneading to obtain PA / PPE1. In addition, the screw rotation speed at this time was 450 rpm. The temperature at which the melt viscosity of the obtained PA / PPE1 at a shear rate of 1000 seconds ⁻¹ was 15 to 100 Pa · s was measured and found to be 300 ° C. The melt viscosity at 280 ° C. was 220 Pa · s.

<Manufacture of PA / PPE2>
Using the same extruder as in the manufacture of PA / PPE1, 40 parts by mass of PPE-2 and 0.4 parts by mass of MAH were dry blended from the upstream supply port and supplied to the extruder for melt-kneading. Subsequently, 60 parts by mass of PA9T was supplied from the downstream supply port, and melt kneading was performed to obtain PA / PPE2. All other conditions are the same as in the manufacture of PA / PPE1. The temperature at which the melt viscosity of the obtained PA / PPE2 at a shear rate of 1000 sec ⁻¹ was 15 to 100 Pa · s was measured and found to be 330 ° C.

<Manufacture of PA / PPE3>
Except for changing the polyphenylene ether to PPE-3, all were carried out in the same manner as in the production of PA / PPE1 to obtain PA / PPE3.

<Manufacture of PA / PPE4>
Except for changing the polyphenylene ether to PPE-4, all was carried out in the same manner as in the production of PA / PPE1 to obtain PA / PPE4.

<Production of PP / PPE1 to PP / PPE5>
The cylinder temperature of the extruder used in PA / PPE1 is set to 290 to 310 ° C., and the resin mixture mixed at the ratio shown in Table 1 is supplied from the upstream supply port of the extruder, melt-kneaded, and at two locations. From the installed vacuum vent port, the degree of vacuum: absolute vacuum pressure of 95 kPa or less was degassed and melt-kneaded to produce five types of resin mixtures of PP / PPE1 to PP / PPE5. The role of SEBS here has both a function as a compatibilizer of PP and polyphenylene ether and a function as an impact modifier. The resulting resin mixture was measured for melt viscosity at a shear rate of 1000 seconds ⁻¹ at 280 ° C. and 300 ° C., and is shown in Table 1.

<Manufacture of PPS / PPE1 to PPS / PPE16>
The cylinder temperature of the extruder used in PA / PPE1 is set to 290 to 310 ° C., and the resin mixture mixed at the ratio shown in Table 2 is supplied from the upstream supply port of the extruder, melt-kneaded, and in two locations. From the installed vacuum vent port, degassing was performed at a degree of vacuum: absolute vacuum pressure of 95 kPa or less, and melt-kneading to produce 16 kinds of resin mixtures of PPS / PPE1 to PPS / PPE16. In addition, the melt viscosity of the obtained resin mixture at 300 ° C. and 1000 seconds ⁻¹ was measured and listed in Table 2.

<Manufacture of LCP / PPE1>
The maximum cylinder temperature of the extruder used in the production of PS / PPE1 was set to 330 ° C., 30 parts by mass of PPE-2, 15 parts by mass of LCP, and 5 parts by mass of SG-C from the upstream supply port. Each is supplied to the extruder, 55 parts by mass of LCP is supplied from the downstream supply port, melt-kneaded while evacuating from the vent port provided after the downstream supply port, and the strand is cooled with water and cut off. LCP / PPE1 was obtained. In addition, the screw rotation speed at this time was 300 rpm. As a result of measuring the melt viscosity of the obtained LCP / PPE1 using a capillary rheometer, the temperature at 20 to 100 Pa · s at a shear rate of 1000 seconds ⁻¹ was about 330 ° C.

<Manufacture of LCP / PPE2>
All except for supplying 55 parts by mass of PPE-1 and 15 parts by mass of LCP and 5 parts by mass of SG-C from the upstream supply port, and supplying 30 parts by mass of LCP from the downstream supply port, It implemented like LCP / PPE1 and obtained LCP / PPE2. As a result of measuring the melt viscosity of the obtained LCP / PPE2 using a capillary rheometer, the temperature for obtaining a viscosity of 200 Pa · s at a shear rate of 1000 sec ⁻¹ exceeded 330 ° C.

<Manufacture of LCP / PPE3>
40 parts by mass of PPE-2, 30 parts by mass of LCP, and 5 parts by mass of SG-C are supplied to the extruder from the upstream supply port, melt kneaded, and then 30 LCPs are supplied from the downstream supply port. LCP / PPE3 was obtained in the same manner as in the production of LCP / PPE1 except that 7 parts by mass of FR-1 was supplied from the downstream liquid addition nozzle. As a result of measuring the melt viscosity of the obtained LCP / PPE3 using a capillary rheometer, the temperature at 20 to 100 Pa · s at a shear rate of 1000 seconds ⁻¹ was about 320 ° C.

<Manufacture of LCP / PPE4>
Except that the polyphenylene ether supplied from the upstream supply port was changed to PPE-3, everything was carried out in the same manner as the production of LCP / PPE2 to obtain LCP / PPE4.

<Manufacture of PEEK / PPE>
The maximum cylinder temperature of the extruder used in the production of PS / PPE1 was set to 355 ° C., and 30 parts by mass of PPE-2, 15 parts by mass of PEEK, and 5 parts by mass of PAR from the upstream supply port. The PEEK is supplied to the extruder, 55 parts by mass of PEEK is supplied from the downstream supply port, melt-kneaded while being evacuated from the vent port provided after the downstream supply port, and the strand is cooled with water, taken off, and cut into PEEK / PPE. Got. In addition, the screw rotation speed at this time was 300 rpm. As a result of measuring the melt viscosity of the obtained PEEK / PPE using a capillary rheometer, the temperature at 20 to 100 Pa · s at a shear rate of 1000 seconds ⁻¹ was about 380 ° C.

[Examples 1 to 5] (Examples and Comparative Examples)
An immersion bath (made by Kobe Steel, Ltd.) having a resin impregnating roller was installed at the tip of a co-rotating twin-screw extruder (ZSK25: manufactured by Coperion Co., Ltd.) equipped with one supply port on the upstream side. Set the extruder cylinder temperature of the long fiber reinforced resin production equipment to 320 ° C, supply PS / PPE1 from the extruder supply port, melt at a screw rotation speed of 300 rpm, and fill the bath for immersion with a resin impregnation roller I let you. On the other hand, two roving-like glass fiber bundles (ER2400T-448N: manufactured by Nippon Electric Glass Co., Ltd.) having a filament diameter of 17 μm were introduced from a roving table into a bath for immersion having a resin impregnation roller. The roving glass fiber bundle is impregnated with the molten resin in the bath for immersion, and is continuously drawn out from the nozzle (diameter: 3.2 mm) portion of the bath for immersion at a take-up speed of 15 m / min. After cooling and solidifying in a water-cooled bath, various twists were applied to the resin strands through a twisting roller, and then the pellets were cut to a length of 10 mm with a pelletizer. At this time, the set temperature of the immersion bath was 300 ° C. At this time, the discharge amount of the extruder was adjusted so that the glass fiber content was about 50% by mass.
Examples 1 to 5 differ only in the twist strength applied to the strands, and the rest are the same.
Various evaluations were performed using the obtained resin pellets and strands. The results are shown in Table 3. At this time, the Charpy impact strength, bending strength, and high load DTUL were measured by dry mixing 60 parts by mass of the obtained long fiber reinforced pellets and 40 parts by mass of PS / PPE6 pellets at a cylinder temperature of 310 ° C., gold Molding was performed under the condition of a mold temperature of 90 ° C. and subjected to evaluation. The results are shown in Table 3.

[Example 6] (Example)
Except having changed to PS / PPE2 instead of PS / PPE1, everything was performed in the same manner as in Example 3, and a long fiber filler reinforced resin pellet was obtained and evaluated. The results are shown in Table 3.

[Example 7] (Comparative Example)
Chopped strand glass fiber having a filament diameter of 17 μm and a fiber length of 3 mm (surface treatment with the same compound as roving glass fiber), 28% by mass of PS / PPE-1, 42% by mass of PS / PPE-6, and chopped strand glass The composition pellet which consists of 30 mass% of fibers was prepared. At that time, using the extruder used to prepare PS / PPE1, the resin component is supplied from the upstream supply port and the chopped strand glass fiber is supplied from the downstream supply port at the maximum setting temperature of 300 ° C. of the cylinder. Then, the strand was cut to obtain composition pellets having a length of about 3 mm and a diameter of about 3 mm.
Table 3 shows the measurement results of Charpy impact strength, bending strength, and high load DTUL.

[Example 8] (Example)
The extruder cylinder temperature of the same long fiber reinforced resin production apparatus as in Examples 1 to 5 is set to 330 ° C., PS / PPE 3 is supplied from the extruder supply port, and melted at a screw speed of 300 rpm. The bath for immersion was filled. In the same manner as in Examples 1 to 5, the roving glass fiber bundle was introduced into the immersion bath having a resin impregnation roller, and the roving glass fiber bundle was impregnated with the molten resin in the immersion bath. It is continuously drawn from the nozzle part at a take-up speed of 23 m / min, made into one strand, cooled and solidified in a water-cooled bath, and then twisted with a lead width of 30 mm to the resin strand through a twisting roller. After being twisted, the pellet length was cut to 10 mm with a pelletizer. The set temperature of the immersion bath at this time was 320 ° C.
At this time, the discharge amount of the extruder was adjusted so that the glass fiber content was about 50% by mass. The amount of glass fiber determined by measuring the ash later was 52.5% by mass.
Evaluation items similar to those of Examples 1 to 5 were carried out using the obtained resin pellets and strands. At that time, with respect to the impact strength and DTUL of the molded piece, 57 parts by mass of the long fiber filler reinforced resin pellet obtained in this example and 43 parts by mass of PS / PPE6 were set so that the glass fiber content was 30% by mass. The pellets were mixed and the characteristics were measured in the same manner. The results are shown in Table 3.

[Example 9] (Example)
Except that the cylinder temperature of the extruder in Example 8 was set to 280 ° C., the screw rotation speed was set to 150 rpm, and the temperature of the bath for immersion was set to 280 ° C., long fiber filler reinforced resin pellets were obtained. Evaluation was performed. The results are shown in Table 3.

[Examples 10 to 12] (Examples and Comparative Examples)
As described in Table 3, the PS / PPE resin mixture was used in the same manner as in Example 3 except that PS / PPE4, PS / PPE5, or PS-1 containing no polyphenylene ether was used. did. The results are also shown in Table 3. For Example 12, 60 parts by mass of the obtained long fiber reinforced pellets were mixed with 40 parts by mass of PS-1 pellets in order to evaluate the composition with no polyphenylene ether, and the cylinder temperature was 210 ° C. What was shape | molded on the conditions of the temperature of 80 degreeC was used for evaluation. The results are shown in Table 3.

From the results of Table 3, the long fiber filler reinforced resin pellets of the examples all have excellent wettability, and the vertical cracking during pellet transportation and the detachment of the long fiber filler from the pellet are extremely suppressed. This is a long fiber filler reinforced resin pellet that can be molded into a molded product with extremely high heat resistance and impact resistance because it has excellent pellet appearance and excellent defibration properties of the long fiber filler during molding. It was.
On the other hand, in the long fiber filler reinforced resin pellets of Example 1 and Example 5 in which the spiral lead is outside the range of 20 mm to 80 mm, only the flow end portion retains the shape in comparison of the defibration properties of the long fiber filler. However, the defibration property was not sufficient.
In Example 5 in which the spiral lead was 100 mm, many long fiber fillers were detached.
In Example 7 in which chopped strand glass fibers were used instead of long fiber fillers, the glass fiber length in the molded product was not sufficient, so that the impact properties, bending strength and heat resistance were insufficient.
Further, the long fiber filler reinforced resin pellet of Example 12 containing no polyphenylene ether was not sufficiently defibrated, and the molded article did not have sufficient strength in bending strength.

[Examples 13 to 23] (Examples and Comparative Examples)
Using the same extruder as in Example 1, the cylinder set temperature was set to 230 to 300 ° C., the set temperature of the immersion bath was set to 220 ° C., 280 ° C. or 300 ° C., and PP / PPE 1 PP / PPE5 and PP-1 are respectively supplied and impregnated into a roving-shaped glass fiber bundle in a bath for immersion adjusted to 280 ° C. or 300 ° C., and at a take-up speed of 20 m / min from the outlet nozzle of the bath for immersion. It was continuously drawn out as a strand, twisted, and then cut into a pellet length of 10 mm with a pelletizer. At this time, the discharge amount of the extruder was adjusted so that the glass fiber content in the polymer alloy reinforced with long fibers was 39% by mass.
Evaluation was performed using the obtained resin pellets and strands. The results are shown in Table 4. Here, the mixing of the long fiber filler reinforced pellet and the pellet not containing the long fiber filler as in Example 1 was not performed, and the long fiber filler reinforced pellet alone was injection molded, and its characteristics were evaluated. .

From the results in Table 4, the long fiber filler reinforced resin pellets of the examples all have excellent wettability, and the vertical cracking during pellet transportation and the detachment of the long fiber filler from the pellets are extremely suppressed. This is a long fiber filler reinforced resin pellet that can be molded into a molded product with extremely high heat resistance and impact resistance because it has excellent pellet appearance and excellent defibration properties of the long fiber filler during molding. It was.
On the other hand, in the long fiber filler reinforced resin pellets of Examples 21 and 22 in which the cross-sectional area of the core part exceeds 70% of the pellet cross-sectional area, longitudinal cracks occur in many pellets, and the long fiber filler is detached. Many were produced. Furthermore, the defibration property was not sufficient, and the appearance characteristics of the pellet surface were not glossy.
In addition, the long fiber filler reinforced resin pellet of Example 23 containing no polyphenylene ether has vertical cracks caused by a large number of pellets, and the defibration property is not sufficient, and the appearance characteristics of the pellet surface are glossy. I didn't have it. Further, the molded body does not have sufficient strength in impact resistance or the like.

[Examples 24 to 29] (Examples and Comparative Examples)
The cylinder temperature of the same long fiber reinforced resin production apparatus as in Example 1 is set to 280 ° C., PA / PPE1 is supplied from the extruder supply port, melted at a screw speed of 300 rpm, and a bath for immersion having a resin impregnation roller Charged. On the other hand, 2400 TEX roving-like glass fiber bundles (ER2400T-448N: manufactured by Nippon Electric Glass Co., Ltd.) having a fiber diameter of 17 μm were introduced into a bath for immersion having a resin impregnation roller from a roving table and melted in the bath for immersion. The resin is impregnated into the roving-like glass fiber bundle, continuously pulled out from the nozzle portion of the bath for immersion at a take-up speed of 15 m / min, made into one strand, cooled and solidified in a water-cooled bath, and then twisted Various twists were applied to the resin strand through a roller so that various lead widths could be twisted, and then the pellet length was cut to 10 mm with a pelletizer. At this time, the set temperature of the immersion bath was 300 ° C.
At this time, the discharge amount of the extruder was adjusted so that the glass fiber content was about 50% by mass. The amount of glass fiber determined by measuring the ash later was 54% by mass.
Examples 24-29 differ only in the strength of the twist applied to the strands, and the rest are all the same.
Evaluation was performed using the obtained resin pellets and strands. The results are shown in Table 5. Here, the mixing of the long fiber filler reinforced pellet and the pellet not containing the long fiber filler as in Example 1 was not performed, and the long fiber filler reinforced pellet alone was injection molded, and its characteristics were evaluated. .

[Example 30] (Example)
All were carried out in the same manner as in Example 26 except that the set temperature of the immersion bath was 280 ° C. The results are shown in Table 5.
[Examples 31 to 33] (Examples and Comparative Examples)
Immersion with a roller for resin impregnation in which the extruder cylinder temperature of the same long fiber reinforced resin production apparatus as in Example 1 is set to 320 ° C., PA / PPE2 is supplied from the extruder supply port, melted at a screw rotation speed of 300 rpm The bus was filled. In the same manner as in Examples 24 to 29, the roving glass fiber bundle was introduced into an immersion bath having a resin impregnating roller, and the roving glass fiber bundle was impregnated with the molten resin in the immersion bath. It is continuously drawn out from the nozzle part at a take-up speed of 23 m / min, made into one strand, cooled and solidified in a water-cooled bath, and then twisted with various lead widths to the resin strand through a twisting roller. Thus, after applying various twists, the pellet length was cut to 10 mm with a pelletizer. The set temperature of the immersion bath at this time was 330 ° C.
At this time, the discharge amount of the extruder was adjusted so that the glass fiber content was about 50% by mass. The amount of glass fiber determined by measuring the ash later was 47% by mass.
Examples 31 to 33 differ only in the twist strength applied to the strands, and the rest are the same.
Evaluation items similar to those in Examples 24 to 29 were performed using the obtained resin pellets and strands. The results are shown in Table 5.
[Examples 34 to 36] (Examples and Comparative Examples)
The evaluation was performed in the same manner as in Example 26 except that the resin supplied from the extruder supply port was changed to that shown in Table 5. The results are also shown in Table 5.

From the results of Table 5, the long fiber filler reinforced resin pellets of the examples all have excellent wettability, and the vertical cracking during pellet transportation and the detachment of the long fiber filler from the pellets are extremely suppressed. This is a long fiber filler reinforced resin pellet that can be molded into a molded product with extremely high heat resistance and impact resistance because it has excellent pellet appearance and excellent defibration properties of the long fiber filler during molding. It was.
On the other hand, all of the long fiber filler reinforced resin pellets of Examples 24, 28, 31, 33 and Example 29 in which the spiral lead is outside the range of 20 mm to 80 mm and the untwisted example 29 are longitudinal cracks, detachment, and appearance of the pellets. It was not a well-balanced pellet to all of the defibrating properties.
The long fiber filler reinforced resin pellet of Example 36 containing no polyphenylene ether was not sufficiently defibrated, and the molded article did not have sufficient strength in impact resistance.

[Examples 37 to 53] (Examples and Comparative Examples)
The cylinder temperature of the same long fiber reinforced resin production apparatus as in Example 1 is set to 290 to 310 ° C., and PPS / PPE1 to PPS / PPE16 are supplied as shown in Tables 6 and 7 from the extruder supply port, and screw rotation It was melted at several 300 rpm and filled in a bath for immersion having a roller for resin impregnation. On the other hand, 2400 TEX roving-like glass fiber bundles (ER2400T-448N: manufactured by Nippon Electric Glass Co., Ltd.) having a fiber diameter of 17 μm were introduced into a bath for immersion having a resin impregnation roller from a roving table and melted in the bath for immersion. The resin is impregnated into the roving-like glass fiber bundle, continuously pulled out from the nozzle part of the immersion bath at a take-up speed of 20 m / min, made into one strand, cooled and solidified in a water-cooled bath, and then twisted. Various twists were applied to the resin strand through a roller so that various lead widths could be twisted, and then the pellet length was cut to 10 mm with a pelletizer. The set temperature of the immersion bath at this time was 310 ° C.
At this time, the discharge amount of the extruder was adjusted so that the glass fiber content was about 40% by mass. The amount of glass fiber determined by measuring the ash later was 39% by mass.
Using the obtained resin pellets and strands, the evaluation items shown in Table 6 and Table 7 were performed. The results are shown in Tables 6 and 7. Here, the mixing of the long fiber filler reinforced pellet and the pellet not containing the long fiber filler as in Example 1 was not performed, and the long fiber filler reinforced pellet alone was injection molded, and its characteristics were evaluated. .

From the results of Table 6 and Table 7, the long fiber filler reinforced resin pellets of the examples all have excellent wettability, and vertical cracks during pellet transportation and detachment of the long fiber filler from the pellets are observed. Long fiber filler reinforced resin capable of molding molded products with extremely high heat resistance and impact resistance due to extremely suppressed, excellent appearance of pellets and excellent fibrillation of long fiber filler during molding It was a pellet.
On the other hand, the long fiber filler reinforced resin pellets of Examples 43 and 44 in which the spiral lead is outside the range of 20 mm to 80 mm and the cross sectional area of the core part exceeds 70% of the pellet cross sectional area are long fibers In all of the filler-reinforced resin pellets, many detachment of pellets occurred, and vertical cracks occurred in many pellets, and the appearance characteristics of the pellet surface were not glossy.
The long fiber filler reinforced resin pellet of Example 53 containing no polyphenylene ether was not sufficiently defibrated, and the molded article did not have sufficient strength in impact resistance or the like.

[Examples 54 to 58] (Examples and Comparative Examples)
The cylinder temperature of the same long fiber reinforced resin production apparatus as in Example 1 is set to 330 ° C., LCP / PPE1 is supplied from the extruder supply port, melted at a screw speed of 300 rpm, and a bath for immersion having a resin impregnation roller Charged. On the other hand, 2400 TEX roving-like glass fiber bundles (ER2400T-448N: manufactured by Nippon Electric Glass Co., Ltd.) having a fiber diameter of 17 μm were introduced into a bath for immersion having a resin impregnation roller from a roving table and melted in the bath for immersion. The resin is impregnated into the roving-like glass fiber bundle, continuously pulled out from the nozzle part of the bath for immersion at a take-up speed of 22 m / min, made into one strand, cooled and solidified in a water-cooled bath, and then twisted. Various twists were applied to the resin strand through a roller so that various lead widths could be twisted, and then the pellet length was cut to 10 mm with a pelletizer. The set temperature of the immersion bath at this time was 330 ° C.
At this time, the discharge amount of the extruder was adjusted so that the glass fiber content was about 50% by mass.
Various evaluations were performed using the obtained resin pellets and strands. The results are shown in Table 7. At this time, Charpy impact strength, bending strength, and high load DTUL were measured by dry-mixing 60 parts by mass of the obtained long fiber reinforced pellets and 40 parts by mass of LCP / PPE1 pellets at a cylinder temperature of 330 ° C., gold Molding was performed under conditions of a mold temperature of 110 ° C., and the evaluation was performed. The results are shown in Table 8.

[Example 59] (Example)
Using LCP / PPE2 instead of LCP / PPE1, the same operation as in Example 55 was carried out to obtain long fiber filler reinforced resin pellets. In addition, 60 parts by mass of the obtained long fiber reinforced pellets and 40 parts by mass of LCP / PPE1 pellets were dry-mixed and molded under conditions of a cylinder temperature of 330 ° C. and a mold temperature of 110 ° C. Provided. The results are shown in Table 8.

[Example 60] (Comparative example)
A chopped strand glass fiber having a filament diameter of 17 μm and a fiber length of 3 mm (surface treatment with the same compound as the long fiber glass fiber) is used, the resin component ratio is the same as that of LCP / PPE1, and the chopped strand glass fiber is from 30% by mass. The resulting composition pellets were prepared. At that time, using the extruder used to prepare LCP / PPE1, the resin component is supplied from the upstream supply port and the chopped strand glass fiber is supplied from the downstream supply port at the maximum setting temperature of 330 ° C. of the cylinder. Then, the strand was cut to obtain composition pellets having a length of about 3 mm and a diameter of about 3 mm.
Composition pellets having the same composition as the test pieces for which the molded article properties of Examples 54 to 58 were measured were measured for Charpy impact strength, bending strength, and high load DTUL. The results are shown in Table 8.

[Example 61] (Example)
The extruder cylinder temperature of the same long fiber reinforced resin production apparatus as in Examples 54 to 58 is set to 330 ° C., LCP / PPE3 is supplied from the extruder supply port, and melted at a screw rotation speed of 300 rpm. The bath for immersion was filled. In the same manner as in Examples 54 to 58, the roving-like glass fiber bundle was introduced into an immersion bath having a resin impregnation roller, and the roving-like glass fiber bundle was impregnated with the molten resin in the immersion bath. After being continuously drawn out from the nozzle part at 15 m / min and made into a single strand, cooled and solidified in a water-cooled bath, the resin strand is passed through a twisting roller and twisted with a lead width of 30 mm. After that, the pellet length was cut to 10 mm with a pelletizer. The set temperature of the immersion bath at this time was 320 ° C.
At this time, the discharge amount of the extruder was adjusted so that the glass fiber content was about 50% by mass. The amount of glass fiber determined by measuring the ash later was 52.5% by mass.
Using the obtained resin pellets and strands, the same evaluation items as in Examples 54 to 58 were performed. At that time, with respect to the impact strength and DTUL of the molded piece, 57 parts by mass of the long fiber filler reinforced resin pellets obtained in this example and 43 parts by mass of the LCP / PPE3 pellets so that the glass fiber content becomes 30% by mass. The pellets were mixed and molded, and the characteristics were measured in the same manner. The results are shown in Table 8.

[Example 62] (Example)
A long fiber filler reinforced resin pellet was obtained in the same manner as in Example 61 except that the extruder cylinder temperature was set to 300 ° C., the screw rotation speed was 150 rpm, and the temperature of the immersion bath was set to 290 ° C. The results are shown in Table 8.
[Example 63] (Example)
In Example 56, it carried out like Example 56 except having used LCP / PPE4 instead of LCP / PPE1. Using the obtained resin pellets and strands, the above evaluation items were evaluated. The results are shown in Table 8.
[Example 64] (Example)
In Example 56, it carried out like Example 56 except having used PEEK / PPE instead of LCP / PPE1 and having set the preset temperature of the bath for immersion to 380 degreeC. Using the obtained resin pellets and strands, the above evaluation items were evaluated. The results are shown in Table 8.

From the results shown in Table 8, the long fiber filler reinforced resin pellets of the examples all have excellent wettability, and the vertical cracking during pellet transportation and the detachment of the long fiber filler from the pellets are extremely suppressed. This is a long fiber filler reinforced resin pellet that can be molded into a molded product with extremely high heat resistance and impact resistance because it has excellent pellet appearance and excellent defibration properties of the long fiber filler during molding. It was.
On the other hand, the long fiber filler reinforced resin pellets of Examples 54 and 58 in which the spiral lead was outside the range of 20 mm to 80 mm were not glossy in the surface appearance of the pellets.
In Example 60 using chopped strand glass fibers instead of long fiber fillers, it can be seen that the properties of the molded article, impact strength, bending strength and heat resistance, are significantly inferior and insufficient.

[Example 65] (Comparative example)
In Example 56, it carried out like Example 56 except having used only LCP-1 instead of LCP / PPE1. The Charpy impact value was measured using the obtained resin pellets, and the average value was 16 (J) (N number = 10). However, the variation was about plus or minus 4 (J) (12J to 20J) with respect to the average value. On the other hand, the variation of Example 56 was plus or minus 2 with respect to the average value.
Furthermore, in the observation after the molded piece was incinerated, most of the glass fibers were present in the form of undefibrated bundles, and the shape retention was not good at all.
From the comparison of each of the above Examples and Comparative Examples, in the present invention, by adding polyphenylene ether to a thermoplastic resin other than polyphenylene ether, the fibrillation property of the long fiber filler is greatly improved, and further, physical properties It can be seen that the effect of greatly improving the quality stability of can be obtained. This can be said to be a result of the resin composition of the present invention that the polyphenylene ether was alloyed to improve the defibration property of the inorganic filler and lead to quality stability.

[Example 66] (Example)
Immersion bath (Kobe Steel Corporation) having a resin impregnating roller at the tip of a co-rotating twin screw extruder (ZSK25: manufactured by Coperion Co., Ltd.) with one supply port on the upstream side and one supply port on the downstream side Set the extruder cylinder temperature of the long fiber reinforced resin manufacturing apparatus installed at 320 ° C. at a rate shown in Table 8, PS / PPE4 from the upstream supply port of the extruder to 100 parts by mass. , 10 parts by weight of Irg1098 and 1 part by weight of zinc sulfide as a white colorant are supplied, and FR-2 is supplied from the downstream supply port to 13 parts by weight with respect to 100 parts by weight of PS / PPE4. The molten resin was filled in a bath for immersion having a resin impregnating roller. On the other hand, the molten resin in the bath for immersion, in which two filament diameters of 17 μm and 2400 TEX roving-like glass fiber bundles (using urethane-based resin as a sizing agent) were introduced from the roving table into a bath for immersion having a resin impregnation roller, It is impregnated into a roving-like glass fiber bundle, continuously drawn out from the nozzle (diameter 3.2 mm) portion of the bath for immersion at a take-up speed of 40 m / min, made into one strand, and cooled and solidified in a water-cooled bath. After passing through a twisting roller, the resin strand was twisted with a lead width of 30 mm and obtained as a resin strand. At this time, the discharge amount of the extruder was adjusted so that the glass fiber content was about 40% by mass.
The flame resistance and color tone of the obtained long fiber filler reinforced resin strand were observed. In Table 9, flame retardancy and color tone when Irg1098 and Fr-2 are not blended are shown together for comparison. Here, the flame retardancy of the long fiber filler reinforced resin strand is that the resin strand cut to 10 cm is indirectly flamed for 5 seconds by the UL94 vertical test, and after the flame is removed, self-extinguishes. Judged by whether or not. For those that self-extinguished, the time to extinguishment was measured. The color tone is a visual judgment of the color. The results are shown in Table 9.

[Example 67 to Example 70] (Example)
PS / PPE4 of Example 66 was changed to PP / PPE2, PA / PPE3, PPS / PPE6, and LCP / PPE4, respectively, and was carried out as Examples 67 to 70, respectively. The temperatures of the extruder and the immersion bath at this time are shown in Table 9. The obtained strand was evaluated for flame retardancy and color tone in the same manner as in Example 66. The results are shown in Table 9.
Table 9 shows the properties of the long fiber filler reinforced resin pellets and strands obtained in Examples 66 to 70. In order to clarify the effect, the properties in the composition containing no stabilizer and flame retardant are listed in the lower column as a comparison of the properties of the strands. Thus, it can be seen that by including the flame retardant and the stabilizer, the flame retardancy is improved and the color tone is improved even though the flame retardant and the stabilizer are included.

  According to the present invention, it has become possible to stably supply long fiber filler reinforced resin pellets that can be formed into molded pieces having excellent handling properties and high thermal and mechanical properties, which the market has been waiting for. It was.

Claims (25)

A pellet composed of a long fiber filler and a thermoplastic resin mixture,
The long fiber filler is disposed in the pellet in a spiral shape with the length direction of the pellet as the central axis direction in the pellet, and the spiral lead is 20 mm to 80 mm ,
The pellet has a skin layer portion with a low long fiber filler content and a core portion with a high long fiber filler content, and is cut in the thickness direction of the pellet with a microtome to form a smooth cross section, using an optical microscope The cross-sectional area of the core part obtained by observing, photographing with reflected light, and calculating by image analysis is in the range of 30% to 70% of the cross-sectional area of the pellet,
Long fiber filler reinforced resin pellets, wherein the thermoplastic resin mixture comprises polyphenylene ether and a thermoplastic resin other than polyphenylene ether.   The long fiber filler reinforced resin pellet according to claim 1, wherein a ratio of an average fiber length of the long fiber filler to a length of the long fiber filler reinforced resin pellet exceeds 1.0.   The long fiber filler reinforced resin pellet according to claim 1 or 2, wherein a ratio of the long fiber filler in the long fiber filler reinforced resin pellet is 30 to 70% by mass.   The long fiber filler reinforced resin pellet according to any one of claims 1 to 3, wherein the long fiber filler is a glass fiber.   5. The reduced viscosity (0.5 g / dl concentration chloroform solution, measured at 30 ° C.) of the polyphenylene ether is in a range of 0.30 to 0.55 dl / g according to claim 1. Long fiber filler reinforced resin pellets.   The polyphenylene ether is a copolymer containing 2,3,6-trimethylphenol, and the proportion of 2,3,6-trimethylphenol units in the polyphenylene ether is 10 to 30% by mass. The long fiber filler reinforced resin pellet of any one of -5.   The thermoplastic resin other than the polyphenylene ether is selected from the group consisting of styrene resin, olefin resin, polyester, polyamide, polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone, polysulfone, and polyarylketone 1 The long fiber filler reinforced resin pellet according to any one of claims 1 to 6, which is a seed or more.   The thermoplastic resin other than the polyphenylene ether is at least one selected from the group consisting of homopolystyrene, rubber-modified polystyrene, acrylonitrile-styrene copolymer, and a copolymer of N-phenylmaleimide and styrene. 8. The long fiber filler reinforced resin pellet according to any one of 7 above.   The long fiber filler reinforced resin pellet according to claim 8, wherein a ratio of polyphenylene ether in the thermoplastic resin mixture is 10 to 90 mass%.   The thermoplastic resin other than the polyphenylene ether is at least one selected from the group consisting of polypropylene, liquid crystal polyester, polyamide, polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone, polysulfone and polyarylketone, The long fiber filler reinforced resin pellet of any one of Claims 1-7.   The long fiber filler reinforced resin pellet of Claim 10 whose ratio of the polyphenylene ether which occupies in the said thermoplastic resin mixture is 1-50 mass%.   Furthermore, the long fiber filler reinforced resin pellet of any one of Claims 1-11 containing a compatibilizing agent.   The long fiber filler reinforcement according to claim 12, wherein the compatibilizing agent is a compound having one or more functional groups selected from the group consisting of an epoxy group, an oxazolyl group, an imide group, a carboxylic acid group, and an acid anhydride group. Resin pellets.   The long fiber filler reinforced resin pellet according to any one of claims 1 to 13, further comprising 0.1 to 5 parts by mass of a sterically hindered phenol-based antioxidant with respect to 100 parts by mass of the thermoplastic resin mixture.   Furthermore, the long fiber filler reinforced resin pellet of any one of Claims 1-14 which contains 5-50 mass parts of flame retardants which do not contain a halogen with respect to 100 mass parts of the said thermoplastic resin mixture.   Furthermore, the long fiber filler reinforced resin pellet of any one of Claims 1-15 containing fillers other than a long fiber filler.   The resin pellet mixture containing 100 mass parts of long fiber filler reinforced resin pellets of any one of Claims 1-16, and 0.5-150 mass parts of resin pellets which do not contain a long fiber filler.   The ratio of the said long fiber filler which occupies in the said resin pellet mixture is 10-60 mass%, The resin pellet mixture of Claim 17   The resin pellet mixture of Claim 17 or 18 in which the resin pellet which does not contain the said long fiber filler contains fillers other than a long fiber filler.   The filler other than the long fiber filler is an hydroxide of an element selected from magnesium and calcium, an oxide of an element selected from the group consisting of magnesium, titanium, iron, copper, zinc and aluminum, zinc sulfide, zinc borate, It is at least one filler selected from the group consisting of calcium carbonate, talc, wollastonite, glass, carbon black, carbon nanotube, and silica, and the average particle diameter of fillers other than the long fiber filler is 1 mm or less. The resin pellet mixture according to claim 19. A pellet composed of a long fiber filler and a thermoplastic resin mixture,
The long fiber filler is disposed in the pellet in a spiral shape with the length direction of the pellet as the central axis direction in the pellet, and the spiral lead is 20 mm to 80 mm ,
The pellet has a skin layer portion with a low long fiber filler content and a core portion with a high long fiber filler content, and is cut in the thickness direction of the pellet with a microtome to form a smooth cross section, using an optical microscope The cross-sectional area of the core part obtained by observing, photographing with reflected light, and calculating by image analysis is in the range of 30% to 70% of the cross-sectional area of the pellet,
The thermoplastic resin mixture is made of polyphenylene ether and a thermoplastic resin other than polyphenylene ether, and is a method for producing long fiber filler reinforced resin pellets,
(1) A step of producing the molten thermoplastic resin mixture using an extruder,
(2) a step of impregnating the long fiber filler into the molten thermoplastic mixture;
(3) A process of taking a twisted strand to form a resin strand,
(4) A step of cutting the resin strand into a pellet shape,
A method for producing a long fiber filler reinforced resin pellet. It is a manufacturing method of the long fiber filler reinforced resin pellet of Claim 21 , Comprising: Here, the long fiber filler reinforced resin pellet of Claim 21 which contains process (1)-(4) continuously in this order. Manufacturing method. In the step (1), wherein the polyphenylene ether and the poly further comprising polyphenylene and a thermoplastic resin other than ether, the step of mixing to the production of the thermoplastic resin mixture in a molten state, according to claim 21 or 22 Manufacturing method of long fiber filler reinforced resin pellets. The set temperature of the immersion bath for impregnating the long-fiber filler in the step (2) into the molten thermoplastic resin mixture is 20 ° C. or more higher than the set temperature of the extruder in the step (1). there, the method of producing the long fiber filler reinforced resin pellet according to any one of claims 21 to 23. Said step take-off speed in the (3) is in the range of 10 to 150 m / min, the production method of the long fiber filler reinforced resin pellet according to any one of claims 21-24.