WO2021251431A1 - 射出成形体の製造方法、並びに射出成形機用のノズル及びノズル付射出ユニット - Google Patents

射出成形体の製造方法、並びに射出成形機用のノズル及びノズル付射出ユニット Download PDF

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Publication number
WO2021251431A1
WO2021251431A1 PCT/JP2021/021917 JP2021021917W WO2021251431A1 WO 2021251431 A1 WO2021251431 A1 WO 2021251431A1 JP 2021021917 W JP2021021917 W JP 2021021917W WO 2021251431 A1 WO2021251431 A1 WO 2021251431A1
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Prior art keywords
melt
injection
nozzle
component
capillary
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PCT/JP2021/021917
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English (en)
French (fr)
Japanese (ja)
Inventor
貴章 三好
一洋 谷本
涼子 平嶋
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旭化成株式会社
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Application filed by 旭化成株式会社 filed Critical 旭化成株式会社
Priority to JP2022530606A priority Critical patent/JP7343703B2/ja
Publication of WO2021251431A1 publication Critical patent/WO2021251431A1/ja
Priority to JP2023140996A priority patent/JP7608543B2/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/20—Injection nozzles

Definitions

  • the present invention relates to a method for manufacturing an injection molded product, and a nozzle for an injection molding machine and an injection unit with a nozzle.
  • capillary nozzles having various hole diameters are known.
  • the capillary nozzle is usually a nozzle having a gentle taper shape toward the capillary portion so that the melt received from the cylinder of the injection molding machine can be guided to the injection port without applying excessive pressure and shearing force. It has a hole (for example, Patent Document 1).
  • a mixture obtained by blending a desired amount of dyeing pigment masterbatch with a base resin is plasticized and molded by an injection molding machine to obtain the desired color of the entire molded body. Color is being made.
  • each compounding component is prepared in advance by using equipment such as an extruder that can be homogenized by melt-kneading. After keeping the dispersed state in an ideal state and ensuring the desired dispersion uniformity, it was necessary to perform injection molding.
  • a desired molded product can be obtained simply by mixing a plurality of raw materials and a masterbatch to a desired composition at a molding site without using a kneading device such as an extruder and then molding with a molding machine.
  • a kneading device such as an extruder and then molding with a molding machine.
  • thermoplastic resin molded product having excellent dispersion uniformity from a thermoplastic resin mixture containing a plurality of compounding components that are difficult to uniformly disperse with each other by a molding machine.
  • the present invention solves the above-mentioned market needs and problems, and provides an injection-molded article having excellent dispersion uniformity of each compound component, for example, even from a thermoplastic resin mixture containing a plurality of compound components that are difficult to uniformly disperse with each other. It is an object of the present invention to provide a method for manufacturing an injection molded product, which can be stably manufactured, and a nozzle for an injection molding machine and an injection unit with a nozzle.
  • the present invention includes the following aspects.
  • Preliminary melt forming step of obtaining a pre-melt containing the first component and the second component An injection melt forming step of dispersing the second component in the first component in the preliminary melt to obtain an injection melt, and an injection step of injecting the injection melt from the ejection port of a nozzle.
  • an elongation strain is applied to the preliminary melt to form the injection melt.
  • the method is A pre-melt forming step of melting a mixture containing the first component and the second component at a temperature equal to or higher than the melting point of the thermoplastic resin contained in the mixture to obtain a pre-melt.
  • An injection melt forming step of introducing the preliminary melt into the melt supply portion of the nozzle to form an injection melt, and an injection pressure of 40 MPa from the injection port of the capillary hole portion of the injection melt. Injection process to inject with the above, Including, how. [3] The method according to the second aspect, wherein the nozzle hole diameter in the connecting portion is 4.0 mm or less.
  • the nozzle has a capillary hole having an injection port and a melt supply section for supplying a melt for injection, which is fluidly connected to the capillary hole.
  • Hole diameter change rate D X /d/1.4
  • Dx is the nozzle hole diameter (mm) of the melt supply section at a position 1.4 mm from the connecting section
  • d is the capillary hole diameter (mm) at the connecting portion.
  • the first component contains a crystalline resin and the second component contains an amorphous resin.
  • the preliminary melt forming step after the first component and the second component are separately supplied, the first component and the second component are melt-kneaded and pre-melted.
  • Each of the first component and the second component contains a thermoplastic resin and a filler, and the filler content of the first component and the filler content of the second component are different from each other.
  • the nozzle has a capillary hole having an injection port and a melt supply section for supplying an injection melt, which is fluid-connected to the capillary hole.
  • the nozzle hole diameter of the capillary hole is 4.0 mm or less.
  • Cross-sectional area change rate S X / s / 1.4 [During the ceremony: Sx is the flow path cross-sectional area (mm 2 ) of the melt feeder at a position 1.4 mm from the connection; s is the capillary hole cross-sectional area (mm 2 ) at the connecting portion.
  • the melt supply unit is configured to receive the pre-melt and apply elongation strain to the pre-melt to form the injection melt. It has been a nozzle.
  • the melt supply unit has a hole wall having a hole wall parallel to the nozzle axis and having an angle of 70 ° or more and 100 ° or less with respect to the direction toward the upstream of the melt flow.
  • Hole diameter change rate D X /d/1.4
  • Dx is the nozzle hole diameter (mm) of the melt supply section at a position 1.4 mm from the connecting section
  • d is the capillary hole diameter (mm) at the connecting portion.
  • the ratio (l / d) of the capillary hole length l to the capillary hole diameter d at the connecting portion between the capillary hole portion and the melt supply portion is 2 or more and 10 or less, according to the above aspects 11 to 13. Nozzle described in either.
  • an injection molding machine for injecting a thermoplastic resin mixture containing a first component containing a thermoplastic resin and a second component containing one or more selected from the group consisting of a thermoplastic resin and a filler.
  • the injection molding unit with a nozzle has a nozzle portion and a cylinder portion.
  • the nozzle portion has a capillary hole portion having an injection port and a melt supply unit for supplying an injection melt, which is fluidly connected to the capillary hole portion.
  • the nozzle hole diameter of the capillary hole is 4.0 mm or less.
  • Cross-sectional area change rate S X / s / 1.4
  • Sx is the flow path cross-sectional area (mm 2 ) of the melt feeder at a position 1.4 mm from the connection
  • s is the capillary hole cross-sectional area (mm 2 ) at the connecting portion.
  • the melt supply unit is configured to receive the pre-melt and apply elongation strain to the pre-melt to form the injection melt. Injection unit with nozzle.
  • the ratio (l / d) of the capillary hole length l to the capillary hole diameter d at the connecting portion between the capillary hole portion and the melt supply portion is 2 or more and 10 or less, according to the above embodiments 15 to 17. Injection unit with nozzle described in either.
  • a method for manufacturing an injection molded article, and a nozzle for an injection molding machine and an injection unit with a nozzle may be provided.
  • FIG. 1 is a schematic cross-sectional view showing a nozzle according to an aspect of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a nozzle according to an aspect of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing a nozzle according to an aspect of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing an injection unit with a nozzle according to one aspect of the present invention.
  • One aspect of the present invention is an injection molded article of a thermoplastic resin mixture containing a first component containing a thermoplastic resin and a second component containing one or more selected from the group consisting of a thermoplastic resin and a filler.
  • a method including an injection step of injecting an injection melt from an injection port of a nozzle.
  • thermoplastic resin mixture composed of a plurality of compounding components When a thermoplastic resin mixture composed of a plurality of compounding components is injection-molded, a phenomenon occurs in which the resin, filler, etc. dispersed in the prior extrusion processing are united and aggregated due to retention in the molding machine, resulting in performance. If stabilization is difficult or if an attempt is made to dilute a masterbatch that is highly filled with an inorganic filler using only a molding machine, it is difficult to uniformly disperse the compounded components depending on the type and concentration of the compounded components, which is desirable.
  • the condition design of the injection molding machine for achieving the dispersion uniformity of the above may be complicated, and further, the desired dispersion uniformity may not be achieved even by such a complicated condition design.
  • the present inventors unexpectedly It has been found that the dispersed state of the compounding components in the melt can be further improved by controlling the flow of the melt of the thermoplastic resin mixture in the vicinity of the injection nozzle. Furthermore, it was found that by adopting such a method, the thermal history of the material can be reduced and the physical properties more than expected can be exhibited.
  • injection molding is excellent in the dispersion uniformity of each compounding component. It enables stable production of the body.
  • the method of the present embodiment is performed using an injection molding machine, and the nozzle used is a nozzle of the injection molding machine.
  • an elongation strain is applied to the preliminary melt to form an injection melt.
  • the pre-melt contains the first and second components, and in one embodiment, it is composed of two or more phases having one or more dispersed phases. Applying elongation strain to the pre-molten metal causes a change in the dispersion morphology (for example, phase separation morphology) due to elongation deformation of the melt, which contributes to reduction of dispersion size and improvement of dispersion uniformity.
  • the second component forms one or more phases in the pre-molten, and the dispersion diameter of the second component in the injection molded product is the dispersion diameter of the second component of the pre-molten. Smaller than.
  • the dispersion diameter of each phase (for example, when the second component contains a thermoplastic resin and a filler and each of them forms a phase)
  • the agglomerate particle size can be smaller in the injection molded body than in the pre-molten material, respectively.
  • the dispersion diameter of the second component of the present disclosure is a number measured by the method described in the [Examples] section of the present disclosure or a method understood by those skilled in the art to be equivalent thereto. Average particle size (for thermoplastic resin) or average aggregate diameter (for filler).
  • the dispersed particle size of the dispersed phase in the raw material pellets described in the [Example] section of the present disclosure is set to the dispersion diameter of the second component in the preliminary melt.
  • the dispersion diameter of the thermoplastic resin as the second component can be determined by the number average particle diameter and / or the particle diameter distribution.
  • the dispersion diameter can be compared at the upper limit (that is, the maximum diameter) of the particle size distribution or at the lower limit (that is, the minimum diameter). In one embodiment, it is desirable to compare the dispersion diameter by the number average particle diameter.
  • thermoplastic resin in the pre-melted product A comparison of the dispersion diameter of the thermoplastic resin in the pre-melted product with the dispersion diameter of the thermoplastic resin in the injection molded product is described in the section of [Example] of the present disclosure of the dispersed phase in the raw material pellets. This can be done by comparing the number average particle size with the number average particle size of the dispersed phase in the injection molded piece.
  • the aggregate diameter of the filler (CNF, etc.) in the raw material pellets described in the [Example] section of the present disclosure is set to the dispersion of the second component in the preliminary melt. It can be regarded as a diameter. This is because the aggregate diameter as the dispersion diameter of the second component in the preliminary melt does not change from the aggregate diameter as the dispersion diameter of the second component in the raw material pellets.
  • the aggregate diameter as the dispersion diameter of the filler as the second component can be determined by the average aggregate diameter and / or the aggregate diameter distribution.
  • the aggregate diameter can be compared at the upper limit of the aggregate diameter distribution or at the lower limit. In one embodiment, it is desirable to compare the aggregate diameters with the average aggregate diameter.
  • a comparison of the dispersion diameter of the filler in the premelt and the dispersion diameter of the filler in the injection molded article is based on the average aggregate diameter of the filler in the raw material pellets described in the [Example] section of the present disclosure. , It can be done by comparison with the average aggregate diameter of the filler in the injection molded piece.
  • the ratio of the dispersion diameter in the injection molded product to the dispersion diameter in the preliminary melt of the second component is such that the dispersion size is small and the dispersion size is small.
  • 0.90 or less, 0.85 or less, or 0.80 or less, 0.70 or less, or 0.60 or less, or 0.50 may be the following, and in one embodiment, it may be 0.01 or more, 0.05 or more, or 0.10 or more from the viewpoint of ease of manufacturing the injection molded product.
  • the fact that the ratio is 0.90 or less can be an index that the elongation strain is applied to the preliminary melt.
  • the thermoplastic resin mixture contains a first component and a second component.
  • the first component comprises a thermoplastic resin.
  • the first component may further contain a filler in addition to the thermoplastic resin.
  • the filler may be an organic filler, an inorganic filler, or a combination thereof.
  • the organic filler include cellulose (for example, cellulose nanofibers, cellulose whiskers, cellulose microfibers, etc.), organic substance-containing carbon fillers (carbon black, carbon fibers, etc.), various synthetic polymers, and the like.
  • the inorganic filler include glass fiber, zeolite, ceramics, talc, mica, titanium dioxide, silica, wollastonite, dragonite, calcium carbonate, metal powder and the like.
  • an injection-molded article having excellent dispersion uniformity can be produced even when a filler that is generally difficult to uniformly disperse in a resin is used. Therefore, when the filler contains a filler (for example, cellulose nanofibers) which is generally difficult to uniformly disperse in the resin, the advantages of the present invention are more remarkable and preferable.
  • a filler for example, cellulose nanofibers
  • the first component is, in addition to the thermoplastic resin and any filler, various additives (for example, compatibilizer, plasticizer, colorant, fragrance, pigment, flow conditioner, leveling agent, conductive agent, antistatic agent, etc. It may contain an ultraviolet absorber, an ultraviolet dispersant, a deodorant, etc.).
  • various additives for example, compatibilizer, plasticizer, colorant, fragrance, pigment, flow conditioner, leveling agent, conductive agent, antistatic agent, etc. It may contain an ultraviolet absorber, an ultraviolet dispersant, a deodorant, etc.).
  • the second component comprises one or more selected from the group consisting of thermoplastic resins and fillers.
  • specific examples of the thermoplastic resin and the filler may be the same as those exemplified in the first component.
  • the second component may further contain various additives in addition to one or more selected from the group consisting of thermoplastic resins and fillers.
  • the additives that can be contained in the second component may be the same as those exemplified as the additives in the first component.
  • first component and the second component can be selected according to the purpose.
  • the method of the present embodiment can form an injection-molded article having excellent dispersion uniformity of the compounded components even when the affinity between the first component and the second component is low.
  • the first component may contain a crystalline resin and the second component may contain an amorphous resin.
  • the method of the present embodiment can produce an injection-molded article having excellent dispersion uniformity.
  • each of the first component and the second component contains a thermoplastic resin and a filler, and the filler content of the first component and the filler of the second component (even if they are the same as the filler in the first component). The contents may be different from each other.
  • the thermoplastic resin mixture may further contain an additional component in addition to the first component and the second component.
  • additional components thermoplastic resins of different types and / or properties from the thermoplastics contained in the first component and the thermoplastic resins that may be contained in the second component; and / or the first component and / Alternatively, a filler having a different type and / or characteristics from the filler that can be contained in the second component; and the like can be exemplified.
  • the thermoplastic resin mixture may be composed only of the first component and the second component.
  • thermoplastic resin and the organic / inorganic filler will be described later.
  • FIGS. 1 to 3 are schematic cross-sectional views showing a nozzle according to one aspect of the present invention.
  • the capillary hole portion 1 having the injection port P and the melt supply unit 2 fluidly connected to the capillary hole portion 1 to supply the injection melt are provided.
  • Nozzles 11 and 21 also referred to as capillary nozzles in the present disclosure
  • the capillary nozzle is attached to an injection molding machine.
  • the rate of change in cross-sectional area is increased (that is, the cross-sectional area of the melt supply unit 2 is rapidly reduced toward the downstream side of the melt flow), the pre-melt is stretched and flowed, and the stretch strain (also known as stretch strain) is applied to the pre-melt.
  • stretch strain also known as stretch strain
  • a cross-sectional area change rate of 5 mm -1 or more is advantageous in that the effect of improving the dispersed state of the compounding components is satisfactorily exhibited.
  • Sectional area change rate from the viewpoint of satisfactorily express the effect of improving the dispersion state of ingredients, preferably, 8 mm -1 or higher, or 10 mm -1 or more, or 20 mm -1 or more.
  • the cross-sectional area change rate is preferably 300 mm -1 or less, 200 mm -1 or less, or 150 mm. It may be -1 or less.
  • the flow path cross-sectional area for calculating the cross-sectional area change rate is calculated from the nozzle hole diameter.
  • the capillary hole diameter (d) in the connecting portion C is important in order to allow the preliminary melt to elongate and flow and to impart an elongate strain to the pre-melt. From the viewpoint of stably achieving fine dispersion of the dispersant, it is preferably 4.0 mm or less, 3.0 mm or less, 2.5 mm or less, 2.0 mm or less, or 1.8 mm or less. Further, from the viewpoint of suppressing excessive injection pressure, preferably 0.1 mm or more, 0.2 mm or more, 0.4 mm or more, 0.6 mm or more, 0.8 mm or more, or 1. It may be 0 mm or more.
  • the nozzle hole diameter at the injection port P may be equal to or larger than the capillary hole diameter at the connecting portion C, but is preferably 1 mm or more, 1.5 mm or more, or 2 mm or more. Further, it may be preferably 10 mm or less, 6 mm or less, 5 mm or less, 4 mm or less, or 3 mm according to the spool tip diameter of the molded product.
  • a preferred embodiment of the ratio of l (l / d) is 2 or more and 20 or less.
  • the ratio (l / d) is preferably 2 or more, 3 or more, or 5 or more from the viewpoint of adjusting the flow direction of the injection melt to form a uniform injection molded product, and excessive pressure is applied. From the viewpoint of suppressing such a situation and performing injection molding stably and easily, it is preferably 20 or less, 10 or less, 8 or less, or 7 or less.
  • the capillary hole 1 may have the same hole diameter over the entire area, and the nozzle hole diameter at the injection port P may be larger than the capillary hole diameter at the connecting portion C. That is, the molten resin reaches from the upstream side of the molten metal flow through the nozzle hole in the connecting portion C to the nozzle hole outlet in the injection port P, but the capillary hole passing in this process may be a straight pipe having the same diameter. It may have a trumpet-like shape in which the diameter gradually increases.
  • a better embodiment is to maintain the capillary hole diameter in the connecting portion C by at least a length corresponding to the capillary hole diameter in the connecting portion C, and then gradually expand the diameter of the nozzle hole in the ejection port P.
  • the length to be maintained is preferably 1.5 times or more, 2 times or more, or 5 times or more the length corresponding to the capillary hole diameter in the connecting portion C from the viewpoint of suppressing the turbulence of the resin flow. From the viewpoint of reducing such pressure and facilitating injection molding, it is preferably 10 times or less, 7 times or less, or 6 times or less.
  • the nozzles 11 and 21 supply a melt to supply a melt for injection, which is fluidly connected to the capillary hole 1 having the injection port P and the capillary hole 1.
  • a melt supply unit having a hole wall W parallel to the nozzle axis and having an angle ⁇ of 70 ° or more and 100 ° or less with respect to the direction toward the upstream of the melt flow (direction of arrow U in the figure). Has 2 and.
  • the angle ⁇ may be 70 ° or more and 100 ° or less at any part of the melt supply part 2, but in a preferred embodiment, the angle ⁇ of the part in contact with the connecting part C of the melt supply part 2 ( That is, the rising angle of the hole wall of the melt supply portion) is 70 ° or more and 100 ° or less.
  • the hole diameter of the melt supply part is toward the capillary hole.
  • the melt received from the cylinder is guided to the ejection port without being subjected to excessive pressure or shearing force.
  • the melt supply portion 2 having the hole wall W having the angle ⁇ that is, a steep hole wall close to perpendicular to the flow path direction
  • the melt supply unit 2 provided with the hole wall W having the angle ⁇ has an advantage that the melt for injection can be formed in which the compounding components are extremely uniformly dispersed.
  • the angle ⁇ is preferably 75 ° or more, 80 ° or more, 82 ° or more, 84 ° or more, or 85 ° or more.
  • the angle ⁇ may be, for example, an acute angle (that is, 70 ° or more and less than 90 °) as shown in FIG. 2, but when the angle is 90 ° or more as shown in FIG. 1, for example, the melt supply unit 2 In some cases, it is preferable in that a very large elongation strain is applied to the pre-melted material. However, from the viewpoint of suppressing resin retention in the nozzle and generation of black spot foreign matter, the angle ⁇ is preferably 100 ° or less, 95 ° or less, or 90 ° or less.
  • the hole diameter change rate is increased (that is, the nozzle hole diameter of the melt supply unit 2 is rapidly reduced toward the downstream side of the melt flow)
  • the preliminary melt is extended in the same manner as when the cross-sectional area change rate is increased.
  • a high shearing force is applied to the pre-melted body, and the dispersed state of the compounded components in the pre-melted body is improved.
  • a cross-sectional area change rate of 2 mm -1 or more is advantageous in that the effect of improving the dispersed state of the compounding components is satisfactorily exhibited.
  • Sectional area change rate from the viewpoint of satisfactorily express the effect of improving the dispersion state of ingredients, preferably, 2.5 mm -1 or higher, or 3 mm -1 or more, or 4 mm -1 or more.
  • the pore size change rate is determined from the viewpoint of stable injection of the injection melt from the injection port. Preferably, it may be 20 mm -1 or less, 15 mm -1 or less, or 10 mm -1 or less.
  • FIG. 4 is a schematic cross-sectional view showing an injection unit with a nozzle according to one aspect of the present invention.
  • an injection molding unit 40 with a nozzle attached to the injection molding machine may be used.
  • the injection molding unit 40 with a nozzle may have a nozzle portion 41 and a cylinder portion 42, and the nozzle portion 41 may be the capillary nozzle of the present disclosure as described above.
  • the cylinder portion 42 may have a general configuration known to those skilled in the art as a cylinder of an injection molding machine, and is provided with members such as a plunger, a screw, a check valve, and a heater, and can be made of a molding material supplied from a hopper.
  • FIG. 4 shows an example in which the nozzle portion 41 and the cylinder portion 42 are separate members, the nozzle portion 41 and the cylinder portion 42 may be a single member.
  • a preliminary melt containing the first component and the second component is obtained.
  • the preliminary melt is (1) A method of subjecting a kneaded product obtained by kneading the first component and the second component in advance to a pre-melt forming step, or (2) pre-melting the first component and the second component.
  • the kneading conditions include a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a sheet extruder, a kneader, a lavender, a plast mill, a continuous high shearing machine, and a roller. Processing and the like can be exemplified. Processing conditions such as temperature differ depending on the properties of the first component and the second component, but general conditions for those skilled in the art can be applied without problems. For example, the temperature is preferably set according to the resin that starts flowing at the highest temperature among the thermoplastic resins used.
  • Examples of combinations of the first component and the second component include a polymer alloy of a thermoplastic resin A and another thermoplastic resin, a composite of a thermoplastic resin A and fillers, and a thermoplastic resin polymer alloy and a filler.
  • a kneaded product obtained by kneading the first component and the second component in advance is introduced into, for example, an injection molding machine, and the molding machine is used.
  • the conditions for forming the preliminary melt by shearing with the screw of No. 1 can be exemplified.
  • the set temperature is set according to, for example, the resin that starts flowing at the highest temperature among the thermoplastic resins used.
  • the step of melt-kneading with a screw, introducing the melt into the plunger region, and weighing is also included in this step.
  • the above (2) is a method in which the first component and the second component are separately provided in the preliminary melt forming step.
  • the first component is separately supplied with a thermoplastic resin
  • the second component is separately supplied with one or more selected from the group consisting of the thermoplastic resin and the filler. Examples thereof include a step of forming a melt.
  • the thermoplastic resin and other components are kneaded in advance using the processing machine or the like described in detail in (1) above.
  • the obtained kneaded product can also be used.
  • the second component includes one or more selected from the same or different thermoplastic resin, organic and / or inorganic filler as the first component, the thermoplastic resin and other components (other thermoplastic resin and / or filler). Etc.) can be kneaded in advance to obtain a kneaded product.
  • Specific examples of the embodiment of the first component include various examples, such as thermoplastic resin A alone, a resin composition in which a stabilizer or the like is previously mixed with thermoplastic resin A, thermoplastic resin A and other thermoplastic resins. Examples thereof include a composite of a thermoplastic resin A and fillers, a composite of a thermoplastic resin polymer alloy and fillers, and the like.
  • thermoplastic resin B alone, the resin composition in which a stabilizer or the like is previously mixed with the thermoplastic resin B, the thermoplastic resin B and the thermoplastic resin A.
  • examples thereof include a polymer alloy with another thermoplastic resin containing the above, a composite of the thermoplastic resin B and the fillers, a composite of the thermoplastic resin polymer alloy and the fillers, and the like.
  • the first component is a composition composed of the thermoplastic resin A and other components, and it is also possible to use the thermoplastic resin A as the second component in order to dilute the composition.
  • thermoplastic resin mixture containing a first component containing a thermoplastic resin and a second component containing one or more selected from the group consisting of thermoplastic resins and fillers.
  • the conditions of the preliminary melt forming step here may be the same as in (1) above.
  • this step is equal to or higher than the melting point of the thermoplastic resin contained in the mixture containing the first component and the second component (the highest melting point when a plurality of types of thermoplastic resins having a melting point are present).
  • the mixture is melted at temperature to give a pre-melt.
  • Such melting conditions are advantageous in obtaining an injection-molded article having excellent dispersion uniformity.
  • the difference between the melting temperature (° C) of the mixture and the melting point (° C) that is, melting temperature (° C) -melting point (° C)
  • the pre-melt has good fluidity, so that the dispersion uniformity is improved. It may be + 70 ° C. or lower, or + 60 ° C. or lower, or + 50 ° C. or lower in terms of ease of use, preferably above the melting point, or above + 5 ° C., or above + 10 ° C. ..
  • the melting temperature referred to here may be a set temperature in the process of obtaining a preliminary melt.
  • injection melt forming process In this step, an injection melt is obtained from the preliminary melt.
  • the injection melt forming step is performed by introducing the preliminary melt into the melt supply section of the capillary nozzle described above.
  • the first component and the second component in the preliminary melt are dispersed with each other to obtain an injection melt.
  • dispersing the first component and the second component with each other means improving the dispersed state of the first component and the second component, and more specifically, the first component. It means reducing the dispersion size and / or improving the dispersion uniformity of at least one compounding component in the component and / or the second component.
  • the second component is dispersed in the first component in the preliminary melt to obtain an injection melt.
  • the improvement in the dispersed state means that, for example, in the case of improving the dispersibility between thermoplastic resins, a section is prepared, and an optical microscope, a transmission electron microscope, or the like is used to prepare a dispersed phase before and after the injection melt forming step. It can be confirmed by actually measuring the size of. For example, if the etching treatment can be performed using a solvent that dissolves the component to be measured, which is a dispersed phase, and does not dissolve the continuous phase component, the treated sample can be confirmed with a laser microscope or a scanning electron microscope.
  • the continuous phase resin may be dissolved using a solvent that dissolves the continuous phase component and does not dissolve the dispersed phase component that is the measurement target component, and the diameter of the dispersed phase may be measured using a laser particle size meter. It is possible. Further, for example, in order to improve the dispersibility of the filler in the thermoplastic resin, a section is prepared, and the dispersion state of the filler before and after the injection melt forming step is actually measured using an optical microscope, a transmission electron microscope, or the like. A method well known to those skilled in the art, such as a method or a method of measuring the dispersed state of the internal filler in a non-destructive manner using an X-ray CT measuring device, can be applied. There are various methods, but it is desirable to adopt the same measurement method at least for confirming the change in the dispersion state before and after the injection melt forming step.
  • an elongation strain and / or a shear strain is applied to the pre-melted body.
  • the method can be exemplified, a method of applying elongation strain to a preliminary melt by using the capillary nozzle of the present disclosure, and injection molding under extremely high injection speed conditions exceeding 1000 mm / sec using a special ultra-high speed injection molding machine.
  • the method may be performed, such as a method of plasticizing a composition having a high filler content and a high melt viscosity while applying a high back pressure at the time of plasticizing in a molding machine.
  • an elongation strain is applied to the preliminary melt to form an injection melt.
  • Elongation strain can be imparted to the pre-melt by increasing the flow rate per unit cross-sectional area of the pre-melt, and such flow rate is, in one aspect, using a nozzle having a unique configuration of the present disclosure. It can be realized by controlling the shear rate and / or the injection pressure at the time of injection, which will be described later. Therefore, the presence or absence of extension strain applied to the preliminary melt can be determined in one embodiment by the magnitude of the change rate of the capillary cross-sectional area and the injection speed.
  • the injection melt is injected into the cavity of the mold from the injection port of the nozzle (in one embodiment, the capillary hole of the capillary nozzle).
  • the apparent shear rate (SR) at the time of injection is preferably 5,000 seconds-1 or more, or from the viewpoint of producing an injection-molded article having excellent dispersion uniformity of compounding components, particularly from the viewpoint of producing good elongation strain. It is 10,000 seconds- 1 or more, 50,000 seconds- 1 or more, or 100,000 seconds- 1 or more, and is preferably 5,000,000 seconds from the viewpoint of stable injection from the injection port. -1 or less, or 3,000,000 seconds- 1 or less, or 2,000,000 seconds- 1 or less.
  • the apparent shear rate is a numerical value expressed by the following equation and can be controlled by the injection speed of the injection molding machine (screw moving speed, piston moving speed in the case of a pre-plastic injection molding machine).
  • Apparent shear rate SR 32Q / ( ⁇ ⁇ d 3 )
  • Q represents the injection volume per second (mm 3 / sec)
  • d represents the capillary hole diameter (mm) in the connecting portion C.
  • the injection pressure in the injection step is preferably 40 MPa or more, 50 MPa or more, 60 MPa or more, or 70 MPa from the viewpoint of producing an injection-molded article having excellent dispersion uniformity of compounding components, particularly from the viewpoint of satisfactorily generating elongation strain. That is all.
  • the injection pressure is preferably high, but in one embodiment, it may be 200 MPa or less, 180 MPa or less, or 170 MPa or less from the viewpoint of suppressing heat generation at the nozzle portion.
  • the injection pressure is, in one embodiment, the maximum injection pressure in the injection molding machine.
  • the thermoplastic resin contained in the first component and the thermoplastic resin contained in the second component may be a crystalline resin having a melting point in the range of 100 ° C to 350 ° C or a glass in the range of 100 to 250 ° C. Examples thereof include an amorphous resin having a transition temperature and a thermoplastic elastomer having a glass transition temperature below room temperature (23 ° C.) and exhibiting elasticity at room temperature.
  • the melting point of the crystalline resin here is the peak top temperature of the endothermic peak that appears when the temperature is raised from 23 ° C to 10 ° C / min using a differential scanning calorimetry device (DSC). When two or more endothermic peaks appear, it means the peak top temperature of the endothermic peak on the highest temperature side.
  • DSC differential scanning calorimetry device
  • the glass transition temperature of the amorphous resin and the thermoplastic elastomer referred to here is from 23 ° C. in the case of the amorphous resin and in the case of the thermoplastic elastomer using a dynamic viscoelastic modulus measuring device.
  • the peak top temperature of the peak at which the storage elastic modulus is greatly reduced and the loss elastic modulus is maximized is obtained.
  • thermoplastic resin examples include olefin resins, styrene resins, polyesters, polyamides, polyphenylene ethers, polyacetals, polyphenylene sulfides, polyarylates, polyetherimides, and polyether monkeys. It is selected from the group consisting of phon, polysulfone, polyarylketone, a block copolymer of an aromatic vinyl compound and a conjugated diene compound, a partially hydrogenated additive of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, and a mixture thereof. At least one is mentioned.
  • polyethylene-based resin polypropylene-based resin, homopolystyrene, rubber-modified polystyrene, acrylonitrile-styrene copolymer, N-phenylmaleimide and styrene copolymer, polyamide, polyphenylene ether, polyarylene sulfide, polyallylate, Polyetherimide, polyethersulphon, polysulfone, liquid crystal polyester, polyarylketone, block copolymer of aromatic vinyl compound and conjugated diene compound, partial hydrogen additive of block copolymer of aromatic vinyl compound and conjugated diene compound , And at least one selected from the group consisting of mixtures thereof.
  • examples of the olefin resin include polyethylene, polypropylene, a copolymer of ethylene and ⁇ -olefin, a polymer of ethylene and acrylates, and the like, and polypropylene (hereinafter, simply “" It may be abbreviated as "PP").
  • polypropylene propylene homopolymer; after obtaining the propylene homopolymer, the propylene homopolymer and propylene, ethylene and / or at least one other ⁇ -olefin (for example, 1-butene, 1-hexene, etc.) are mixed.
  • ⁇ -olefin for example, 1-butene, 1-hexene, etc.
  • examples thereof include a propylene-ethylene block copolymer having a propylene homopolymer moiety and a propylene-ethylene random copolymer moiety obtained by copolymerization; and the like.
  • Polypropylene may be a mixture of propylene homopolymer and propylene-ethylene block copolymer.
  • the density of the propylene polymer portion of polypropylene is usually 0.90 g / cm 3 or more, preferably 0.90 to 0.93 g / cm 3 , and 0.90 to 0. More preferably, it is 92 g / cm 3.
  • the density of the propylene polymer moiety can be determined by the JIS K-7112 underwater substitution method.
  • polypropylene is a copolymer with ⁇ -olefin containing propylene as a main component
  • the copolymer component is extracted using a solvent such as hexane, and the density of the remaining propylene polymer portion is determined by the above JIS K.
  • -7112 Can be determined by the underwater substitution method.
  • the crystal nucleating agent is not particularly limited as long as it improves the crystallinity of polypropylene, but is, for example, an organic salt such as a metal salt of an aromatic carboxylic acid, a sorbitol derivative, an organic phosphate, or an aromatic amide compound. Examples thereof include a nucleating agent and an inorganic nucleating agent such as talc.
  • the melt flow rate (MFR) of polypropylene may be 10 g / 10 minutes or more from the viewpoint of improving injection moldability. 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.
  • styrene resin examples include homopolystyrene, rubber-modified polystyrene (generally referred to as high-impact polystyrene), a styrene-butadiene block copolymer and / or a hydrogenated product thereof, a styrene-isoprene block copolymer and the like. / Or a hydrogenated product thereof, a copolymer of styrene and a vinyl monomer capable of radical copolymerization with the styrene, and the like can be mentioned.
  • vinyl monomers that can be radically copolymerized with styrene include: vinyl cyanide compounds such as acrylonitrile and methacrylic nitrile; vinyl such as acrylic acid, butyl acrylate, methacrylic acid, methyl methacrylate, and ethylhexyl methacrylate. Carboxylic acids and esters thereof; unsaturated dicarboxylic acid anhydrides such as maleic anhydride and N-phenylmaleimide and derivatives thereof; and diene compounds such as butadiene and isoprene; etc., and copolymerization of two or more thereof in combination. Is also possible.
  • styrene resin examples include homopolystyrene, rubber-modified polystyrene, acrylonitrile-styrene copolymer, N-phenylmaleimide-styrene copolymer, and mixtures thereof from the viewpoint of commercially available availability. ..
  • the reduced viscosity (at a concentration of 0.5 g / 100 ml in a toluene solution at 30 ° C.) is used from the viewpoint of maintaining a balance between the fluidity of the melt and the mechanical strength of the obtained injection molded product.
  • Homopolystyrene and rubber-modified polystyrene having a measurement in the range of 0.5 to 2.0 dl / g are preferable.
  • the reduced viscosity of the homopolystyrene and the rubber-modified polystyrene is more preferably 0.7 dl / g or more, and further preferably 0.8 dl / g or more. Further, the reduced viscosity of the homopolystyrene and the rubber-modified polystyrene is preferably 1.5 dl / g or less, and more preferably 1.2 dl / g or less.
  • the acrylonitrile-styrene copolymer a copolymer containing 3 to 30% by mass of an acrylonitrile structural unit is preferable from the viewpoint of chemical resistance and heat resistance of the obtained resin molded product.
  • the content of the acrylonitrile structural unit is more preferably 5% by mass or more, further preferably 7% by mass or more.
  • the content of the acrylonitrile structural unit 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 copolymerizing 30 parts by mass or less of butadiene with a total of 100 parts by mass of acrylonitrile and styrene.
  • N-phenylmaleimide-styrene copolymer a copolymer containing 15 to 70% by mass of N-phenylmaleimide structural unit is preferable from the viewpoint of heat resistance of the obtained resin molded product.
  • the content of the N-phenylmaleimide structural unit is more preferably 20% by mass or more, further preferably 25% by mass or more.
  • the content of the N-phenylmaleimide structural unit is more preferably 65% by mass or less, and further preferably 60% by mass or less.
  • the N-phenylmaleimide-styrene copolymer 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 total of N-phenylmaleimide and styrene.
  • the glass transition temperature of the N-phenylmaleimide-styrene copolymer is preferably in the range of 140 ° C to 220 ° C from the viewpoint of maintaining the heat resistance of the obtained resin molded product.
  • the glass transition temperature is a value measured by a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.
  • polyester examples include polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate, and liquid crystal polyesters, and among these, liquid crystal polyesters are preferable.
  • the liquid crystal polyester is a polyester called a thermotropic liquid crystal polymer.
  • the thermotropic liquid crystal polymer is not particularly limited, and for example, thermotropic liquid crystal polyester containing p-hydroxybenzoic acid, alkylene glycol, and terephthalic acid as main constituent units, p-hydroxybenzoic acid, and 2-hydroxy.
  • thermotropic liquid crystal polyester having -6-naphthoic acid as a main constituent unit
  • p-hydroxybenzoic acid examples thereof include thermotropic liquid crystal polyester having 4,4'-dihydroxybiphenyl and terephthalic acid as main constituent units.
  • liquid crystal polyester those composed of the following structural units (1), (2) and, if necessary, (3) and / or (4) are preferably used.
  • Structural units (1) and (2) are structural units of polyester produced from p-hydroxybenzoic acid and structural units of polyester produced from 2-hydroxy-6-naphthoic acid, respectively.
  • Structural units (1) and (2) are preferable from the viewpoint of obtaining a resin having an excellent balance of mechanical properties such as heat resistance, fluidity, and rigidity.
  • the liquid crystal polyester has the following structural unit (5), which is composed of a structural unit (3) and a structural unit (4). May include.
  • X in the structural units (3), (4) and (5) are independently ⁇ (CH 2 ) n ⁇ (in the formula, n is an integer of 1 to 6), and the following structural group (6) :.
  • Y is halogen, alkyl or aryl. It is a divalent group selected from the group consisting of.
  • the structural unit (3) is preferably a structural unit produced from one or more selected from ethylene glycol, hydroquinone, 4,4'-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, bisphenol A and the like, more preferably. , Ethylene glycol, 4,4'-dihydroxybiphenyl and hydroquinone, and more preferably, one or more selected from ethylene glycol and 4,4'-dihydroxybiphenyl. It is a structural unit.
  • the structural unit (4) is preferably a structural unit produced from one or more selected from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and the like, more preferably 2,6-naphthalenedicarboxylic acid and the like. It is a structural unit produced from one selected from terephthalic acid.
  • each of the structural unit (3) and the structural unit (4) two or more of the above-mentioned structural units may be used in combination.
  • the structural unit produced from ethylene glycol and hydroquinone the structural unit produced from ethylene glycol and 4,4'-dihydroxybiphenyl are used.
  • Examples thereof include a combination of structural units produced from hydroquinone and structural units produced from 4,4'-dihydroxybiphenyl.
  • the ratio of the structural units (1), (2), (3), and (4) used in the liquid crystal polyester is not particularly limited, but the structural units (3) and (4) have almost equal molar amounts, for example, a structure.
  • the ratio of the number of moles of the structural unit (4) to the number of moles of the unit (3) is preferably 0.9 or more and 1.1 or less.
  • the structural unit (5) includes a structural unit produced from ethylene glycol and a structural unit produced from terephthalic acid, a structural unit produced from hydroquinone and a structural unit produced from terephthalic acid, and a structure produced from 4,4'-dihydroxybiphenyl.
  • Each combination of the produced structural unit and 2,6-naphthalenedicarboxylic acid can be mentioned.
  • the liquid crystal polyester is a structural unit produced from other aromatic dicarboxylic acids, aromatic diols, and / or aromatic hydroxycarboxylic acids, if necessary, in a small amount range that does not impair the characteristics and effects of the present embodiment. May be further included.
  • the temperature at which the liquid crystal state at the time of melting of the liquid crystal polyester (hereinafter referred to as the liquid crystal start temperature) is preferably 150 to 350 ° C., preferably 180 to 320 ° C., from the viewpoint of the balance between color tone, heat resistance and moldability. It is more preferably ° C.
  • the liquid crystal start temperature of the present disclosure an anisotropic molten phase is observed when the liquid crystal polyester is observed under polarized light while heating the liquid crystal polyester at a heating rate of 1 ° C./min using a polarizing microscope having a heating stage. Temperature.
  • the dielectric loss tangent (tan ⁇ ) of the liquid crystal polyester at 25 ° C. and 1 MHz is preferably 0 from the viewpoint of reducing the dielectric loss and suppressing electrical noise when the injection molded product of the present embodiment is used for electronic / electronic components. It is 0.03 or less, more preferably 0.025 or less. In particular, it is preferable that the dielectric loss tangent (tan ⁇ ) at 25 ° C. under a high frequency region (1 to 10 GHz region in one embodiment) is 0.03 or less, or 0.025 or less.
  • the dielectric loss tangent of the present disclosure is a value determined by a test method based on JIS-K6911.
  • the apparent melt viscosity of the liquid crystal polyester (shear rate 100 / sec at the liquid crystal start temperature + 30 ° C.) is preferably 10 to 3,000 Pa ⁇ s, more preferably 10 to 2,000 Pa ⁇ s. It is more preferably ⁇ 1,000 Pa ⁇ s.
  • 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 the shear rate using a capillary rheometer.
  • the melt viscosity at 300 ° C. at a shear rate of 100 sec-1 can be measured by a capillary rheometer.
  • a capillary graph manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • the capillary has a capillary length of 10 mm and a capillary diameter of 1 mm. Therefore, it can be measured at a temperature of 300 ° C. and a shear rate of 100 sec -1.
  • 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.
  • diamines examples include aliphatic diamines, alicyclic diamines, and aromatic diamines.
  • examples of the diamine include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4.
  • dicarboxylic acid examples include an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid.
  • dicarboxylic acid examples 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 and the like.
  • lactams examples include ⁇ -caprolactam, enantractam, and ⁇ -laurolactam.
  • aminocarboxylic acid examples include ⁇ -aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 13-aminotridecanoic acid and the like. Can be mentioned.
  • the polyamide may be a copolymerized polyamide obtained by polycondensing lactams, diamines, dicarboxylic acids, and / or ⁇ -aminocarboxylic acids alone or in a mixture of two or more kinds. Further, a copolymerized polyamide obtained by polymerizing lactams, diamines, dicarboxylic acids, and / or ⁇ -aminocarboxylic acids to the stage of low molecular weight oligomers in a polymerization reactor and then polymerizing by an extruder or the like is also preferably used. can do.
  • polyamide 6T examples include polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612, polyamide MXD (m-xylylene diamine) 6, polyamide 6T, and the like.
  • 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 preferably used.
  • polyamide 6I means a polymerized polyamide of hexamethylenediamine and isophthalic acid
  • polyamide 6 / 6T means a copolymerized polyamide of ⁇ -aminocaproic acid, hexamethylenediamine, and terephthalic acid.
  • a polyamide further copolymerized by an extruder or the like using two or more of these polyamides can also be used.
  • polyamide a polyamide having an aromatic ring in the repeating structural unit is useful from the viewpoint of improving the heat resistance of the molded product.
  • a mixture of two or more selected from the above polyamides is also preferable.
  • the viscosity of the polyamide is a viscosity measured in 96% sulfuric acid according to ISO307 from the viewpoint of suppressing the outflow from the nozzle during molding and excessive shear heat generation, preferably 70 to 160 ml / g, or 80 to 150 ml. / G.
  • the polyamide a mixture of two or more kinds of polyamides having the same type of polyamide but different viscosity numbers can be used.
  • the combination of the viscosity numbers may be determined as desired, and is, for example, a mixture of a polyamide having a viscosity number of 150 to 200 ml / g and a polyamide having a viscosity number of 50 to 100 ml / g, and the viscosity number is in the range of 50 to 150 ml / g. Examples thereof include a mixture of a plurality of polyamides.
  • the viscosity of the polyamide mixture is a value measured according to the above ISO307 by dissolving the polyamide mixture in 96% sulfuric acid.
  • the terminal amino group concentration of the polyamide is preferably 5 ⁇ mol / g or more, 10 ⁇ mol / g or more, or 12 ⁇ mol / g or more, or from the viewpoint of improving the compatibility of the polyamide with other resins and / or various fillers. It may be 15 ⁇ mol / g or more, and is preferably 45 ⁇ mol / g or less, 40 ⁇ mol / g or less, 35 ⁇ mol / g or less, or 30 ⁇ mol / g or less from the viewpoint of satisfactorily controlling the injection moldability.
  • the concentration of the terminal carboxyl group of the polyamide is preferably 20 ⁇ mol / g or more, or 30 ⁇ mol / g or more, and preferably 150 ⁇ mol / g or less, or 100 ⁇ mol, from the viewpoint of obtaining a resin having excellent mechanical properties such as fluidity and rigidity. It is / g or less, or 80 ⁇ mol / g or less.
  • 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 preferably 1.0 or less, or 0. It is 9 or less, 0.8 or less, or 0.7 or less, and is preferably 0.1 or more from the viewpoint of stabilizing compatibility with other materials.
  • a known method can be used.
  • a diamine compound, a monoamine compound, or a dicarboxylic acid compound so as to have a predetermined terminal concentration at the time of polymerization of the polyamide.
  • a method of adding a terminal modifier such as a monocarboxylic acid compound, an acid anhydride, a monoisocyanate, a monoacid halide, monoesters, and monoalcohols.
  • Terminal modifiers that react with terminal amino groups include, for example: acetic acid, propionic acid, butylic acid, valeric acid, caproic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and iso.
  • Alicyclic monocarboxylic acids such as butyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatics such as benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
  • Group monocarboxylic acids as well as mixtures of two or more of these can be mentioned.
  • These monocarboxylic acid compounds include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, and palmitin in terms of reactivity, stability of the sealed end, price, and the like. Acids, stearic acids, and benzoic acids are preferred, with benzoic acid being more preferred.
  • Terminal modifiers that react with terminal carboxyl groups include, for example: methylamines, ethylamines, propylamines, butylamines, hexylamines, octylamines, decylamines, stearylamines, dimethylamines, diethylamines, dipropylamines, and fats such as dibutylamines.
  • butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, stability of sealed end, price, and the like.
  • the concentration of the terminal amino group and the terminal carboxyl group of the polyamide is preferably obtained from the integrated value of the characteristic signal corresponding to each terminal group by 1 H-NMR, and is preferable in terms of accuracy and convenience.
  • the method disclosed in the publication can be followed.
  • the measurement solvent trifluoroacetic acid is preferably used. It is preferable that the number of integrations of 1 1 H-NMR is at least 300 scans even when measured with an instrument having sufficient resolution.
  • the measurement method by titration as disclosed in JP-A-2003-055549 can also be used.
  • the active end is sealed.
  • benzoic acid which is a monocarboxylic acid
  • an end group sealed with a phenyl group terminal is produced.
  • the concentration of the sealed terminal group of the polyamide is preferably 20% or more, more preferably 40% or more, further preferably 45% or more, and further preferably 50% or more on a molar basis. It is even more preferably 85% or less, more preferably 80% or less, and even more preferably 75%.
  • the terminal encapsulation rate of the polyamide can be determined by measuring the number of terminal carboxyl groups, terminal amino groups and terminal groups enclosed by the terminal encapsulant existing in the polyamide, respectively, and according to the following formula.
  • End sealing rate (%) [( ⁇ - ⁇ ) / ⁇ ] ⁇ 100 (In the formula, ⁇ represents the total number of terminal groups in the molecular chain (which is usually equal to twice the number of polyamide molecules), and ⁇ is the total number of unsealed terminal carboxyl groups and terminal amino groups. Represents.)
  • the water content of the polyamide is preferably in the range of 500 to 3000 mass ppm, and more preferably in the range of 500 to 2000 mass ppm.
  • the water content is a value measured by a water vaporization method based on the B method of ISO15512.
  • the polyphenylene ether is used in the following general formula (7):
  • R 1 to R 4 are independently hydrogen, halogen atom, primary or secondary C1 to C7 alkyl group, phenyl group, C1 to C7 haloalkyl group, C1 to C7 aminoalkyl group, respectively.
  • the method for producing polyphenylene ether is not particularly limited as long as it is a known method.
  • the production method described in Japanese Patent Publication No. 63-152628 and the like can be mentioned.
  • polyphenylene ether examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6-phenyl).
  • polyphenylene ether examples 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 can be mentioned.
  • polymer of the polyphenylene ether examples include a copolymer of 2,6-dimethylphenol and other phenols, for example, a copolymer of 2,3,6-trimethylphenol and 2-. Examples thereof include a polymer with methyl-6-butylphenol.
  • the polyphenylene ether is a copolymer of poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethylphenol from the viewpoint of commercial availability. Phenol or a mixture thereof is preferred.
  • the ratio of each monomer unit is 2,3,6-in the polyphenylene ether copolymer.
  • the ratio of the trimethylphenol structural unit is preferably 10 to 30% by mass, or 15 to 25% by mass, or 20 to 25% by mass.
  • the reduced viscosity ( ⁇ sp / c: dl / g, 0.5 g / dl concentration chloroform solution, measured at 30 ° C.) of the polyphenylene ether is preferably 0.30 dl / g or more from the viewpoint of mechanical strength, and is another material. From the viewpoint of improving compatibility with, it is preferably 0.55 dl / g or less, 0.53 dl / g or less, 0.45 dl / g or less, or 0.36 dl / g or less.
  • the polyphenylene ether may be a mixture of two or more kinds having different reducing viscosities.
  • Examples thereof include a mixture with polyphenylene ether of about .50 dl / g.
  • the reduction viscosity of a mixture of two or more kinds of polyphenylene ethers having different reduction viscosities is preferably in the range of 0.30 to 0.55 dl / g.
  • the polyphenylene ether may be modified with a denaturing agent.
  • the modifier include saturated or unsaturated dicarboxylic acids such as maleic anhydride, N-phenylmaleimide, apple acid, citric acid and fumaric acid and derivatives thereof, and vinyl compounds such as styrene, acrylic acid ester and methacrylic acid ester. Will be.
  • the polyphenylene ether may be modified in advance, or may be modified at the same time as extrusion by adding a modifying agent when the resin is melt-extruded.
  • Polyarylene sulfide has the following general formula: [-Ar-S-] (In the formula, Ar represents a divalent group including an arylene structure.) It may be a polymer containing 50 mol% or more, 70 mol% or more, or 90 mol% or more of the arylene sulfide unit represented by. Examples of Ar include p-phenylene group, m-phenylene group, substituted phenylene group, p, p'-diphenylene sulfone group, p, p'-biphenylene group, p, p'-diphenylene carbonyl group, naphthylene group and the like. Can be mentioned.
  • the arylene structure may be a substituted arylene. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and a phenyl group.
  • the polyarylene sulfide may be a homopolymer having one type of arylene group as a constituent unit, and is a copolymer obtained by mixing two or more different types of arylene groups from the viewpoint of processability and heat resistance. There may be.
  • polyarylene sulfide polyphenylene sulfide having an arylene group as a phenylene group is preferable, and polyphenylene sulfide having a repeating unit of p-phenylene sulfide as a main component (hereinafter, may be simply abbreviated as "PPS”) is used. It is more preferable because it has excellent workability and heat resistance and is easily available industrially.
  • the cross-linked PPS also includes a semi-cross-linked PPS in which the degree of cross-linking is kept to a minimum.
  • linear type PPS and crosslinked type PPS may be used in combination.
  • the combined use of linear PPS and crosslinked PPS is preferable from the viewpoint of the balance between fluidity and toughness.
  • the melt viscosity of the polyarylene sulfide at a shear rate of 100 sec -1 at 300 ° C. is preferably 10 Pa ⁇ s or more from the viewpoint of giving the resin excellent mechanical properties, and is preferable from the viewpoint of obtaining good injection moldability. Is 150 Pa ⁇ s or less, 100 Pa ⁇ s or less, or 80 Pa ⁇ s or less.
  • the melt viscosity is a value measured by a capillary rheometer. For example, using a capillary graph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a capillary having a capillary length of 10 mm and a capillary diameter of 1 mm has a temperature of 300 ° C. , Can be measured at a shear rate of 100 sec -1.
  • Polyarylate is a polymer containing an aromatic ring and an ester bond as a structural unit, and is also called a polyaryl ester.
  • the polyarylate includes, for example, bisphenol A and terephthalic acid and / or isophthalic acid according to the following formula (8):
  • Polyarylate having a repeating unit represented by is preferably used.
  • Polyarylate having a molar ratio of terephthalic acid to isophthalic acid of about 1: 1 is suitable from the viewpoint of heat resistance in the molded product and toughness of the resin.
  • polyarylate a commercially available product can also be used, and examples thereof include the trade name "U polymer” manufactured by Unitika Ltd.
  • the polystyrene-equivalent number average molecular weight measured by gel permeation chromatography is preferably 5000 to 300,000, more preferably 10,000 to 300,000, and more preferably 10,000 to 100,000. Is even more preferable.
  • the number average molecular weight of the polyarylate is 5000 or more, the heat resistance of the molded product tends to be good and the mechanical strength of the resin tends to be high, and when it is 300,000 or less, the fluidity of the resin becomes good. Tend.
  • the polystyrene-equivalent number average molecular weight is obtained from the detection time-molecular weight curve of standard polystyrene measured in advance under the same conditions under the conditions of a column temperature of 40 ° C. using GPC and chloroform as a solvent. ..
  • the concentration of the chloroform solution of polyarylate is 1 g / liter.
  • the detector is preferably measured at about 280 nm using an ultraviolet absorption detector.
  • Polyether sulfone, polyetherimide, polysulfone Polyether sulfone, polyetherimide, and polysulfone can be appropriately selected from the known amorphous super engineering plastic group.
  • polyether sulfone examples include, for example, Radel A (registered trademark) and Radel R (registered trademark) manufactured by Solvay Advanced Polymers, MITSUI PES manufactured by Mitsui Chemicals, and Ultrazone E (registered) manufactured by BASF Japan. Trademark) and the like.
  • polyetherimide examples include Ultem (registered trademark) manufactured by SABIC Innovative Plastics.
  • Examples of commercially available products of Polysulfon include Eudel (registered trademark) and Mindell (registered trademark) manufactured by Solvay Advanced Polymers, and Ultrazone S (registered trademark) manufactured by BASF Japan.
  • the polyarylketone is a thermoplastic resin containing an aromatic ring and an ether bond and a ketone bond as its structural unit, and examples thereof include polyetherketone, polyetheretherketone, and polyetherketoneketone.
  • polyetheretherketone a commercially available product may be used, for example, trade names "PEEK151G”, “PEEK90G”, “PEEK381G”, “PEEK450G”, “PEK” (registered trademark) manufactured by VICTREX, and BASF.
  • trade name "Ultrapek” (PEKEKK) (registered trademark) and the like can be used, and the trade name “PEEK” (registered trademark) manufactured by VICTREX is preferably used.
  • the polyarylketone may be used alone or in combination of two or more.
  • the melt viscosity can be used as an index.
  • the melt viscosity is preferably 50 Pa ⁇ s or more, 70 Pa ⁇ s or more, or 100 Pa ⁇ s or more in that the mechanical strength of the resin is good, and the moldability of the resin is good. It is preferably 5000 Pa ⁇ s or less, 3000 Pa ⁇ s or less, 2500 Pa ⁇ s or less, or 1000 Pa ⁇ s or less.
  • the melt viscosity of the polyarylketone is the apparent melt viscosity measured when the polyarylketone heated to 400 ° C. is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 100 kg.
  • Polyacetal examples include polyacetal homopolymers and polyacetal copolymers, and known polyacetals may be used.
  • polyacetal homopolymer is obtained by homopolymerizing a formaldehyde monomer or a cyclic oligomer of formaldehyde such as a trimer (trioxane) and a tetramer (tetraoxane) thereof. Therefore, polyacetal homopolymers consist substantially of oximethylene units.
  • Polyacetal copolymers include formaldehyde monomers or cyclic oligomers of formaldehyde such as trioxane and tetraoxane thereof, glycols (ethylene oxide, propylene oxide, etc.), and cyclic ethers (epichlorohydrin, 1, It is obtained by copolymerizing with 3-dioxolane or the like) or cyclic formaldehyde (1,4-butanediol formal or the like).
  • formaldehyde monomers or cyclic oligomers of formaldehyde such as trioxane and tetraoxane thereof, glycols (ethylene oxide, propylene oxide, etc.), and cyclic ethers (epichlorohydrin, 1, It is obtained by copolymerizing with 3-dioxolane or the like) or cyclic formaldehyde (1,4-butanediol formal or the like).
  • the polyacetal copolymer includes a branched polyacetal copolymer obtained by copolymerizing a formaldehyde monomer and / or a cyclic oligomer with a monofunctional glycidyl ether, and a formaldehyde monomer and / or a cyclic oligomer. And a polyacetal copolymer having a crosslinked structure, which is obtained by copolymerizing with polyfunctional glycidyl ether, can also be exemplified.
  • Polyacetal may have a functional group such as a hydroxyl group at both ends or one end.
  • it may be a polyacetal homopolymer having a blocking component, which is obtained by polymerizing a formaldehyde monomer or a cyclic oligomer in the presence of polyalkylene glycol.
  • Polyacetal is a formaldehyde monomer or its trioxane and tetraoxane in the presence of a compound having a functional group such as a hydroxyl group at both ends or one end (for example, hydrogenated polybutadiene glycol). It may be a polyacetal copolymer having a blocking component, which is obtained by copolymerizing a cyclic oligomer of formaldehyde with a cyclic ether or a cyclic formal.
  • Polyacetal can be used alone or as a mixture of two or more. From the viewpoint of thermal stability, the mixture preferably contains a polyacetal copolymer in an amount of 50% by mass or more, 80% by mass or more, or 95% by mass or more.
  • the polyacetal copolymer can be obtained, for example, by the following method.
  • the commonomer such as 1,3-dioxolane is generally 0.1 to 60 mol%, preferably 0.1 to 20 mol%, based on 100 mol% of trioxane. More preferably, 0.13 to 10 mol% is used.
  • the preferred melting point of the polyacetal copolymer is 162 ° C to 173 ° C, more preferably 167 ° C to 173 ° C, and even more preferably 167 ° C to 171 ° C.
  • the comonomer can be obtained by using a comonomer of about 1.3 to 3.5 mol% with respect to 100 mol% of trioxane.
  • the comonomer can be polymerized by a known method in the presence of a known polymerization catalyst, a polymerization chain agent (chain transfer agent), or the like to obtain the desired polyacetal copolymer.
  • thermoplastic elastomer is selected from the group consisting of an olefin resin, a block copolymer of an aromatic vinyl compound and a conjugated diene compound, and a partially hydrogenated compound of a block copolymer of an aromatic vinyl compound and a conjugated diene compound. At least one of them can be mentioned.
  • the olefin resin examples include polyethylene (high density polyethylene, medium density polyethylene, high pressure method low density polyethylene, linear low density polyethylene, ultralow density polyethylene), polypropylene, ethylene-propylene copolymer, and ethylene-butene copolymer.
  • Examples thereof include a polyethylene-vinyl acetate copolymer.
  • the olefin resin may be a modified product.
  • the modified product is a graft copolymer grafted with one or more vinyl compounds different from the monomers constituting the olefin resin; ⁇ , ⁇ -unsaturated carboxylic acid (acrylic acid, methacrylic acid, maleic acid). , Fumaric acid, Itaconic acid, Citraconic acid, Nasic acid, etc.) or acid anhydrides thereof (with a peroxide if necessary) modified; Monomers constituting olefinic resins and acid anhydrides were copolymerized. Things can be mentioned.
  • the block copolymer of the aromatic vinyl compound and the conjugated diene compound the block copolymer of one or more bonding modes selected from AB type, ABA type and ABAB type consisting of the aromatic vinyl compound block and the conjugated diene compound block. Coalescence is preferred.
  • the partially hydrogenated additive of the block copolymer of the aromatic vinyl compound and the conjugated diene compound is a block copolymer obtained by hydrogenating the block copolymer of the above-mentioned aromatic vinyl compound and the conjugated diene compound.
  • the hydrogenation rate of the aliphatic double bond in the compound is controlled in the range of more than 0% and less than 100%.
  • the hydrogenation rate of the partially hydrogenated block copolymer is preferably 50% or more, more preferably 80% or more, and most preferably 98% or more.
  • the aromatic vinyl compound block referred to here refers to a polymer block mainly composed of an aromatic vinyl compound
  • the conjugated diene compound block refers to a polymer block mainly composed of a conjugated diene compound.
  • the subject means that it contains at least 50% by mass, but more preferably 80% by mass or more.
  • aromatic vinyl compound constituting the aromatic vinyl compound block examples include styrene, ⁇ -methylstyrene, vinyltoluene and the like, and one or more compounds selected from these are used. Of these, styrene is particularly preferable.
  • conjugated diene compound constituting the conjugated diene compound block examples include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, and one or more compounds selected from these are used. Of these, butadiene, isoprene and combinations thereof are preferable.
  • the microstructure of the conjugated diene compound block portion of the block copolymer is that the 1,2-vinyl content, or the total amount of the 1,2-vinyl content and the 3,4-vinyl content is 5 to 80%. It is preferable, more preferably 10 to 50%, and most preferably 15 to 40%.
  • the mass ratio of the aromatic vinyl compound to the conjugated diene compound in the block copolymer is preferably 10/90 to 90/10, or 15/85 to 80/20, or 15/85 to 65/35. , Or 20/80 to 45/55.
  • the number average molecular weight of the block copolymer is measured at 40 ° C. using chloroform as a solvent using gel permeation chromatography, and is a value obtained in terms of standard polystyrene, preferably 10,000 to 500,000, preferably 200,000 to 200,000. 300,000 is more preferable, and 200,000 to 250,000 is most preferable.
  • the number average molecular weight of one aromatic vinyl compound block in the block copolymer is more preferably 20,000 or more.
  • Block copolymers have different binding forms, different number average molecular weights, different aromatic vinyl compound species, different conjugated diene compound species, 1,2-vinyl content, or 1,2-vinyl content. Two or more kinds of compounds having different total amounts of 3 and 4-vinyl, different amounts of aromatic vinyl compound components, different hydrogen addition rates, etc. may be used in combination. It is desirable to mix two or more of these mixed forms having different number average molecular weights.
  • block copolymer two or more kinds of aromatic vinyl compounds and conjugated diene compounds having different mass ratios may be blended.
  • the block copolymer may be a modified product.
  • the modified product is an ⁇ , ⁇ -unsaturated carboxylic acid (acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, etc.) or an acid anhydride thereof, and if necessary, a peroxide. Examples include those that have been denatured in combination.
  • the preferred modification rate is 0.1 to 5% by mass.
  • For the denaturation rate for example, a sample mixed with a denaturant in advance is used to prepare a calibration curve by infrared spectrum measurement, the sample is dissolved in a soluble solvent and reprecipitated, and the sample from which the unreacted denaturant is removed is measured. It is required by doing.
  • the filler that the first component and / or the second component may contain may be an organic filler and / or an inorganic filler.
  • Organic fillers are preferred because of their low specific density.
  • the organic filler include cellulose (for example, cellulose nanofibers, cellulose whiskers, cellulose microfibers, etc.), organic substance-containing carbon fillers (carbon black, carbon fibers, etc.), various synthetic polymers, and the like.
  • the nozzle shape of the present embodiment is useful for organic fillers such as cellulose nanofibers and carbon black, which are difficult to finely disperse.
  • the compatibilizer is useful when changing the dispersion state.
  • the compatibilizer for example, when the resin is a polymer alloy of polyamide and polyphenylene ether, or a polymer alloy of polyamide and polypropylene, organic acids such as maleic anhydride, citric acid, and fumaric acid are useful.
  • the resin is an alloy of polyphenylene sulfide and polyphenylene ether, a thermoplastic resin having a glycidyl group and an epoxy compound are useful.
  • a plasticizer is also useful. Since the plasticizer lowers the melt viscosity of the resin, the moldability can be improved.
  • an ester composed of an acid component and an alcohol component is useful. Examples of the ester include phthalate ester compounds such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate and dibutyl phthalate, adipic acid ester compounds such as dioctyl adipate and diisononyl adipate, and trimellitic acids such as trioctyl trimellitic acid.
  • Ester compounds citric acid ester compounds, sebacic acid ester compounds, azelaic acid ester compounds, benzoic acid ester compounds, low molecular weight polyesters, tricresyl phosphate, triphenyl phosphate, bisphenol A-bis (diphenyl phosphate) and other phosphate esters.
  • examples thereof include compounds and modified vegetable oils typified by epoxidized vegetable oils.
  • the cellulose nanofibers as a filler that can be contained in the first component and / or the second component may be obtained from various cellulose fiber raw materials selected from natural cellulose and regenerated cellulose.
  • the cellulose fiber raw material may be chemically modified.
  • Cellulose nanofibers are made by beating and fibrilizing cellulose fiber raw materials by mechanical force such as beaters and refiners, and then defibrating by a crushing method such as a high-pressure homogenizer, a microfluidizer, a ball mill, a disc mill, or a mixer (for example, a homomixer). Can be obtained.
  • the number average fiber diameter of the cellulose nanofibers is 2 nm or more, preferably 4 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, and particularly preferably 20 nm or more in one embodiment, in that the crystallinity of the cellulose is well maintained. It is 30 nm or more.
  • the upper limit is less than 1000 nm, preferably 800 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less in one embodiment in that the effect as a filler is good.
  • the number average fiber length / number average fiber diameter (L / D) of the cellulose nanofibers is preferably 50 from the viewpoint of satisfactorily improving the mechanical properties of the injection molded product containing the cellulose nanofibers with a small amount of cellulose nanofibers. More than or equal to, or more than 80, or more than 100, or more than 120, or more than 150.
  • the upper limit is not particularly limited, but is preferably 5000 or less from the viewpoint of handleability.
  • the number average fiber diameter, number average fiber length and L / D ratio of the cellulose nanofibers are 0. Dilute to 001 to 0.1% by mass, use a high shear homogenizer (for example, manufactured by IKA, trade name "Ultratalax T18"), and disperse under treatment conditions: rotation speed 25,000 rpm x 5 minutes to make a hydrophilic substrate (for example, IKA). For example, it is cast on mica) and air-dried as a measurement sample, and measured with a high-resolution scanning electron microscope (SEM) or an atomic force microscope (AFM). Specifically, the length (L) and diameter (D) of 100 fibrous substances randomly selected in the observation field adjusted so that at least 100 fibrous substances can be observed. Is measured and the ratio (L / D) is calculated. For the cellulose nanofibers, the number average value of the length (L), the number average value of the diameter (D), and the number average value of the ratio (L / D) are calculated.
  • a high shear homogenizer
  • the crystal structure of cellulose nanofibers has cellulose type I and / or type II.
  • type I, type II, type III, type IV and the like are known.
  • Type I and type II celluloses are widely used, while type III and type IV celluloses are available on the laboratory scale but not on the industrial scale.
  • the crystallinity of the cellulose nanofibers of the present embodiment is preferably 50% or more, more preferably 60% or more, still more preferably 65% or more, and most preferably 70% or more from the viewpoint of obtaining good mechanical characteristics. ..
  • the crystallinity is determined by the Segal method from the diffraction pattern (2 ⁇ / deg. Is 10 to 30) when the sample is measured by wide-angle X-ray diffraction. Therefore, it is calculated by the following formula.
  • Crystallinity (%) [I (200) -I (amorphous) ] / I (200) x 100
  • the degree of polymerization (DP) of the cellulose nanofibers is preferably 100 or more, more preferably 150 or more, preferably 12000 or less, and more preferably 12000 or less, in terms of good tensile breaking strength and elastic modulus. It is preferably 8000 or less.
  • the degree of polymerization was determined by determining the ultimate viscosity of a diluted cellulose solution using a copper ethylenediamine solution (JIS P 8215: 1998), and then utilizing the relationship between the ultimate viscosity of cellulose and the degree of polymerization DP by the following formula. Obtained as the degree of polymerization DP.
  • the weight average molecular weight (Mw) of the cellulose nanofibers is preferably 100,000 or more, more preferably 200,000 or more.
  • the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight (Mn) of the cellulose nanofibers is preferably 6 or less, and preferably 5.4 or less. The larger the weight average molecular weight, the smaller the number of terminal groups of the cellulose molecule. Further, since the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight represents the width of the molecular weight distribution, it means that the smaller the Mw / Mn, the smaller the number of ends of the cellulose molecule.
  • the weight average molecular weight (Mw) of the cellulose fiber may be, for example, 600,000 or less, or 500,000 or less, from the viewpoint of availability of the cellulose raw material.
  • the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight (Mn) may be, for example, 1.5 or more, or 2 or more, from the viewpoint of ease of producing cellulose fibers.
  • the Mw can be controlled within the above range by selecting a cellulose raw material having Mw according to the purpose, appropriately performing physical treatment and / or chemical treatment on the cellulose raw material within an appropriate range, and the like.
  • Mw / Mn also has the above range by selecting a cellulose raw material having Mw / Mn according to the purpose, appropriately performing physical treatment and / or chemical treatment on the cellulose raw material within an appropriate range, and the like.
  • the physical processing includes dry or wet pulverization of microfluidizers, ball mills, disc mills, etc., shearing machines, homomixers, high-pressure homogenizers, ultrasonic devices. Physical treatments such as impact, shearing, shearing, friction, etc. due to the above can be exemplified, and examples of the chemical treatments include cooking, bleaching, acid treatment, regenerated cellulose formation, and the like.
  • the weight average molecular weight and the number average molecular weight of the cellulose nanofibers are defined by dissolving the cellulose nanofibers in N, N-dimethylacetamide to which lithium chloride is added, and then gelling with N, N-dimethylacetamide as a solvent. It is a value obtained by permeation chromatography.
  • the cellulose nanofiber may be a chemically modified cellulose nanofiber chemically modified by a modifying agent.
  • a modifying agent a compound that reacts with the hydroxyl group of cellulose can be used, and examples thereof include an esterifying agent, an etherizing agent, a silylating agent, and an isocyanate.
  • the chemical modification is acylation with an esterifying agent.
  • the esterifying agent a compound selected from a compound that reacts with a hydroxyl group of cellulose to generate an acyl group, for example, a carboxylic acid halide, an acid anhydride (that is, a carboxylic acid anhydride), a carboxylic acid vinyl ester, or a carboxylic acid. Can be used.
  • the esterification is acetylation.
  • the degree of modification of chemically modified cellulose nanofibers is expressed as the average degree of substitution of hydroxyl groups (the average number of substituted hydroxyl groups per glucose, which is the basic building block of cellulose, also referred to as DS).
  • DS is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, particularly preferably 0.2 or more, most preferably, in terms of obtaining a high thermal decomposition start temperature. It is preferably 0.3 or more, and is preferably 2.0 or less, more preferably 1.8, in that good tensile strength, dimensional stability, and thermal decomposition temperature can be obtained due to the residual unmodified cellulose skeleton. Below, it is more preferably 1.5 or less, particularly preferably 1.2 or less, and most preferably 1.0 or less.
  • the degree of acyl substitution (DS) of the esterified cellulose nanofibers is calculated from the reflected infrared absorption spectrum of the esterified cellulose nanofibers based on the peak intensity ratio between the peak derived from the acyl group and the peak derived from the cellulose skeleton. be able to.
  • the peak of the C O absorption band based on the acyl group appears at 1730 cm -1, and the peak of the CO absorption band based on the cellulose skeleton chain appears at 1030 cm -1 .
  • the method for calculating the DS of esterified cellulose nanofibers by solid NMR is to perform 13 C solid NMR measurements on freeze-crushed esterified cellulose nanofibers, and to carbon C1-C6 derived from the pyranose ring of cellulose appearing in the range of 50 ppm to 110 ppm. It can be obtained by the following formula from the area intensity (Inf) of the signal assigned to one carbon atom derived from the modifying group with respect to the total area intensity (Inp) of the attributed signal.
  • DS (Inf) x 6 / (Inp)
  • the modifying group is an acetyl group, a 23 ppm signal attributed to —CH 3 may be used.
  • the carbon black as a filler that can be contained in the first component and / or the second component may be used as a simple uniform coloring or may be used for the purpose of imparting conductivity.
  • the carbon black manufacturing method is not particularly limited, and examples thereof include an oil furnace method, a lamp black method, a channel method, a gas furnace method, an acetylene decomposition method, and a thermal method, and any of them may be used.
  • the oil absorption of dibutyl phthalate (DBP) of carbon black is 50 mL / 100 g or more and 600 mL / 100 g or less.
  • the amount of DBP oil absorbed is preferably 100 mL / 100 g or more, 150 mL / 100 g or more, 200 mL / 100 g or more, or 300 mL / 100 g or more from the viewpoint of imparting a function such as conductivity. From the viewpoint of imparting uniform colorability, it is preferably 70 mL / 100 g or more, 80 mL / 100 g or more, 100 mL / 100 g or more, or 120 mL / 100 g or more.
  • the viewpoint of suppressing deterioration of fluidity it is preferably 500 mL / 100 g or less, 400 mL / 100 g or less, 350 mL / 100 g or less, or 300 mL / 100 g or less. From the viewpoint of maintaining conductivity while suppressing deterioration of fluidity, it is preferably 550 mL / 100 g or less, 530 mL / 100 g or less, 510 mL / 100 g or less, or 500 mL / 100 g or less.
  • the amount of dibutyl phthalate oil absorbed is disclosed in the catalogs of each carbon black manufacturer.
  • Coloring or imparting conductivity with carbon black is often insufficient only by mixing in a molding machine, and in general, in order to improve reliability, a method of molding into a molded product using raw material pellets melt-kneaded by an extruder is used. It has been taken. By using the nozzle of the present embodiment, it is possible to significantly reduce the formation of aggregates in these carbon black molded bodies. There are various methods for confirming the reduction of aggregates, and the preferred method is illustrated below.
  • the size and abundance ratio of carbon black aggregates are measured by the methods described below. Specifically, using a reflective optical microscope (for example, PME3: manufactured by Olympus Corporation), the dispersed state of carbon black on the smooth surface of the observation sample is observed at a magnification of 100 times, and an image is taken. The captured reflection micrograph is digitally imaged (capture resolution: 400 dpi) with a scanner (for example, CC-600PX: manufactured by Epson), and the black phase (carbon black) observed in the field of view of the obtained digital image. The number of secondary aggregates) is counted by automatic measurement using image processing software. By the above method, the number of aggregates which are black phases in the visual field is calculated, and the average value of 10 photographs (total visual field 10 mm 2) is obtained.
  • a reflective optical microscope for example, PME3: manufactured by Olympus Corporation
  • PME3 manufactured by Olympus Corporation
  • the captured reflection micrograph is digitally imaged (capture resolution: 400 dpi) with
  • Examples of the inorganic filler that can be contained in the first component and / or the second component include glass fiber, zeolite, ceramics, talc, mica, titanium dioxide, silica, wollastonite, dragonite, calcium carbonate, metal powder and the like. Be done.
  • the nozzle shape of the present embodiment is particularly useful for inorganic fillers such as glass fiber and wollastonite, which increase the viscosity of the resin and make it difficult to dilute and disperse when blended at a high concentration. ..
  • any glass having a fibrous shape can be used without any particular problem.
  • Specific examples thereof include chopped strand glass fiber, milled glass fiber, and glass fiber roving.
  • chopped strand glass fiber and milled glass fiber are preferable from the viewpoint of handleability, and chopped strand glass fiber is more preferable because the strength of the resin molded body is increased.
  • These glass fibers may be used alone or in combination of two or more.
  • the preferable average fiber diameter of the glass fiber is 7 ⁇ m or more and 20 ⁇ m or less. From the viewpoint of fluidity, 8 ⁇ m or more, 9 ⁇ m or more, or 10 ⁇ m or more is preferable, and from the viewpoint of preventing scraping of the mold surface during molding, 18 ⁇ m or less, 15 ⁇ m or less, or 14 ⁇ m or less is preferable.
  • the average fiber diameter is a value measured by incinerating the object to be measured at a temperature of about 650 ° C., removing the resin component, observing the obtained ash with a scanning electron microscope, and measuring the diameter. be. At this time, in order to eliminate an error, it is desirable to measure the diameter of at least 100 glass fibers and calculate the number average fiber diameter. When two or more kinds of glass fibers having different glass fiber diameters are blended, it is preferable that the number average fiber diameter is within the above range.
  • the number average fiber length of the glass fiber is preferably in the range of 150 ⁇ m or more and 350 ⁇ m or less. From the viewpoint of maintaining physical properties, 160 ⁇ m or more, 170 ⁇ m or more, 180 ⁇ m or more, 190 ⁇ m or more, or 200 ⁇ m or more is preferable, and from the viewpoint of suppressing deterioration of fluidity, 340 ⁇ m or less, 320 ⁇ m or less, 300 ⁇ m or less, or 290 ⁇ m or less is preferable. preferable.
  • the number average fiber length referred to here is obtained by incinerating the object to be measured at a temperature of 500 ° C. or lower for 5 hours or more, and then using the ash content obtained by slow cooling. It is preferable to heat the glass fiber at a low temperature for a long time and then slowly cool it because it is possible to prevent the glass fiber from breaking due to a thermal shock.
  • a dynamic powder image analyzer for example, PITA-3 manufactured by Seishin Enterprise Co., Ltd.
  • the length of the glass fiber is made by using soapy water containing a small amount of a neutral detergent as a developing solvent. It is measured by actually measuring at least 1000 fibers.
  • the information corresponding to the glass fiber diameter at the time of measurement using the dynamic powder image analyzer is obtained as the circumscribing rectangular minor axis, and the information corresponding to the glass fiber length is obtained as the circumscribing rectangular major axis.
  • information on a diameter deviating from the glass fiber diameter confirmed by a scanning electron microscope or the like by 2 ⁇ m or more is deleted.
  • the glass fiber diameter confirmed by a scanning electron microscope or the like is 10 ⁇ m
  • the information on the particles having a minor axis of the circumscribing rectangle of 8 ⁇ m or less and the information on the particles having a minor axis of 12 ⁇ m or more are deleted, and the number of remaining particles is 1000. Calculated with more than a book of information.
  • wollastonite can be used as the inorganic filler.
  • Preferred wollastonites have an average particle size in the range of 2-9 ⁇ m and an aspect ratio of 5 or more.
  • 0.75 g of wollastonite particles were added to 45 ml of a 0.05% Calgon solution using a particle size analyzer (for example, a Sedigraf particle size analyzer (Med., Micrometrics Instrument, USA, model 5100)).
  • the diameter is equivalent to a sphere measured and calculated after being sufficiently dispersed in an ultrasonic bath.
  • the aspect ratio is a value calculated from the summed average value obtained by measuring the diameter and length of at least 5000 wollastonite particles using photographs taken by observing with a scanning electron microscope. Two or more kinds of wollastonite particles having different aspect ratios may be used in combination.
  • One aspect of the present invention also provides a capillary nozzle as described in the section ⁇ Nozzle> described above, and an injection unit with a nozzle comprising the capillary nozzle.
  • one aspect of the present invention is Attached to the cylinder of an injection molding machine that injects a thermoplastic resin mixture containing a first component containing a thermoplastic resin and a second component containing one or more selected from the group consisting of thermoplastic resins and fillers.
  • one aspect of the present invention is to inject a thermoplastic resin mixture containing a first component containing a thermoplastic resin and a second component containing one or more selected from the group consisting of a thermoplastic resin and a filler.
  • An injection molding unit with a nozzle that is attached to an injection molding machine.
  • the injection molding unit with a nozzle has a nozzle portion and a cylinder portion, and the nozzle portion has a capillary hole portion having an injection port and a fluid in the capillary hole portion.
  • the rate of change in pore size obtained in 1 is 2 mm -1 or more, so that the melt supply unit receives the pre-melt and applies elongation strain to the pre-melt to form an injection melt. , Provides an injection unit with a nozzle.
  • Injection molding machine configuration Injection molding machine: "LA60” manufactured by Sodick Co., Ltd.
  • Plasticization / injection method Screw pre-plastic method Screw and plunger diameter: 28 mm
  • Plunger stroke 135mm
  • mPPE Maleic anhydride-modified polyphenylene ether
  • a screw having a function of melting the resin is arranged in the portion of C3
  • a screw having a function of renewing the interface for modifying the resin is arranged in the portions of C6 and C8.
  • CNF Hydrophobicized Cellulose Nanofiber Powder
  • the rotation speed of the bead mill was 2500 rpm and the peripheral speed was 12 m / s.
  • the beads were made of zirconia, ⁇ 2.0 mm, and the filling rate was 70% (the slit gap of the bead mill at this time was 0.6 mm).
  • the slurry temperature was controlled to 40 ° C. by a chiller in order to absorb heat generated by friction.
  • the diameter was 65 nm
  • the L / D was 30 or more (about 450)
  • the weight average molecular weight (Mw) was 340,000
  • the degree of acetylation was high.
  • Wet cake was diluted with tert-butanol to 0.01% by mass, and treated using a high-shear homogenizer (manufactured by IKA, trade name "Ultratalax T18") under treatment conditions: rotation speed 25,000 rpm x 5 minutes. It was cast on mica and air-dried, and measured with a high-resolution scanning electron microscope. The measurement was performed by adjusting the magnification so that at least 100 cellulose fibers were observed, and the length (L), major axis (D) and ratios of 100 randomly selected cellulose fibers were determined. The added average of 100 cellulose fibers was calculated.
  • a high-shear homogenizer manufactured by IKA, trade name "Ultratalax T18”
  • H1730 and H1030 are the absorbances at 1730 cm -1 and 1030 cm -1 (absorption band of cellulose skeleton chain CO expansion and contraction vibration).
  • each of the line connecting the lines and 800 cm -1 and 1500 cm -1 connecting 1900 cm -1 and 1500 cm -1 as a baseline means absorbance when the baseline was zero absorbance.
  • the average degree of substitution at each measurement location was calculated from the IR index according to the following formula, and the average value was taken as DS.
  • DS 4.13 x IR index
  • hydrophobicized cellulose nanofiber powder was obtained by vacuum drying at about 40 ° C. using V-mini300 manufactured by EME.
  • Carbon black (CB) Ketjen Black EC600JD manufactured by Lion Corporation
  • Examples A1 to A5 and Comparative Examples A1 to A2 (single-screw extruded product)> [Raw material pellet preparation process] 80 parts by mass of PA6 as the first component and 20 parts by mass of mSBS as the second component were dry-blended to prepare a pellet mixture for extrusion.
  • a double dalmagage type screw is mounted on a 32 mm screw single-screw extruder with an L / D of 24, and the cylinder temperature is set to 230 ° C for cylinder 1 and 245 ° C for cylinders 2 to 3 and the die head, and screw rotation. Extrusion was carried out at several 75 rpm, and the strands from the die head were cooled and cut to obtain pellets.
  • the double dalmage is located in the latter half of C2, and decompression suction was performed from the decompression degassing port of C3.
  • the dispersed particle diameters of the obtained injection-molded article test piece and the dispersed phase (in this case, the mSBS phase) in the raw material pellets were measured.
  • the dispersed particle size was determined by cutting a cross section from a part of the pellet or molded piece with a microtome, immersing the dispersed phase in soluble chloroform, and then observing the treated sample with a scanning electron microscope. The diameters of at least 50 holes were randomly measured, and the diameters from the maximum diameter to the minimum diameter were measured as an index of the particle size distribution, and the size of the dispersed particle size was compared with the number average particle size of 50 pieces. .. Since the components of the dispersed phase are extracted with chloroform, the dispersed particle size in the raw material pellets can be regarded as the dispersed diameter of the dispersed phase in the preliminary melt of the present disclosure.
  • the tensile elongation (based on ISO 527-1 and 2) measured at a crosshead speed of 5 mm / min at 23 ° C and the Charpy impact strength (based on ISO 179-1 / 1eA). ) was measured.
  • Example A4 and Comparative Example A1 and Comparative Example A2 In comparison with Example A4 and Comparative Example A1 and Comparative Example A2, by increasing the angle ( ⁇ ) formed by the hole wall of the melt supply portion in the direction parallel to the nozzle axis and toward the upstream of the melt flow. It can be seen that the number of large particles with a particle size distribution decreases. Further, it can be seen that by increasing the pore diameter change rate and the cross-sectional area change rate in comparison with Examples A1 to A3, the particle size becomes very fine and the distribution becomes narrow.
  • Example A2 when continuous molding was continued, some black spots were observed on the surface of the molded piece. It is presumed that ⁇ exceeds 90 ° and a stagnant portion is formed.
  • Examples A6 to A8 and Comparative Examples A3 to A4 (biaxially extruded product)> [Raw material pellet preparation process]
  • the same procedure as in Example A1 was carried out except that the extrusion was carried out by taking care of the air.
  • the screw design has a configuration in which a screw having a function of melting the resin is arranged in the portion of C5 and a screw having a function of dispersing and mixing the resin is arranged in the portion of C7.
  • the physical characteristics tended to be slightly lower than those for the raw material for the single-screw extruded product.
  • the details are unknown, it is considered that the biaxially extruded raw material has a low flexibility due to a cross-linking reaction at the double bond portion of the SBS component due to the high thermal history in the extrusion process.
  • Examples A9 to A11 and Comparative Example A5 masterbatch diluted product> [Raw material pellet preparation process] 30 parts by mass of PA6 and 20 parts by mass of mSBS were dry-blended to prepare a pellet mixture for extrusion.
  • a high-concentration elastomer masterbatch (PA6 / SBS-MB) was obtained in the same manner as in Example A1 except that the screw of the extruder was changed to a single darmage type screw.
  • Example A1 except that PA6 as the first component was changed to 50 parts by mass and the pellet PA6 / SBS-MB obtained in the raw material pellet preparation step as the second component was changed to a dry blend of 50 parts by mass. It was carried out in the same manner.
  • the nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • Examples A12 to A13 and Comparative Example A6 pellet blended product
  • Example A1 [Raw material pellet preparation process] All of the pellets obtained in the raw material pellet preparation step were the same as in Example A1 except that PA6 as the first component was changed to 80 parts by mass and mSBS as the second component was changed to a pellet dry blend product of 20 parts by mass. It was carried out in the same manner.
  • the nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • the method of eliminating the prior melt-kneading and directly introducing the pellets of the two kinds of blend into the injection molding machine was adopted. Therefore, the measured value of the diameter of the pellet itself of the second component was regarded as the particle diameter of the dispersed phase in the preliminary melt.
  • Examples A14 to A15 and Comparative Example A7 (single-screw extruded product)>
  • [Raw material pellet preparation process] Dry blend 85 parts by mass of PA66 as the first component and 15 parts by mass of mEOR as the second component, and set the cylinder temperature of the extruder to 260 ° C for cylinders 1 and 2 and 280 ° C for cylinder 3 and die head. It was carried out in the same manner as in Example A1 except that it was set to.
  • [Injection molding process] It was carried out in the same manner as in Example A1. The nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • Examples A16 to A17 and Comparative Example A8 Single-screw extruded product
  • [Raw material pellet preparation process] Dry blend 85 parts by mass of PA12 as the first component, 7.5 parts by mass of SEBS-1 as the second component, and 7.5 parts by mass of mSEBS, and set the cylinder temperature of the extruder to 220 ° C. Everything was carried out in the same manner as in Example A1 except that it was set to.
  • [Injection molding process] It was carried out in the same manner as in Example A1. The nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • Examples A18 to A19 and Comparative Example A9 single-screw extruded product
  • [Raw material pellet preparation process] The raw material pellets of Example A1 were used.
  • [Injection molding process] The nozzle of the same injection molding machine as in Example A1 was changed to the nozzle type shown in Table 4, and the injection speed was changed to the speed shown in Table 4 for molding. The maximum injection pressure obtained at this time is also shown in Table 4. Except for the above, all of them were carried out in the same manner as in Example A1. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • Examples B1 to B5 and Comparative Examples B1 to B2 (biaxially extruded products)> [Raw material pellet preparation process]
  • SEBS-2 is supplied from the upstream raw material supply port, 60 parts by mass of PA6, which is the first component, is supplied from the downstream raw material supply port (side feed port) installed in C5, melt kneading is performed, and the die head is performed.
  • the strands from were cold cut and obtained as pellets.
  • the screw rotation speed was set to 300 rpm, and decompression degassing was performed at the position of C9.
  • a screw having a function of melting the resin is arranged in the portion of C3
  • a screw having a function of dispersing and mixing the resin is arranged in the portions of C6 and C8.
  • Molding was performed using the pellets obtained in the raw material pellet preparation step.
  • Molding was carried out in the same manner as in Example A1 except that the nozzle portion, the tip and center portion of the plunger, and the screw plasticized portion of the injection molding machine were set to 280 ° C. and the rearmost portion of the plunger was set to 255 ° C.
  • the nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • a flat plate-shaped molded piece having a length of 90 mm, a width of 50 mm, and a thickness of 2.5 mm for measuring low-temperature surface impact strength was also collected as a separate process.
  • the injection molding was the same as the conditions for obtaining the multipurpose test piece.
  • the obtained multipurpose test piece and the dispersed particle size of the dispersed phase (in this case, the phase composed of mPPE and SEBS-2) in the raw material pellets were measured.
  • the method was carried out by the same method as in Example A1 in which the dispersed phase was etched with chloroform.
  • the multipurpose test piece obtained at this time the tensile elongation measured at a crosshead speed of 5 mm / min at 23 ° C. was measured, and the low temperature surface impact strength was measured using a flat plate-shaped molded piece.
  • Example B4 and Comparative Example B1 and Comparative Example B2 In comparison with Example B4 and Comparative Example B1 and Comparative Example B2, it can be seen that by increasing the ⁇ of the nozzle, the huge particles having a particle size distribution are reduced. Further, it can be seen that by increasing the pore diameter change rate and the cross-sectional area change rate in comparison with Examples B1 to B3, the particle size becomes very fine and the distribution becomes narrow.
  • Example B2 when continuous molding was continued, some black spots were observed on the surface of the molded piece. This phenomenon was slightly more frequent than in Example A2. This is also considered to be the effect of carbides due to the stagnant portion.
  • the tensile elongation and low-temperature surface impact strength are dramatically improved by increasing the pore diameter change rate and cross-sectional area change rate while increasing the ⁇ of the nozzle. It is considered that this is because the dispersed particle size is uniformly reduced as described above.
  • Examples B6 to B8 and Comparative Examples B3 to B4 (masterbatch diluted product)> [Raw material pellet preparation process]
  • SEBS-2 is supplied, melt-kneaded, the strands from the die head are cooled and cut, and a masterbatch pellet of a polyphenylene ether and a partially hydrogenated aromatic vinyl compound and a conjugated diene compound block copolymer (particle size:: 2.5-3.0 mm) was obtained.
  • the screw rotation speed was set to 250 rpm, and decompression degassing was performed at the position of C9.
  • a screw having a function of melting the resin is arranged in the portion of C3
  • a screw having a function of dispersing and mixing the resin is arranged in the portions of C6 and C8.
  • Example B1 The same procedure as in Example B1 was carried out except that PA6 as the first component was changed to a dry blend of 60 parts by mass and 40 parts by mass of the pellets obtained in the raw material pellet preparation step as the second component.
  • the nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • the particle size of the dispersed phase before injection molding is the size of the raw material pellets, so the measured value of the diameter of the pellet itself of the second component is regarded as the particle size of the dispersed phase in the preliminary melt. I'm sorry.
  • Examples B9 to B11 and Comparative Example B5 (biaxially extruded product)> [Raw material pellet preparation process]
  • MSEBS is supplied from the upstream raw material supply port, 20 parts by mass of PA6, which is the first component, is supplied from the downstream raw material supply port (side feed port) installed in C5, melt kneading is performed, and strands from the die head are performed. Was cooled and cut to obtain pellets.
  • the conditions and screw design at this time were carried out in the same manner as in Example B1.
  • the test piece was exposed to a smooth surface using a microtome, the section was stained with phosphotung acid, washed thoroughly with water, and observed with an energy dispersive X-ray spectroscopy (EDX method) of a scanning electron microscope. The shading was measured by image analysis. At least 100 randomly selected PA phase diameters were measured.
  • Example B1 the tensile elongation measured at a crosshead speed of 5 mm / min at 23 ° C. was measured, and the low temperature surface impact strength was measured using a flat plate-shaped molded piece. The method was carried out in the same manner as in Example B1.
  • Examples B12 to B14 and Comparative Example B6 masterbatch blend product
  • the screw rotation speed was set to 300 rpm, and decompression degassing was performed at the position of C9.
  • a screw having a function of melting the resin is arranged in the portion of C3
  • a screw having a function of dispersing and mixing the resin is arranged in the portions of C6 and C8.
  • the temperature of the extruder was set to 320 ° C for C1 to C4, 280 ° C for C5 to C10 and the die head, and PPS / except that 25 parts by mass of PPE and 10 parts by mass of SEBS-2 were supplied.
  • the same procedure as for SG-MB pellets was carried out to obtain PPE / SEBS-2-MB pellets (pellet diameter: 2.5 to 2.8 mm) composed of PPE and SEBS-2.
  • Molding was performed using the pellets obtained in the raw material pellet preparation step. 65 parts by mass of PPS / SG-MB pellets as the first component and 35 parts by mass of PPE / SEBS-2-MB pellets as the second component were dry blended.
  • Example B1 Molding was carried out in the same manner as in Example B1 except that the nozzle portion, the tip and center portion of the plunger, and the screw plasticized portion of the injection molding machine were set to 300 ° C. and the rearmost portion of the plunger was set to 275 ° C.
  • the nozzle type of the molding machine is as shown in the table.
  • an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • the dispersion particle size measurement of the dispersed phase in this case, the phase composed of PPE and SEBS-2) in the raw material pellet was also carried out in the same manner as in Example B1.
  • the tensile elongation measured at a crosshead speed of 5 mm / min at 23 ° C. was measured at room temperature using a flat plate-shaped molded piece collected under the same conditions as when the multipurpose test piece was obtained. The surface impact strength was measured.
  • the room temperature surface impact strength was such that the plate-shaped molded piece was conditioned at 23 ° C. in a 50% RH environment for at least 48 hours, and then the sample holder diameter was 40 mm, the striker diameter was 12.7 mm, the load was 6.5 kg, and the striker collided with the sample.
  • the measurement was performed using a graphic impact tester set under the condition of a speed of 5 m / sec.
  • the surface impact strength is expressed by the value of the total absorption energy, which is the sum of the crack generation energy and the propagation energy. At this time, each of the 10 sheets was measured, and the average value was calculated from the respective values.
  • the particle size was small and the distribution was narrowed. Although the original impact resistance and elongation were low, the PPS-based composition still had high physical characteristics, and was improved to the extent that the pellets were uniformly mixed in advance by an extruder.
  • a CT measurement was performed on the object to be measured using a high-resolution 3DX beam microscope (nano3DX: manufactured by Rigaku Co., Ltd.) for an X-ray tube voltage of 40 kV, a tube current of 30 mA, and 600 cubic ⁇ m.
  • the number of projections was 1000, and the exposure time was 24 seconds per image.
  • the spatial resolution at this time was 0.54 ⁇ m / pixel.
  • the obtained data was binarized by the Otsu method. This measurement was performed on three different sites, the number of aggregates detected was counted and arithmetically averaged.
  • the particle size data of each of the obtained aggregates was calculated by arithmetically averaging to calculate the average aggregate diameter, and the aggregate diameter of 25% (d25%) and the aggregate diameter of 75% (d75) from the smallest aggregate diameter. %) Ratio (d75% / d25%) was calculated and used as an aggregate diameter distribution.
  • the data of the diameter equivalent to the circle is used as a substitute for the flat aggregate having a major axis and a minor axis.
  • the tensile elongation measured at a crosshead speed of 5 mm / min at 23 ° C. and the coefficient of thermal expansion as an index of thermal expandability were measured.
  • the coefficient of thermal expansion is determined by cutting a sample with a length of 10 mm, a width of 4 mm, and a thickness of 2 mm from the center of the multipurpose test piece with a precision cut-and-sew, and in the measurement temperature range of -10 ° C to 120 ° C, the flow direction of the resin during molding ( The coefficient of expansion in the MD direction and the length direction of the sample) was measured, and the coefficient of thermal expansion between 20 ° C. and 100 ° C. was calculated. At this time, prior to the measurement, annealing was performed by allowing the mixture to stand for 5 hours in an environment of 120 ° C.
  • Examples C5 to C7 and Comparative Example C3 (masterbatch diluted product)> [Raw material pellet preparation process]
  • Melt kneading was carried out, and the strands from the die head were cooled and cut to obtain pellets as a second component.
  • the screw rotation speed was set to 300 rpm, and decompression degassing was performed at the position of C9.
  • a screw having a function of melting the resin is arranged in the portion of C3
  • a screw having a function of dispersing and mixing the resin is arranged in the portions of C6 and C8.
  • the second component obtained in the raw material pellet preparation step was diluted and molded with PA6 as the first component so that the CNF concentration was 10%.
  • Example C1 molding was carried out in the same manner as in Example C1.
  • the nozzle type of the molding machine is as shown in the table.
  • an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • Example C1 Similar to Example C1, the number of CNF aggregates, tensile elongation, and coefficient of thermal expansion in the multipurpose test piece were measured.
  • Example C8 to C10 and Comparative Example C4 (masterbatch diluted product)> [Raw material pellet preparation process] It was carried out in the same manner as in Example C5. [Injection molding process] The second component obtained in the raw material pellet preparation step was diluted and molded with PA6 as the first component so that the CNF concentration was 5%. For injection molding, all molding was performed in the same manner as in Example C1, and the number of CNF aggregates, tensile elongation, and coefficient of thermal expansion in the multipurpose test piece were measured. The nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • Examples C11 to C12 and Comparative Example C5 (masterbatch diluted product)> [Raw material pellet preparation process]
  • a screw having a function of melting the resin is arranged in the portion of C3
  • a screw having a function of dispersing and mixing the resin is arranged in the portions of C6 and C8.
  • the second component obtained in the raw material pellet preparation step was diluted and molded with PP6 as the first component so that the CNF concentration was 5% by mass. Molding was carried out in the same manner as in Example C1 except that the nozzle portion, the tip and center portion of the plunger, and the screw plasticized portion of the injection molding machine were set to 220 ° C. and the rearmost portion of the plunger was set to 180 ° C. In addition, the number of CNF aggregates, tensile elongation, and coefficient of thermal expansion in the multipurpose test piece were measured. The nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • the screw rotation speed was set to 300 rpm, and decompression degassing was performed at the position of C9.
  • a screw having a function of melting the resin is arranged in the portion of C3
  • a screw having a function of dispersing and mixing the resin is arranged in the portions of C6 and C8.
  • all the obtained particle size data of each agglomerate are arithmetically averaged to calculate the average agglomerate diameter, and 25% agglomerate diameter (d25%) and 75% agglomerate diameter (from the smallest agglomerate diameter).
  • the ratio (d75% / d25%) of (d75%) was calculated and used as the aggregate diameter distribution.
  • the average of the major axis and the minor axis was taken as the aggregate diameter. The results obtained are shown in Table 9.
  • the cylinder temperature of the ZSK26MC extruder was also set to 320 ° C. for C1 to 4 and 280 ° C. for C5 to C10 and the die head, and 30 parts by mass of mPPE and 10 parts by mass of SEBS as the first component.
  • -2 is supplied from the upstream raw material supply port, and 40 parts by mass of PA66 as the first component and 10 parts by mass of PA / CB-MB pellets as the second component are installed in the downstream raw material supply port in C5. It was supplied from (side feed port), melt-kneaded, and the strands from the die head were cooled and cut to obtain pellets.
  • the screw rotation speed was set to 320 rpm, and decompression degassing was performed at the position of C9.
  • the screw design is the same as the design used in PA / CB-MB.
  • Molding was performed using the pellets obtained in the raw material pellet preparation step. Molding was carried out in the same manner as in Example B1 except that the nozzle portion, the tip and center portion of the plunger, and the screw plasticized portion of the injection molding machine were set to 290 ° C. and the rearmost portion of the plunger was set to 280 ° C.
  • the nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • the number of CB aggregates in the raw material pellets and the obtained multipurpose test piece was measured according to the method used in the measurement in MB in the raw material pellet preparation step.
  • the notched Charpy impact strength at 23 ° C was measured. Furthermore, the volume resistivity was measured by the following method.
  • the obtained multipurpose test piece is scratched in advance with a cutter knife, immersed in dry ice / methanol at ⁇ 75 ° C. to ⁇ 70 ° C. for about 1 hour, then taken out, and both ends are cut off to have a uniform cross-sectional area of 10 ⁇ .
  • a test piece having a fracture surface of 4 mm and a length of about 70 mm was obtained at both ends.
  • Silver paint was applied to the fracture surfaces at both ends and dried, and the volume resistivity between both fracture surfaces was measured at an applied voltage of 250 V using a digital insulation resistance tester [DG525: manufactured by Sanwa Electric Instrument Co., Ltd.]. The measurement was performed on 5 different test pieces, and the summing average was used as the volume resistivity.
  • Examples D5 to D7 and Comparative Example D3 (masterbatch raw material)> [Injection molding process] A mixture of the pellets obtained in the raw material pellet preparation step and other raw materials was molded. The nozzle part, plunger tip and center part, and screw plasticized part of the injection molding machine were set to 290 ° C, respectively, and the last part of the plunger was set to 280 ° C. Injection molding was carried out using a raw material in which 10 parts by mass of mPPE by mass and 10 parts by mass of SEBS-2 and 10 parts by mass of PA / CB-MB as the second component were dry-blended. All other conditions were carried out in the same manner as in Example D1. The nozzle type of the molding machine is as shown in the table. As a result, an injection-molded article to which elongation strain (for each example) or shear strain (for each comparative example) was applied was formed.
  • the number of CB aggregates in the obtained multipurpose test piece was measured. Further, using the obtained multipurpose test piece, the notched Charpy impact strength and the volume resistivity at 23 ° C. were measured.
  • the number of CB aggregates in Comparative Example D3 is equivalent to the number obtained by diluting PA / CB-MB, but by using the nozzle of the present invention, a twin-screw extruder is used and the nozzle of the present invention is used. It can be seen that the number of aggregates and the physical properties are at the same level as those of the extruded one. This suggests that not only the number of aggregates but also the compatibilization in the resin phase was sufficiently performed. As for the volume resistivity, the defective sample showed no continuity, but the good sample showed a good volume resistivity. In the defective sample, it is considered that carbon was non-uniformly dispersed, although it did not appear in the number of aggregates.
  • the present invention can be suitably applied to the production of a wide range of injection molded products which can contain various compounding components.

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Publication number Priority date Publication date Assignee Title
US20240117127A1 (en) * 2021-02-03 2024-04-11 Asahi Kasei Kabushiki Kaisha Method for Producing Resin Composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01244814A (ja) * 1988-03-28 1989-09-29 Toyota Central Res & Dev Lab Inc 樹脂成形物の製造方法
JP2016175210A (ja) * 2015-03-18 2016-10-06 コニカミノルタ株式会社 射出成形装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01244814A (ja) * 1988-03-28 1989-09-29 Toyota Central Res & Dev Lab Inc 樹脂成形物の製造方法
JP2016175210A (ja) * 2015-03-18 2016-10-06 コニカミノルタ株式会社 射出成形装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240117127A1 (en) * 2021-02-03 2024-04-11 Asahi Kasei Kabushiki Kaisha Method for Producing Resin Composition

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