WO2023238789A1 - Composition de résine, corps moulé et corps moulé par injection multicolore - Google Patents

Composition de résine, corps moulé et corps moulé par injection multicolore Download PDF

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Publication number
WO2023238789A1
WO2023238789A1 PCT/JP2023/020626 JP2023020626W WO2023238789A1 WO 2023238789 A1 WO2023238789 A1 WO 2023238789A1 JP 2023020626 W JP2023020626 W JP 2023020626W WO 2023238789 A1 WO2023238789 A1 WO 2023238789A1
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Prior art keywords
resin composition
resin
volume
mass
elastomer
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PCT/JP2023/020626
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English (en)
Japanese (ja)
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裕太 山元
大輔 須長
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グローバルポリアセタール株式会社
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Priority to JP2023552592A priority Critical patent/JP7398029B1/ja
Publication of WO2023238789A1 publication Critical patent/WO2023238789A1/fr

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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
    • B29C45/16—Making multilayered or multicoloured articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals

Definitions

  • the present invention relates to a resin composition, a molded article, and a multicolor injection molded article.
  • a resin composition containing polyacetal resin as a main component e.g., polyacetal resin as a main component.
  • Polyacetal (POM) resin a type of engineering plastic, has excellent properties such as mechanical properties, thermal properties, electrical properties, sliding properties, and moldability, and is mainly used as a structural material and mechanical parts. It is widely used in electrical and electronic equipment, automobile parts, office equipment parts, and daily miscellaneous goods parts. Furthermore, in order to impart flexibility to polyacetal resin, elastomers are blended into the polyacetal resin. On the other hand, when molding a polyacetal resin composition containing a polyacetal resin and an elastomer, injection molding is often applied because it allows molding of complex shapes and is suitable for mass production. many.
  • a molded article formed from a polyacetal resin composition with a high proportion of elastomer tends to have high flexibility.
  • molded bodies formed from polyacetal resin compositions containing a low proportion of elastomer or no elastomer tend to be hard. It would be beneficial if such a hard member and a highly flexible member could be molded into a composite by multicolor injection molding. Also, depending on the application, quietness is required.
  • the present invention aims to solve such problems, and is to provide a polyacetal resin composition with high flexibility, which can be molded by multicolor injection molding with a hard polyacetal member, and which is quiet.
  • the purpose of the present invention is to provide an excellent resin composition, molded product, and multicolor injection molded product.
  • a resin composition containing a polyacetal resin and a core-shell elastomer The resin composition is molded into a multi-purpose test piece (ISO test piece) with a thickness of 4 mm, and the resin composition has a flexural modulus of 50 to 1000 MPa measured according to ISO 178, and is used for multicolor injection molding.
  • ISO test piece multi-purpose test piece
  • ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the proportion of the polyacetal resin is 10 to 50% by volume with respect to the total volume of resin components in the resin composition.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein 30 to 90% by volume of the total volume of resin components in the resin composition is a core-shell elastomer.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the core-shell elastomer shell contains an acrylic resin.
  • the compound capable of capturing ions includes at least one selected from the group consisting of a compound containing a triazine skeleton, a hindered amine, an alkaline earth metal hydroxide salt, a hydrotalcite, and a fatty acid metal salt. , the resin composition according to ⁇ 6>.
  • the resin composition according to any one of ⁇ 1> to ⁇ 7> which is for multicolor injection molding with the resin composition (B) in which the proportion of polyacetal resin is 50 to 100% by volume. . ⁇ 9> 30 to 90% by volume of the total volume of resin components in the resin composition is a core-shell elastomer, and ion trapping is possible for a total of 100 parts by mass of the resin components in the resin composition.
  • ⁇ 10> Any one of ⁇ 1> to ⁇ 8>, wherein 35 to 50 volume % of the total volume of the resin components in the resin composition is polyacetal resin, and 35 to 50 volume % is core shell elastomer.
  • the resin composition according to item 1. ⁇ 11> A pellet of the resin composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 12> A molded article formed from the resin composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 13> A molded article formed from the pellets described in ⁇ 11>.
  • ⁇ 14> A multicolor injection molded article comprising the resin composition according to any one of ⁇ 1> to ⁇ 10> and a resin composition (B) in which the proportion of polyacetal resin is 50 to 100% by volume.
  • a polyacetal resin composition having high flexibility which can be molded by multicolor injection molding with a hard polyacetal member, and having excellent quietness, a molded article, and a multicolor resin composition are provided. Now we can provide injection molded products.
  • this embodiment a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail.
  • the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment.
  • " ⁇ " is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
  • various physical property values and characteristic values are assumed to be at 23° C. unless otherwise stated. If the measurement methods, etc. explained in the standards shown in this specification differ from year to year, unless otherwise stated, they shall be based on the standards as of January 1, 2022.
  • the total volume of the resin components in the resin composition means the total volume of the polyacetal resin, elastomer, stress relaxation agent, and other resin components.
  • the resin composition of the present embodiment (hereinafter sometimes referred to as resin composition (A)) is a resin composition containing a polyacetal resin and a core-shell elastomer. It is characterized in that it has a flexural modulus of 50 to 1000 MPa when molded into an ISO test piece and measured according to ISO 178, and is suitable for multicolor injection molding. With such a configuration, it becomes possible to provide a polyacetal resin composition that is highly flexible, can be multicolored injection molded with a hard polyacetal member, and has excellent quietness. . That is, in order to obtain a highly flexible member, it is conceivable to mix an elastomer with the polyacetal resin to lower the flexural modulus.
  • the present inventor has developed a polyacetal resin composition containing a large amount of elastomer as a hard polyacetal resin composition, for example, a resin composition (B) in which the proportion of polyacetal resin is 50 to 100% by volume.
  • a resin composition (B) in which the proportion of polyacetal resin is 50 to 100% by volume.
  • the present inventor conducted a more specific study and found that the reason why a soft polyacetal resin composition containing a large amount of elastomer and a hard resin composition (B) cannot be molded by two-color injection molding is that the elastomer part is layered.
  • a core-shell elastomer When a core-shell elastomer is used, it is dispersed in the form of particles in a polyacetal resin, so in a molded article formed from a resin composition containing such a core-shell elastomer, the outermost layer contains a relatively large amount of polyacetal resin. Furthermore, in the outermost layer, the polyacetal resin covers the core-shell elastomer (particles). Therefore, it was assumed that two-color injection molding with the hard resin composition (B) became possible.
  • the resin composition (A) of this embodiment contains a polyacetal resin.
  • the polyacetal resin is not particularly limited, and even if it is a homopolymer containing only divalent oxymethylene groups as a constituent unit, it may contain a divalent oxymethylene group and a divalent oxyalkylene having 2 to 6 carbon atoms. It may also be a copolymer containing the group as a constituent unit.
  • Examples of the oxyalkylene group having 2 to 6 carbon atoms include oxyethylene group, oxypropylene group, and oxybutylene group.
  • the proportion of the oxyalkylene group having 2 to 6 carbon atoms in the total number of moles of the oxymethylene group and the oxyalkylene group having 2 to 6 carbon atoms is not particularly limited, and is 0.5 to 10 mol. % is sufficient.
  • 1,3-dioxolane may be used as the main raw material
  • 1,3-dioxane may be used as the main raw material
  • 1,3-dioxepane may be used as the main raw material.
  • the amount of hemiformal terminal groups, the amount of formyl terminal groups, and the amount of terminal groups unstable to heat, acids, and bases is preferably small.
  • the hemiformal end group is represented by -OCH 2 OH
  • the formyl end group is represented by -CHO.
  • polyacetal resin in addition to the above, polyacetal resins described in paragraphs 0018 to 0043 of JP 2015-074724A can be used, the contents of which are incorporated herein.
  • the resin composition (A) of this embodiment contains a core-shell elastomer.
  • a core-shell elastomer By including the core-shell elastomer, a molded article with excellent flexibility can be obtained, and multicolor injection molding is also possible.
  • a core-shell elastomer is a polymer with a multilayer structure having a core part and a shell layer covering part or all of the core part, and Kaneka Corporation's Kane Ace series and Mitsubishi Chemical Corporation's Metablen series are known.
  • non-core-shell elastomer examples include polyolefin elastomer, polystyrene elastomer, polyurethane elastomer, polyester elastomer, copolyester/ether elastomer, acrylic elastomer, and vinyl chloride/nitrile elastomer, with polyurethane elastomer being preferred.
  • the total of the polyacetal resin, elastomer, and stress relaxation agent preferably accounts for 90% by mass or more, more preferably 95% by mass or more, It may be 97% by mass or more.
  • the resin composition (A) of the present embodiment preferably contains 0.01 to 1 part by mass of a compound capable of capturing ions based on 100 parts by mass of the resin composition (A).
  • a compound capable of ion scavenging By including such a compound capable of ion scavenging, extrusion becomes possible even if the content of the elastomer, particularly the non-core-shell elastomer, is increased, and excellent multicolor injection moldability can be achieved.
  • the compound capable of capturing ions preferably contains at least one selected from the group consisting of a compound containing a triazine skeleton, a hindered amine, an alkaline earth metal hydroxide salt, a hydrotalcite, and a fatty acid metal salt. .
  • the description in paragraphs 0095 to 0097 of JP-A No. 2014-005385 can be referred to, the contents of which are incorporated herein.
  • the description in paragraphs 0030 to 0031 of JP 2019-038990 A can be referred to, the contents of which are incorporated herein.
  • the description in paragraph 0044 of JP-A-2014-234511 can be referred to, the contents of which are incorporated herein.
  • hydrotalcite the descriptions in paragraphs 0042 and 0043 of JP 2019-065221 A can be referred to, and the contents thereof are incorporated herein.
  • the description in paragraphs 0028 and 0029 of JP-A-2021-080443 can be referred to, the contents of which are incorporated herein.
  • the content thereof is 0.01 parts by mass or more based on a total of 100 parts by mass of the resin components in the resin composition (A). It is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.07 parts by mass or more, and 0.09 parts by mass. It is even more preferable that it is above. By setting it to the above lower limit or more, acid ions in the polyacetal resin are captured, and the extrudability of the resin composition (A) tends to be further improved.
  • the upper limit of the content of the compound capable of capturing ions is preferably 1 part by mass or less, and 0.8 parts by mass, based on a total of 100 parts by mass of the resin components in the resin composition (A). It is more preferably at most 0.6 parts by mass, even more preferably at most 0.4 parts by mass, even more preferably at most 0.2 parts by mass. By setting it below the upper limit, mold contamination during continuous injection molding tends to be more effectively suppressed.
  • the resin composition (A) of this embodiment may contain only one kind of compound capable of ion trapping, or may contain two or more kinds of compounds. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition (A) of this embodiment may further contain a stress relaxation agent.
  • a stress relaxation agent By including a stress relaxation agent, it is expected that the elastic modulus of the resin composition can be further lowered and residual strain generated during molding can be effectively removed.
  • the stress relaxation agent used in this embodiment is a polyether ester amide block copolymer, a polyolefin/polyether copolymer, a polyamide/polyalkylene glycol block copolymer, a polyethylene glycol having a number average molecular weight of 20,000 or more, and , polyethylene oxide having a number average molecular weight of 20,000 or more is preferable, and polyethylene oxide having a number average molecular weight of 20,000 or more is more preferable.
  • the polyether ester amide block copolymer has a melting point equivalent to that of polyacetal (for example, the difference in melting point is within 10 °C) or the actual temperature during polyacetal processing (for example, 200 °C) (for example, the copolymer It is preferable that the difference between the melting point of and the temperature during processing is within 10°C.
  • the polyolefin constituting the polyolefin/polyether copolymer is preferably polyethylene or polypropylene.
  • the polyether is preferably polyethylene glycol, and the melting point is equivalent to that of polyacetal (e.g., the difference in melting point is within 10°C) or the actual temperature at the time of processing polyacetal (e.g., 200°C) (e.g.
  • the difference between the melting point of the copolymer and the temperature during processing is preferably within 10°C).
  • the polyethylene glycol having a number average molecular weight of 20,000 or more preferably has a number average molecular weight of 20,000 to 100,000, more preferably 20,000 to 50,000.
  • the polyethylene oxide having a number average molecular weight of 20,000 or more preferably has a number average molecular weight of 20,000 to 500,000, more preferably 80,000 to 30,000, and more preferably 100,000 to 200,000. is even more preferable.
  • catalog values can be adopted in the case of a commercially available product.
  • the content thereof shall be 0.1 parts by mass or more based on a total of 100 parts by mass of the resin components in the resin composition (A). is preferably 0.2 parts by mass or more, more preferably 0.7 parts by mass or more, even more preferably 1.0 parts by mass or more, and 1.2 parts by mass or more. It is even more preferable. By setting it to the above lower limit or more, the softness of the obtained molded product tends to be further improved. Further, the upper limit of the content of the stress relaxation agent is preferably 10 parts by mass or less, and preferably 8 parts by mass or less, based on the total 100 parts by mass of the resin components in the resin composition (A).
  • the resin composition (A) of the present embodiment may contain any conventionally known additives and fillers within a range that does not impair the object of the present invention.
  • additives and fillers used in this embodiment include thermoplastic resins other than polyacetal resins, ultraviolet absorbers, antioxidants, antistatic agents, carbon fibers, glass fibers, glass flakes, potassium titanate whiskers, etc. Can be mentioned. For these details, the descriptions in paragraphs 0113 to 0124 of JP 2017-025257 A can be referred to, and the contents thereof are incorporated herein.
  • the resin composition (A) of the present embodiment has a flexural modulus of 50 to 1000 MPa when the resin composition (A) is molded into a 4 mm thick multipurpose test piece (ISO test piece) and measured according to ISO178. By setting it below the above upper limit, a molded article with excellent flexibility can be obtained. Furthermore, lowering the bending elastic modulus is preferable because the resonance frequency (Hz) decreases and a material with high quietness tends to be obtained.
  • the bending elastic modulus is preferably 900 MPa or less, more preferably 800 MPa or less, even more preferably 750 MPa or less, and may be 500 MPa or less, or 400 MPa or less depending on the application. Further, the lower limit of the bending elastic modulus is determined depending on the application and the like, but it may usually be 100 MPa or more, 350 MPa or more, or 500 MPa or more.
  • the resin composition (A) of this embodiment is for multicolor injection molding.
  • “for multicolor injection molding” means for multicolor injection molding with a resin composition (B) in which the proportion of polyacetal resin is 50 to 100% by volume, and more specifically, for multicolor injection molding.
  • the resin composition (A) of this embodiment can be molded into a two-color injection molded body with polyacetal resin pellets (B) (manufactured by Mitsubishi Engineering Plastics, F20-03, polyacetal resin). , and that the member (A) and member (B) constituting the two-color injection molded product are adhered with such an adhesive strength that the base material is destroyed when the member (A) and the member (B) are separated.
  • FIG. 1 shows an example of a multicolor injection molded article using the resin composition (A) and resin composition (B) of this embodiment.
  • 1 is a two-color injection molded article
  • 2 is a hard member (a molded article made from the resin composition (B))
  • 3 is a soft member (a molded article made from the resin composition (A)).
  • the molded bodies) are shown respectively.
  • a resin composition (B) is injected into a mold. Thereafter, after the resin composition (B) is solidified, the resin composition (A) is also injected into the mold. Thereafter, a two-color injection molded article is obtained by cooling within the mold.
  • the order of the resin composition (B) and the resin composition (A) may be reversed.
  • it may be a multicolor injection molded article of three or more types using the resin composition (A), the resin composition (B), or other resin compositions.
  • Substantially free means that the content of the elastomer is 10% by mass or less of the resin composition (B), preferably 5% by mass or less, more preferably 3% by mass or less. , more preferably 1% by mass or less.
  • the resin composition (B) is preferably molded into a 4 mm thick multi-purpose test piece (ISO test piece) and has a flexural modulus of more than 1000 MPa, which is usually about 2000 to 3000 MPa. .
  • the resin composition (A) of this embodiment contains the above-mentioned essential components and, if necessary, the above-mentioned arbitrary components.
  • the manufacturing method is arbitrary, and any conventionally known manufacturing method for resin compositions may be used to mix and knead these raw materials.
  • the shape of the die nozzle is also not particularly limited, but in terms of pellet shape, a circular nozzle with a diameter of 1 mm or more is preferable, a circular nozzle with a diameter of 2 mm or more is more preferable, a circular nozzle with a diameter of 10 mm or less is preferable, and a circular nozzle with a diameter of 7 mm or less is preferable. Nozzles are more preferred.
  • the discharge rate is preferably 5 kg/hr or more, more preferably 7 kg/hr or more, preferably 1,000 kg/hr or less, and more preferably 800 kg/hr or less.
  • the rate is preferably 5 kg/hr or more, more preferably 7 kg/hr or more, preferably 1,000 kg/hr or less, and more preferably 800 kg/hr or less.
  • the resin composition of the present embodiment and molded products formed from the resin composition are, for example, automotive parts such as trim clips, seatbelt members, and headrest guides, building material parts, electric/electronic parts, office equipment parts, and daily miscellaneous goods.
  • automotive parts such as trim clips, seatbelt members, and headrest guides
  • building material parts such as trim clips, seatbelt members, and headrest guides
  • electric/electronic parts such as ados, hose bands, gaskets, and cable ties.
  • home appliances such as refrigerator gaskets, hose bands, gaskets, and cable ties.
  • the pellets (A) obtained above were heat-treated for 4 hours in a hot air circulation dryer at a temperature of 80°C.
  • the injection molding machine used was EC-100S manufactured by Shibaura Kikai Co., Ltd.
  • a fully automatic bending tester manufactured by Shimadzu Corporation was used.
  • the results are shown in Tables 3 to 6.
  • the unit is MPa.
  • ⁇ Resonance frequency> A wire was attached to one end of the ISO test piece obtained above, and the test piece was hung in an environment where it would not be affected by external vibrations. With a vibration sensor connected to the Ono Sokki measurement system (DS2000) attached to the other end, a shock was applied to the center of the test piece using an impulse hammer also connected to the DS2000. The vibrations generated at this time were analyzed using DS2000 to obtain a frequency response function, and the peak frequency of the frequency response function was defined as the resonance frequency. At this time, if the resonant frequency was 120 Hz or less, it was determined that the material was excellent in quietness.
  • DS2000 Ono Sokki measurement system
  • polyacetal resin pellets (B) were injection molded at a resin temperature of 230°C and a mold temperature of 80°C to form a test film of 123 mm x 13 mm x 0.8 mm (thickness), and then After rotating the mold with It was bent at 90° to form an L-shape.
  • the dimensions of the laminated part were 63 mm x 13 mm x 2.0 mm (thickness), and the dimensions of the bent part were 15 mm x 13 mm x 2.0 mm (thickness). Further, the laminated portion and the test film were laminated so that their longitudinal directions coincided.
  • the bent part of the thus obtained multicolor injection molded body was fixed to the upper jig (fixed side) of a tensile tester (manufactured by Instron, product name "5544"), and the bent part was fixed to the lower jig (movable side).
  • the test film was fixed to.
  • a peel test of the multicolor injection molded article was conducted by displacing the upper jig upward at a speed of 200 mm/min.
  • POM volume ratio means the volume ratio of polyacetal resin to the total volume of resin components in the resin composition
  • elastomer volume ratio means the volume ratio of polyacetal resin to the total volume of resin components in the resin composition. It refers to the volume ratio of elastomer to the total volume of the components.
  • Comparative Example 4 Although a core-shell elastomer was blended, no compound capable of capturing ions was blended, and when the volume ratio of the elastomer was increased, pellets could not be produced. In Comparative Example 5, two-color injection molding was not possible when no compound capable of capturing ions was blended and an elastomer other than the core-shell elastomer was used.

Abstract

Cette composition de résine contient une résine de polyacétal et un élastomère à noyau-enveloppe. La composition de résine est utilisée pour le moulage par injection multicolore et a un module de flexion de 50 à 1000 MPa tel que déterminé conformément à l'ISO178, une pièce test polyvalente (pièce test ISO), qui est obtenue par moulage de cette composition de résine dans une épaisseur de 4 mm, étant utilisée.
PCT/JP2023/020626 2022-06-09 2023-06-02 Composition de résine, corps moulé et corps moulé par injection multicolore WO2023238789A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001518403A (ja) * 1997-09-30 2001-10-16 ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング 複合材料物品の製造方法
JP2003048252A (ja) * 2001-08-08 2003-02-18 Polyplastics Co ポリアセタール樹脂組成物／熱可塑性エラストマー複合成形体及びその成形方法
JP2021011562A (ja) * 2019-07-03 2021-02-04 三菱エンジニアリングプラスチックス株式会社 樹脂組成物および成形品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001518403A (ja) * 1997-09-30 2001-10-16 ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング 複合材料物品の製造方法
JP2003048252A (ja) * 2001-08-08 2003-02-18 Polyplastics Co ポリアセタール樹脂組成物／熱可塑性エラストマー複合成形体及びその成形方法
JP2021011562A (ja) * 2019-07-03 2021-02-04 三菱エンジニアリングプラスチックス株式会社 樹脂組成物および成形品

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