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WO2023095891A1 - Composition de résine et article moulé la contenant - Google Patents

Composition de résine et article moulé la contenant Download PDF

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Publication number
WO2023095891A1
WO2023095891A1 PCT/JP2022/043618 JP2022043618W WO2023095891A1 WO 2023095891 A1 WO2023095891 A1 WO 2023095891A1 JP 2022043618 W JP2022043618 W JP 2022043618W WO 2023095891 A1 WO2023095891 A1 WO 2023095891A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
elastomer
mass
acid
polyethylene
Prior art date
Application number
PCT/JP2022/043618
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English (en)
Japanese (ja)
Inventor
雅也 隣
大介 堂山
Original Assignee
Ｕｂｅ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ｕｂｅ株式会社 filed Critical Ｕｂｅ株式会社
Priority to JP2023563763A priority Critical patent/JPWO2023095891A1/ja
Publication of WO2023095891A1 publication Critical patent/WO2023095891A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to resin compositions, particularly polyamide resin compositions, and molded articles containing the same.
  • Elastomers having a polyether structure as a soft segment have been proposed as resin compositions to replace rubber used in packings, vibration-isolating rubbers, rubber hoses, etc.
  • resin compositions containing polyester elastomers and polyamide elastomers have been proposed.
  • there is No. 5,200,000 describes a composition comprising a polyamide, a polyamide elastomer that is a copolymer comprising polyamide blocks and polyether blocks, and a single polyolefin functionalized with maleic anhydride units or epoxy units, and exhibits low flexural modulus. It is disclosed to show the rate.
  • Patent Document 2 a composition containing predetermined amounts of a semicrystalline polyamide, an amorphous polyamide, a compatibilizer for the polyamide, and a polyamide elastomer that is a flexible polyamide has a high breaking elongation and a low bending It is disclosed to exhibit elastic modulus and high impact resistance.
  • compositions containing polyamide elastomers elastomers having polyether structures as soft segments
  • Patent Documents 1 and 2 there is room for further improvement in terms of tensile set and mechanical properties.
  • an object of the present invention is to provide a resin composition that is excellent in tensile set and mechanical properties.
  • the present invention relates to the following.
  • the present invention particularly relates to a resin composition, a molded article, and a production method, wherein the elastomer (A) is an elastomer having a polyether structure as a soft segment in the following aspects [1] to [10].
  • Mw weight average molecular weight
  • each component in the composition refers to the total amount of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means.
  • "-" indicating a numerical range means that the numerical values described before and after it are included as lower and upper limits.
  • 50.00 to 90.00% by mass means “50.00% by mass or more and 90.00% by mass or less”.
  • a product obtained by mixing includes a product simply containing each component and a product in which at least a part of them has reacted.
  • the resin composition of the present invention comprises an elastomer (A) having a soft segment containing a polyether and a modified polyethylene (B), wherein the modified polyethylene (B) comprises a modified low-density polyethylene and a modified ultra-high molecular weight It is at least one selected from the group consisting of polyethylene, and contains 50.00 to 90.00% by mass of the elastomer (A) in the resin composition.
  • the elastomer (A) has, in its structure, a soft segment exhibiting rubber elasticity and a hard segment acting as a pseudo cross-linking point, and the soft segment includes a polyether structure.
  • the elastomer (A) As hard segments contained in the elastomer (A), polyamide units, polyester units, polypropylene units, urethane bonds, etc. can be used.
  • the elastomer (A) preferably has polyamide units or polyester units as hard segments. That is, the elastomer (A) preferably contains at least one selected from the group consisting of polyamide elastomers and polyester elastomers. Elastomer (A) is particularly preferably a polyamide elastomer.
  • Polyamide elastomers include polyamide elastomers having polyamide units as hard segments and polyether units as soft segments.
  • Polyamide elastomers are selected from the group consisting of polyether polyester amide elastomers in which hard segments and soft segments are linked by ester bonds, and polyether amide elastomers in which hard segments and soft segments are linked by amide bonds, from the viewpoint of the balance of mechanical properties. At least one selected is preferred.
  • the hard segment can be derived from a polyamide having carboxyl groups at both end groups, and polyamide-forming units and at least one dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and aromatic dicarboxylic acids.
  • a segment containing an acid can be derived from a polyamide having carboxyl groups at both end groups, and polyamide-forming units and at least one dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and aromatic dicarboxylic acids.
  • the polyamide-forming units in the hard segment are units formed from lactams, aminocarboxylic acids, and/or diamines and dicarboxylic acids (nylon salts).
  • Examples of the aforementioned components include units obtained by reacting one or more selected from the group consisting of lactams, aminocarboxylic acids, diamines and dicarboxylic acids (nylon salts).
  • Lactams include aliphatic lactams having 4 to 20 carbon atoms such as 2-pyrrolidinone, ⁇ -caprolactam, ⁇ -heptalactam, ⁇ -undecalactam and ⁇ -dodecanelactam.
  • Aminocarboxylic acids include 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. 5 to 20 aliphatic ⁇ -aminocarboxylic acids and the like.
  • Diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, ,4-trimethylhexane-1,6-diamine, 2,4,4-trimethylhexane-1,6-diamine, 3-methylpentane-1,5-diamine and other aliphatic diamines having 2 to 20 carbon atoms, etc. and diamine compounds.
  • ⁇ -undecalactam ⁇ -dodecanelactam
  • 11-aminoundecanoic acid ⁇ -dodecanelactam
  • 12-aminododecanoic acid from the viewpoint of dimensional stability due to low water absorption, chemical resistance, and mechanical properties. At least one is preferred.
  • Dicarboxylic acids include linear aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid; triglycerides; Aliphatic dicarboxylic acids such as dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms (dimer acids) and hydrogenated products thereof (hydrogenated dimer acids) obtained by dimerizing unsaturated fatty acids obtained by fractional distillation of; terephthalic acid , isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-pheny
  • a polyamide having carboxyl groups at both ends can be obtained by ring-opening polymerization or polycondensation of the above polyamide-forming units in the presence of a dicarboxylic acid in a conventional manner.
  • adipic acid, oxalic acid, dodecanedioic acid, sebacic acid and dimer acid are preferred.
  • dimer acid and the hydrogenated dimer acid trade names such as "PRIPOL 1004", "PRIPOL 1006", “PRIPOL 1009” and “PRIPOL 1013" manufactured by Croda can be used.
  • the number average molecular weight of the hard segment is preferably 300 to 15,000, more preferably 300 to 6,000 from the viewpoint of flexibility and moldability.
  • Soft segments include polyether.
  • the soft segment is preferably polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ABA-type triblock polyether represented by the following formula (1), or the like. These can be used alone or in combination of two or more. Also, polyether diamine or the like obtained by reacting the end of polyether with ammonia or the like can be used.
  • the soft segment preferably has a number average molecular weight of 200 to 6,000, more preferably 650 to 2,000.
  • Each of x and z is independently an integer of preferably 1 to 18, more preferably an integer of 1 to 16, more preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12.
  • y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, even more preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.
  • polyester elastomer having polyester units as hard segments preferably contains an aromatic polyester as a constituent unit of the hard segments.
  • aromatic polyesters introduced into the hard segment of elastomer (A) include polymethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate and polybutylene naphthalate.
  • aromatic polyester used to form polyester units as hard segments can be formed, for example, from an aromatic dicarboxylic acid and an aliphatic diol.
  • Aromatic dicarboxylic acids may be derivatives capable of forming esters by reaction with alcohols, such as acid anhydrides and acid halides.
  • Dicarboxylic acids from which polyester units as hard segments are formed include isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, derivatives thereof, and the like.
  • Diols used to form polyester units as hard segments include aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol; Alicyclic diols such as methanol and tricyclodecanedimethylol; xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl ] propane, bis[4-(2-hydroxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′ -dihydroxy-p-quarterphenyl and other aromatic diols. These diols preferably have a molecular weight of 300 or less because they are advantageous in forming hard segments.
  • each combination of the hard segment and the soft segment mentioned above can be mentioned.
  • a ring-opening polycondensate/ABA-type triblock polyether combination a combination of polybutylene terephthalate/polyethylene glycol, a combination of polybutylene terephthalate/polypropylene glycol, and a combination of polybutylene terephthalate/polybutylene glycol are preferred, and a combination of lauryl lactam is preferred.
  • a ring polycondensate/ABA-type triblock polyether combination is particularly preferred.
  • the hard segment/soft segment (mass ratio) is more preferably 90/10 to 35/65, particularly preferably 80/20 to 40/60.
  • the hard segment/soft segment (mass ratio) may be 95/5 to 70/30, or 70/30 to 30/70.
  • the hard segment/soft segment (mass ratio) is an average value according to the mass of each component.
  • elastomers such as those described above include Daiamide (registered trademark) manufactured by Daicel-Evonik, Pebax (registered trademark) manufactured by ARKEMA, Grilamid (registered trademark) manufactured by Em Chemie Japan, Hyper Alloy Actimer (registered trademark), manufactured by DSM: Novamit (registered trademark), manufactured by UBE Ube Industries: UBESTA (registered trademark) XPA series, manufactured by Toray DuPont: Hytrel (registered trademark), and the like.
  • UBE registered trademark
  • Pebax Registered Trademarks 2533, 3533, 4033, 5533, 6333, 7033 and 7233 (manufactured by ARKEMA) are preferred.
  • Modified polyethylene (B) is at least one selected from the group consisting of modified low-density polyethylene and modified ultra-high molecular weight polyethylene.
  • Modified low density polyethylene is low density polyethylene that has been modified with a compound containing modifying groups.
  • Modified ultra-high molecular weight polyethylene is ultra-high molecular weight polyethylene modified with a compound containing a modifying group.
  • the molecular weight of the modified low-density polyethylene is not particularly limited, and the density of the modified ultra-high molecular weight polyethylene is not particularly limited.
  • the polyethylene (unmodified polyethylene) in the modified polyethylene (B) is a low-density polyethylene having a density of 0.910 g/cm 3 or more and 0.925 g/cm 3 or less, and an ultra-high-density polyethylene having a weight average molecular weight (Mw) of 1 million or more.
  • Molecular weight polyethylene UHMWPE
  • ultra high molecular weight polyethylene UHMWPE
  • Mw weight average molecular weight of ultra high molecular weight polyethylene
  • GPC gel permeation chromatography
  • ultra-high molecular weight polyethylene UHMWPE
  • 1,2,4-trichlorobenzene 1 ml
  • 200 ⁇ l of the sample solution obtained are then injected into a high temperature GPC equipped with an infrared detector at a column zone of 145° C. and a detector zone of 160° C. at a flow rate of 0.5 ml/min.
  • the low density polyethylene may be linear low density polyethylene (LLDPE) or branched low density polyethylene (LDPE).
  • the polyethylene (unmodified polyethylene) in the modified polyethylene (B) is at least one selected from the group consisting of branched low-density polyethylene (LDPE) and ultra-high molecular weight polyethylene (UHMWPE) from the viewpoint of reducing tensile set. is preferred.
  • the unmodified polyethylene may be a homopolymer of ethylene, but if it is mainly composed of ethylene, it may contain a small amount of other monomers, such as 5 mol% or less of ⁇ -olefin monomers, or 1 mol% or less of non-modified polyethylene. It may be a copolymer containing an olefin monomer.
  • modifying groups in compounds containing modifying groups include acid modifying groups such as carboxyl groups and sulfonic acid groups; and carboxyl metal salts, acid anhydride groups, amino groups, hydroxyl groups, silanol groups, alkoxy groups, hydroxyl groups, and epoxy groups. , an isocyanate group, a mercapto group, an oxazoline group, and other modifying groups other than acid modifying groups.
  • the compound containing a modifying group is preferably an unsaturated carboxylic acid or derivative thereof, a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, a vinyl group-containing organosilicon compound, or the like.
  • Examples of unsaturated carboxylic acids or derivatives thereof include unsaturated compounds having one or more carboxyl groups, esters of compounds having carboxyl groups and alkyl alcohols, and unsaturated compounds having one or more anhydrous carboxyl groups.
  • Examples of unsaturated groups include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups.
  • the compound containing a modifying group is preferably a compound containing an acid modifying group, particularly preferably an unsaturated carboxylic acid or a derivative thereof, from the viewpoint of reactivity with functional groups present at the ends of the elastomer.
  • unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, mesaconic acid, citraconic acid, crotonic acid, isocrotonic acid, endocis-bicyclo[2,2,1]hept- Unsaturated dicarboxylic acids such as 5-ene-2,3-dicarboxylic acid are included.
  • unsaturated carboxylic acid derivatives include acid halides, amides, imides, anhydrides and esters of the unsaturated carboxylic acids.
  • the unsaturated carboxylic acid or derivative thereof is more preferably at least one selected from the group consisting of maleic anhydride and acrylic acid, and particularly preferably maleic anhydride.
  • Modification of unmodified polyethylene with a compound containing a modifying group can be performed during or after synthesis of unmodified polyethylene.
  • the amount of the compound containing the modifying group to be used can be appropriately set according to the desired modification amount of the polyethylene.
  • modified polyethylene (B) includes F3000 (trade name) manufactured by Ube Maruzen Polyethylene Co., Ltd., Admer (registered trademark) NF528T manufactured by Mitsui Chemicals, Inc., Lubmer (registered trademark) LY1040 manufactured by Mitsui Chemicals, Inc., and Admer (registered trademark) NB550, Modic (registered trademark) M545 manufactured by Mitsubishi Chemical Corporation, Adtex (registered trademark) L6100M manufactured by Japan Polyethylene Co., Ltd., Admer (registered trademark) NB508 manufactured by Mitsui Chemicals, Admer manufactured by Mitsui Chemicals, Inc. (registered trademark) HE810, Admer (registered trademark) NF567 manufactured by Mitsui Chemicals, Inc., and the like.
  • modified polyethylene (B) is a modified low density polyethylene, it is preferably a branched modified low density polyethylene (LDPE).
  • LDPE branched modified low density polyethylene
  • the modified polyethylene (B) may be a single component or a combination of two or more components.
  • the above-mentioned unmodified polyethylene can also be added.
  • unmodified polyethylene its amount is preferably 20.00 mass % or less of the total composition.
  • the amount of unmodified polyethylene is preferably 50.00 mass % or less based on the total amount of modified polyethylene (B).
  • Additive (C) The resin composition may contain an additive (C) as long as the effects of the present invention are not impaired.
  • Additives (C) include, for example, weathering agents, cross-linking agents, further polyamide resins (excluding elastomer (A)), antioxidants, heat stabilizers, heat-resistant agents, thickeners, molecular weight (viscosity) Regulators, UV absorbers, light stabilizers, antistatic agents, lubricants, antiblocking agents, antifogging agents, crystal nucleating agents, release agents, plasticizers, foaming agents, colorants (pigments, dyes, etc.), etc. be done.
  • a component corresponding to the additive (C) for example, an antioxidant
  • the component corresponding to the additive (C) shall be contained as the (C) component in the resin composition.
  • cross-linking agents include cross-linking agents having at least one group selected from the group consisting of carbodiimide groups, carboxyl groups, acid anhydride groups, isocyanate groups, epoxy groups, alkoxysilane groups and allyl groups.
  • the cross-linking agent is preferably a cross-linking agent having a carbodiimide group, and particularly preferably a cross-linking agent having a carbodiimide group having a cyclic structure, from the viewpoint of the need to efficiently form a cross-linked structure.
  • cross-linking agent having a carbodiimide group having a cyclic structure does not liberate an isocyanate group when reacting with at least one selected from the group consisting of the elastomer (A) and the modified polyethylene (B) from the viewpoint of working environment conservation. is particularly preferred from
  • antioxidants examples include organic antioxidants and inorganic antioxidants.
  • organic antioxidants include phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. From the viewpoint of improving the antioxidant performance of the molded article, the organic antioxidant is preferably at least one selected from the group consisting of phenol antioxidants, phosphorus antioxidants and sulfur antioxidants. , a phenolic antioxidant and a phosphorus antioxidant.
  • phenolic antioxidants include N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide (Irganox (registered trademark) 1098; BASF Japan Ltd.
  • phosphorus antioxidants include tris(2,4-di-t-butylphenyl) phosphite (Irgafos (registered trademark) 168; manufactured by BASF Japan Ltd.), bis(2,6-di-t -Butyl-4-methylphenyl)pentaerythritol diphosphite (ADEKA STAB (registered trademark) PEP-36; manufactured by ADEKA Corporation), tetrakis(2,4-di-tert-butylphenoxy)-4,4-bi
  • a reaction product of bifinyl which is mainly composed of finyldiphosphine, phosphorus trichloride and 2,4-di-tert-butylphenol (Hostanox (registered trademark) P-EPQ (registered trademark) P; manufactured by Clariant Japan Co., Ltd.).
  • Phosphorus-based antioxidants may be used singly or in combination of two or more.
  • sulfur-based antioxidants include thioether-based antioxidants, specifically, distearyl-3,3-thiodipropionate (Irganox (registered trademark) PS802; manufactured by BASF Japan Ltd.), pentaeris Lityl tetrakis (3-laurylthiopropionate) (Sumilizer (registered trademark) TP-D; manufactured by Sumitomo Chemical Co., Ltd.), didodecyl (3,3'-thiodipropionate) (Irganox (registered trademark) PS800; BASF Japan Co., Ltd.), and at least one selected from the group consisting of these is preferable.
  • Sulfur-based antioxidants may be used singly or in combination of two or more.
  • the content of the organic antioxidant is preferably 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, in 100% by mass of the polyamide resin composition. , 0.02 to 1.5% by weight.
  • inorganic antioxidants include metal halide antioxidants.
  • the metal halide antioxidant is a component that mainly imparts long-term heat resistance.
  • a metal halide antioxidant is a compound of a halogen and a metal. Halogen includes fluorine, chlorine, bromine, iodine and the like.
  • metals include Group 1 elements (alkali metals), Group 2 elements (alkaline earth metals), Group 3 to Group 12 elements (eg, transition metals), and the like.
  • the metal in the metal halide is preferably a group 1 element (alkali metal) or a group 11 element (copper group) metal.
  • the metal halide includes potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride, and the like.
  • the metal halide includes cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, Cupric iodide etc. are mentioned.
  • the metal halide antioxidant is more preferably a mixture of cuprous iodide and potassium halide, or a mixture of cuprous bromide and potassium halide.
  • a mixture or a mixture of cuprous bromide and potassium bromide is particularly preferred.
  • the inorganic antioxidants may be used singly or in combination of two or more.
  • the content of the inorganic antioxidant is preferably 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, in 100% by mass of the polyamide resin composition. , 0.05 to 1.0% by weight.
  • Weather stabilizers include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, hindered amine compounds, phenyl salicylate compounds, cyanoacrylate compounds, malonic acid ester compounds, and oxalic acid anilide. system compounds and the like.
  • the weathering agents may be used singly or in combination of two or more.
  • hindered amine compounds are highly effective in scavenging radicals and suppressing photo-oxidation of resins, and can be used in combination with other weather resistance agents to enhance the effect of resins in suppressing ultraviolet absorption.
  • polyamide resins are not particularly limited, and include polyamide resins having the polyamide-forming units described above for elastomer (A).
  • Specific examples of further polyamide resins include aliphatic polyamides (e.g., PA5, PA6, PA11, PA12, PA46, PA56, PA510, PA66, PA610, PA612, PA1010, PA1012, etc.) ), aromatic polyamides (e.g. PA4T, PA6T, PA9T, PA10T, PA6I, PAMXD6) and copolymers of two or more monomers forming said polyamides (e.g.
  • PA means "polyamide”.
  • Additives (C) other than those described above can be appropriately selected from components usually added to resin compositions. From the viewpoint of better mechanical properties, the resin composition preferably further contains a cross-linking agent. Further, when the resin composition contains an elastomer (A) having a mass ratio between the hard segment and the soft segment of 95/5 to 70/30, a cross-linking agent is added as the additive (C) from the viewpoint of permanent tensile set. It is preferable to use Additives (C) may each be one component or a combination of two or more components.
  • the content of the elastomer (A) is 50.00-90.00% by mass.
  • the content of the elastomer (A) is preferably 60.00 to 90.00% by mass from the viewpoint of mechanical properties and moldability.
  • the content of the modified polyethylene (B) is more than 0% by mass and 50.00% by mass or less, and from the viewpoint of tensile set, mechanical properties, and moldability, it is 5.00 to 50.00% by mass. Preferably, it is particularly preferably 10.00 to 50.00% by mass.
  • the resin composition further contains an additive (C)
  • the total amount of (A) to (C) in the resin composition can be 100% by mass. Therefore, when the content of the modified polyethylene (B) is more than 0% by mass and less than 50.00% by mass, the resin composition further contains the additive (C) more than 0% by mass and less than 50.00% by mass. can be used.
  • the resin composition may further contain 5.00% by mass or more of additive (C).
  • the upper limit of the content of the modified polyethylene (B) can be a value obtained by subtracting the total content of the elastomer (A) and the additive (C) from 100.00% by mass.
  • the content of additive (C) is preferably 0 to 45.00% by mass.
  • the content of the further polyamide resin (excluding the elastomer (A)) is 0 mass from the viewpoint of not affecting the mechanical properties, molding processability and the effects of the present invention. % or more and less than 10.00 mass %, more preferably 0 mass % or more and less than 5.00 mass %, and particularly preferably 0 mass % or more and less than 3.00 mass %.
  • the content of the weathering agent is preferably 0.01 to 5.00% by mass, more preferably 0.01 to 3.00, from the viewpoint of durability such as light resistance of the molded product. % by weight is particularly preferred.
  • the content of the cross-linking agent is preferably 0.01 to 5.00% by mass, more preferably 0.01 to 4.00% by mass, from the viewpoint of tensile set and moldability. is particularly preferred.
  • the content of the antioxidant is preferably 0.01 to 5.00% by mass from the viewpoint of appearance immediately after molding, deterioration over time, and maintenance of physical properties after heat deterioration. 0.01 to 3.00 mass % is particularly preferred.
  • the content of the component corresponding to the additive (C) is It is defined as the content of the component (C) with respect to the mass.
  • an ISO TYPE A-shaped 2 mm thick test piece prepared according to ISO 294-1 is subjected to 20% strain in a tensile tester according to JIS K 6273 in an environment of 23 ° C. and 50% relative humidity.
  • the tensile permanent strain when a 30-minute tensile permanent strain test is performed is preferably 30.0% or less, more preferably 29.5% or less, and further preferably 29.0% or less. preferable.
  • the tensile permanent strain is preferably 5.0 to 30.0%, more preferably 5.0 to 29.5%, and 5.0 to 29.0. % is particularly preferred.
  • the above resin composition preferably has a tensile modulus of 100 MPa or more, measured according to ISO 527 on a 4 mm thick test piece of ISO TYPE A shape prepared according to ISO 294-1. From the viewpoint of mechanical properties, the tensile modulus is more preferably 100 to 800 MPa, particularly preferably 100 to 600 MPa.
  • the resin composition When the resin composition has a tensile yield stress, it preferably has a tensile yield stress of 9 MPa or more when subjected to a tensile test under an atmosphere of 23°C based on ISO-527-1 and 2. Although some resins do not have a yield point and a tensile yield stress cannot be defined, it is also preferred that such resins have no tensile yield stress, as such resins are considered to be strain resistant.
  • the above resin composition can be designed to have appropriate fluidity according to the molding method.
  • the resin composition does not contain a cross-linking agent, it preferably has fluidity such that the flow length under the following conditions is 70 mm or more.
  • Flow length measurement conditions are as follows. An injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., product name: PS40E, screw diameter : 26 mm), 20 pieces are injection molded under the following molding conditions: cylinder temperature 230°C, mold temperature 40°C, injection pressure 100 MPa, injection speed 38 mm/sec, injection time 4 seconds, cooling time 15 seconds. Using the final 10 molded products out of 20 molded products, the distance from the gate to the end of the flow is measured, and the average value is defined as the flow length.
  • the method for producing the resin composition is not particularly limited as long as it is a method capable of kneading each component. .
  • the above resin composition is not particularly limited, and can be used for producing molded articles using known methods. Molded articles containing the resin composition can also be used for automobile parts, electric parts, electronic parts, power tools, general industrial parts (packings, vibration-isolating rubbers, rubber hoses, etc.), machine parts, sporting goods, and the like.
  • the method for producing a molded article containing the resin composition is not particularly limited, and a known method for producing a molded article containing a resin, such as injection molding, extrusion molding, blow molding, co-extrusion molding or multi-injection molding. is mentioned.
  • the method for producing a molded article containing a resin composition is preferably injection molding from the viewpoint of efficiency in obtaining molded articles. It is particularly preferable that the method for producing a molded article using injection molding includes a step of injection molding the resin composition at a cylinder temperature of 200 to 250°C and a mold temperature of 30 to 50°C. The conditions of the method for manufacturing a molded article other than those described above can be appropriately set.
  • Elastomer (A) (Production of polyetheramide elastomer (PAE-1)) 20.0 kg of 12-aminododecanoic acid (manufactured by UBE Corporation), adipic acid (Asahi Kasei Corporation 3.73 kg, ELASTAMINE (registered trademark) RT-1000 (manufactured by Huntsman, USA, number average molecular weight of about 1,000, XYX type triblock polyether diamine compound, formula (1), where x is about 3, y is About 9, z is about 2) 26.3 kg, 0.08 kg sodium hypophosphite, and 0.15 kg Irganox® 245 (BASF hindered phenolic antioxidant) were added.
  • PAE-4 Polyetheramide elastomer 44.0 kg of 12-aminododecanoic acid (manufactured by UBE Corporation), adipic acid (Asahi Kasei Co., Ltd., company) 0.75 kg, ELASTAMINE (registered trademark) RT-1000 (manufactured by Huntsman in the United States, number average molecular weight of about 1,000, XYX type triblock polyether diamine compound, in formula (1), x is about 3, y of about 9 and z of about 2), 0.10 kg of sodium hypophosphite, and 0.15 kg of Irganox® 245 (a hindered phenolic antioxidant manufactured by BASF) were added.
  • polyether polyester amide elastomer (Pebax (registered trademark) 6333, manufactured by ARKEMA) was used as the polyamide elastomer, and Hytrel 4047N (manufactured by Toray DuPont) was used as the polyether polyester elastomer.
  • F3000 Maleic anhydride-modified low-density polyethylene (F3000 (trade name), manufactured by Ube Maruzen Polyethylene Co., Ltd.) F3000 is a modified polyethylene obtained by modifying branched low-density polyethylene (LDPE) with maleic anhydride.
  • LDPE branched low-density polyethylene
  • Additive (C) Weathering agent BASF, Tinuvin 312
  • Cross-linking agent cyclic carbodiimide, manufactured by Teijin Limited, Carbosista (registered trademark) TCC-NP
  • Antioxidant hindered phenolic antioxidant, manufactured by BASF, Irganox (registered trademark) 245)
  • Elastomer (A), modified polyethylene (B), and additive (C) are melt-kneaded at 200 to 260° C. using a twin-screw kneader at the mass ratio (parts by mass) shown in Table 1, and Examples 1 to 18 are prepared. , to obtain resin compositions of Comparative Examples 1 to 6. Next, the obtained pellets of the resin compositions of Examples 1 to 18 and Comparative Examples 1 to 6 were injection molded at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. to produce various test pieces and evaluate various physical properties. bottom.
  • Elastomer (A) is the content of PAE-1 and the like excluding the antioxidant used in its production.
  • the antioxidant and its content in the additive (C) are the antioxidant used in the production of the elastomer (A) and its content.
  • the tensile yield stress is 9 MPa or more or has no tensile yield stress
  • the tensile elastic modulus is 100 MPa or more
  • the bending strength is 7 MPa or more
  • the bending elastic modulus is 100 MPa or more
  • the Charpy impact strength was 40 KJ/m 2 or more, it was judged to be "excellent in mechanical properties”.
  • a case satisfying all of the above five items was judged to be "excellent in mechanical properties", and a case satisfying three or more of the above five items was judged to be "slightly excellent in mechanical properties".
  • the resin compositions of Examples 1-18 were excellent in tensile set and mechanical properties. Further, it was found that by adding a cross-linking agent, a resin composition having better tensile set while maintaining mechanical properties can be obtained (Examples 5 and 11). On the other hand, since the resin compositions of Comparative Examples 1 to 6 did not contain the modified polyethylene (B), they were inferior in at least one of tensile set and mechanical properties.

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Abstract

La présente invention concerne une composition de résine qui est obtenue par mélange d'un élastomère (A) qui comporte un segment souple comprenant un polyéther et d'un polyéthylène modifié (B). Le polyéthylène modifié (B) est obtenu par modification d'un polyéthylène ayant une densité de 0,910 à 0,925 g/cm3 3 et/ou un poids moléculaire (Mw) moyen en poids supérieure ou égale à 1 000 000. La composition de résine contient de 50,00 à 90,00 % en masse de l'élastomère (A) lorsque le total de l'élastomère (A) et du polyéthylène modifié (B) est défini comme étant de 100 % en masse. Selon la présente invention, il est possible de fournir une composition de résine qui présente des propriétés mécaniques et une déformation permanente à la traction d'ordre supérieur.
PCT/JP2022/043618 2021-11-26 2022-11-25 Composition de résine et article moulé la contenant WO2023095891A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57147519A (en) * 1981-03-10 1982-09-11 Daicel Chem Ind Ltd Polyamide resin composition
JPS59193959A (ja) * 1983-04-18 1984-11-02 Dainippon Ink & Chem Inc ポリアミド系エラストマ−組成物
JPS6140356A (ja) * 1984-07-31 1986-02-26 Dainippon Ink & Chem Inc ポリアミド組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57147519A (en) * 1981-03-10 1982-09-11 Daicel Chem Ind Ltd Polyamide resin composition
JPS59193959A (ja) * 1983-04-18 1984-11-02 Dainippon Ink & Chem Inc ポリアミド系エラストマ−組成物
JPS6140356A (ja) * 1984-07-31 1986-02-26 Dainippon Ink & Chem Inc ポリアミド組成物

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