WO2023190543A1 - エチレン系重合体組成物およびその用途 - Google Patents

エチレン系重合体組成物およびその用途 Download PDF

Info

Publication number
WO2023190543A1
WO2023190543A1 PCT/JP2023/012569 JP2023012569W WO2023190543A1 WO 2023190543 A1 WO2023190543 A1 WO 2023190543A1 JP 2023012569 W JP2023012569 W JP 2023012569W WO 2023190543 A1 WO2023190543 A1 WO 2023190543A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene polymer
mass
ethylene
component
molecular weight
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2023/012569
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
千紘 小松
充 藤澤
洋平 宝谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Original Assignee
Mitsui Chemicals Inc
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 Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to CN202380026480.6A priority Critical patent/CN118922487A/zh
Priority to EP23780552.8A priority patent/EP4502041A4/en
Priority to JP2024512581A priority patent/JP7770543B2/ja
Priority to KR1020247029216A priority patent/KR20240137691A/ko
Priority to US18/850,037 priority patent/US20250206927A1/en
Publication of WO2023190543A1 publication Critical patent/WO2023190543A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene

Definitions

  • the present invention relates to an ethylene polymer composition and its uses.
  • Patent Document 1 discloses a high-density polyethylene resin composition containing a high-density polyethylene resin and a layered silicate, and an injection molded product of this composition.
  • Patent Document 2 discloses a resin composition comprising a polyolefin resin (polyethylene resin, polypropylene resin, etc.), multi-walled carbon nanotubes, and an inorganic filler, and a molded article of this composition.
  • Patent Document 3 discloses an ethylene polymer containing ultra-high molecular weight polyethylene and low molecular weight to high molecular weight polyethylene, and an ethylene polymer composition containing carbon nanotubes, and this resin composition , low surface resistivity and volume resistivity, and good thermal conductivity; a molded article obtained from the ethylene polymer composition has good sliding properties; It is described that it has rigidity.
  • an object of the present invention is to provide an ethylene polymer composition and a molded product thereof, which can provide a molded product having excellent moldability, rigidity, electrical conductivity, wear resistance, and heat resistance. .
  • ethylene polymer component (A) having an intrinsic viscosity [ ⁇ ] of 1.5 to 10 dl/g and a density of 930 to 980 kg/m 3 as measured in a decalin solvent at 135°C; and containing 1 to 100 parts by mass of carbon fiber (B),
  • the ethylene polymer component (A) is an ethylene polymer containing an ultra-high molecular weight ethylene polymer (a1) having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g as measured in a decalin solvent at 135°C. Composition.
  • the ethylene polymer component (A) is a low molecular weight to high molecular weight ethylene polymer (a2) having an intrinsic viscosity [ ⁇ ] of 0.1 to 9 dl/g as measured in a decalin solvent at 135°C.
  • the ethylene polymer component (A) contains 10 to 90% by mass of the ethylene polymer component (AI) and 90 to 10% by mass of the ethylene polymer component (AII) (components (AI) and The total amount of component (AII) is 100% by mass.)
  • a multistage polymer comprising a system polymer (a2) (the total amount of polymer (a1) and polymer (a2) is 100% by mass), Item [2], wherein the ethylene polymer component (AII) contains an ethylene polymer (a3) having an intrinsic viscosity [ ⁇ ] of 0.1 to 2.9 dl/g as measured in a decalin solvent at 135°C.
  • AII ethylene polymer component
  • the ethylene polymer component (AI) includes a step of producing the ultra-high molecular weight ethylene polymer (a1) and a step of producing the low molecular weight to high molecular weight ethylene polymer (a2).
  • the content of the carbon fiber (B) is 20 to 60 parts by mass with respect to 100 parts by mass of the ethylene polymer component (A). Ethylene polymer composition.
  • a molded article comprising the ethylene polymer composition according to any one of items [1] to [10].
  • [12] The molded body according to item [11], wherein the proportion of carbon fibers having an acicular ratio of 1.5 or more among the carbon fibers (B) contained in the molded body is 30% or more.
  • an ethylene polymer composition and a molded product thereof which can yield a molded product having excellent moldability, rigidity, electrical conductivity, wear resistance, and heat resistance.
  • FIG. 1 is a schematic diagram illustrating the location where an observation sample for evaluating orientation in Examples is taken from an ASTM D671 Type A test piece (molded body) and the observation surface of the observation sample.
  • a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower limit and upper limit.
  • composition of the present invention has an intrinsic viscosity [ ⁇ ] of 1.5 to 10 dl/g and a density of 930 to 980 kg/m. 3 , and 1 to 100 parts by mass of carbon fiber (B), and the ethylene polymer component (A) has an intrinsic viscosity [ ⁇ ] of 10 to 100 parts by mass. It is characterized by containing an ultra-high molecular weight ethylene polymer (a1) of 40 dl/g.
  • the intrinsic viscosity [ ⁇ ] is the intrinsic viscosity [ ⁇ ] measured in a decalin solvent at 135° C. unless otherwise specified.
  • the ethylene polymer component (A) is an ethylene homopolymer or a copolymer of ethylene and ⁇ -olefin, and is generally a high-pressure low-density polyethylene (HP-LDPE) or a linear low-density polyethylene (LLDPE). ), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ultra-high molecular weight ethylene polymer, etc., and is a polymer mainly composed of ethylene.
  • HP-LDPE high-pressure low-density polyethylene
  • LLDPE linear low-density polyethylene
  • MDPE medium-density polyethylene
  • HDPE high-density polyethylene
  • ultra-high molecular weight ethylene polymer etc.
  • the ethylene polymer component (A) when the ethylene polymer component (A) is a copolymer, it may be a random copolymer or a block copolymer.
  • the ⁇ -olefin copolymerized with ethylene is preferably an ⁇ -olefin having 3 to 20 carbon atoms, and specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1- Heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, Examples include 9-methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene. These ⁇ -olefins may be used alone or in combination of two or more.
  • the ethylene polymer component (A) may be a single type of polymer or a composition (mixture) of two or more types of ethylene polymers.
  • the intrinsic viscosity [ ⁇ ] of the ethylene polymer component (A) is 1.5 to 10 dl/g, preferably 2.0 to 8.0 dl/g, more preferably 2.5 to 7.0 dl/g. It is. Since the ethylene polymer component (A) has an intrinsic viscosity [ ⁇ ] within the above range, the composition of the present invention can improve wear resistance, self-lubricity, impact strength, chemical resistance, appearance and A molded article with excellent balance of properties such as moldability can be obtained.
  • the density of the ethylene polymer component (A) is 930 to 980 kg/m 3 , preferably 940 to 970 kg/m 3 .
  • a molded article having excellent wear resistance and flexibility can be obtained.
  • the ethylene polymer component (A) contains an ultra-high molecular weight ethylene polymer (a1) (hereinafter also referred to as "polymer (a1)”) having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g. I'm here. Since the ethylene polymer component (A) contains the polymer (a1), the composition of the present invention can produce a molded article with excellent wear resistance, self-lubricity, impact strength, chemical resistance, etc. can get.
  • the intrinsic viscosity [ ⁇ ] of the polymer (a1) is preferably 15 to 35 dl/g, more preferably 20 to 35 dl/g.
  • the ethylene polymer component (A) is a low molecular weight to high molecular weight ethylene polymer (a2) (hereinafter also referred to as "polymer (a2)") having an intrinsic viscosity [ ⁇ ] of 0.1 to 9 dl/g. .) may be included.
  • the polymer (a2) may be a wax.
  • the intrinsic viscosity [ ⁇ ] of the polymer (a2) is preferably 0.1 to 5 dl/g, more preferably 0.5 to 3.0 dl/g, and even more preferably 1.0 to 2.5 dl/g. be.
  • the composition of the present invention preferably includes, as the ethylene polymer component (A), More than 35% by mass and not more than 90% by mass of the ultra-high molecular weight ethylene polymer (a1), A multistage polymer comprising 10% by mass or more and less than 65% by mass of the low molecular weight to high molecular weight ethylene polymer (a2) (the total amount of polymer (a1) and polymer (a2) is 100% by mass). 10 to 90% by mass of an ethylene polymer component (AI) which is a coalescence, and 90 to 10% by mass of an ethylene polymer component (AII) having an intrinsic viscosity [ ⁇ ] of 0.1 to 2.9 dl/g. (The total amount of component (AI) and component (AII) is 100% by mass.) Contains.
  • the ethylene polymer component (AI) preferably includes a step of producing the ultra-high molecular weight ethylene polymer (a1) and a step of producing the low molecular weight to high molecular weight ethylene polymer (a2). It can be obtained by a multistage polymerization method.
  • the polymer (a1) is usually produced in the first step, and then the polymer (a2) is produced in the second step.
  • the proportion of the ethylene polymer component (AI) is preferably 15 to 90% by mass, more preferably 20 to 80 mass%, even more preferably 26.7 to 49% by mass, and the proportion of the ethylene polymer component (AI ) is preferably 85 to 10% by mass, more preferably 80 to 20% by mass, and even more preferably 73.3 to 51% by mass (the total amount of component (AI) and component (AII) is 100% by mass). ).
  • the ultra-high molecular weight ethylene polymer (a1) constituting the ethylene polymer component (AI) is usually obtained in the first stage of polymerization in a multi-stage polymerization method.
  • the low molecular weight to high molecular weight ethylene polymer (a2) constituting the ethylene polymer component (AI) is usually produced in the second stage of polymerization after the polymerization of the polymer (a1) in a multi-stage polymerization method. can get.
  • the ethylene polymer component (AI) can be produced by polymerizing ethylene and, if desired, an ⁇ -olefin in multiple stages in the presence of a catalyst. It can be carried out by a method similar to the polymerization method described in Japanese Patent No. 289636.
  • the ethylene polymer component (AI) can be made to have a compatibility with the ethylene polymer component (AII).
  • AII ethylene polymer component
  • the ultra-high molecular weight ethylene polymer (a1) is uniformly dispersed in the composition of the present invention, and the ultra-high molecular weight ethylene polymer (a1) is bonded to the ethylene polymer component (AII). do. That is, the interfacial strength between the polymer (a1) and the ethylene polymer component (AII) increases.
  • the composition of the present invention has a balance of properties such as wear resistance, self-lubricating property, impact strength, chemical resistance, appearance, and moldability. Excellent, especially wear resistance, excellent balance between appearance and moldability.
  • the ethylene polymer component (AI) contains the ultra-high molecular weight ethylene polymer (a1), preferably more than 35% by mass and 90% by mass or less, more preferably more than 40% by mass and not more than 80% by mass, and further It preferably contains the low molecular weight to high molecular weight ethylene polymer (a2) in an amount of 41 to 75% by mass, preferably 10% by mass or more and less than 65% by mass, more preferably 20% by mass or more and less than 60% by mass. , more preferably in an amount of 25 to 59% by mass.
  • the ratio of polymer (a1) and polymer (a2) within the above range, the compatibility between component (AI) and component (AII) is improved, and the composition of the present invention has particularly high resistance to Excellent wear resistance, appearance and moldability.
  • the ethylene polymer component (AI) substantially contains only an ultra-high molecular weight ethylene polymer (polymer (a1)) and a low to high molecular weight ethylene polymer (polymer (a2)). .
  • the component (AI) includes additives added to ordinary polyolefins (for example, stabilizers such as heat-resistant stabilizers and weather-resistant stabilizers, crosslinking agents, crosslinking aids, antistatic agents, slip agents, antiblocking agents, Antifogging agents, lubricants, dyes, mineral oil softeners, petroleum resins, waxes, etc.) may be added, and the composition of the present invention may contain the above-mentioned components (AI) to the extent that the effects of the present invention are not impaired. It may also contain additives added to.
  • additives added to ordinary polyolefins for example, stabilizers such as heat-resistant stabilizers and weather-resistant stabilizers, crosslinking agents, crosslinking aids, antistatic agents, slip agents, antiblocking agents, Antifogging agents, lubricants, dyes, mineral oil softeners, petroleum resins, waxes, etc.
  • additives added to ordinary polyolefins for example, stabilizers such as heat-
  • the density of the ethylene polymer component (AI) (measured according to ASTM D1505) is usually 930 to 980 kg/m 3 , preferably 940 to 970 kg/m 3 .
  • the intrinsic viscosity [ ⁇ ] of the ethylene polymer component (AI) is usually 3.0 to 10.0 dl/g, preferably 3.0 to 8.0 dl/g, and more preferably 3.0 to 7.0 dl. /g.
  • the ethylene polymer component (AI) has the density as described above, the coefficient of dynamic friction of the molded product is reduced, so that a molded product with excellent self-lubricating properties can be obtained. Furthermore, since the ethylene polymer component (AI) has an intrinsic viscosity [ ⁇ ] within the above range, the dispersion state of the ethylene polymer component (AI) and the ethylene polymer component (AII) is becomes better.
  • the polymer (a2) contained in the ethylene polymer component (AI) and the ethylene polymer component (AII) melt-blended in an extruder etc. are finely dispersed into each other, so that the dispersion state is maintained.
  • the composition of the present invention can be molded with excellent wear resistance, self-lubricity, impact strength, chemical resistance, appearance, and moldability. You get a body.
  • the ethylene polymer component (AII) preferably contains an ethylene polymer (a3) having an intrinsic viscosity [ ⁇ ] of 0.1 to 2.9 dl/g.
  • the ethylene polymer (a3) includes high-pressure polyethylene (HP-LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and ethylene/ ⁇ -olefin copolymer. Coalescence, ethylene/vinyl alcohol copolymer, ethylene/vinyl acetate copolymer, saponified ethylene/vinyl acetate copolymer, ethylene/(meth)acrylic acid copolymer, ethylene/ ⁇ -olefin/diene (triene, polyene) ) terpolymer, etc.
  • HP-LDPE high-pressure polyethylene
  • LLDPE linear low-density polyethylene
  • MDPE medium-density polyethylene
  • HDPE high-density polyethylene
  • ethylene/ ⁇ -olefin copolymer Coalescence, ethylene/vinyl alcohol copolymer, ethylene/vinyl acetate copolymer,
  • ⁇ -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and Examples include 3-methyl-1-pentene.
  • diene toner, polyene
  • examples of the diene (triene, polyene) include 5-ethylidene-2-norbornene, vinylnorbornene, etc., including conjugated or non-conjugated dienes, trienes, and polyenes.
  • the ethylene polymer component (AII) may be a single type of ethylene polymer (a3) or a composition of two or more types of ethylene polymers (a3). It may be a composition of polymer (a3) and polyolefin (polypropylene, polybutene, etc.). Further, the ethylene polymer component (AII) may be a wax.
  • ethylene polymer (a3) among those mentioned above, high density polyethylene (HDPE) and low density polyethylene (LDPE) are preferable, and high density polyethylene (HDPE) is more preferable.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • the density of the ethylene polymer (a3) (measured according to ASTM D1505) is usually 820 to 980 kg/m 3 , preferably 930 to 980 kg/m 3 , and more preferably 950 to 980 kg/m 3 .
  • the intrinsic viscosity [ ⁇ ] of the ethylene polymer (a3) is usually 0.1 to 2.9 dl/g, preferably 0.3 to 2.8 dl/g, more preferably 0.5 to 2.5 dl/g. g, more preferably 1.0 to 2.5 dl/g.
  • the ethylene polymer component (AII) contains the ethylene polymer (a3), it is well dispersed when mixed with the ethylene polymer component (AI). That is, during melt blending in an extruder or the like, the ethylene polymer component (AII) and the low molecular weight to high molecular weight ethylene polymer (a2) contained in the ethylene polymer component (AI) are finely blended into each other. By dispersing, the dispersion state becomes uniform. Therefore, by using an ethylene polymer component (AI) and an ethylene polymer component (AII) as the ethylene polymer component (A), it is possible to improve wear resistance, self-lubricity, impact strength, and chemical resistance. A molded article with excellent appearance, flexibility, moldability, etc. can be obtained.
  • the component (AII) includes additives added to ordinary polyolefins (for example, stabilizers such as heat-resistant stabilizers and weather-resistant stabilizers, crosslinking agents, crosslinking aids, antistatic agents, slip agents, antiblocking agents, Antifogging agents, lubricants, dyes, mineral oil softeners, petroleum resins, waxes, etc.) may be added, and the composition of the present invention may contain the aforementioned components (AII) to the extent that the effects of the present invention are not impaired. ) may also contain additives added to it.
  • additives added to ordinary polyolefins for example, stabilizers such as heat-resistant stabilizers and weather-resistant stabilizers, crosslinking agents, crosslinking aids, antistatic agents, slip agents, antiblocking agents, Antifogging agents, lubricants, dyes, mineral oil softeners, petroleum resins, waxes, etc.
  • additives added to ordinary polyolefins for example, stabilizers such as heat
  • the carbon fiber (B) is not particularly limited, and various known carbon fibers can be used, such as polyacrylonitrile, rayon, pitch, polyvinyl alcohol, regenerated cellulose, and mesophase. Examples include pitch-based carbon fibers manufactured from pitch. These may be used alone or in combination of two or more.
  • the carbon fiber (B) may be a general-purpose fiber or a high-strength fiber. Further, the carbon fiber (B) may be a long fiber, a short fiber, a chopped fiber, or a recycled fiber.
  • the carbon fiber (B) is preferably a surface-treated carbon fiber.
  • a method for surface treatment of carbon fibers commonly used known methods may be used. For example, electrolytic surface treatment is performed on carbon fibers with an acid or alkaline aqueous solution to impart functional groups to the carbon fiber surfaces.
  • method, and a method of treatment using a sizing agent are preferred.
  • the average length of the carbon fibers (B), that is, the average fiber length, is preferably 0.1 mm or more and 15.0 mm or less, more preferably 0.3 mm or more and 13.0 mm or less, and even more preferably 0.5 mm or more and 13.0 mm or less. It is as follows. When the average fiber length is at least the above-mentioned lower limit, the effect of reinforcing mechanical properties by the carbon fibers tends to be sufficiently exhibited. When the average fiber length is less than or equal to the above upper limit, the appearance of the molded article tends to be improved due to the dispersion of the carbon fibers in the ethylene polymer composition.
  • the average fiber length of the carbon fibers (B) extracted from the composition of the present invention is preferably 100 ⁇ m or more and 400 ⁇ m or less, more preferably 120 ⁇ m or more and 380 ⁇ m or less, and even more preferably 150 ⁇ m or more and 360 ⁇ m or less.
  • the average fiber length of the carbon fibers (B) extracted from the composition of the present invention is within the above range, the processability during production of the molded article becomes good.
  • the average fiber length is outside the above range, it will be difficult to uniformly knead the carbon fibers and the resin during molding, which may cause deterioration in the physical properties of the composition and molded product.
  • the proportion of carbon fibers having a fiber length of 100 ⁇ m or more and 300 ⁇ m or less is preferably 30% or more, more preferably 35 to 99%, and Preferably it is 40-98%.
  • the proportion of carbon fibers having a fiber length of 100 ⁇ m or more and 300 ⁇ m or less is within the above range, it becomes possible to increase mechanical strength and obtain a molded article with excellent wear resistance.
  • the fiber length and average fiber length of the carbon fiber (B) extracted from the composition of the present invention can be determined, for example, by the method described in the Examples below.
  • the average diameter of the carbon fibers (B) is preferably 0.5 ⁇ m or more and 30 ⁇ m or less, more preferably 1 ⁇ m or more and 21 ⁇ m or less, and even more preferably 1 ⁇ m or more and 19 ⁇ m or less.
  • the average diameter of the carbon fibers is equal to or greater than the lower limit, the carbon fibers are less likely to be damaged during molding, and the resulting molded product tends to have high impact strength.
  • the average diameter of the carbon fibers is below the above upper limit, the appearance of the molded product is good, the aspect ratio of the carbon fibers does not decrease, and the molded product has sufficient mechanical properties such as rigidity and heat resistance. It tends to have a reinforcing effect.
  • the content of the carbon fiber (B) is 1 to 100 parts by mass, preferably 4 to 70 parts by mass, when the content of the ethylene polymer component (A) is 100 parts by mass. , more preferably 7 to 65 parts by weight, still more preferably 10 to 60 parts by weight, particularly preferably 20 to 60 parts by weight.
  • the composition of the present invention has excellent moldability, and the composition of the present invention can be formed into a molded article having excellent rigidity, conductivity, abrasion resistance, and heat resistance. can be obtained.
  • Carbon fibers (B) include, for example, Teijin Tenax Co., Ltd. (HT P802 (polyolefin polymer sizing), HT C605 (nylon polymer sizing), HT C503 (urethane polymer sizing)), Toray Industries, Inc. Examples include Torayka Cut Fiber T008-006 (epoxy polymer sizing) manufactured by Nippon Polymer Sangyo Co., Ltd. and EX-1LC (epoxy polymer sizing) manufactured by Nippon Polymer Sangyo Co., Ltd.
  • the composition of the present invention may contain a modified olefin polymer (C).
  • the modified olefin polymer (C) is used, for example, as a compatibilizer to improve the compatibility between the ethylene polymer component (A) and the carbon fiber (B).
  • the modified olefin polymer (C) is not particularly limited, but examples include acid-modified homopolymers or copolymers of ethylene and ⁇ -olefins having 3 to 12 carbon atoms (for example, acid-modified products modified with maleic anhydride). ), air oxides, or styrene-modified products.
  • ethylene polymers ethylene homopolymers and copolymers of ethylene and at least one ⁇ -olefin selected from ⁇ -olefins having 3 to 12 carbon atoms
  • propylene polymers propylene homopolymers
  • Polymers and copolymers of propylene and at least one ⁇ -olefin selected from ⁇ -olefins having 4 to 12 carbon atoms) are preferred.
  • examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4 -Methyl-1-pentene and 1-octene.
  • the modified olefin polymer (C) is preferably a modified ethylene polymer.
  • the modified olefin polymer (C) is more preferably a modified ethylene polymer (c11) in which the following ethylene polymer (c1) is graft-modified with an unsaturated carboxylic acid or a derivative thereof.
  • the ethylene polymer (c1) has a density of 930 to 975 kg/m 3 and a melt flow rate (MFR) of 0.1 to 10 g/10 at 190° C. and a load of 2.16 kg, measured based on ASTM D1238. It is preferable that the melt flow rate (MFR) at 190° C. and a load of 10 kg is 0.1 to 20 g/10 minutes, as measured in accordance with ASTM D1238.
  • the density of the ethylene polymer (c1) is preferably 940 to 970 kg/m 3 .
  • the compatibility between the ethylene polymer component (A) and the carbon fiber (B) is high.
  • the melt flow rate of the ethylene polymer (c1) (according to ASTM D1238, 190°C, 2.16 kg load) is preferably 0.2 to 8 g/10 minutes, more preferably 0.5 to 6 g/10 minutes, More preferably, it is 0.5 to 3 g/10 minutes.
  • the melt flow rate (according to ASTM D1238, 190°C, 10 kg load) of the ethylene polymer (c1) is preferably 0.1 to 15 g/10 minutes, more preferably 0.1 to 10 kg/10 minutes, and Preferably it is 0.1 to 8 g/10 minutes. When the melt flow rate is within the above range, the compatibility between the ethylene polymer component (A) and the carbon fiber (B) is high.
  • the amount of grafting of the unsaturated carboxylic acid or its derivative in the modified ethylene polymer (c11) is usually 0.01 to 10% by mass, preferably 0.02 to 10% by mass. When the amount of grafting is within the above range, the compatibility between the ethylene polymer component (A) and the carbon fiber (B) is high.
  • Examples of the unsaturated carboxylic acids or derivatives thereof include (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocys-bicyclo[2. 2.1] hept-5-ene-dicarboxylic acid), and derivatives thereof, such as acid halides, amidimides, anhydrides, and esters.
  • the derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylate. )
  • Esters and half esters such as glycidyl acrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconate, and diethyl itaconate.
  • unsaturated dicarboxylic acids and their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are more preferred.
  • the modified ethylene polymer (c11) can be produced by various known methods. For example, an ethylene polymer is dissolved in an organic solvent, and then an unsaturated carboxylic acid or a derivative thereof and, if necessary, a radical initiator such as an organic peroxide are added to the resulting solution, and the temperature is usually 60 to 350°C. An ethylene polymer and an unsaturated carboxyl group are reacted at a temperature of preferably 80 to 190°C for 0.5 to 15 hours, preferably 1 to 10 hours, or without a solvent using an extruder or the like.
  • a method can be adopted in which an acid or a derivative thereof and, if necessary, a radical initiator such as an organic peroxide are added, and the reaction is carried out at a temperature higher than the melting point of the ethylene polymer, preferably at 160 to 350°C, for 0.5 to 10 minutes. .
  • the ethylene polymer before modification can be produced by a known method, such as a high-pressure method or a low-pressure method using a Ziegler-type Ti-based catalyst, a Co-based catalyst, a metallocene-based catalyst, or the like.
  • the ethylene polymers (c1) may each contain one type of ethylene polymer or two or more types of ethylene polymers. When the ethylene polymer (c1) contains two or more ethylene polymers, each of the two or more ethylene polymers satisfies the density and melt flow rate requirements of the ethylene polymer (c1) above. .
  • the content of the modified olefin polymer (C) in the composition of the present invention is the same as that of the ethylene polymer component (A).
  • the content is 100 parts by weight, it is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 8 parts by weight, and still more preferably 0.5 to 7 parts by weight.
  • the content of the modified olefin polymer (C) is within the above range, the ethylene polymer component (A) and the carbon fiber (B) can be made to be well compatible.
  • the ethylene polymer composition of the present invention contains, in addition to the above-mentioned ethylene polymer component (A), carbon fiber (B), and modified olefin polymer (C), if necessary, carbon fiber (B).
  • the amount thereof is not particularly limited, but is, for example, in the range of 0.01 to 30% by mass.
  • wax is preferable.
  • wax include polyethylene wax (excluding those corresponding to the ethylene polymer component (AII)) and polypropylene wax.
  • the ethylene polymer composition of the present invention contains wax, the agglomeration of carbon fibers (B) in the ethylene polymer component (A) is suppressed, making kneading easier. It is considered that the carbon fibers (B) are easily dispersed in (A).
  • the amount thereof is preferably in the range of 0.01 to 10% by mass based on the total amount of the composition.
  • the MFR of the ethylene polymer composition of the present invention measured at 190°C under a load of 10 kg according to JIS K 7210-1:2014 is preferably 0.01 to 20 g/10 min, more preferably 0. 01-10g/10 minutes.
  • the ethylene polymer composition of the present invention comprises the ethylene polymer component (A), the carbon fiber (B), optionally the modified olefin polymer (C), and optionally the optional component, which is known from the prior art. It can be obtained by mixing, for example, dry blending each component, followed by melt-kneading in a single- or twin-screw extruder, extruding into strands and granulating into pellets.
  • the carbon fiber (B) may be mixed in advance with a polymer component such as the ethylene polymer component (A) and used in the form of a masterbatch.
  • the molded article of the present invention contains the ethylene polymer composition.
  • the method for manufacturing the molded article includes conventionally known polyolefin molding methods, such as extrusion molding, injection molding, film molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, Known thermoforming methods include press molding, vacuum molding, powder slush molding, calendar molding, and foam molding.
  • the molded body may be a molded body formed from the ethylene polymer composition, or may be a molded body having a portion, such as a surface layer, formed from the ethylene polymer composition. good.
  • the proportion of carbon fibers having an acicular ratio of 1.5 or more is preferably 30% or more, more preferably 30 to 70%, even more preferably 31 to 65%, particularly preferably 32 to 60%.
  • the proportion of carbon fibers having an acicular ratio of 1.5 or more can be determined by the method described in the Examples below.
  • the shrinkage percentage of the molded article of the present invention in both the length direction and the width direction is preferably 2.0% or less, more preferably 1.5% or less, and 0.05 to 1.0%. It is particularly preferable that The shrinkage rate can be determined by the method described in Examples below.
  • the flexural modulus of the molded article of the present invention is preferably 5,000 MPa or more, more preferably 6,000 to 20,000 MPa, and still more preferably 7,000 to 15,000 MPa.
  • the bending elastic modulus can be determined by the method described in Examples described later.
  • the number of repetitions when the displacement amount reaches 8 mm in the vibration fatigue test (35 MPa) of the molded article of the present invention is preferably 1500 times or more, more preferably 2000 times or more, and still more preferably 5000 times or more.
  • the upper limit of the number of repetitions is not particularly limited as the higher the number, the better, but it is preferably 10 million times, more preferably 1 million times, still more preferably 500,000 times.
  • the number of repetitions can be determined by the method described in Examples described later.
  • Molded objects are used in a wide range of applications, including household goods such as daily necessities and recreational use, general industrial use, and industrial goods.
  • Specific examples of molded bodies include home appliance material parts, communication equipment parts, electrical parts, electronic parts, automobile parts, other vehicle parts, ships, aircraft materials, mechanical mechanism parts, building material-related parts, civil engineering parts, agricultural materials, Examples include power tool parts, food containers, films, sheets, and textiles.
  • the molded product of the present invention can be widely used in conventionally known polyethylene applications, but it has an excellent balance of properties such as wear resistance, rigidity, self-lubricity, impact strength, and thin-walled molding, which are particularly required.
  • Applications include, for example, metal coatings (laminates) for steel pipes, electric wires, automobile sliding door rails, etc.; various rubber coatings such as pressure-resistant rubber hoses, automobile door gaskets, clean room door gaskets, automobile glass run channels, automobile weather strips, etc. (Laminated): Used for linings of hoppers, chutes, etc., sliding materials such as gears, bearings, rollers, tape reels, various guide rails and elevator rail guides, and various protective liner materials.
  • the molded article of the present invention also has excellent conductivity, it is possible to suppress the charging properties of various mechanical parts and sliding members, and it can be suitably used in applications that require conductivity and antistatic properties.
  • the density of the ethylene polymer component (A) was measured by a density gradient method in accordance with ASTM D1505.
  • the density of the compositions obtained in Examples and Comparative Examples was measured in water at 23°C by a submerged weighing method in accordance with JIS Z8807:2012.
  • the produced observation sample was observed using a "Scanning Electron Microscope S-3700N" manufactured by Hitachi High-Technology Co., Ltd. at an acceleration voltage of 10 kV and a backscattered electron image at a magnification of 150 times.
  • the observation direction of the observation sample is such that the polished surface of the part cut out from the molded body is the front as shown in Figure 1, and the observation surface seen from this observation direction and the long side on the imaging screen are The photo was taken so that the two were parallel.
  • the photographed image was centered at a depth of 0.7 to 0.8 mm from the surface (top surface) of the molded body.
  • Heat resistance heat distortion temperature HDT
  • ISO-75-1 2
  • the shape of the test piece was set to the shape described in JIS K7162 1A, and the heat distortion temperature was determined.
  • the heat distortion temperature was measured when the bending stress was 0.45 MPa (HDT 0.45 MPa) and when the bending stress was 1.80 MPa (HDT 1.80 MPa).
  • the molding shrinkage rate in the length direction was defined as the shrinkage rate MD
  • the molding shrinkage rate in the width direction was defined as the shrinkage rate TD.
  • Test piece was shaped as described in JIS K7162 1A, and the tensile strength and elongation at break were determined at a tensile speed of 50 mm/min. Further, in accordance with ISO 527-1, 2, the tensile modulus was determined using a test piece shape as described in JIS K7162 1A and a tensile speed of 1 mm/min.
  • ethylene polymer component (AI-2) ⁇ Production of ethylene polymer component (AI-2) ⁇
  • an ultra-high molecular weight ethylene polymer (polymer (a1)) having an intrinsic viscosity [ ⁇ ] of 30 dl/g was prepared in the first stage of polymerization, and then an ultra-high molecular weight ethylene polymer (polymer (a1)) with an intrinsic viscosity [ ⁇ ] of 30 dl/g was prepared in the second stage of polymerization.
  • a low molecular weight ethylene polymer (polymer (a2)) with 1.5 dl/g was subjected to two-stage polymerization at a mass ratio (polymer (a1)/polymer (a2)) of 75/25.
  • an ethylene polymer component (AI-2) having an intrinsic viscosity [ ⁇ ] of 6.9 dl/g was obtained.
  • Ethylene polymer component (AII) The following ethylene polymer components were used.
  • Ethylene polymer component (AII-1) High-density, low-molecular-weight polyethylene with an intrinsic viscosity [ ⁇ ] of 1.1 dl/g and a density of 965 kg/m 3 (“Hi-ZEX 1700J” manufactured by Prime Polymer Co., Ltd.)
  • (Ethylene polymer component (A)) ⁇ Production of ethylene polymer component (A-1)>> Blending the ethylene polymer component (AI-1) and the ethylene polymer component (AII-1) at a mass ratio ((AI-1)/(AII-1)) of 49/51, Melt blending was performed using a PCM twin-screw extruder made by Ikegai Iron Works to obtain a pellet-like ethylene polymer component (A-1) with an intrinsic viscosity [ ⁇ ] of 3.0 dl/g and a density of 968 kg/cm 3 . Ta. The content of the ultra-high molecular weight ethylene polymer (polymer (a1)) in the ethylene polymer component (A-1) was 20% by mass.
  • ethylene polymer component (A-2) ⁇ Production of ethylene polymer component (A-2)>> The ethylene polymer component (AI-2) and the ethylene polymer component (AII-1) are blended in a ratio such that the mass ratio ((AI-2)/(AII-1)) is 33/67, Melt blending was performed using a PCM twin-screw extruder made by Ikegai Iron Works to obtain a pellet-like ethylene polymer component (A-2) with an intrinsic viscosity [ ⁇ ] of 5.8 dl/g and a density of 966 kg/cm 3 . Ta. The content of the ultra-high molecular weight ethylene polymer (polymer (a1)) in the ethylene polymer component (A-2) was 25% by mass.
  • Carbon fiber (B) Carbon fiber (B) The following carbon fibers were used. Carbon fiber (B-1): “Tenax HT P802” manufactured by Teijin Ltd. (polyolefin polymer sizing treatment, fiber length: 3 mm, diameter: 7 ⁇ m, carbon fiber content ratio: 98% by mass) Carbon fiber (B-2): “Tenax HT C605" manufactured by Teijin Ltd. (nylon polymer sizing treatment, fiber length: 6 mm, diameter: 7 ⁇ m, carbon fiber content ratio: 95.5% by mass) Carbon fiber (B-3): Toray Industries, Inc. "TORAYCA T008-006” (epoxy polymer sizing treatment, fiber length: 6 mm, diameter: 7 ⁇ m, carbon fiber content: 99% by mass)
  • Carbon nanotube "NC7000” manufactured by Nanosil (average diameter: 9.5 nm, average length: 1.5 ⁇ m)
  • a carbon nanotube-containing masterbatch was prepared by mixing 15% by mass of the carbon nanotubes, 75% by mass of the ethylene polymer component (A-1), and 10% by mass of wax (polyethylene wax) using an existing method.
  • Modified olefin polymer (C) The following modified olefin polymers were used as compatibilizers.
  • Modified olefin polymer (C-1) Maleic acid-modified polymer produced based on the method for producing ethylene polymer PE-0 described in International Publication No.
  • Ethylene polymer (density: 965 kg/cm 3 , MFR (190°C, 2.16 kg load): 5 g/10 min, degree of modification: 2.4)
  • Modified olefin polymer (C-2): Maleic acid-modified ethylene polymer (density 967 kg/ cm 3 , intrinsic viscosity [ ⁇ ] 5 dl/g [ ⁇ ], MFR (190°C, 10 kgf): 6.2, degree of modification: 0.8)
  • Example 1 After dry blending 78% by mass of ethylene polymer component (A-1), 20% by mass of carbon fiber (B-1), and 2% by mass of modified olefin polymer (C-1), Parker Co., Ltd. A composition was obtained by melt extrusion using a twin-screw kneading extruder "HK-25D” manufactured by Corporation under the conditions of a cylinder temperature of 260° C., a screw rotation speed of 200 rpm, and a discharge rate of 12 kg/h. Table 1 shows the blending amount of each component in the obtained composition (the total amount of the ethylene polymer is 100 parts by mass). In addition, the physical properties of the obtained composition were measured by the method described above. The results are shown in Table 1.
  • Example 2 Example 1 except that the amounts of the ethylene polymer component (A-1), carbon fiber (B-1), and modified olefin polymer (C-1) were adjusted to the amounts shown in Table 1. A composition was produced in the same manner as above, and its physical properties were measured. The results are shown in Table 1.
  • Example 3 Using a modified olefin polymer (C-2) instead of the modified olefin polymer (C-1), ethylene polymer component (A-1), carbon fiber (B-1), modified olefin polymer A composition was produced in the same manner as in Example 1, except that the amount of (C-2) was adjusted to be as shown in Table 1, and its physical properties were measured. The results are shown in Table 1.
  • Example 4 Using ethylene polymer component (A-2) instead of ethylene polymer component (A-1), ethylene polymer component (A-2), carbon fiber (B-1), modified olefin polymer A composition was produced in the same manner as in Example 1, except that the amount of (C-1) was adjusted to be as shown in Table 1, and its physical properties were measured. The results are shown in Table 1.
  • Example 5 Using carbon fiber (B-2) instead of carbon fiber (B-1), ethylene polymer component (A-1), carbon fiber (B-2), modified olefin polymer (C-1) A composition was produced in the same manner as in Example 1, except that the amounts were adjusted to be as shown in Table 1, and its physical properties were measured. The results are shown in Table 1.
  • Example 6 Using carbon fiber (B-3) instead of carbon fiber (B-1), ethylene polymer component (A-1), carbon fiber (B-3), modified olefin polymer (C-1) A composition was produced in the same manner as in Example 1, except that the amounts were adjusted to be as shown in Table 1, and its physical properties were measured. The results are shown in Table 1.
  • composition was prepared in the same manner as in Example 1 except that only the ethylene polymer component (A-1) was used without using the carbon fiber (B-1) and the modified olefin polymer (C-1). It was manufactured and its physical properties were measured. The results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inorganic Fibers (AREA)
PCT/JP2023/012569 2022-03-31 2023-03-28 エチレン系重合体組成物およびその用途 Ceased WO2023190543A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN202380026480.6A CN118922487A (zh) 2022-03-31 2023-03-28 乙烯系聚合物组合物及其用途
EP23780552.8A EP4502041A4 (en) 2022-03-31 2023-03-28 COMPOSITION OF ETHYLENE-BASED POLYMER AND ITS USE
JP2024512581A JP7770543B2 (ja) 2022-03-31 2023-03-28 エチレン系重合体組成物およびその用途
KR1020247029216A KR20240137691A (ko) 2022-03-31 2023-03-28 에틸렌계 중합체 조성물 및 그의 용도
US18/850,037 US20250206927A1 (en) 2022-03-31 2023-03-28 Ethylene-based polymer composition and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022059750 2022-03-31
JP2022-059750 2022-03-31

Publications (1)

Publication Number Publication Date
WO2023190543A1 true WO2023190543A1 (ja) 2023-10-05

Family

ID=88201799

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/012569 Ceased WO2023190543A1 (ja) 2022-03-31 2023-03-28 エチレン系重合体組成物およびその用途

Country Status (7)

Country Link
US (1) US20250206927A1 (https=)
EP (1) EP4502041A4 (https=)
JP (1) JP7770543B2 (https=)
KR (1) KR20240137691A (https=)
CN (1) CN118922487A (https=)
TW (1) TW202402926A (https=)
WO (1) WO2023190543A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024203987A1 (ja) * 2023-03-31 2024-10-03 三井化学株式会社 エチレン系樹脂組成物および成形体

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01161035A (ja) * 1987-12-17 1989-06-23 Mitsui Petrochem Ind Ltd ポリオレフィン製軸受
JPH02289636A (ja) 1989-02-14 1990-11-29 Mitsui Petrochem Ind Ltd 熱可塑性樹脂組成物
JPH07329263A (ja) * 1994-06-10 1995-12-19 Nippon Petrochem Co Ltd 強化積層体
JP2006036988A (ja) * 2004-07-29 2006-02-09 Mitsui Chemicals Inc ポリエチレン樹脂組成物および成形体
JP2010196012A (ja) 2009-02-27 2010-09-09 Toyo Ink Mfg Co Ltd 樹脂組成物
JP2012025904A (ja) * 2010-07-27 2012-02-09 Mitsui Chemicals Inc ポリエチレン樹脂組成物
JP2014019733A (ja) 2012-07-12 2014-02-03 Asahi Kasei Chemicals Corp 高密度ポリエチレン樹脂組成物、及びその製造方法
WO2019208169A1 (ja) 2018-04-25 2019-10-31 三井化学株式会社 接着性樹脂組成物および積層体
JP2019218568A (ja) 2019-09-27 2019-12-26 三井化学株式会社 樹脂組成物及びその成形体
WO2022038941A1 (ja) 2020-08-18 2022-02-24 三井化学株式会社 エチレン系重合体組成物およびその用途

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY103793A (en) * 1987-11-05 1993-09-30 Mitsui Petrochemical Ind Olefin resin composition for injection molding

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01161035A (ja) * 1987-12-17 1989-06-23 Mitsui Petrochem Ind Ltd ポリオレフィン製軸受
JPH02289636A (ja) 1989-02-14 1990-11-29 Mitsui Petrochem Ind Ltd 熱可塑性樹脂組成物
JPH07329263A (ja) * 1994-06-10 1995-12-19 Nippon Petrochem Co Ltd 強化積層体
JP2006036988A (ja) * 2004-07-29 2006-02-09 Mitsui Chemicals Inc ポリエチレン樹脂組成物および成形体
JP2010196012A (ja) 2009-02-27 2010-09-09 Toyo Ink Mfg Co Ltd 樹脂組成物
JP2012025904A (ja) * 2010-07-27 2012-02-09 Mitsui Chemicals Inc ポリエチレン樹脂組成物
JP2014019733A (ja) 2012-07-12 2014-02-03 Asahi Kasei Chemicals Corp 高密度ポリエチレン樹脂組成物、及びその製造方法
WO2019208169A1 (ja) 2018-04-25 2019-10-31 三井化学株式会社 接着性樹脂組成物および積層体
JP2019218568A (ja) 2019-09-27 2019-12-26 三井化学株式会社 樹脂組成物及びその成形体
WO2022038941A1 (ja) 2020-08-18 2022-02-24 三井化学株式会社 エチレン系重合体組成物およびその用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4502041A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024203987A1 (ja) * 2023-03-31 2024-10-03 三井化学株式会社 エチレン系樹脂組成物および成形体

Also Published As

Publication number Publication date
KR20240137691A (ko) 2024-09-20
TW202402926A (zh) 2024-01-16
CN118922487A (zh) 2024-11-08
JP7770543B2 (ja) 2025-11-14
JPWO2023190543A1 (https=) 2023-10-05
EP4502041A1 (en) 2025-02-05
EP4502041A4 (en) 2026-04-01
US20250206927A1 (en) 2025-06-26

Similar Documents

Publication Publication Date Title
JP7341353B2 (ja) エチレン系重合体組成物およびその用途
Yang et al. Effect of different compatibilizing agents on the mechanical properties of lignocellulosic material filled polyethylene bio-composites
EP2918624A1 (en) Semiaromatic polyamide, semiaromatic polyamide resin composition, and molded article
JPWO2003022920A1 (ja) ポリエチレン樹脂組成物
JP5351108B2 (ja) ポリエチレン樹脂組成物
EP2895551A1 (en) High impact polypropylene compositions
JP7770543B2 (ja) エチレン系重合体組成物およびその用途
CN1230918A (zh) 聚酯树脂复合模制品
CN102432947B (zh) 一种复合纤维增强聚丙烯材料及其制备方法
KR20190069223A (ko) 실릴화 마이크로 피브릴 셀룰로오스를 포함하는 폴리프로필렌 복합수지 조성물 및 이를 이용한 자동차 필러트림
KR101580957B1 (ko) 내충격성 및 내스크래치성이 우수한 폴리프로필렌 수지 조성물
JP7814164B2 (ja) エチレン系重合体組成物およびその用途
JP2011157519A (ja) 自動車内装部品用樹脂組成物及びその用途
KR102187566B1 (ko) 폴리프로필렌 수지 조성물 및 이의 성형품
JP5131910B2 (ja) ポリプロピレン樹脂組成物及びその製造方法
JP2025044612A (ja) エチレン系重合体組成物およびその用途
JP2022098911A (ja) オレフィン系重合体組成物およびその用途
JPWO2019065465A1 (ja) 耐ダスト摺動性部材用樹脂組成物、耐ダスト摺動性部材及びその製造方法、ウィンドウレギュレータ用キャリアプレート、耐ダスト摺動性の発現方法
JP7398989B2 (ja) 樹脂組成物および積層体の製造方法
KR101583924B1 (ko) 폴리프로필렌-폴리유산 복합재 조성물 및 이의 제조방법
JP2006161045A (ja) エチレン−ビニルアルコールコポリマー及び反応性基を有する架橋性ゴムの混合物、並びに、良好なバリア特性を有する成形品の製造のためのその使用
JP2021123649A (ja) 樹脂組成物および積層体
JPH07329263A (ja) 強化積層体
KR102394764B1 (ko) Lft용 친환경 열가소성 복합수지 조성물
JP2023041362A (ja) 成形品および摺動部品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23780552

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20247029216

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2024512581

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202380026480.6

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 18850037

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2023780552

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2023780552

Country of ref document: EP

Effective date: 20241031

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 18850037

Country of ref document: US