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
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/24—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/06—Rod-shaped
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • 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
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2021/00—Use of unspecified rubbers as moulding material
  • B29K2021/003—Thermoplastic elastomers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/18—Polymers of hydrocarbons having four or more carbon atoms, e.g. polymers of butylene, e.g. PB, i.e. polybutylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
  • B29K2025/04—Polymers of styrene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2023/00—Tubular articles
  • B29L2023/005—Hoses, i.e. flexible
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/10—Homopolymers or copolymers of propene
  • C08J2423/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • 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
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• the present invention relates to a 4-methyl-1-pentene copolymer composition, a molded article, a mandrel, and a method for producing a rubber hose.
• 4-Methyl-1-pentene-based polymers containing 4-methyl-1-pentene as a main constituent monomer are widely used in various applications due to their excellent releasability, heat resistance, water resistance, and solvent resistance.
• 4-Methyl-1-pentene polymer for example, is used for FPC (Flexible Printed Circuits) release film, composite material molding release film, etc.
• 4-methyl-1-pentene polymer moldings are used for laboratory instruments and mandrels, taking advantage of their chemical resistance and water resistance.
• 4-methyl-1-pentene-based polymers are not only used alone, but are also being used in compositions with elastomers.
• a resin composition to which a small amount of an olefinic elastomer or a liquid olefinic oligomer is added (see, for example, Patent Documents 2-4.).
• 4-methyl-1-pentene-based A resin composition is disclosed to which a small amount of polymer is added.
• the composition is used in the engine room of automobiles and near heat generating elements such as electronic components, so heat resistance and shape retention are required. Destruction resistance of time is required.
• compositions of two kinds of 4-methyl-1-pentene copolymers satisfying specific conditions and a thermoplastic resin have also been disclosed, mainly in the form of films and hollow molded articles (see, for example, Patent Document 7).
• Patent Documents 1 to 3 and 7 above have been studied with 4-methyl-1-pentene-based polymer alone, and the content of 4-methyl-1-pentene copolymer is large. , and 4-methyl-1-pentene-based polymers, which are brittle at low temperatures and have poor fracture resistance at low temperatures.
• the resin composition disclosed in Patent Document 4 may cause the liquid olefin-based oligomer to bleed out, resulting in stickiness and poor releasability during repeated use.
• An object to be solved by one embodiment of the present invention is to provide a 4-methyl-1-pentene copolymer composition that can maintain its shape at high temperatures and has excellent low-temperature toughness of the resulting molded product. to provide.
• Another problem to be solved by an embodiment of the present invention is to provide a compact that can maintain its shape at high temperatures and has excellent toughness at low temperatures.
• A 4-methyl-1-pentene polymer having a melting point in the range of 200 to 250° C. as measured by differential scanning calorimetry (DSC)
• DSC differential scanning calorimetry
• thermoplastic elastomer (C) other than the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene polymer (B) ((A), (B The total amount of ) and (C) is 100 parts by mass), and A 4-methyl-1-pentene copolymer composition (X) that satisfies the following requirements (a) and (b);
• the temperature at which the value of the loss tangent tan ⁇ obtained by dynamic viscoelasticity measurement by The value at which the value of loss tangent tan ⁇ obtained by dynamic viscoelasticity measurement by 1.6 Hz) becomes maximum is 0.15 to 0.8.
• the 4-methyl-1-pentene polymer (A) satisfies the following requirements (c) and (d), and the 4-methyl-1-pentene polymer (B) satisfies the following requirements
• Requirement (d) The density is in the range of 820 to 850 kg/m 3 ;
• ⁇ 6> A step of extruding the 4-methyl-1-pentene copolymer composition (X) according to any one of ⁇ 1> to ⁇ 4> to obtain a mandrel;
• a method of manufacturing a rubber hose comprising:
• a 4-methyl-1-pentene copolymer composition that is capable of maintaining its shape at high temperatures and that the resulting molded product has excellent toughness at low temperatures.
• a compact that can maintain its shape at high temperatures and has excellent toughness at low temperatures.
• ⁇ indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
• ⁇ indicating a numerical range means that the unit described either before or after it indicates the same unit unless otherwise specified.
• polymer includes homopolymers and copolymers unless otherwise specified.
• the present invention will be described in detail below.
• the 4-methyl-1-pentene copolymer composition (X) according to the present invention has a melting point (Tm) in the range of 200 to 250° C. measured by differential scanning calorimetry (DSC). 50 to 90 parts by mass of a pentene-based polymer (A) (hereinafter also simply referred to as "4-methyl-1-pentene-based polymer (A)"); A 4-methyl-1-pentene-based polymer (B) having a melting point measured by differential scanning calorimetry (DSC) of less than 200° C.
• Tm melting point
• DSC differential scanning calorimetry
• thermoplastic elastomer (C) other than the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene polymer (B) ((A), (B The total amount of ) and (C) is 100 parts by mass), and satisfies the following requirements (a) and (b).
• the 4-methyl-1-pentene copolymer composition (X) according to the present invention has the above configuration, so that the resulting molded article has flexibility at room temperature and good flexibility at low temperatures while maintaining heat resistance. Excellent toughness. The reason for this is not clear, but is presumed as follows.
• the 4-methyl-1-pentene copolymer composition (X) contains a 4-methyl-1-pentene polymer (A) and a 4-methyl-1-pentene polymer (B) having different melting points. Therefore, it is possible to soften more effectively than other thermoplastic elastomers while maintaining the heat resistance that is a feature of 4-methyl-1-pentene-based polymers, so it is possible to maintain shape at high temperatures. In addition, it has good dispersibility with the thermoplastic elastomer, so it is presumed that it has excellent toughness at low temperatures.
• the molded article made of the 4-methyl-1-pentene copolymer composition (X) of the present invention has the above structure, it has appropriate elongation and hardness. Also, when the mandrel is pulled out after manufacturing the rubber hose, the mandrel is not deformed, and releasability can be exhibited.
• the 4-methyl-1-pentene copolymer composition (X) according to the present invention satisfies both requirements (a) and (b) below.
• the 4-methyl-1-pentene copolymer composition (X) has a loss tangent tan ⁇ value determined by dynamic viscoelasticity measurement at a frequency of 10 rad/s (1.6 Hz) in a temperature range of 0 to 240 ° C.
• the maximum temperature (hereinafter also referred to as "tan ⁇ peak temperature”) is 0°C to 60°C.
• the lower limit of the tan ⁇ peak temperature in the temperature range of 0 to 240°C is preferably 5°C or higher, more preferably 10°C or higher.
• the upper limit of the tan ⁇ peak temperature is preferably 55° C. or lower, more preferably 50° C. or lower, and particularly preferably 45° C. or lower. If the tan ⁇ peak temperature in the temperature range of 0 to 240° C. is within the above temperature range, the molded article and mandrel obtained from the 4-methyl-1-pentene copolymer composition (X) will have pullability and flexibility. can be compatible.
• the details of the dynamic viscoelasticity measurement method are as described in Examples below.
• ⁇ Requirement (b)>> The 4-methyl-1-pentene copolymer composition (X) has a loss tangent tan ⁇ value determined by dynamic viscoelasticity measurement at a frequency of 10 rad/s (1.6 Hz) in a temperature range of 0 to 100 ° C.
• the maximum value (hereinafter also referred to as “tan ⁇ peak value”) is 0.15 to 0.8.
• the tan ⁇ peak value in the temperature range of 0 to 100°C changes flexibly in slow deformation such as bending, and occurs when the manufactured rubber hose is pulled out from the mandrel by hand or using compressed air. With regard to the rapid deformation of the mandrel, the mandrel becomes hard and can be easily pulled out.
• the lower limit of the tan ⁇ peak value in the temperature range of 0 to 100°C is preferably 0.16 or more, more preferably 0.20 or more.
• the upper limit of the tan ⁇ peak value in the temperature range of 0 to 100° C. is preferably 0.8 or less, more preferably 0.5 or less, and 0.4 or less. More preferred.
• tan ⁇ peak temperature and tan ⁇ peak value are adjusted by the composition and content of the 4-methyl-1-pentene-based polymer (A) and 4-methyl-1-pentene-based polymer (B) described later. can be done.
• the 4-methyl-1-pentene-based polymer (A), the 4-methyl-1-pentene-based Polymer (B), and 4-methyl-1-pentene polymer (A) and thermoplastic elastomer (C) other than 4-methyl-1-pentene polymer (B) (hereinafter simply referred to as “thermoplastic Also referred to as “elastomer (C)”) will be described.
• thermoplastic Also referred to as “elastomer (C) will be described.
• DSC differential scanning calorimetry
• the resin composition containing the 4-methyl-1-pentene polymer (A) can improve the strength of the molded article obtained using the product, and when the melting point is 250 ° C. or less, it is obtained using the resin composition containing the 4-methyl-1-pentene polymer (A).
• the impact strength and toughness of the formed body can be improved.
• the 4-methyl-1-pentene polymer (A) has a melting point (Tm) measured by differential scanning calorimetry (DSC) of preferably 210 to 245°C, more preferably 220 to 240°C. It is in.
• Tm melting point measured by differential scanning calorimetry
• the melting point is measured using a differential scanning calorimeter, for example, as follows. A 3-7 mg sample is sealed in an aluminum pan and heated from room temperature at 10° C./min to 280° C. and the sample is held at 300° C. for 5 minutes for complete melting. It is then cooled at 10°C/min to -50°C and after 5 minutes at -50°C, the sample is reheated at 10°C/min to 300°C. The peak temperature in this second heating test is taken as the melting point (Tm).
• the melting points of the 4-methyl-1-pentene polymer (B) and the olefin polymer (C), which will be described later, can also be measured in the same manner.
• the 4-methyl-1-pentene polymer (A) must satisfy the following requirements (c) and (d) from the viewpoint of being able to maintain its shape at high temperatures and having excellent toughness at low temperatures for the resulting molded product. is preferred.
• ⁇ Requirement (c)>> Structural unit derived from 4-methyl-1-pentene (hereinafter sometimes referred to as “structural unit (i)”) is 100 to 90 mol% (preferably 99.9 to 92 mol%, more preferably 99 ⁇ 95 mol%), a structural unit derived from at least one selected from ethylene and an ⁇ -olefin having 10 to 20 carbon atoms (hereinafter sometimes referred to as “structural unit (iii)”) is 0 to 10 It is preferably in the range of mol % (preferably 0.1 to 8 mol %, more preferably 1 to 5 mol %) [however, the structural unit derived from 4-methyl-1-pentene and ethylene and the number of carbon atoms The total amount of structural
• a structural unit derived from an ⁇ -olefin is a structural unit corresponding to an ⁇ -olefin, that is, a structural unit represented by —CH 2 —CHR— (R is a hydrogen atom or an alkyl group).
• R is a hydrogen atom or an alkyl group.
• Structural units derived from 4-methyl-1-pentene can be similarly interpreted, and structural units corresponding to 4-methyl-1-pentene (that is, --CH 2 --CH(--CH 2 CH(CH 3 ) 2 )- is a structural unit).
• Examples of ⁇ -olefins having 10 to 20 carbon atoms that can be copolymerized with 4-methyl-1-pentene include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. mentioned. These ⁇ -olefins having 10 to 20 carbon atoms may be used singly or in combination of two or more.
• the density of the 4-methyl-1-pentene polymer (A) is preferably in the range of 820-850 kg/m 3 , more preferably 825-845 kg/m 3 , still more preferably 830-840 kg/m 3 .
• the 4-methyl-1-pentene-based polymer (A) satisfies the above requirements (c) and (d), it has excellent heat resistance, and the molded article obtained from such a polymer (A) has a separation property. Excellent balance with type.
• the 4-methyl-1-pentene polymer (A) preferably satisfies the following requirement (e) in addition to the above requirements (c) and (d). ⁇ Requirement (e)>>
• the 4-methyl-1-pentene polymer (A) has a melt flow rate (MFR) measured at a temperature of 260° C. and a load of 5.0 kgf (49.03 N) according to ASTM D1238. is preferably 1 to 200 g/10 minutes, more preferably 5 to 100 g/10 minutes, and still more preferably 10 to 60 g/10 minutes.
• the 4-methyl-1-pentene-based polymer (A) can maintain its shape at high temperatures, and the resulting molded product has excellent toughness at low temperatures.
• the temperature at which the value of the loss tangent tan ⁇ obtained by dynamic viscoelasticity measurement at 10 rad/s (1.6 Hz) is maximized (tan ⁇ peak temperature) is preferably 0 ° C. to 60 ° C., more preferably 5 °C to 55 °C, more preferably 10 °C to 50 °C.
• the 4-methyl-1-pentene-based polymer (A) can maintain its shape at high temperatures, and the obtained molded article has excellent toughness at low temperatures.
• the value (tan ⁇ peak value) at which the loss tangent tan ⁇ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad/s (1.6 Hz) is maximum is preferably 0.05 to 0.8, more preferably It is 0.05 to 0.5, more preferably 0.07 to 0.4.
• the content of the 4-methyl-1-pentene polymer (A) is 50 to 90 parts by mass with respect to 100 parts by mass in total of (A), (B) and (C).
• the molded article obtained from the 4-methyl-1-pentene copolymer composition (X) is 4-methyl- The heat resistance inherent in the 1-pentene polymer can be exhibited. Further, when the content of the 4-methyl-1-pentene-based polymer (A) is 90 parts by mass or less, the 4-methyl-1-pentene-based polymer (B) described below and the thermoplastic elastomer are contained in the composition. (C) cannot be contained in a large amount, and the molded article obtained from such a resin composition has excellent low-temperature toughness, flexibility, suppressed cracking at room temperature, and excellent pull-out properties.
• the upper limit of the content of the 4-methyl-1-pentene polymer (A) is preferably 80 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C). Department.
• the lower limit of the content of the 4-methyl-1-pentene polymer (A) is preferably 55 parts by mass, more preferably 55 parts by mass with respect to 100 parts by mass of (A), (B) and (C) in total. is 60 parts by mass.
• the 4-methyl-1-pentene polymer (A) can be produced by a known method.
• ⁇ 4-methyl-1-pentene polymer (B)> A 4-methyl-1-pentene-based polymer (B) having a melting point measured by differential scanning calorimetry (DSC) of less than 200°C or having no observed melting point (DSC) has a melting point of less than 200°C.
• the melting point it is not particularly limited, and may be a homopolymer of 4-methyl-1-pentene, 4-methyl-1-pentene and 4-methyl It may be a copolymer with an ⁇ -olefin other than -1-pentene.
• 4-methyl-1-pentene polymer (B) has a melting point of less than 200 ° C. in differential scanning calorimetry (DSC), or no melting point is observed, 4-methyl-1-pentene copolymer High flexibility can be imparted to the molded article obtained from the combined composition (X).
• the 4-methyl-1-pentene-based polymer (B) preferably has a melting point of 160° C. or less in differential scanning calorimetry (DSC), or the melting point is not observed, and the melting point is 150 C. or no melting point is observed, more preferably 150.degree. C. or less.
• DSC differential scanning calorimetry
• the 4-methyl-1-pentene polymer (B) preferably has a lower limit of melting point of 110° C. or more in differential scanning calorimetry (DSC), or the melting point is not observed. More preferably, the melting point is 110° C. or higher, and even more preferably 130° C. or higher.
• the 4-methyl-1-pentene polymer (B) preferably has the following requirements (f) to (j ), more preferably two or more, still more preferably three or more, and particularly preferably all of them.
• the 4-methyl-1-pentene-based polymer (B) is a structural unit (i) derived from 4-methyl-1-pentene, ethylene and an ⁇ - and a structural unit (ii) derived from at least one selected from olefins (excluding 4-methyl-1-pentene) in a specific ratio.
• ⁇ -olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1- Examples include dodecene, 1-octadecene, 1-hexadecene, etc.
• structural unit (ii) is preferably at least one selected from ethylene, propylene, and 1-butene.
• the structural unit (ii) may be used alone or in combination of two or more.
• the lower limit of the content of structural units derived from 4-methyl-1-pentene is preferably 55 mol% or more, and 65 mol% or more. and more preferably 68 mol % or more.
• the upper limit of the content of structural units derived from 4-methyl-1-pentene is preferably 97 mol% or less, more preferably 93 mol% or less, and 87 mol% or less. is more preferred.
• the tan ⁇ peak temperature of the 4-methyl-1-pentene copolymer composition (X) can also be easily adjusted within the range described above.
• the content of the structural unit (i) derived from 4-methyl-1-pentene is equal to or less than the above upper limit value, the polymer has relaxation properties at room temperature.
• structural units derived from ethylene and an ⁇ -olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) in the 4-methyl-1-pentene polymer (B) The upper limit of the content of (ii) is preferably 45 mol% or less, the content of the structural unit (ii) is more preferably 35 mol% or less, and further preferably 32 mol% or less. preferable.
• the lower limit of the content of structural units (ii) derived from ethylene and an ⁇ -olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 3 mol% or more. is preferred, 7 mol % or more is more preferred, and 13 mol % or more is even more preferred.
• the value of the content (mol%) of each structural unit constituting the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene polymer (B) is determined by 13 C-NMR. measured. The details of the measuring method are as described in Examples below.
• the structural unit (ii) is a structural unit derived from propylene
• the tan ⁇ peak temperature can be set within the above range, and the 4-methyl-1-pentene copolymer composition (X) was used as a mandrel.
• the 4-methyl-1-pentene polymer (B) preferably consists of only the structural unit (i) and the structural unit (ii).
• the 4-methyl-1-pentene-based polymer (B) has a tan ⁇ peak temperature of 15°C, which is obtained by dynamic viscoelasticity measurement at a frequency of 10 rad/s (1.6 Hz) in a temperature range of -40 to 150°C. It is preferably up to 45°C, more preferably 20°C to 45°C, even more preferably 25°C to 45°C.
• the hardness of the molded product obtained from the 4-methyl-1-pentene copolymer composition (X) changes around room temperature.
• the mandrel is pulled out from the manufactured rubber hose, the mandrel is quickly deformed to increase the storage elastic modulus and become hard, thereby improving the pullability.
• the details of the dynamic viscoelasticity measurement method are as described in Examples described later.
• the density of the 4-methyl-1-pentene polymer (B) is preferably 830-870 kg/m 3 , more preferably 830-860 kg/m 3 , still more preferably 830-850 kg/m 3 .
• the details of the measuring method are as described in Examples below.
• the density of the 4-methyl-1-pentene-based polymer (B) can be appropriately changed by the comonomer composition ratio of the 4-methyl-1-pentene/ ⁇ -olefin copolymer.
• the density of the 4-methyl-1-pentene polymer (B) is within the above range, good transparency and releasability are obtained.
• the 4-methyl-1-pentene polymer (B) is one of the requirements (i) to (k) from the viewpoint that the shape can be maintained at high temperatures and the obtained molded product has excellent toughness at low temperatures. It is preferable to satisfy two or more of the requirements (i) to (k), more preferably to satisfy two or more of the requirements (i) to (k), and further preferably to satisfy all of the requirements (i) to (k). ⁇ requirement (i)>>
• the 4-methyl-1-pentene polymer (B) preferably has an intrinsic viscosity [ ⁇ ] measured at 135°C in decalin in the range of 0.1 to 5.0 dl/g, more preferably 0.
• the 4-methyl-1-pentene polymer (B) has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000 to 1,000,000 in terms of polystyrene. is preferred, 5,000 to 800,000 is more preferred, and 10,000 to 500,000 is even more preferred.
• Mw weight average molecular weight measured by gel permeation chromatography
• the 4-methyl-1-pentene polymer (B) has a molecular weight distribution (Mw/ Mn) is preferably in the range of 1.0 to 3.5, more preferably 1.2 to 3.0, still more preferably 1.5 to 2.8 or less.
• Mw/Mn molecular weight distribution
• the effect of the low-molecular-weight polymer derived from the composition distribution and the low-stereoregular polymer is small, and the mechanical strength of the resulting molded article is less likely to decrease. preferable.
• Melt flow rate (MFR; ASTM D1238 compliant, temperature 230°C, load 2.16kgf (21.18N) of 4-methyl-1-pentene polymer (B) should be 0.1 to 100g/10min. is preferred, more preferably 0.5 to 50 g/10 min, even more preferably in the range of 1.0 to 30 g/10 min.
• melt flow rate (MFR) of the 4-methyl-1-pentene polymer (B) is at least the lower limit in the above range, the fluidity is good and the 4-methyl-1-pentene polymer ( Good dispersibility with A) is obtained.
• the molecular weight of the 4-methyl-1-pentene-based polymer (B) is not too small, and sufficient mechanical strength of the resulting molded product can be obtained, which is preferable.
• the content of the 4-methyl-1-pentene polymer (B) is 5 to 30 parts by mass with respect to the total of 100 parts by mass of (A), (B) and (C).
• the compatibility with the 4-methyl-1-pentene polymer (A) is improved, and a small amount of 4-methyl-1 can be efficiently added.
• the 4-methyl-1-pentene polymer (A) can be made flexible, and the effect of the 4-methyl-1-pentene polymer (B) tends to improve the pull-out property of the resulting molded article.
• the lower limit of the content of the 4-methyl-1-pentene polymer (B) is preferably 10 parts by mass with respect to the total 100 parts by mass of (A), (B) and (C). or more, more preferably 15 parts by mass or more.
• the upper limit of the content of the 4-methyl-1-pentene polymer (B) is preferably 25 parts by mass or less with respect to a total of 100 parts by mass of the above (A), (B) and (C). is.
• the method for producing the 4-methyl-1-pentene-based polymer (B) is not particularly limited. It can be produced by polymerizing 3 to 20 ⁇ -olefins (excluding 4-methyl-1-pentene) in the presence of an appropriate polymerization catalyst such as a magnesium supported titanium catalyst or a metallocene catalyst.
• the polymerization catalyst that can be used includes conventionally known catalysts such as magnesium-supported titanium catalysts, International Publication Nos. 01/53369, WO 01/27124, JP-A-3-193796, Alternatively, metallocene catalysts described in JP-A-2-41303, WO 2011/055803, WO 2014/050817, etc. are preferably used.
• Polymerization can be carried out by appropriately selecting from a liquid phase polymerization method including solution polymerization and suspension polymerization, a gas phase polymerization method, and the like.
• an inert hydrocarbon solvent can be used as a solvent that constitutes the liquid phase.
• inert hydrocarbons include aliphatic hydrocarbons including propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like.
• alicyclic hydrocarbons including aromatic hydrocarbons, including benzene, toluene, and xylene; and halogenated hydrocarbons, including ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof, and the like. included.
• the monomer corresponding to the structural unit (i) derived from the above-mentioned 4-methyl-1-pentene (that is, 4-methyl-1-pentene), the above-mentioned ethylene and 3 to 3 carbon atoms Bulk polymerization can also be carried out using the monomer itself corresponding to the structural unit (ii) derived from the ⁇ -olefin of 20 (excluding 4-methyl-1-pentene) as a solvent.
• structural unit (i), and structural unit (ii) can also be moderately controlled.
• the polymerization temperature is preferably -50 to 200°C, more preferably 0 to 100°C, even more preferably 20 to 100°C.
• the polymerization pressure is preferably normal pressure to 10 MPa gauge pressure, more preferably normal pressure to 5 MPa gauge pressure.
• Hydrogen may be added during polymerization for the purpose of controlling the molecular weight and polymerization activity of the polymer to be produced.
• the amount of hydrogen to be added is the amount of 4-methyl-1-pentene and the amount of ethylene and ⁇ -olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) per 1 kg of the total. 0.001 to 100 NL is appropriate.
• the 4-methyl-1-pentene copolymer composition (X) is a thermoplastic elastomer other than the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene polymer (B).
• C) thermoplastic elastomer (C)).
• thermoplastic elastomer (C) means a polymer that exhibits thermoplastic properties when heated above its melting point, while exhibiting rubber elasticity at room temperature.
• the thermoplastic elastomer (C) is not particularly limited as long as it is a polymer other than the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene polymer (B). Specifically, an olefin elastomer (C-1) and a styrene elastomer (C-2) are suitable. ⁇ Olefin Elastomer (C-1)>>
• a first embodiment of the olefinic elastomer (C-1) includes one selected from the group consisting of ethylene and propylene, and one selected from the group consisting of butadiene, hydrogenated butadiene, isoprene, hydrogenated isoprene isobutylene, and ⁇ -olefin. and a copolymer of at least one
• the form of copolymerization may be either block copolymerization or graft copolymerization, but only in the case of a copolymer consisting of one selected from the group consisting of ethylene and propylene and an ⁇ -olefin, the form of copolymerization is It may be random copolymerization.
• the ⁇ -olefin is an olefin having a double bond at one end of the molecular chain, and 1-butene, 1-octene, etc. are preferably used.
• the olefin-based elastomer (C-1) is, for example, a block copolymer of a polyolefin block forming a highly crystalline polymer such as polypropylene as the hard portion and a monomer copolymer exhibiting amorphous property as the soft portion.
• Specific examples include olefin (crystalline)/ethylene/butylene/olefin block copolymers, propylene/olefin (amorphous)/propylene block copolymers, and the like.
• a second aspect of the olefinic elastomer includes one selected from the group consisting of ethylene and propylene, an ethylene/propylene copolymer, an ethylene/propylene/diene copolymer, an ethylene/butene copolymer, and a hydrogenated styrene butadiene.
• olefinic elastomers include Milastomer (registered trademark) from Mitsui Chemicals, trade name Esporex (registered trademark) from Sumitomo Chemical Co., Ltd., and Thermolan (trade name) from Mitsubishi Chemical Corporation. (registered trademark), Xerasu (registered trademark), and those commercially available from Celanese under the trade name: Santoprene (registered trademark).
• the olefin elastomer according to the present invention is at least one selected from the group consisting of acid anhydride groups, carboxyl groups, amino groups, imino groups, alkoxysilyl groups, silanol groups, silyl ether groups, hydroxyl groups and epoxy groups.
• styrene-based elastomer C-2
• HSBR hydrogenated styrene/butadiene/styrene block copolymer Polymer
• SEPS Styrene/Ethylene/Propylene/Styrene Block Copolymer
• SEBS Styrene/Ethylene/Butene/Styrene Block Copolymer
• SEBS Styrene/Isoprene/Styrene Block Copolymer
• Styrene - Examples include isobutylene/styrene copolymer (SIBS) and styrene/isobutylene
• the styrene-based elastomer may be used singly or in combination of two or more.
• hydrogenated styrene/butadiene/styrene block copolymer examples include those commercially available from ENEOS Materials Co., Ltd. under the trade name: Dynalon (registered trademark).
• a styrene/ethylene/propylene/styrene block copolymer is obtained by hydrogenating a styrene/isoprene/styrene block copolymer (SIS).
• SIS styrene/isoprene/styrene block copolymer
• SIS styrene/isoprene/styrene block copolymer
• SIS styrene/isoprene/styrene block copolymer
• SEPS styrene/ethylene/propylene/styrene block copolymer
• Septon registered trademark
• Kraton registered trademark
• SEBS include those commercially available from Asahi Kasei Corporation under the trade name: Tuftec (registered trademark), or from Clayton Polymer Japan Co., Ltd. under the trade name: Kraton (registered trademark).
• SIB styrene/isobutylene copolymer
• SIBS styrene/isobutylene/styrene copolymer
• the melt flow rate (MFR; ASTM D1238 compliant, temperature 230°C, load 2.16 kgf ( 21.18N) is preferably 0.1 to 100 g/10 minutes, more preferably 0.5 to 50 g/10 minutes, and is in the range of 1.0 to 30 g/10 minutes. More preferred.
• the thermoplastic elastomer (C) has a melting point of less than 200° C. as measured by differential scanning calorimetry (DSC) from the viewpoint of being able to maintain its shape at high temperatures and having excellent toughness at low temperatures.
• the melting point is preferably not observed, and more preferably the melting point is 160° C. or lower, or the melting point is not observed.
• thermoplastic elastomer (C) The content of the thermoplastic elastomer (C) is 5 to 30 parts by mass with respect to the total of 100 parts by mass of (A), (B) and (C).
• thermoplastic elastomer (C) When the content of the thermoplastic elastomer (C) is within the above range, flexibility at room temperature and toughness at low temperatures are improved.
• the lower limit of the content of the thermoplastic elastomer (C) is preferably 10 parts by mass or more with respect to 100 parts by mass as the total amount of (A), (B) and (C).
• the upper limit of the content of the thermoplastic elastomer (C) is preferably 25 parts by mass or less with respect to 100 parts by mass as the total of (A), (B) and (C).
• the 4-methyl-1-pentene copolymer composition (X) comprises the 4-methyl-1-pentene polymer (A), the 4-methyl-1-pentene polymer (B), and a thermoplastic elastomer.
• the 4-methyl-1-pentene-based polymer (A), 4-methyl-1-pentene-based polymer (B), and resins or polymers other than the thermoplastic elastomer (C) and/or additives for resins hereinafter also referred to as "other components").
• Such resin additives include, for example, pigments, dyes, fillers, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, weather resistant agent, heat stabilizer, anti-slip agent, anti-blocking agent, blowing agent, crystallization aid, anti-fogging agent, (transparent) nucleating agent, anti-aging agent, hydrochloric acid absorber, impact modifier, cross-linking agent, co-cross-linking agent , cross-linking aids, adhesives, softeners, processing aids, and the like. These additives can be used singly or in combination of two or more.
• resins or polymers to be added include polystyrene, acrylic resin, polyphenylene sulfide resin, polyetheretherketone resin, polyester resin, polysulfone, polyphenylene oxide, polyimide, polyetherimide, acrylonitrile-butadiene-styrene copolymer (ABS ), ethylene/ ⁇ -olefin copolymer rubber, conjugated diene rubber, phenol resin, melamine resin, polyester resin, silicone resin, and epoxy resin.
• the content of these resins or polymers is preferably 0.1 to 30% by mass with respect to the total mass of the olefin polymer composition (M).
• Pigments include inorganic content (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake-based, thioindigo-based, phthalocyanine-based, anthraquinone-based).
• dyes include azo dyes, anthraquinone dyes, and triphenylmethane dyes.
• the content of these pigments and dyes is not particularly limited, but the total is preferably 5% by mass or less, more preferably 0.1 to 3% by weight, based on the total mass of the olefin polymer composition (M). %.
• Fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal oxide ( iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, glass flakes and the like. These fillers may be used alone or in combination of two or more.
• Lubricants include waxes (carnauba wax, etc.), higher fatty acids (stearic acid, etc.), higher alcohols (stearyl alcohol, etc.), higher fatty acid amides (stearic acid amide, etc.), and the like.
• Plasticizers include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetyl ricinoleate, etc.), aliphatic dicarboxylic acid esters (adipic acid-propylene glycol polyester, etc.), aliphatic tricarboxylic acids. Examples include esters (triethyl citrate, etc.), phosphate triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), petroleum resins, and the like.
• Release agents include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hydrogenated castor oil, etc.), glycol esters of fatty acids, liquid paraffin, etc. is mentioned.
• antioxidants examples include phenolic (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenolic (2,2′-methylenebis(4-methyl-6-t-butylphenol, etc.), Phosphorus-based (tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate, etc.) and amine-based (N,N-diisopropyl-p-phenylenediamine, etc.) antioxidants can be mentioned. be done.
• Flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). mentioned.
• UV absorbers examples include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based.
• Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.
• Surfactants include nonionic, anionic, cationic or amphoteric surfactants.
• nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, polyethylene oxide, and fatty acid esters of glycerin. , pentaerythritol fatty acid esters, sorbit or sorbitan fatty acid esters, alkyl ethers of polyhydric alcohols, and polyhydric alcohol type nonionic surfactants such as fatty amides of alkanolamine.
• polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, polyethylene oxide, and fatty acid esters of glycerin.
• anionic surfactants include sulfate ester salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzenesulfonates, alkylsulfonates and paraffinsulfonates, and higher alcohol phosphates. Phosphate ester salts and the like, and cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts.
• Amphoteric surfactants include amino acid-type double-faced surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines.
• Antistatic agents include the above surfactants, fatty acid esters, and polymeric antistatic agents.
• fatty acid esters include esters of stearic acid and oleic acid
• polymeric antistatic agents include polyether ester amides.
• the content of various additives such as fillers, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, and antistatic agents impairs the purpose of the present invention.
• it is not particularly limited depending on the application within the range, it is preferably 0.1 to 30% by mass with respect to the total mass of the 4-methyl-1-pentene copolymer composition (X).
• the method for producing the 4-methyl-1-pentene copolymer composition (X) is not particularly limited.
• the united body (B), the thermoplastic elastomer (C), and other optional components are mixed in the above-described addition ratios, and then melt-kneaded to obtain the mixture.
• the melt-kneading method is not particularly limited, and can be carried out using a generally commercially available melt-kneading device such as an extruder.
• the cylinder temperature of the portion where kneading is performed by a kneader is usually preferably 220 to 300°C, more preferably 250 to 290°C.
• the melt-kneading can be sufficiently performed, and the physical properties of the 4-methyl-1-pentene copolymer composition (X) can be improved.
• the cylinder temperature is 300° C.
• the thermal decomposition of C) can be suppressed.
• the kneading time is generally preferably 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. When the kneading time is 0.1 minute or more, sufficient melt-kneading can be performed, and when the kneading time is within 30 minutes, the 4-methyl-1-pentene polymer (A) and 4-methyl
• the thermal decomposition of the -1-pentene polymer (B) and the thermoplastic elastomer (C) can be suppressed.
• the molded article according to the present invention preferably comprises the 4-methyl-1-pentene copolymer composition (X).
• the molded article is not particularly limited, and examples thereof include extrusion molded articles and injection molded articles.
• the method for manufacturing the molded body is not particularly limited, and for example, conventionally known manufacturing methods can be used, including extrusion molding, compression molding, injection molding, 3D modeling, microwave heating molding, and the like. Among these molding methods, extrusion molding or injection molding is preferred.
• Applications include mandrels and sheaths as well as automobile parts (front ends, fan shells, cooling fans, engine undercovers, engine covers, radiator boxes, side doors, back door inners, back door outers, outer panels, Roof rails, door handles, luggage boxes, wheel covers, handles, cooling modules, air cleaners, spoilers, fuel tanks, platforms and side members, motor connector housings, bumpers, instrument panel coverings, control cable coverings, wire coverings ), home appliance material parts, electric/electronic members, building members, civil engineering members, agricultural materials, daily necessities, and the like.
• mandrels are preferable for use as molded articles, and mandrels for manufacturing rubber hoses are particularly preferable.
• the mandrel is preferably formed from the 4-methyl-1-pentene copolymer composition (X).
• the molded article made of the 4-methyl-1-pentene copolymer composition (X) according to the present invention is preferably a mandrel, more preferably a mandrel for manufacturing rubber hoses.
• the 4-methyl-1-pentene copolymer composition (X) satisfies the specific requirements (a) and (b). It has good workability without cracking or chipping due to softening even when wound, and has sufficient toughness even at low temperatures.
• the tan ⁇ peak temperature and peak value are in an appropriate range when the mandrel is pulled out by inserting a hand or compressed air. Dimensional change is less likely to occur at the time of pulling out, and it can be pulled out easily.
• the mandrel according to the present invention is molded in a continuous cylindrical shape. From the viewpoint of efficient production of rubber hoses, the length of the mandrel is generally 100 m or longer, preferably 200 m or longer. After the mandrel is pulled out from the rubber hose thus obtained, the rubber hose is cut to a desired length. This is preferable because it improves productivity.
• the inner diameter of the rubber hose is designed with the diameter of the mandrel.
• the mandrel has a diameter of 2-30 mm, preferably a diameter of 3-28 mm.
• the dimensional accuracy of the mandrel is required to have a tolerance of less than ⁇ 0.18 mm for the diameter of the mandrel (that is, the difference between the maximum and minimum allowable dimensional errors), preferably ⁇ 0.18 mm. A dimensional accuracy of less than 0.15 mm is required.
• the method for producing a rubber hose according to the present invention includes the steps of extruding the 4-methyl-1-pentene copolymer composition (X) to obtain a mandrel, and using the mandrel obtained in the above step to produce a rubber hose. and a step of injection molding the 4-methyl-1-pentene copolymer composition (X) to obtain a mandrel, and an unvulcanized rubber hose obtained in the above step. It is further preferable to include the steps of inserting the vulcanized rubber hose into a mandrel and vulcanizing it to obtain a vulcanized rubber hose, and pulling out the vulcanized rubber hose from the mandrel.
• an unvulcanized rubber composition forming a rubber inner layer is supplied to an extruder equipped with a crosshead so that the crosshead is perpendicular to the extrusion direction.
• An unvulcanized rubber composition layer may be formed by uniformly covering the outer circumference of the mandrel with the unvulcanized rubber composition to a desired thickness while extruding and moving the mandrel thus obtained. Then, if necessary, two layers of the reinforcing material are wound on the outer side of the unvulcanized rubber composition layer or so as to cross each other. Additionally, other extruders may be used to coat the outer layer of the unvulcanized rubber composition layer with a rubber material.
• the vulcanization reaction is then carried out in suitable equipment such as a high temperature steam oven or continuous oven.
• suitable equipment such as a high temperature steam oven or continuous oven.
• the vulcanization reaction temperature is generally 160°C.
• it is obtained by applying hydraulic pressure to the mandrel and withdrawing the rubber hose.
• Methods for measuring physical properties of compositions, polymers used, methods for preparing test pieces, and evaluation methods in the following examples and comparative examples are as follows.
• the intrinsic viscosity is a value measured at 135° C. in decalin using an Ubbelohde viscometer. About 20 mg of the polymerized powder and pellets or resin lumps obtained below were collected and dissolved in 15 mL of decalin, and the specific viscosity ⁇ sp of the resulting decalin solution was measured in an oil bath heated to 135°C. 5 mL of decalin was added to this decalin solution to dilute it, and then the specific viscosity ⁇ sp was measured under the same conditions. This dilution operation was repeated twice, and the value of ⁇ sp/C when the polymer concentration (C) was extrapolated to zero was calculated as the intrinsic viscosity [ ⁇ ] (see the formula below).
• [ ⁇ ] lim( ⁇ sp/C) (C ⁇ 0) ⁇ Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn)> Molecular weights were measured by gel permeation chromatography (GPC).
• a Waters ALC/GPC150-Cplus type integrated differential refractometer detector
• Tosoh Corporation GMH6-HT and GMH6-HTL are used as separation columns.
• Two tubes are connected in series, o-dichlorobenzene is used as the mobile phase medium, 0.025% by mass dibutylhydroxytoluene (manufactured by Takeda Pharmaceutical Co., Ltd.) is used as the antioxidant, and the mobile phase medium is 1.0 mL/
• the sample concentration was 15 mg/10 mL
• the sample injection volume was 500 ⁇ L
• a differential refractometer was used as the detector.
• standard polystyrene standard polystyrene manufactured by Tosoh Corporation with a weight average molecular weight (Mw) of 1,000 to 4,000,000 was used.
• the tensile strength at break and tensile elongation at break of the molded product were measured by a tensile test using the above dumbbell-shaped test piece.
• the tensile test was performed using a 5-hook tensile tester (manufactured by Intesco Co., Ltd., model number: 2005X-5) at 23° C. and a test speed of 50 mm/min according to ASTM D638.
• the flexural modulus was tested using a test piece with a thickness of 3.2 mm.
• the test was performed using a 5-bending tester (manufactured by Shimadzu Corporation, model number: AG-1kNX plus) at 23°C in accordance with ASTM D790, with a span distance of 51 mm and a test speed of 1.3 mm/min. Ta.
• the Izod impact test was performed on each of five test pieces, and the average value of the obtained impact values was obtained and evaluated. It can be said that the higher the impact value, the better the toughness (fracture resistance).
• the average value was calculated using the impact values of only the destroyed test pieces. made an evaluation.
• ⁇ Dynamic viscoelasticity> A test piece having dimensions of 35 mm in length and 10 mm in width was punched out from the 2.0 mm-thick square plate compact obtained by the above-described method.
• test pieces of the methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer composition (X) had a tan ⁇ peak temperature in the temperature range of 0 to 240°C and a temperature range of 0 to 100°C. A tan ⁇ peak value at was observed. Under the same measurement conditions, the test piece of 4-methyl-1-pentene polymer (B) was observed to have a tan ⁇ peak temperature and a tan ⁇ peak value in the temperature range of -40 to 150°C.
• the shrinkage rate is obtained by measuring the length (four sides) of the rectangular plate molded body having a thickness of 2.0 mm prepared above, obtaining the average value, and calculating the dimension according to the following formula. Calculated using change.
• Dimensional change rate (%) [(length of injection mold - length of rectangular plate molded body) / (length of injection mold)] ⁇ 100 It can be said that the smaller the value of the dimensional change rate, the better the shape retention performance under high temperature.
• the horizontal axis is the surface tension value of the tension test mixture
• the vertical axis is the measured value of the contact angle (cos ⁇ by converting the angle into radians).
• a strand of 4-methyl-1-pentene polymerization composition (X) was collected using a circular nozzle (5.0 mm ⁇ ). After winding an unvulcanized rubber (thickness: 0.5 mm) composition around the strand, both were heated at 160° C. for 60 minutes to be vulcanized to form a rubber hose. After cooling to 23° C., an air gun connected to compressed air is inserted into the end of the vulcanized hose, and the mandrel is pulled out from the vulcanized rubber hose by pushing out from the end of the vulcanized hose. reproduced.
• the autoclave was heated to an internal temperature of 60°C and pressurized with propylene so that the total pressure was 0.13 MPa (gauge pressure). Subsequently, 1 mmol of previously prepared methylaluminoxane in terms of Al, and diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) 0.34 mL of a toluene solution containing 0.01 mmol of zirconium dichloride was pressurized into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60°C.
• the autoclave was heated to an internal temperature of 60°C and pressurized with propylene so that the total pressure was 0.19 MPa (gauge pressure). Subsequently, 1 mmol of previously prepared methylaluminoxane in terms of Al, and diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) 0.34 mL of a toluene solution containing 0.01 mmol of zirconium dichloride was pressurized into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60°C.
• the powdery polymer containing the obtained solvent was dried at 100°C under reduced pressure for 12 hours.
• the amount of the obtained polymer (B-2) was 44.0 g
• the content of the structural unit (i) in the polymer was 84.1 mol%
• the content of the structural unit (ii) was 15.9 mol. %Met.
• Table 1 shows the physical properties of the obtained polymer (B-2).
• "type of ⁇ -olefin” means the type of ⁇ -olefin other than 4-methyl-1-pentene.
• the "structural unit (ii) derived from an ⁇ -olefin” is at least one selected from ethylene and an ⁇ -olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).
• "structural unit (iii) derived from an ⁇ -olefin” means a structural unit derived from at least one selected from ethylene and an ⁇ -olefin having 10 to 20 carbon atoms. ing.
• thermoplastic elastomer (C) The following was used as the thermoplastic elastomer (C).
• Example 2 4-methyl-1-pentene polymer (A-1) 70 parts by mass, 4-methyl-1-pentene polymer (B-1) 20 parts by mass, thermoplastic elastomer (C-1-1) Pellets and various test pieces were prepared using the same method as in Example 1 except that the resin composition containing 10 parts by mass was used, and the physical properties were evaluated as described above. Table 2 shows the results.
• Example 3 4-methyl-1-pentene polymer (A-1) 60 parts by mass, 4-methyl-1-pentene polymer (B-1) 20 parts by mass, thermoplastic elastomer (C-1-1) Pellets and various test pieces were prepared in the same manner as in Example 1 except that the resin composition containing 20 parts by mass was used, and the physical properties were evaluated as described above. Table 2 shows the results.
• Example 4 4-methyl-1-pentene polymer (A-1) 70 parts by mass, 4-methyl-1-pentene polymer (B-2) 10 parts by mass, thermoplastic elastomer (C-1-1) Pellets and various test pieces were prepared in the same manner as in Example 1 except that the resin composition containing 20 parts by mass was used, and the physical properties were evaluated as described above. Table 2 shows the results.
• Example 5 4-methyl-1-pentene polymer (A-1) 60 parts by mass, 4-methyl-1-pentene polymer (B-2) 20 parts by mass, thermoplastic elastomer (C-1-1) Pellets and test pieces were prepared in the same manner as in Example 1, except that the resin composition contained 20 parts by mass, and the physical properties were evaluated as described above.
• Table 2 shows the results.
• A-2 4-methyl-1-pentene polymer
• B-1 4-methyl-1-pentene polymer
• C-1-1 thermoplastic elastomer
• Example 7 4-methyl-1-pentene polymer (A-2) 60 parts by mass, 4-methyl-1-pentene polymer (B-2) 20 parts by mass, thermoplastic elastomer (C-1-1) Pellets and various test pieces were prepared in the same manner as in Example 1 except that the resin composition containing 20 parts by mass was used, and the physical properties were evaluated as described above. Table 2 shows the results.
• Example 8 4-methyl-1-pentene polymer (A-1) 60 parts by mass, 4-methyl-1-pentene polymer (B-1) 20 parts by mass, thermoplastic elastomer (C-1-2) Pellets and various test pieces were prepared in the same manner as in Example 1 except that the resin composition containing 20 parts by mass was used, and the physical properties were evaluated as described above. Table 2 shows the results.
• Example 9 4-methyl-1-pentene polymer (A-1) 80 parts by mass, 4-methyl-1-pentene polymer (B-1) 10 parts by mass, thermoplastic elastomer (C-2-1) Pellets and various test pieces were prepared in the same manner as in Example 1 except that the resin composition contained 10 parts by mass of the resin composition, and the physical properties were evaluated as described above. Table 2 shows the results.
• Comparative Example 1 Pellets and various test pieces were prepared in the same manner as in Example 1 except that the resin composition containing 100 parts by mass of the 4-methyl-1-pentene polymer (A-1) was prepared and described above. A physical property evaluation was performed. Table 2 shows the results.
• Example 2 Example except that a resin composition containing 80 parts by mass of 4-methyl-1-pentene polymer (A-1) and 20 parts by mass of 4-methyl-1-pentene polymer (B-1) Pellets and various test pieces were prepared using the same method as in 1, and the physical properties were evaluated as described above. Table 2 shows the results.
• Comparative Example 3 The same method as in Example 1 except that the resin composition contains 80 parts by mass of the 4-methyl-1-pentene polymer (A-1) and 20 parts by mass of the thermoplastic elastomer (C-1-1). was used to prepare pellets and various test pieces, and the physical properties were evaluated as described above. Table 2 shows the results.
• [Comparative Example 4] The same method as in Example 1 except that the resin composition contains 60 parts by mass of the 4-methyl-1-pentene polymer (A-1) and 40 parts by mass of the thermoplastic elastomer (C-1-2). was used to prepare pellets and various test pieces, and the physical properties were evaluated as described above. Table 2 shows the results.
• [Comparative Example 5] 4-Methyl-1-pentene polymer (A-1) 25 parts by mass and 4-methyl-1-pentene polymer (B-1) 75 parts by mass, except for using a resin composition Pellets and various test pieces were produced using the same method as in Example 1, and the physical properties were evaluated as described above. Table 2 shows the results.
• the molded article made of the 4-methyl-1-pentene copolymer composition (X) according to the present invention can maintain its shape at high temperatures, and the obtained molded article has excellent toughness at low temperatures. Also.
• the molded article made of the 4-methyl-1-pentene copolymer composition (X) according to the present invention has flexibility while maintaining the heat resistance of the 4-methyl-1-pentene polymer (A). And the toughness at low temperature is improved, for example, even when the mandrel is pulled out from the rubber hose manufactured on the mandrel at a high speed, sufficient releasability can be obtained without deformation.

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