Classifications

• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0014—Use of organic additives
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0066—Use of inorganic compounding ingredients
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
  • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
  • C08J9/102—Azo-compounds
  • C08J9/103—Azodicarbonamide
• • E—FIXED CONSTRUCTIONS
  • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
  • E01B—PERMANENT WAY; PERMANENT-WAY TOOLS; MACHINES FOR MAKING RAILWAYS OF ALL KINDS
  • E01B9/00—Fastening rails on sleepers, or the like
  • E01B9/68—Pads or the like, e.g. of wood, rubber, placed under the rail, tie-plate, or chair
• • E—FIXED CONSTRUCTIONS
  • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
  • E01B—PERMANENT WAY; PERMANENT-WAY TOOLS; MACHINES FOR MAKING RAILWAYS OF ALL KINDS
  • E01B9/00—Fastening rails on sleepers, or the like
  • E01B9/68—Pads or the like, e.g. of wood, rubber, placed under the rail, tie-plate, or chair
  • E01B9/681—Pads or the like, e.g. of wood, rubber, placed under the rail, tie-plate, or chair characterised by the material
• • 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
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/026—Crosslinking before of after foaming
• • 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
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/08—Copolymers of ethene
• • 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
  • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2314/00—Polymer mixtures characterised by way of preparation
  • C08L2314/06—Metallocene or single site catalysts

Definitions

• the present invention relates to a rail pad for a railroad rail and a cross-linked foam made of a cross-linked body or a cross-linked foam. More specifically, the present invention relates to a railroad track pad and a crosslinked foam obtained from a rubber composition exhibiting sufficiently high foaming properties, and more specifically, various elastic modulus, high tensile strength and elongation, small compression set, and the like. The present invention relates to a railroad track pad and a cross-linked foam made of a cross-linked body or cross-linked foam made of a low specific gravity rubber molded body, which requires physical properties (including weather resistance), but also has excellent workability.
• rail pads are used as anti-vibration materials to reduce vibration and noise generated when the vehicle is running.
• the rail pad includes a track pad inserted between the rail and the sleeper, a sleeper pad laid under the sleeper, and a vibration isolator for the track slab laid under the slab of the slab track.
• SBR-based non-foamed rubber has been used as a material for rail pads.
• use of a polyurethane foam elastomer has been proposed (Patent Document 1).
• SBR type non-foamed rubber or foamed polyurethane elastomer is used for the track pad, the weather resistance tends to be inferior.
• EPDM ethylene / propylene / diene copolymer rubber
• the main chain does not contain diene, so that the weather resistance is good, but the foaming property and physical property balance are insufficient.
• Patent Document 3 discloses a rubber molded article having a low specific gravity and excellent surface smoothness obtained by providing a rubber composition exhibiting flame retardancy and sufficient foamability, and crosslinking and foaming the rubber composition. Has been proposed.
• composition for a railroad track track pad various physical properties (including weather resistance) such as an appropriate elastic modulus, high tensile strength and elongation, and a small compression set are required. It is desirable.
• An object of the present invention is to provide a railroad rail track pad made of a cross-linked or cross-linked foam having such various physical properties and excellent workability, and a cross-linked foam suitable for the use of the rail pad for the rail. To provide a body.
• the present inventors have found that the use of a specific ethylene / ⁇ -olefin / non-conjugated diene random copolymer is very useful for railroad track track applications.
• the present invention has been found to be suitable, and the present invention has been completed.
• a railroad track track pad obtained by crosslinking a composition containing an ethylene / ⁇ -olefin / non-conjugated polyene random copolymer that satisfies the condition (6).
• the structural unit derived from the ⁇ -olefin [B] having 3 to 20 carbon atoms is 10 to 50 mol% in 100 mol% of all structural units
• the sum of mol% of structural units derived from non-conjugated polyene [C-1] and mol% of structural units derived from non-conjugated polyene [C-2] is 1.0 to 6.0 mol%.
• Ratio of mol% of structural units derived from non-conjugated polyene [C-1] to mol% of structural units derived from non-conjugated polyene [C-2] ([C-1] / [C-2 ]) Is 75/25 to 99.5 / 0.5
• Mooney viscosity [ML 1 + 4 (100 ° C.)] measured at 100 ° C. is 10 to 90
• the apparent iodine value (IV) of the structural unit derived from the non-conjugated polyene [C-2] is 0.1 to 3.0 g / 100 g
• the present invention is a crosslinked foam obtained by crosslinking and foaming a composition containing an ethylene / ⁇ -olefin / non-conjugated polyene random copolymer, (A) A crosslinked foam having a specific gravity of 0.75 or less and (b) an elastic modulus of 3.0 N / mm 2 or more.
• the present invention also provides a crosslinked foam obtained by crosslinking / foaming a composition containing an ethylene / ⁇ -olefin / non-conjugated polyene random copolymer, (A) Specific gravity is 0.75 or less, and (c) It has the 10th largest diameter from the bubble which has the largest diameter among the bubbles observed in the fixed area (2.2 cm ⁇ 2 >) of the cross section of a molded object. An average value of the diameter of the bubbles up to the bubbles is 80 ⁇ m or less.
• a railway comprising a crosslinked body or a crosslinked foamed body having various physical properties (including weather resistance) such as an appropriate elastic modulus, high tensile strength and elongation, and a small compression set, and excellent workability. It is possible to provide a rail track pad and a crosslinked foam suitable for the use of the rail pad for the rail.
• the copolymer used in the present invention comprises ethylene [A], an ⁇ -olefin [B] having 3 to 20 carbon atoms, and one partial structure represented by the general formula (I) or (II) in the molecule.
• ⁇ -olefin [B] having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene and the like. Of these, ⁇ -olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are particularly preferable. Such ⁇ -olefins are preferred because the raw material costs are relatively low and the resulting copolymer exhibits excellent mechanical properties.
• the copolymer used in the present invention contains at least one structural unit derived from an ⁇ -olefin [B] having 3 to 20 carbon atoms, and has two or more types of ⁇ having 3 to 20 carbon atoms.
• -It may contain a structural unit derived from olefin [B].
• Examples of the non-conjugated polyene [C-1] containing only one partial structure represented by the general formula (I) or (II) in the molecule include vinyl groups (CH 2 ⁇ CH—) at both molecular ends. Aliphatic polyenes are not included. Examples of the component [C-1] include the following aliphatic polyenes and alicyclic polyenes.
• aliphatic polyene examples include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradecadiene, 3- Methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octa
• Examples of the alicyclic polyene include an alicyclic portion having one carbon / carbon double bond (unsaturated bond) and a carbon atom constituting the alicyclic portion bonded by a carbon / carbon double bond. And polyenes composed of chain-like moieties (ethylidene, propylidene, etc.). Specific examples include 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornene, 5-butylidene- Examples thereof include 2-norbornene, and 5-ethylidene-2-norbornene (ENB) is preferably used. Specific examples of the other alicyclic polyenes include 2-methyl-2,5-norbornadiene and 2-ethyl-2,5-norbornadiene.
• the copolymer used in the present invention contains at least one constituent unit derived from component [C-1] and contains two or more constituent units derived from component [C-1]. Also good.
• 5-alkenyl-2-norbornene such as 5-vinyl-2-norbornene (VNB) and 5-allyl-2-norbornene
• VNB 5-vinyl-2-norbornene
• DCPD dicyclopentadiene
• norbornadiene norbornadiene
• alicyclic polyenes such as deca-3,8-diene
• ⁇ , ⁇ -dienes such as 1,7-octadiene, 1,9-decadiene, etc.
• Aliphatic polyenes are mentioned.
• VNB 5-vinyl-2-norbornene
• VNB 5-alkenyl-2-norbornene
• dicyclopentadiene 2,5-norbornadiene
• 1,7-octadiene 1,9-decadiene
• VNB 5-vinyl -2-Norbornene
• the copolymer used in the present invention contains at least one structural unit derived from component [C-2], and contains a structural unit derived from two or more components [C-2]. Also good.
• the structural unit derived from the ⁇ -olefin [B] having 3 to 20 carbon atoms is 10 to 50 mol%, preferably 25 to 45 mol in 100 mol% of all structural units. Mol%.
• the structural unit (mol%) derived from the component [B] is in the above range, it is preferable from the viewpoint of the flexibility of the crosslinked foam obtained from the rubber composition containing the copolymer and the mechanical properties at low temperature. is there.
• the molar ratio can be determined by 13 C-NMR.
• the copolymer used in the present invention has a total of 1.0 to 6 mol% of structural units derived from non-conjugated polyene [C-1] and mol% of structural units derived from non-conjugated polyene [C-2].
• the amount is 0.0 mol, and preferably 1.0 to 5.0 mol%. It is preferable that the total of the mol% is within the above range because the vulcanization reaction rate can be controlled relatively easily.
• the sum of the mol% can be determined by adding the molar amounts of ENB and VNB determined by, for example, 13 C-NMR.
• the copolymer used in the present invention has a ratio between the mol% of structural units derived from non-conjugated polyene [C-1] and the mol% of structural units derived from non-conjugated polyene [C-2] ([C-1 ] / [C-2]) is 75/25 to 99.5 / 0.5, preferably 78/22 to 97/3. It is preferable that the ratio with respect to mol% is within the above range since the balance between vulcanization reactivity and gas retention during foaming reaction is excellent. This ratio with mol% can be determined by 13 C-NMR.
• copolymers obtained from the copolymers used in the present invention ethylene, propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB), and A method for obtaining 1) to (3) will be specifically described.
• the mol% of the structural unit derived from ENB and VNB was calculated.
• the conversion to wt% was carried out with the molecular weight of ethylene being 28.05, the molecular weight of propylene being 42.08, and the molecular weight of ENB and VNB being 120.2.
• the copolymer used in the present invention has a Mooney viscosity [ML 1 + 4 (100 ° C.)] measured at 100 ° C. of 10 to 90.
• the Mooney viscosity is preferably 10 to 80.
• the rubber compound viscosity as a foaming medium can be set relatively easily, and a blending design with excellent kneadability is possible, which is preferable.
• the Mooney viscosity can be measured according to JIS K6300 using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation).
• the copolymer used in the present invention has an apparent iodine value (IV) of a structural unit derived from non-conjugated polyene [C-2] of 0.1 to 3.0 g / 100 g.
• the apparent iodine value of the component [C-2] is preferably 0.4 to 3.0 g / 100 g, more preferably 0.5 to 3.0 g / 100 g.
• the apparent iodine value of the non-conjugated polyene [C-2] is in the above range because of excellent foamability and kneading stability.
• the apparent iodine value of the component [C-2] can be determined by 1 H-NMR and 13 C-NMR.
• VNB 5-vinyl-2-norbornene
• the weight% of each structural unit contained in the copolymer rubber was determined by 13 C-NMR. Subsequently, the integrated value of the peak derived from ENB and the integrated value of the peak derived from the vinyl group of VNB were determined from the 1 H-NMR spectrometer as follows.
• the apparent iodine value derived from VNB (molecular weight 120.2) was calculated from the following formula using the obtained integral value ratio.
• the molecular weight of iodine is 253.81.
• VNB [integral value of peak derived from vinyl group of VNB] / [integral value of peak derived from ENB] ⁇ [wt% of ENB determined from 13C-NMR spectrometer] ⁇ 253 .81 / 120.2
• the copolymer used in the present invention satisfies the following formula (i), and preferably satisfies the following formula (i ′).
• the viscosity of a polymer melt decreases with increasing temperature, like the viscosity of a simple rheological liquid, and at a high temperature (Tg; glass transition temperature + 100 ° C.), the temperature dependence of the viscosity is expressed by the following formula ( It is known to follow the Arrhenius type equation represented by A).
• Viscosity ( ⁇ o) Aexp (Ea / RT) (A) R: gas constant, A: frequency factor, Ea: flow activation energy, T: absolute temperature
• the activation energy of the above flow does not depend on the molecular weight and molecular weight distribution, and is influenced only by the molecular structure, so that it is a useful index representing the structural information of the polymer.
• the viscosity of the composition is too low, the retention of foaming gas is poor, the specific gravity cannot be lowered, and the appearance is further deteriorated. On the other hand, if the viscosity of the composition is too high, foaming will not occur. Further, as one of the factors affecting the viscosity of the composition, there is a network formation by a crosslinking reaction of EPDM, and the control of the crosslinking reaction is also important.
• the copolymer used in the present invention is preferably synthesized by using a metallocene catalyst to uniformly introduce the diene component into the polymer, to control the crosslinking reaction, and as one of the diene components, 5
• a metallocene catalyst to uniformly introduce the diene component into the polymer, to control the crosslinking reaction, and as one of the diene components, 5
• the component [C-2] such as vinyl-2-norbornene (VNB)
• VNB vinyl-2-norbornene
• the cross-linked foam obtained by the composition containing the copolymer exhibits remarkably excellent surface smoothness.
• the flow activation energy (Ea) of the copolymer used in the present invention is the frequency (unit: Hz) of the melt complex viscosity (unit: Pa ⁇ sec) at 190 ° C. based on the temperature-time superposition principle. It is a numerical value calculated by the Arrhenius equation from the shift factor (aT) at the time of creating the master curve showing the dependency, and is obtained by the following method.
• melt complex viscosity-frequency curve (unit of melt complex viscosity; Pa / sec, unit of frequency; Hz) of the copolymer at temperatures of 170 ° C. and 210 ° C. (T, unit; ° C.) is expressed as temperature-time.
• T melting point
• calculation software examples include RSI Orchestrator VER.6.6.3 manufactured by TI Instruments Japan Co., Ltd.
• the melt complex viscosity-frequency curve was measured using a viscoelasticity measuring apparatus (for example, a viscoelasticity tester (model RDS-2) manufactured by Rheometric). Specifically, as a sample, a 2 mm thick sheet obtained by pressing the copolymer at 190 ° C. and formed into a disk shape having a diameter of 25 mm ⁇ 2 mm was used, and the measurement was performed under the following conditions. .
• a viscoelasticity measuring apparatus for example, a viscoelasticity tester (model RDS-2) manufactured by Rheometric.
• a viscoelasticity tester model RDS-2
• a viscoelasticity tester model RDS-2
• a viscoelasticity tester model RDS-2 meter
• the copolymer used in the present invention is a copolymer synthesized using a metallocene catalyst as described above.
• the following formula (I), (II) or (III) is used as the metallocene catalyst.
• the catalyst represented by is preferable.
• each R is independently a group or hydrogen atom selected from hydrocarbyl, halohydrocarbyl, silyl, germyl, and combinations thereof, and the number of atoms other than hydrogen contained in the group is 20 or less. It is.
• M is titanium, zirconium or hafnium.
• Y is —O—, —S—, —NR * — or —PR * —.
• R * is a hydrogen atom, hydrocarbyl group, hydrocarbyloxy group, silyl group, halogenated alkyl group or halogenated aryl group, and when R * is not hydrogen, R * represents up to 20 non-hydrogen atoms. contains.
• Z is a divalent group containing boron or a group 14 element and containing nitrogen, phosphorus, sulfur or oxygen, and the divalent group has 60 or less atoms other than hydrogen atoms. is there.
• X is an anionic ligand having 60 or less atoms independently when a plurality of X are present (except for a cyclic ligand in which ⁇ electrons are delocalized).
• X ′ is a neutral linking compound having 20 or less atoms independently when there are a plurality of X ′.
• P 0, 1 or 2.
• Q is 0 or 1.
• X is halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amide, di (hydrocarbyl) phosphide, hydrocarbyl sulfide, silyl group,
• An anionic ligand selected from a halo-substituted derivative, a di (hydrocarbyl) amino-substituted derivative, a hydrocarbyloxy-substituted derivative and a di (hydrocarbyl) phosphino-substituted derivative, wherein the number of atoms other than hydrogen atoms of X is 20 or less is there.
• M is in an oxidation state of +3
• X is allyl, 2- (N, N′-dimethylaminomethyl) phenyl and 2- (N, N′-dimethyl) aminobenzyl Or M is in an oxidation state of +4, and X is a divalent conjugated diene derivative to form metallacyclopentene with M.
• X ′ is a neutral conjugated or nonconjugated diene which may be substituted with one or more hydrocarbyl groups, and has 40 carbon atoms. It is contained in a number of 1 or less and forms a ⁇ complex with M.
• R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least one of R 1 and R 2 is not a hydrogen atom.
• R 3 to R 6 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 1 to R 6 may be bonded to each other to form a ring.
• M is titanium.
• Y is —O—, —S—, —NR * — or —PR * —.
• Each R * is independently a hydrogen atom, hydrocarbyl group, hydrocarbyloxy group, silyl group, halogenated alkyl group or halogenated aryl group, and when R * is not hydrogen, R * is up to 20 hydrogen atoms; Contains atoms other than.
• Z two binding of the * R * (when R * is not hydrogen) may also form a ring, R * binding to R * and Y bonded to Z * may form a ring.
• p is 0, 1 or 2.
• q is 0 or 1. However, when p is 2, q is 0, M is in a +4 oxidation state, and X is independently a methyl group or a benzyl group.
• R ′ is a hydrogen atom, a hydrocarbyl group, a di (hydrocarbylamino) group, or a hydrocarbyleneamino group, and when R ′ has a carbon atom, the number of carbon atoms is 20 or less.
• R ′′ represents a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom.
• M is titanium.
• Y is —O—, —S—, —NR * —, —PR * —, —NR 2 * , or —PR 2 * .
• Each of R * is independently a hydrogen atom or a group containing at least one selected from the group consisting of hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, and aryl halide, when there are a plurality of R * , R * includes atoms of atomic numbers 2 to 20, and two R * s (if R * is not a hydrogen atom) that Z * optionally may form a ring, and R * and Y of Z * R * in the above may form a ring.
• X is a monovalent anionic ligand having 60 or less atoms, excluding a cyclic ligand in which ⁇ electrons are delocalized.
• X ′ is a neutral linking group having 20 or less atoms.
• X ′′ is a divalent anionic ligand having 60 or less atoms.
• p is 0, 1 or 2;
• q is 0 or 1.
• r is 0 or 1;
• q and r are 0 and M is an oxidation state of +4 (except when Y is -NR * 2 or -PR * 2 ), or M is an oxidation state of +3 (provided that , Y is —NR * 2 or —PR * 2 , and X is a halide group, hydrocarbyl group, hydrocarbyloxy group, di (hydrocarbyl) amide group, di (hydrocarbyl) phosphide group, hydrocarbyl sulfide group, and silyl Groups, as well as groups in which these groups are halogen substituted, groups in which these groups are di (hydrocarbyl) amino substituted, groups in which these groups are hydrocarbyloxy substituted and groups in which these groups are di (hydrocarbyl) phosphino substituted
• An anionic ligand selected from the group consisting of the above groups, wherein the group comprises atoms having atomic numbers from 2 to 30.
• M is an oxidation state of +4
• X ′′ is a dianion selected from the group consisting of a hydrocarbazyl group, an oxyhydrocarbyl group, and a hydrocarbylene dioxy group X ′′ has an atomic number of 2 to 30.
• M is the oxidation state of +3
• X is allyl, 2- (N, N-dimethylamino) phenyl, 2- (N, N-dimethylaminomethyl) )
• An anionic stabilizing ligand selected from the group consisting of phenyl and 2- (N, N-dimethylamino) benzyl.
• X ′ is a neutral conjugated diene or neutral diconjugated, optionally substituted with one or more hydrocarbyl groups It is a diene, and the X ′ has a carbon atom number of 40 or less and forms a bond with M by ⁇ - ⁇ interaction.
• R ′ is a hydrogen atom, a hydrocarbyl group having 1 to 20 carbon atoms
• R ′′ is a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom
• M is titanium
• Y is —NR * —
• Z * is —SiR * 2 —
• each R * is independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms
• X ′ is 1,4-diphenyl-1,3-butadiene or When it is 1,3-pentadiene, p is 1 and q is 0, M is in the +3 oxidation state and X is 2- (N, N-dimethylamino) benzyl.
• Examples of the hydrocarbyl group having 1 to 20 carbon atoms include linear alkyl groups such as a methyl group, an ethyl group, and a butyl group, and branched alkyl groups such as a t-butyl group and a neopentyl group, and examples of the hydrocarbyloxy group include a methyl group.
• Examples include linear alkyloxy groups such as oxy group, ethyloxy group, and butyloxy group, and branched alkyloxy groups such as t-butyloxy group and neopentyloxy group.
• chlorinated, brominated or fluorinated groups or branched alkyl groups are examples of the hydrocarbyloxy group having 1 to 20 carbon atoms.
• halogenated aryl group examples include a chlorinated phenyl group and a chlorinated naphthyl group.
• R ′′ is preferably a hydrogen atom or methyl, more preferably methyl.
• catalysts are (t-butylamido) dimethyl ( ⁇ 5 -2-methyl-s-indasen-1-yl) silane titanium (II) 2,4-hexadiene (IV), (t-butylamido) -dimethyl ( ⁇ 5-methyl -s- indacene-1-yl) silane - titanium (IV) dimethyl (V), (t-butylamido) - dimethyl (eta 5-2,3-dimethyl indenyl) silane titanium (II) 1 , 4-Diphenyl-1,3-butadiene (VI), (t-butyl-amido) -dimethyl ( ⁇ 5 -2,3-dimethyl-s-indasen-1-yl) silane titanium (IV) dimethyl (VII) (T-Butylamido) -dimethyl ( ⁇ 5 -2-methyl-s-indacene-1-yl) silane titanium (II) 1,3-pentadiene (
• the polymerization reaction for obtaining the copolymer used in the present invention is carried out by using a non-conjugated polyene (component [C-1] and component [C-2]. )
• a non-conjugated polyene component [C-1] and component [C-2].
• the copolymer has a narrow molecular weight distribution and composition distribution, and a copolymer having a very uniform molecular structure can be prepared, The formation of gelled spots is significantly suppressed.
• a rubber molded product comprising such a copolymer is excellent in surface appearance because it does not contain gel-like particles, and also has excellent production stability because of excellent shape retention.
• catalysts can be prepared using well-known synthetic techniques. For example, it is disclosed in International Publication WO98 / 49212.
• a metallocene catalyst preferably a catalyst having the structure exemplified above is used. More specifically, the above catalyst is used as a main catalyst, an organoaluminum compound such as a boron compound and / or a trialkyl compound is used as a cocatalyst, an aliphatic hydrocarbon such as hexane is used as a solvent, and a continuous process using a reactor with a stirrer or A batch method is mentioned.
• boron compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, di (hydrogenated tallow alkyl) methylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (penta Fluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylam
• the organoaluminum compound examples include triisobutylaluminum (hereinafter also referred to as “TIBA”).
• the reaction temperature can be raised to 100 ° C. because the catalyst is not deactivated even at high temperatures.
• the polymerization pressure is in the range of more than 0 to ⁇ 8 MPa (gauge pressure), preferably more than 0 to ⁇ 5 MPa (gauge pressure).
• the reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 10 minutes to 3 hours. Further, in the copolymerization, a molecular weight regulator such as hydrogen can be used.
• the molar (feed) ratio ([A] / [B]) of ethylene [A] and the ⁇ -olefin [B] is 25/75 to 80/20, preferably 30/70 to 70/30.
• the molar (charge) ratio ([C-1] / [C-2]) of the nonconjugated polyene [C-1] and the nonconjugated polyene [C-2] was 60/40 to 99.5 / 0. .5, preferably 65/35 to 99/1.
• the molar (feed) ratio ([A] / [C-1]) of ethylene [A] and the non-conjugated polyene [C-1] is 70/30 to 99/1, preferably 80/20 to 98/2. It is.
• the molar (feed) ratio ([A] / [C-2]) of ethylene [A] to the non-conjugated polyene [C-2] is 70/30 to 99.9 / 0.1, preferably 80/20. ⁇ 99.5 / 0.5.
• Polymerization using the above catalyst is preferable because non-conjugated polyene having a double bond is copolymerized at a high conversion rate, and an appropriate amount of long chain branching can be introduced into the resulting copolymer.
• the copolymer used in the present invention thus obtained has 10 to 50 mol% of structural units derived from ⁇ -olefin [B] having 3 to 20 carbon atoms out of 100 mol% of all structural units.
• the preferred range is 25 to 45 mol%.
• the carbon-carbon double bond that can be polymerized by a metallocene catalyst is a mole% of structural units derived from non-conjugated polyene [C-1] in which only one carbon-carbon double bond exists in one molecule,
• the ratio of the carbon / carbon double bond polymerizable by the metallocene catalyst to the mol% of the structural unit derived from the non-conjugated polyene [C-2] existing in one molecule is 75/25 to 99.5 / 0.5, preferably 78/22 to 97/3.
• Polymerization using the above catalyst is preferable because non-conjugated polyene having a double bond is copolymerized at a high conversion rate, and an appropriate amount of long chain branching can be introduced into the resulting copolymer.
• the rubber composition used in the present invention only needs to contain the copolymer [I], and other components are not particularly limited.
• a reinforcing agent such as carbon black
• a softening agent such as oil
• a vulcanizing agent such as a vulcanizing agent
• a vulcanization aid such as a foaming agent and a foaming aid.
• the content of the copolymer (I) in the whole rubber composition is preferably 20% by weight or more.
• Carbon black is used for 100 parts by weight of ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [I] in order to obtain a rubber composition capable of providing an extruded vulcanized rubber molded body having sufficient mechanical strength.
• 30 to 300 parts by weight preferably 50 to 200 parts by weight, more preferably 61 to 200 parts by weight, and most preferably 70 to 200 parts by weight.
• Carbon black is used for 100 parts by weight of ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [I] in order to obtain a rubber composition capable of providing a vulcanized rubber molded product having sufficient mechanical strength.
• Carbon black As carbon black, SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT and the like can be used. Moreover, as a commercial item, FEF carbon black (Asahi # 60G Asahi Carbon Black Co., Ltd.) is preferable. Carbon black preferably has a nitrogen adsorption specific surface area of 10 to 100 m 2 / g from the viewpoint of obtaining a rubber composition capable of providing a vulcanized rubber molded article having good mechanical strength and product skin.
• the rubber composition used in the present invention is a rubber reinforcing agent other than carbon black (B), an inorganic filler, a softening agent, an anti-aging agent, a processing aid, a foaming agent, depending on the intended use of the vulcanizate.
• Conventionally known additives such as foaming aids, vulcanization accelerators, organic peroxides, vulcanization aids, colorants, dispersants, flame retardants and the like can be blended within a range that does not impair the purpose of the present invention. .
• the rubber reinforcing agent has an effect of enhancing mechanical properties such as tensile strength, tear strength, and wear resistance of the crosslinked (vulcanized) rubber.
• Specific examples of such a rubber reinforcing agent include finely divided silicic acid and silica. These may be subjected to a silane coupling treatment in advance.
• silica examples include fumed silica and precipitated silica. These silicas may be surface-treated with a reactive silane such as mercaptosilane, aminosilane, hexamethyldisilazane, chlorosilane, or alkoxysilane, or a low molecular weight siloxane.
• a reactive silane such as mercaptosilane, aminosilane, hexamethyldisilazane, chlorosilane, or alkoxysilane, or a low molecular weight siloxane.
• the type and blending amount of these rubber reinforcing agents can be appropriately selected depending on the application, but the blending amount of the rubber reinforcing agent (excluding carbon black) is usually ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [ I] Up to 150 parts by weight, preferably 100 parts by weight at maximum with respect to 100 parts by weight.
• Inorganic filler Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, and clay.
• the type and blending amount of these inorganic fillers can be appropriately selected depending on the application, but the blending amount of the inorganic filler is usually 100 parts by weight of ethylene / ⁇ -olefin / nonconjugated polyene copolymer rubber [I]. On the other hand, the maximum is 300 parts by weight, preferably 200 parts by weight.
• Softener As the softener, a softener usually used for rubber can be used. Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil Fatty oil softeners such as soybean oil and palm oil; tall oil; sub (factis); waxes such as beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, lauric acid Fatty acids and fatty acid salts such as zinc acid; naphthenic acid; pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, atactic polypropylene, coumarone indene resin; dioctyl phthalate, dioctyl adipate
• Anti-aging agent examples include amine-based, hindered phenol-based or sulfur-based anti-aging agents, and these anti-aging agents are used within the range not impairing the object of the present invention as described above.
• examples of amine-based antioxidants include diphenylamines and phenylenediamines.
• sulfur-based anti-aging agent a sulfur-based anti-aging agent usually used for rubber is used.
• processing aid a processing aid used for ordinary rubber processing can be used. Specifically, higher fatty acids such as linoleic acid, ricinoleic acid, stearic acid, palmitic acid, lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate, calcium stearate; esters of the higher fatty acids, etc. It is done.
• Such a processing aid is usually used in a proportion of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [I]. It is desirable to determine the optimum amount as appropriate according to the required physical property value.
• foaming agents include inorganic foaming agents such as sodium bicarbonate (sodium bicarbonate), sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitrosoterephthalate Nitroso compounds such as amide, N, N′-dinitrosopentamethylenetetramine (DPT); azodicarbonamide (ADCA), azobisisobutyronitrile (AZBN), azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxy Azo compounds such as benzene sulfonyl hydrazide (BSH), toluenesulfonyl hydrazide (TSH), p, p'-oxybis (benzenesulfonyl hydrazide) (OBSH), sulfonyl hydrazides such as di
• blowing agents are usually used in a proportion of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [I]. .
• foaming aid Moreover, you may use a foaming adjuvant together with a foaming agent as needed.
• the foaming auxiliary agent acts to lower the decomposition temperature of the foaming agent, accelerate the decomposition, and make the bubbles uniform.
• foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, urea, and derivatives thereof. These foaming aids are usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [I]. However, it is desirable to appropriately determine the optimum amount according to the required physical property value.
• Rubbers known in the art can be blended and used in the crosslinkable rubber composition used in the present invention as long as the object of the present invention is not impaired.
• examples of such other rubbers include isoprene-based rubbers such as natural rubber (NR) and isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber. Mention may be made of conjugated diene rubbers such as (CR).
• vulcanizing agent crosslinking agent
• examples of the vulcanizing agent used for vulcanization include sulfur and sulfur compounds.
• sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.
• Specific examples of sulfur compounds include sulfur chloride, sulfur dichloride, polymer polysulfides, and sulfur compounds that release and vulcanize active sulfur at the vulcanization temperature, such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram. Disulfide, dipentamethylene thiuram tetrasulfide, selenium dimethyldithiocarbamate and the like can be mentioned. Of these, sulfur is preferred. Sulfur or a sulfur compound is usually used in a proportion of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the copolymer rubber [I].
• vulcanization accelerator when using sulfur or a sulfur compound as a vulcanizing agent, it is preferable to use a vulcanization accelerator together.
• the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-oxydiethylene-2-benzothiazole sulfenamide (OBS), and Nt-butyl-2.
• Sulfenamide compounds such as benzothiazole sulfenamide (BBS) and N, N-diisopropyl-2-benzothiazole sulfenamide; 2-mercaptobenzothiazole (MBT), 2- (2,4-dinitrophenyl) Thiazole compounds such as mercaptobenzothiazole, 2- (4-morpholinodithio) benzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl disulfide; diphenylguanidine (DPG), triphenyl Guanidine, diorthotril guanidine (D TG), guanidine compounds such as orthotolyl biguanide, diphenylguanidine phthalate; acetaldehyde-aniline condensate, butyraldehyde-aniline condensate, aldehyde amine or aldehyde such as hexamethylenet
• Vulcanization aids can be appropriately selected depending on the application, and can be used alone or in combination of two or more.
• Specific examples of the vulcanization aid include magnesium oxide and zinc white (for example, zinc oxide such as “META-Z102” (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).
• the blending amount is usually 1 to 20 parts by weight with respect to 100 parts by weight of the copolymer.
• vulcanization aid examples include quinone dioximes such as p-quinonedioxime; acrylics such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyls such as diallyl phthalate and triallyl isocyanurate; other maleimides; Examples include divinylbenzene.
• the rubber composition used in the present invention is obtained by using an internal mixer (closed mixer) such as a Banbury mixer, a kneader, or an intermix, and the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [I], carbon black.
• an internal mixer closed mixer
• a kneader such as a Banbury mixer, a kneader, or an intermix
• the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [I] carbon black.
• kneading additives such as rubber reinforcing agents, inorganic fillers, softeners, etc. at a temperature of 80 to 170 ° C. for 2 to 20 minutes
• a roll such as an open roll or a kneader to make sulfur necessary.
• a vulcanization accelerator, a vulcanization aid, a foaming agent, and a foaming aid can be additionally mixed, kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensed.
• the crosslinked rubber used in the present invention is obtained by crosslinking the rubber composition.
• Examples of the method for crosslinking the rubber composition include the following two methods.
• a rubber composition blended with the vulcanizing agent usually an extrusion molding machine, a calender roll, a press, an injection molding machine, a transfer molding machine, hot air, a glass bead fluidized bed, UHF (ultra-high frequency electromagnetic wave), steam, LCM (hot molten salt bath), etc. are heated into a desired shape, such as a heating bath, and the molded product is introduced into the vulcanizing tank at the same time as the pre-molding.
• the second method is (ii) a method in which the rubber composition is preformed by the molding method and irradiated with an electron beam.
• the vulcanizing agent is used, and the vulcanization accelerator and / or the vulcanization aid can be used together as necessary.
• the heating temperature is generally 100 to 300 ° C., preferably 120 to 270 ° C., more preferably 120 to 250 ° C., 0.5 to 30 minutes, preferably 0.5 to 20 minutes. More preferably, heating is performed for 0.5 to 15 minutes.
• a mold When molding and vulcanizing the rubber composition, a mold may be used or a mold may not be used. When a mold is not used, the rubber composition is usually molded and vulcanized continuously.
• the crosslinked foam used in the present invention is a crosslinked foam (hereinafter referred to as “crosslinked foam (1)”) obtained by crosslinking and foaming the rubber composition.
• a rubber composition containing a foaming agent is usually used for crosslinking and foaming.
• cross-linked foam molding there is a method in which a rubber composition is filled in a mold having a predetermined shape and cross-linked and foamed by a hot press to obtain a track pad.
• the orbit pad there are those listed in JIS E 1117, but of course, it is not limited to this.
• crosslinked foams (2) and (3) of the present invention are crosslinked foams having the following specific physical properties.
• the crosslinked foam (2) of the present invention is a crosslinked foam obtained by crosslinking and foaming a composition containing an ethylene / ⁇ -olefin / non-conjugated polyene random copolymer, (A) The specific gravity is 0.75 or less, and (b) the elastic modulus is 3.0 N / mm 2 or more.
• the crosslinked foam (3) of the present invention is a crosslinked foam obtained by crosslinking and foaming a composition containing an ethylene / ⁇ -olefin / non-conjugated polyene random copolymer, (A) Specific gravity is 0.75 or less, and (c) It has the 10th largest diameter from the bubble which has the largest diameter among the bubbles observed in the fixed area (2.2 cm ⁇ 2 >) of the cross section of a molded object. The average value of the diameter of the bubbles up to the bubbles is 80 ⁇ m or less.
• crosslinked foams (2) and (3) of the present invention are not necessarily limited to the crosslinked foams obtained using the rubber composition described above. As long as it is a crosslinked foam satisfying the above conditions (a) and (b) or the conditions (a) and (c), it may be a crosslinked foam obtained using a composition other than the rubber composition described above. good. However, the crosslinked foams (2) and (3) are preferably obtained using the rubber composition described above.
• the specific gravity is 0.75 or less, preferably 0.70 or less, more preferably 0.03 to 0.7, and particularly preferably 0.1 to 0.7.
• This specific gravity is a value measured according to JIS Z 8807.
• the modulus of elasticity is at 3.0 N / mm 2 or more, preferably 3.0 ⁇ 5.0N / mm 2.
• This elastic modulus is a value measured according to JIS E 1117.
• the average value of the bubble diameter under the above condition (c) is 80 ⁇ m or less, preferably 50 to 80 ⁇ m.
• the specific gravity is preferably 0.03 to 0.9, more preferably 0.1 to 0.8, particularly preferably 0.1 to 0.75, and most preferably 0.
• the elastic modulus is preferably 3.0 N / mm 2 or more, more preferably 3.0 to 5.0 N / mm 2 , and the bubble diameter of the above condition (c) is preferably 0.1 to 0.7 N
• the average value is preferably 80 ⁇ m or less, more preferably 50 to 80 ⁇ m.
• the railroad track pad of the present invention is a molded product obtained by crosslinking the rubber composition described above, or a molded product obtained by crosslinking and foaming the rubber composition described above. Further, not only the above-described crosslinked foam (1) but also the crosslinked foams (2) and (3) having the specific physical properties described above can provide excellent railroad track pads.
• “Railway rail track pad” means, for example, 1) a track pad as a railroad part, 2) a rubber sheet used as a track pad, and 3) a cross-linked rubber used as a track pad. 4) A molded body such as a rubber cross-linked foam as a track pad.
• Examples 1 and 2 A composition having the composition shown in Table 1 was prepared using the following copolymers 1 and 2, and a mold of 125 mm ⁇ 140 mm ⁇ 10 mmt was used, and the composition of Table 1 was placed in the mold at a volume filling rate of 100%. Fill and perform primary cross-linking foaming under conditions of 130 ° C. ⁇ 15 minutes, then use a 200 mm ⁇ 200 mm ⁇ 1 mmt mold to fill the cross-linked foam obtained by primary cross-linking foaming, 170 ° C. ⁇ 10 min.
• the foamed cross-linked rubber for railroad track pads was produced by secondary cross-linking foaming under the above conditions, and various physical properties were evaluated.
• composition having the composition shown in Table 1 was prepared using the following copolymer 3, and foamed crosslinked rubber for a railroad track pad was produced in the same manner as in Examples 1 and 2, and various physical properties were evaluated. .
• the numerical values of the composition in Table 1 are parts by mass.
• Activated Zinc Hana META-ZL40 Lime Industry Co., Ltd. FEF Carbon Black Asahi # 60G Asahi Carbon Black Co., Ltd.
• the elastic modulus is 3 to 5 N / mm 2
• the tensile strength is 12 N / mm 2 or more
• the elongation is 250% or more
• the compression set 70 ° C., 48 h
• the standard was satisfied, the tensile strength and elongation were superior to those of Comparative Example 1, and the tensile strength, elongation and compression set were superior to Comparative Example 2.
• Examples 1 and 2 are excellent in workability, they are very suitable for railroad track pad applications. Further, in Examples 1 and 2, the average value of the bubble diameter was smaller than that in Comparative Example 2.
• the elastic modulus tends to decrease when an ethylene / ⁇ -olefin / non-conjugated polyene random copolymer having many long chain branches is used.
• the foaming property (foaming ratio, foam uniformity, etc.) is improved due to the presence of the long chain branching, so that various characteristics including the elastic modulus are improved.
• the cross-linked foam of the present invention has a large expansion ratio, and has various physical properties (including weather resistance) such as an appropriate elastic modulus, high tensile strength and elongation, and small compression set, and is excellent in workability. Therefore, it is very suitable for the track pad use for railroad rails.

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