Entitled composition for track pads for railway rails and track pads for railway rails
Technical field
[0001] The present invention relates to a railway rail track for pad obtained by crosslinking a composition for the track for a railway rail pad and the composition.
Background technique
[0002] The railway track (rail), as proof material to reduce vibration and noise generated during vehicle running, the railway pad is used. This rail pad, track pad to be inserted between the rails and sleepers, sleepers pad laid under railroad ties, such as the track slab proof material which is laid under the slab slab track is included that.
[0003] Conventionally, as a material used for railway pad, SBR-based non-foamed rubber was used. Also, moderate modulus, high tensile strength and elongation, in addition to the physical properties such as small compression set, with further processability specific ethylene-alpha-olefin-non-conjugated diene random copolymer is also excellent in crosslinking track pad made of foam has been proposed (Patent Document 1).
[0004] Conventionally, track pads for railway rails, rubber composition (flat rubber material) was filled in a mold, to manufacture were common to pressure forming and heating (Patent Documents 2 and 3).
CITATION
Patent Document
[0005] Patent Document 1: International Publication No. 2013/137231 on behalf of SUPER nn fu TorayッSuites
Patent Document 2: Laid-Open Patent Publication No. 2006-265841
Patent Document 3: Laid-Open Patent Publication No. 2013-002256

Summary of the Invention
Problems that the Invention is to Solve
[0006] It is clear to increase productivity if formed by injection molding a track pad. If the track pad ethylene-propylene-diene copolymer rubber (EPDM) systems, the rubber composition of uncrosslinked and high flowability suitable for injection molding, those of lower molecular weight in the EPDM low viscosity or replacement, it is necessary or reduce the amount of filler. However, these means there is a problem that lowers the rubber elasticity.
[0007] In the present invention, the viscosity of the rubber composition is a forming material, is lowered to suppress the deterioration of the rubber elasticity of the resulting crosslinked molded product, to provide a high flow of the rubber composition suitable for injection molding for the purpose.
Means for Solving the Problems
[0008] The present inventors, the additive in the rubber composition by a particular combination, while realizing a low viscosity, a decrease in rubber elasticity of the crosslinked molded article was found to be suppressed.
[0009] That is, according to one embodiment of the present invention,
contain the following ethylene-alpha-olefin-nonconjugated polyene random copolymer polymer (A), and clay (B), a sulfur atom-containing silane coupling agent and (C) track pad composition for railway rails is provided, characterized in that.
Ethylene-alpha-olefin-nonconjugated polyene random copolymer (A):
Ethylene [a], carbon atoms 3 ~ 20 alpha-olefin [b], represented by the following structural formula (I) or (II) nonconjugated polyene containing only one partial structure in the molecule [c-1],
[0010] [Formula 1]

(wherein, (I) is a partial structure of the cyclic olefin.)
[0011] [Formula 2]

[0012] And includes a structural unit derived from the structural formulas (I) and non-conjugated polyene containing two or more partial structures selected from the group consisting of (II) in the molecule a total [c-2], the following (1) to satisfying copolymer (6).
(1) structural units derived from α- olefin carbon atoms 3 ~ 20 [b] is the total structural units in 100 mole%, 10 to 50
mol%, (2) non-conjugated polyene [c-1] mol% and a non-conjugated polyene of the structural unit derived from the sum of the mole% of structural units derived from [c-2] a is 1.0-6.0
mol%, (3) non-conjugated polyene [c-1 ] the ratio of the mole% of structural units derived from mole percent and non-conjugated polyene [c-2] of the structural units derived from ([c-1] / [ c-2]) is 75/25 to 99.5 is
/0.5, (4) Mooney viscosity measured at 100 ° C. [ML 1 + 4 (100 ° C.)] is 10 to
90, structural units derived from (5) non-conjugated polyene [c-2] apparent iodine value is 0.1 ~ 3.0g /
100g, satisfy (6) the following formula (i).
50> activation energy of flow (Ea) [kJ / mol]> 35 · · · (i)
[0013] According to another aspect of the present invention, track pad for railway rails obtained by crosslinking the composition.
Effect of the Invention
[0014] The rubber composition according to the present invention as a low viscosity shows good injection moldability, the obtained crosslinked molded article exhibiting good rubber elasticity required of the track pad railroad rails.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a view showing the measurement mold for flow length in the embodiment.

DESCRIPTION OF THE INVENTION
[0016] It will be specifically described below for a railway rail track pad composition according to the present invention.
[0017] Ethylene-alpha-olefin-nonconjugated polyene random copolymer (A)]
used in the present invention the ethylene-alpha-olefin-nonconjugated polyene random copolymer (A) (hereinafter, referred to as the copolymer (A)) is , ethylene [a], carbon atoms 3 ~ 20 alpha-olefin [b], the non-conjugated polyene containing only one partial structure in the molecule represented by the structural formula (I) or (II) [c- 1], and includes the structural formula (I) and (II) structural units derived from nonconjugated polyene [c-2] comprising comprising two or more partial structures selected from the group in the molecule a total of the ( 1) is satisfying the ethylene-alpha-olefin-nonconjugated polyene random copolymer to (6). In this specification, the (1) to (6), respectively, also referred to as requirements (1) to (6).
[0018] Ingredient [b]]
The α- olefin carbon atoms 3 ~ 20 [b], specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 - heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, and the like. Of these, propylene, 1-butene, 1-hexene, carbon atoms, such as 1-octene are α- olefins 3-8 preferred. Such α- olefins, raw material costs are relatively inexpensive, and the resulting copolymer are preferred because they exhibit excellent mechanical properties.
[0019] Incidentally, the copolymer used in the present invention includes a structural unit derived from at least one of the carbon atoms 3 ~ 20 alpha-olefin [b], having 2 or more carbon atoms 3 ~ 20 alpha - may contain a constituent unit derived from an olefin [b].
[0020] Ingredient [c-1]]
Examples structural formula (I) or a non-conjugated polyene containing only one partial structure in the molecule represented by (II) [c-1], for example vinyl group at the molecular both ends (CH 2 = CH-) aliphatic polyene does not include having. As component [c-1], aliphatic polyenes, such as described below, such as alicyclic polyenes and the like.
[0021] Specific examples of the aliphatic polyenes 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-octadiene, 5-methyl-1 5- octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1, 6- octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-methyl-1, 4- nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1, 5- nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1, 6 Nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4 decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5 decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7 decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8 decadiene, 8-ethyl -1 , 8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene and the like. In the present invention, it can be used in combination of these aliphatic polyenes one or more. Preferably such 7-methyl-1,6-octadiene is used.
[0022] As the alicyclic polyenes, e.g., binding and alicyclic moiety, by a carbon-carbon double bond to the carbon atoms constituting the alicyclic moiety having one carbon-carbon double bond (unsaturated bond) to have chain moiety (ethylidene, propylidene and the like) include polyenes composed from the, as a specific example, 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornene, 5-butylidene - and 2-norbornene and the like, 5-ethylidene-2-norbornene (ENB) is preferably used. Other alicyclic polyene, specifically, for example, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene and the like.
[0023] Incidentally, the copolymer used in the present invention, comprise at least one component [c-1] includes a constitutional unit derived from a structural unit derived from two or more components [c-1] it may be.
[0024] Ingredient [c-2]]
Examples of the structural formulas (I) and non-conjugated polyene containing two or more partial structures selected from the group consisting of (II) in the molecule a total [c-2], for example, carbon - and alicyclic moiety having a carbon-carbon double bond (unsaturated bond), alicyclic polyenes having a chain moiety containing a chain moiety attached to a carbon atom constituting the alicyclic moiety vinyl group, molecular at both ends include aliphatic polyenes having a vinyl group. Specific examples include 5-vinyl-2-norbornene (VNB), 5-allyl-2-norbornene and the like of 5-alkenyl-2-norbornene; 2,5-norbornadiene, dicyclopentadiene (DCPD), norbornadiene, tetracyclo [ 4,4,0,1 2.5 , 1 7.10 ] alicyclic polyenes deca-3,8-diene and the like; 1,7-octadiene, 1,9-such decadiene alpha, the ω- diene such as It includes aliphatic polyenes.
[0025] Among these, 5-vinyl-2-norbornene (VNB), 5-alkenyl-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, 1,7-octadiene, 1,9-decadiene are preferable, 5-vinyl 2-norbornene (VNB) is particularly preferred.
[0026] Incidentally, the copolymer used in the present invention, comprise at least one component [c-2] contains the structural unit derived from a structural unit derived from two or more components [c-2] it may be.
[0027] [Requirement (1)]
used in the present invention the copolymer, the structural units derived from α- olefin [b] of 3 to 20 carbon atoms, the total structural units in 100 mole%, 10 to 50 mol% , preferably 25 to 45 mol%. When structural units derived from α- olefin [b] (mol%) is in the range obtained from a rubber composition containing the copolymer, from the viewpoint of the mechanical properties of flexibility and low temperature crosslinked foam it is preferred. The ratio is from 13 can be determined by C-NMR.
[0028] [Requirement (2)]
used in the present invention the copolymer (A), the structural units derived from mol% and a non-conjugated polyene of the structural units derived from the nonconjugated polyene [c-1] [c- 2] mol % of the total is 1.0-6.0 mol%, preferably 1.0 to 5.0 mol%. If the total of the mol% is within the range it is preferable because it is possible to control the vulcanization reaction rate relatively easily. The total of the mol%, for example 13 ENB which is obtained by C-NMR, can be determined by summing the molar amount of VNB.
[0029] [Requirement (3)]
copolymer used in the present invention, the non-conjugated polyene [c-1] of the mole% of the molar% and the non-conjugated polyene structural units derived from [c-2] of the structural units derived from the ratio ([c-1] / [ c-2]) is 75/25 to 99.5 / 0.5, preferably 78 / 22-97 / 3. When the mol% ratio is within the above range is preferable since an excellent balance of gas retention during foaming reaction and the vulcanization reactivity. Mol% of the structural unit 13 can be determined by C-NMR.
[0030] The following ethylene copolymers (A) used in the present invention, propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) copolymer obtained from the (A1) taken as an example, specifically showing a method for obtaining the requirement (1) to (3).
[0031] Incidentally, ethylene, propylene and ENB copolymer 13 structure by C-NMR CE Wilkes, Macromolecules, 10, p536-544 (1977), Masahiro Kakugo, Yukio Naito , Kooji Mizunuma, and Tatsuya Miyatake, Macromolecules, 15, p1150-1152 (1982), and G. Van der Velden, Macromolecules, 16 , on the basis of the p85-89 (1983), the structural analysis of the VNB-based copolymer, Harri Lasarov, Tuula T. Pakkanen, Macromol. Rapid Commun., 20, p356-360 (1999), and Harri Lasarov *, Tuula T. Pakkanen, Macromol. Rapid Commun., 22, made on the basis of p434-438 (2001) It was.
[0032] First, 13 by C-NMR, of ethylene, propylene, the integral value of each peak derived from ENB and VNB were determined.
1) ethylene; [integrated value of the ethylene chain derived peak + {ethylene - integrated value of propylene chain derived peak} / 2] 2)
propylene; Propylene chain derived peak integrated value + {ethylene - propylene chain derived peak integrated value }
/ 2] 3) ENB; ENB-3 position the integral value of the peak
4) VNB; VNB-7 position peak of the integrated value
[0033] Structure (E body, Z bodies) derived from ENB in ​​the copolymer (A1) Chemical formula and shows structure derived from VNB Chemical formulas of (endo (n), exo (x)) as follows.
[0034] [Formula 3]

[0035] [Chemical Formula 4]

[0036] From each of the integral values ​​obtained were calculated mol% of structural units derived from ENB and VNB. The conversion to% by weight of the molecular weight of ethylene 28.05, the molecular weight of the propylene 42.08 was performed with 120.2 molecular weight of ENB and VNB.
[0037] [Requirement (4)]
used in the present invention the copolymer (A) has a Mooney viscosity measured at ° C. 100 [ML 1 + 4 (100 ° C.)] is 10 to 90. The Mooney viscosity is preferably 10 to 80.
[0038] When Mooney viscosity is within the above range, the rubber compound viscosity as a foaming medium can be set relatively easily low, preferably enables mix design having excellent kneading property.
Incidentally, the Mooney viscosity can be with Mooney viscometer (manufactured by Shimadzu Corporation SMV202 type) is measured in accordance with JIS K6300.
[0039] [Requirement (5)]
used in the present invention copolymer, the apparent iodine value of the structural units derived from nonconjugated polyene [c-2] is 0.1 ~ 3.0g / 100g. Iodine value of apparent of the components [c-2] is preferably 0.4 ~ 3.0 g / 100 g, more preferably 0.5 ~ 3.0g / 100g.
[0040] By adjusting the iodine value, it is possible to obtain a copolymer having an activation energy of flow, which meets the requirements (6) to be described later. Further, if the apparent iodine value of the non-conjugated polyene [c-2] is within the range, it preferred because of its excellent foaming and kneading stability.
Incidentally, iodine value of apparent non-conjugated polyene [c-2] is, 1 H-NMR and 13 can be determined by C-NMR.
[0041] Taken ethylene as a copolymer of the present invention (A), propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) copolymer obtained from the (A1) as an example, non method of determining the iodine value of the apparent VNB corresponding to conjugated polyene [c-2] be shown specifically.
[0042] First, 13 was determined ethylene in the copolymer than C-NMR spectrum, propylene, the integral value of the structural units derived from each of ENB (3-position peak) and VNB (7-position peak). From the ratio of the obtained integrated value, to calculate the molar ratio of structural units derived from ENB and VNB, ethylene, propylene, a molecular weight of ENB and VNB, to determine the weight percent of ENB.
Then 1 from H-NMR spectra were determined as follows and the integral value of the peak (c) derived from vinyl group of the integrated value and VNB of peak derived from ENB (a).
1) the integral value of the peak (a) derived from ENB: [4.7 total integrated value of a plurality peak near ~ 5.3 ppm] - [integrated value × 2 peak (c)]
4.7 1-5. multiple peak near 3 ppm, includes both peak (a) and peak (b). In the present invention, in order to determine the integral value of the peak (a), regarded as twice the integral value of the peak (c) derived from the integral value of the peak (b) derived from two equivalent protons to one proton, 4.7 is subtracted from the integrated value of the multiple peaks in the vicinity of ~ 5.3ppm.
Integrated value of peak derived from vinyl group of 2) VNB (c): 5.5 ~ total integrated value near the peak 6.0ppm
Note that 1) and 2 peaks of) (a) ~ (c), respectively formula (X), in (Y) (a), it shows the (b) and (c).
[0043] [Formula 5]

[0044] The resulting integral value using VNB Apparent iodine value of structural units derived from (molecular weight 120.2) (IV (VNB) a) was calculated by the following equation. Incidentally, iodine (I 2 molecular weight) is 253.81.
[0045] IV (VNB) = [integrated value of peak (c) derived from vinyl group of VNB] / [integrated value of peak (a) derived from ENB] × [ 13 wt% of ENB determined from C-NMR spectrum] × 253.81 / 120.2
[0046] [Requirement (6)]
used in the present invention the copolymer (A) satisfies the following formula (i), preferably satisfies the following formula (i ').
50> activation energy of flow (Ea) [kJ / mol]> 35 · · ·
(i) 50> activation energy of flow (Ea) [kJ / mol]> 37 ··· (i ')
[0047] The viscosity of the polymer melt are generally, as a simple viscosity of the liquid on the rheology, decreases with increasing temperature, a high temperature; In (Tg glass transition temperature + 100 ° C.), the temperature dependence of the viscosity, the following formula ( it is known according to Arrhenius equation represented by j).
Viscosity (Itao) = Aexp (Ea / RT) · · ·
(j) R; gas constant, A; frequency factor, Ea; flow activation energy, T; absolute temperature
activation energy of the flow is molecular weight and molecular weight distribution does not depend on, it is the fact that affected only by the molecular structure and useful indicator of the structural information of a polymer.
[0048] However, in the olefinic polymer obtained using a Ziegler catalyst, it is difficult to precise molecular structure control, various structural information has been calculated is included in the activation energy of flow. Recently, advances in the discovery and production technology of a metallocene catalyst, molecular weight distribution, degree of short chain branching, it is possible to control up composition distribution and long chain branching degree, the activation energy of flow of the high-density polyethylene (HDPE) is about 27kJ / mol, activation energy of flow of the low density polyethylene (LDPE) has been reported to be about 56kJ / mol.
Although here the difference in the activation energy of flow in is believed to be due to long chain branching, analysis of long chain branching it is possible to detect accurately although a method of evaluation by NMR and light scattering are known is difficult and research focusing on the rheological properties is still are actively performed (reference 1; Masayuki Yamaguchi, molding, Vol. 20, No. 7, 400-404 (2008), reference 2 ; FJ Stadler, C. Gabriel, H. Munstedt, Macromolecular chemistry and Physics, 208, 2449-2454 (2007)).
[0049] On the other hand, the distribution of the diene component to be copolymerized as a cross-linking site by using the EPDM any metallocene catalysts have been reported to be equalized (Reference 3; BA Harrington, MG Williams, Presented at a meeting of the Rubber Division , American Chemical Society October, 14-17 (2003)).
[0050] Therefore, the precise molecular structure control EPDM by using a metallocene catalyst enables the crosslinking reaction of the uniform, to grasp the flow activation energy rubber composition and the relationship between the physical properties of the crosslinked foam, high expansion it is possible to demonstrate structural region that exhibits excellent function in the area.
[0051] Generally by crosslinking foaming molding compositions comprising ethylene-propylene-diene copolymer rubber (EPDM), to produce a crosslinked foam with the properties of the composition, control the vulcanization reaction and foaming reaction it is important to.
For example, retention of the foaming gas viscosity of the composition is too low, poor, not be lower specific gravity, cause further deterioration of the appearance. On the other hand, the not foamed and the viscosity of the composition is too high. Further, as one of the factors affecting the viscosity of the composition, network formation are exemplified by the crosslinking reaction of EPDM, the control of the crosslinking reaction is also important.
[0052] Therefore conventionally, conditions were low viscosity of the composition, in order to improve the retention of the foaming gas, molecules designed to be wider molecular weight distribution of EPDM, improving the gas-retaining property by a high molecular weight component Study It has been made. On the other hand, although considered to be improving the gas retention by introducing long chain branching in the polymer are well known in the polyethylene, the EPDM using conventional Ziegler catalysts, it is difficult to introduce themselves of long chain branching , Furthermore, in the Ziegler catalyst, it is difficult to uniformly introduce the diene component in the polymer, the crosslinking reaction is unevenly distributed, it is difficult to result obtaining sufficiently high foam.
[0053] Therefore, the copolymer (A) used in the present invention, together with preferably by synthesized using a metallocene catalyst, uniformly introducing a diene component in the polymer, to control the crosslinking reaction, one diene component as, by copolymerizing 5-vinyl-2-norbornene (VNB) components such as [c-2], introducing more long chain branching, were identified its structural properties by the activation energy of flow. Activation energy of flow is obtained by crosslinking and foaming a composition comprising a copolymer satisfying the above formula (i) (A) is crosslinked foam, the production of high foam achieved so far been difficult easily and it is possible to stably perform. Further, crosslinked foam obtained by a composition containing the copolymer (A) indicates the surface smoothness is excellent significantly.
[0054] Activation energy of flow of the copolymer used in the present invention (Ea), the temperature - on the basis of the time superposition principle, the melt complex viscosity (unit; Pa · sec) at 190 ° C. frequency (unit; Hz) a value calculated by Arrhenius type equation from the shift factor (aT) for creating a master curve showing the dependency, obtained by the following method.
[0055] That is, each 170 ° C. and 210 ° C. temperature (T, unit; ° C.) melt complex viscosity of the copolymer in - Frequency curve (unit of melt complex viscosity; Pa / sec, unit of frequency; Hz) and temperature - time based on the principle of superposition, the melt complex viscosity at each temperature (T) - in each frequency curve, the melt complex viscosity of the copolymer at 190 ° C. - each obtained when the superimposed frequency curve temperature (T (from the aT), by the method of least squares, [ln (aT)] and [1 / (T + 273.16) ] and the primary approximate expression (the following formula (1) shift factor in) is calculated). Next, determine the Ea from the primary approximate expression of the slope m and the following equation (2).
ln (aT) = m (1 / (T +
273.16)) + n · · · (1) Ea = [.008314 × m] · · ·
(2) aT: shift factor, Ea: activation energy of flow ( units; kJ /
mol) T: temperature (unit; ℃), n: intercept
[0056] The above calculation may be using a commercially available calculation software, the calculation as software, Thi TA Instruments Japan Co., Ltd., RSI Orchestrator VER. 6.6.3, and the like.
[0057] Incidentally, the melt complex viscosity in the shift factor (aT) each temperature (T) - log-log curve of the frequency, log (Y) = - log (X) is moved in the axial direction (however, melt the Y-axis complex viscosity, and the frequency on the X axis), the melt complex viscosity at 190 ° C. - a movement amount when the superimposed frequency curve, in the superposition, the melt complex viscosity at each temperature (T) - both of the frequency logarithmic curve, for each curve, the frequency aT times, moving the melt complex viscosity 1 / aT times, also, 170 ° C., the method of least squares equation (1) from the value of the three points 190 ° C. and 210 ° C. correlation coefficient when determined by is usually 0.99 or more.
[0058] Melt complex viscosity - measured frequency curve, viscoelasticity measuring apparatus (e.g., Rheometrics Co. viscoelasticity tester (Model RDS-2)) was used for the measurement. Specifically, as a sample, the thickness of 2mm was obtained by pressing the copolymer at 190 ° C. sheet and used after molding into a diameter of 25 mm × 2mm thick disc shape was measured under the following conditions . In addition, RSI Orchestrator VER as data processing software. 6.6.3 the (Thi TA Instruments Japan Co., Ltd.) was used. Further, it is preferable to advance the antioxidant suitable amount (e.g., 1000 ppm) incorporated in the measurement sample.
[0059] Geometry: parallel plate
Measurement temperature: 170 ° C., 190 ° C., 210 ° C.
Frequency: 0.5 ~ 79.577Hz
distortion: 1.0%
to measure the frequency dependence of the viscosity under the above conditions, to derive the Arrhenius plot described above It was calculated activation energy of flow by.
[0060] Copolymer used in the present invention is a copolymer synthesized by using a metallocene catalyst as described above, in the present invention, as the metallocene catalyst, the following formula (III), (IV) or (V) in the catalyst, expressed is preferred.
Will be described compound represented by formula (III).
[0061] [Formula 6]

[0062] In the formula (III), R are each independently hydrocarbyl, halohydrocarbyl, silyl, germyl and group or a hydrogen atom selected from these combinations, the number of atoms other than hydrogen contained substrate is 20 or less it is.
M is titanium, zirconium or hafnium.
Y is -O -, - S -, - NR * - or -PR * - a.
R * is a hydrogen atom, a hydrocarbyl group, hydrocarbyloxy group, a silyl group, a halogenated alkyl group or a halogenated aryl group, R * if is not hydrogen, R * is an atom other than hydrogen up to 20 containing.
Z contains boron or a group 14 element, and nitrogen, phosphorus, a divalent group containing sulfur or oxygen, the number of atoms other than hydrogen atoms The divalent group having a 60 or less is there.
X, each independently in the X there are multiple, the number of atoms is an anionic ligand of 60 or less (however,. Excluding cyclic ligands π electrons delocalized).
X 'is, X' if there are multiple independently, the number of atoms is a linking compound of 20 or less neutral.
p is 0, 1 or 2.
q is 0 or 1.
[0063] However, when p is is q 2 of 0, M is in oxidation state of +4, X is a halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amido, di (hydrocarbyl) phosphido, hydrocarbyl sulfide, a silyl group, these halo-substituted derivatives, di (hydrocarbyl) amino-substituted derivatives, an anionic ligand selected from hydrocarbyl-substituted derivatives and di (hydrocarbyl) phosphino-substituted derivatives, the number of atoms other than hydrogen atoms of the X is more than 20 is there. Also when p is q 1 is 0, M is in oxidation state +3, X is allyl, 2- (N, N'- dimethylamino) phenyl and 2- (N, N'- dimethylamino) aminobenzyl or is an anionic stabilizing ligand selected from, or M is in the oxidation state of +4, X forms a M and metallacycle cyclopentene divalent conjugated diene derivative. When q is 1 and in p is 0, M is in oxidation state of +2, X 'is 1 or more conjugated or non-conjugated diene may neutral be substituted with hydrocarbyl groups, and 40 carbon atoms It contains the number of pieces below to form the M and π complex.
[0064] Will be described compound represented by formula (IV).
[Formula 7]

[0065] Wherein (IV), R 1 and R 2 is a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, R 1 and R 2 at least one of is not a hydrogen atom.
R 3 ~ R 6 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Further, R 1 ~ R 6 may be bonded to each other to thereby form a ring.
M is titanium.
Y is -O -, - S -, - NR * - or -PR * - a.
Z * is SiR * 2 , CR * 2 , SiR * 2 SiR * 2 , CR * 2 CR * 2 , CR * = CR * , CR * 2 SiR * 2 , or GeR * 2 is.
R * is independently a hydrogen atom, a hydrocarbyl group, hydrocarbyloxy group, a silyl group, a halogenated alkyl group or a halogenated aryl group, R * if is not hydrogen, R * is hydrogen up to 20 containing atoms other than. Z * two binding of the R * (R * If is not hydrogen) may be to form a ring, Z * R that binds to * R that binds to the Y * 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 oxidation state of +4, X is independently a methyl group or a benzyl group. Also when p is 1, q is 0, M is in oxidation state +3, X is either a 2-(N, N'-dimethyl) aminobenzyl group or q is 0, M is is in the oxidation state of +4, X is 1,3-butadienyl. Also when p is 0, q is 1, M is in oxidation state of +2, X is 1,4-diphenyl-1,3-butadiene, 2,4-hexadiene or 1,3-pentadiene.
[0066] It will be described compound represented by formula (V).
[0067] [Formula 8]

[0068] Wherein (V), R 'is a hydrogen atom, a hydrocarbyl group, a di (hydrocarbylamino) group or a hydrocarbylene group, said R' the number of carbon atoms in the case where the carbon atoms is 20 or less.
Wherein (V), R "is a hydrocarbyl group or a hydrogen atom having 1 to 20 carbon atoms.
In formula (V), M is titanium.
Formula in (V), Y is -O -, - S -, - NR * -, - PR * -, - NR 2 * , or -PR 2 * a is.
in formula (V), Z * is, -SiR * 2 -, - CR * 2 -, - SiR * 2 SiR * 2 -, - CR * 2 CR * 2 -, - CR * = CR * -, - CR * 2 SiR * 2 -, or -GeR * 2 -. a is the R * there are a plurality of each independently when a hydrogen atom or a hydrocarbyl, hydrocarbyloxy, silyl, a group containing at least one selected from an alkyl halide, and the group consisting of halogenated aryl, said R * is the atomic number of 2 to includes atoms of up to 20, Z optionally * is Yusuke Two R * (R * If is not hydrogen atom) may form a ring, Z * of R * and Y R * and may form a ring.
[0069] In formula (V), X, excluding cyclic ligands π electrons are delocalized, anionic ligands atoms 60 mono-. X 'is a linking group of atoms of 20 or less neutral. X "is an anionic ligand having the number of atoms of 60 or less divalent .p is .q is 0, 1 or 2, the .r is 0 or 1, 0 or 1.
[0070] when p is 2, q and r are 0, M is +4 oxidation state (where, Y is -NR * 2 or -PR * 2 unless a), or M is the oxidation state of +3 (where , Y is -NR * 2 or -PR * 2 is a), X is a halide group, a hydrocarbyl group, hydrocarbyloxy group, a di (hydrocarbyl) amido group, di (hydrocarbyl) phosphide group, hydrocarbyl sulfide group, and a silyl group, and groups in which these groups are halogen-substituted, these groups are di (hydrocarbyl) amino-substituted groups, these groups hydrocarbyloxy substituted groups and these groups are di (hydrocarbyl) phosphino-substituted was an anionic ligand selected from the group consisting of group, the group contains atoms up to atomic number 2-30.
[0071] When r is 1, p and q are 0, M is in an oxidation state of +4, X "is a dianionic selected hydrocarbyl basil groups, oxyhydrocarbyl groups, from the group consisting of hydrocarbylene dioxy group a ligand, wherein X "has the atoms to atomic number 2-30. When p is 1, q and r are 0, M is in an oxidation state of +3, X is allyl, 2-(N, N-dimethylamino) phenyl, 2-(N, N-dimethylaminomethyl ) phenyl, and 2- (N, anionic stabilizing ligand selected from the group consisting of N- dimethylamino) benzyl. If p and r is 0, q is 1, M is in an oxidation state of +2, X 'is substituted with one or more hydrocarbyl groups optionally di conjugated diene or a neutral neutral a diene, wherein X 'is a 40 or less carbon atoms carbon, to form a bond by M and [pi-[pi interaction.
[0072] As a more preferred embodiment, in formula (V), p is 2, if q and r is 0, M is in an oxidation state of +4, X is each independently methyl, benzyl or halide, There, if p and q are 0, r is 1, M is in an oxidation state of +4, X "is a 1,4-butadienyl group which forms a M and metallacycle cyclopentene ring, p is 1 If it is, q and r are 0, M is in an oxidation state of +3, X is, 2-(N, N-dimethylamino) benzyl, when p and r are 0, q is 1 in it, M is in an oxidation state of +2, X 'is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.
expression formula among (V) (V' represented by) that compound is particularly preferred.
[0073] [Formula 9]

[0074] 'In, R the formula (V)' is a hydrocarbyl group of hydrogen, carbon atoms 1 to 20, R "is a hydrocarbyl group or a hydrogen atom having 1 to 20 carbon atoms, M is titanium, Y is -NR * - a and, Z * is -SiR * 2 -, as described above, and said R * are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, of p and q one is 0 and the other is 1, when p is 0 and q is 1, M is in an oxidation state of +2, X 'is 1,4-diphenyl-1,3-butadiene or 1 , 3-a pentadiene, when p is 1 and q is 0, M is in an oxidation state of +3, X is 2- (N, N- dimethylamino) benzyl.
[0075] A linear alkyl group such as methyl group, ethyl group, butyl group as a hydrocarbyl group having a carbon number of 1 ~ 20, t-butyl group, and branched alkyl groups such as a neopentyl group, a hydrocarbyloxy group, methyl oxy group, ethyloxy group, a linear alkyl group such as a butyloxy group, t-butyloxy group, and a branched alkyloxy group such as neopentyl group, a halogenated alkyl group, a linear alkyl chlorinating group or branched alkyl group, brominated include those fluorinated. Or halogenated aryl group, chlorinated phenyl group, and a chlorinated naphthyl group.
In the formula (V '), it is preferably R "is hydrogen atom or methyl, when it is methyl.
[0076] Particularly preferred catalysts, (t-butylamido) dimethyl (eta 5 -2-methyl -s- indacene-1-yl) silane titanium (II) 2,4-hexadiene (formula (VI)), (t-butylamido) - dimethyl (eta 5 -2-methyl -s- indacene-1-yl) silane - titanium (IV) dimethyl (formula (VII)), (t-butylamido) - dimethyl (eta 5 -2,3-dimethylindenyl yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene (formula (VIII)), (t-butyl - amide) - dimethyl (eta 5 -2,3-dimethyl -s- indacene -1 - yl) silane titanium (IV) dimethyl (formula (IX)), (t-butylamido) - dimethyl (eta 5 -2-methyl -s- indacene-1-yl) Shiranchi Taniumu (II) is 1,3-pentadiene (the following formula (X)).
Among them, (t-butylamido) - dimethyl (eta 5 -2-methyl -s- indacene-1-yl) silane titanium (II) 1,3-pentadiene (formula (X)) is particularly preferred.
[0077] [Formula 10]

[0078] In particular, when using a catalyst having a structure represented by the above formula (X), in the polymerization reaction for obtaining the copolymer (A) used in the present invention, the non-conjugated polyene (component [c-1] and component [c -2]) is excellent in the copolymerizability, e.g. efficiently capture a double bond VNB ends, can be introduced long chain branching in a high proportion. Moreover, the use of this catalyst can be a molecular weight distribution of the resulting copolymer composition distribution is narrow, to prepare a copolymer having a very uniform molecular structure. Therefore, it is concerned with the long chain branching generation, formation of gel-like hard spots rubber molding surface is remarkably suppressed. As a result, a rubber molded product comprising such a copolymer is excellent in the surface appearance because it contains no gel-like hard spots, also production stability is excellent in shape retention is good.
[0079] These catalysts can be prepared using known synthetic methods. For example, disclosed in International Publication WO98 / 49212.
[0080]
In preparing the copolymer (A) used in the present invention, the metallocene catalyst, preferably using a catalyst having the structure illustrated above. More particularly, the catalyst as a main catalyst, using a boron-based compound and / or an organic aluminum compound such as trialkyl compound as co-catalyst, an aliphatic hydrocarbon such as hexane as a solvent, a continuous process by stirred reactor or batch method.
[0081] As the boron compound, such as trimethyl ammonium tetrakis (pentafluorophenyl) borate, di (hydrogenated tallow alkyl) methyl ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropyl ammonium 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- Buchirutorisu (pentafluorophenyl) borate, N, N-dimethylanilinium Riniu Yichun Jirutorisu (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4-(t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxy tris (pentafluorophenyl) borate, N, N-diethyl anilinium tetrakis (penta fluorophenyl) borate, N, N-dimethyl-2,4,6-trimethyl anilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium Tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropyl ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N, N-diethyl anilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, and N, N- dimethyl-2,4,6-trimethyl tetrakis (2 , 3,4,6-tetrafluorophenyl) borate, dialkyl ammonium salts such as di - (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n- butyl) ammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, dimethyl (t-butyl Le) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, and dicyclohexylammonium tetrakis (pentafluorophenyl) borate; trisubstituted phosphonium salts, e.g., triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate; disubstituted oxonium salts, e.g., diphenyl oxonium tetrakis (pentafluorophenyl phenyl) borate, di - (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, and di (2,6-dimethylphenyl) oxonium tetra key (Pentafluorophenyl) borate; disubstituted sulfonium salts such as diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, and bis (2,6-dimethylphenyl ) sulfonium tetrakis (pentafluorophenyl) borate, and the like.
[0082] The organic aluminum compound (hereinafter also referred to as "TIBA".) Triisobutylaluminum can be mentioned.
[0083] The reaction temperature can be raised to 100 ° C. Since the catalyst is not deactivated even at high temperatures. The polymerization pressure is beyond 0 ~ 8 MPa (gauge pressure), preferably in the range of beyond 0 ~ 5 MPa (gauge pressure). The reaction time (average residence time when the copolymerization is carried out by a continuous method), catalyst concentration, varies depending on the conditions such as polymerization temperature, usually 0.5 minutes to 5 hours, preferably ~ 10 minutes it is 3 hours. Further, the copolymerization can be used a molecular weight modifier such as hydrogen.
[0084] Mol (charged) ratio of ethylene [a] and the α- olefin [b] ([a] / [b]) is 25 / 75-80 / 20, preferably 30 / 70-70 / 30.
The mole (charged) ratio of the non-conjugated polyene [c-1] and the non-conjugated polyene [c-2] ([c -1] / [c-2]) is 60/40 to 99.5 / 0 .5, preferably 65 / 35-99 / 1.
Ethylene [a] in a molar (charged) ratio of the non-conjugated polyene [c-1] ([a ] / [c-1]) is 70 / 30-99 / 1, preferably 80 / 20-98 / 2 it is.
Mol (charged) ratio of ethylene [a] a non-conjugated polyene [c-2] ([a ] / [c-2]) is 70 / 30-99.9 / 0.1, preferably 80/20 ~ is 99.5 / 0.5.
[0085] Thus the copolymer used in the present invention obtained (A) is a structural unit derived from α- olefin [b] of 3 to 20 carbon atoms, the total structural units in 100 mole%, 10 to 50 moles a%, preferably 25 to 45 mol%. The total mole% of structural units derived from structural units and non-conjugated polyene derived from non-conjugated polyene [c-1] [c-2] a is 1.0-6.0 mol%, more preferably it is 1.0 to 5.0 mol%. The ratio of the mole% of structural units derived from mole percent and non-conjugated polyene [c-2] of the structural units derived from among the carbon-carbon double bond to a non-conjugated polyene [c-1] ([c-1] / [c-2]) is 75/25 to 99.5 / 0.5, preferably 78 / 22-97 / 3.
[0086]
railway rail track pad composition according to the present invention (hereinafter, referred to as rubber composition), the copolymer (A), clay (B) and sulfur atom-containing silane coupling it suffices include rings agent (C), although other ingredients are not particularly limited, for example, reinforcing agent such as carbon black, a softening agent such as oil, a vulcanizing agent and a vulcanization aid, a foaming agent and foaming aid it is preferable to include agents.
[0087] The present inventors, is placed a rubber composition according to the present invention, a sulfur atom-containing silane coupling agent (C) an alkoxy group having forms a surface hydrogen bonds with clay (B), also, a sulfur atom interaction of the copolymer (a) and clay (B), especially strengthened interaction vulcanization, has speculated that have high elasticity of the rubber composition.
[0088] The content of the copolymer in the total rubber composition (A) is preferably at least 20 wt%. Clay in the whole rubber composition (B), preferably with respect to 100 parts by weight copolymer (A), 5 ~ 200 parts by weight, and more preferably used in an amount of 30 to 100 parts by weight. Sulfur-containing silane coupling agent (C) is preferably used with respect to 100 parts by weight copolymer (A), 0.1 ~ 10 parts by weight, more preferably in a proportion of 0.5 to 3 parts by weight .
[0089] [Clay (B)]
and clay refers to a white powdery product which was industrially purified from natural ore mainly composed of hydrated aluminum silicate, commercially available as clay for rubber, particularly in the present invention what can be preferably used. Among them, surface-treated clay with a silane coupling agent, for example, Burgess Co., Ltd. under the trade name "Burgess KE" is particularly preferred.
[0090] [Sulfur-containing silane coupling agent (C)]
Examples of the silane coupling agent (C), those which contain at least one sulfur atom in the molecule.
Such silane coupling agent (C), specifically, bis (3-triethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetra sulfide, bis (2-trimethoxysilyl ethyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxy silane, 3-mercaptopropyl methyl dimethoxysilane, 3- sulfur-based silane coupling agent having at least one structure selected from a mercapto group and a sulfide such as mercaptopropyl methyl diethoxy silane.
[0091] [Carbon Black]
carbon black, in order to obtain a rubber composition capable of providing a vulcanized rubber molded article having sufficient mechanical strength with respect to 100 parts by weight of the copolymer (A), 30 ~ 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 61 to 200 parts by weight, and most preferably used in a ratio of 80 to 200 parts by weight.
[0092] The carbon black may be used SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT, and the like. Carbon black, in order to increase the rubber composition capable of providing a good vulcanized rubber molded product of mechanical strength and product skin, nitrogen adsorption specific surface area of 10 ~ 100 m 2 is preferably / g.[0093] The rubber composition according to the present invention, the rubber reinforcing agent other than carbon black, clay (B) other than the inorganic filler, softening agent, antioxidant, processing aid, foaming agent, foaming aid, a vulcanization accelerator, organic peroxides, vulcanization aid, a colorant, dispersing agent, conventionally known additives such as flame retardants, can be added in amounts not detrimental to the object and effect of the present invention.
[0094] The rubber reinforcing agent, tensile strength of the crosslinked (vulcanized) rubber, an effect of increasing tear strength, mechanical properties such as abrasion resistance. Such rubber reinforcing agent, specifically, finely divided silicic acid, silica, and the like. It may be pre-silane coupling treatment.
[0095] Specific examples of the silica, fumed silica, precipitation silica, and the like. These silicas are mercaptosilane, aminosilane, hexamethyldisilazane, chlorosilane, may be surface treated with a siloxane such as reactive silanes or low molecular weight, such as alkoxysilanes.
[0096] The type and amount of these rubber reinforcing agent may be appropriately selected depending on the use, the amount of the rubber reinforcing agent (excluding carbon black) is usually the copolymer (A) 100 parts by mass of the maximum 150 parts by weight, preferably at most 100 parts by weight. Incidentally, rubber reinforcing agent other than the carbon black in the injection molding is preferably not used.
[0097] [Inorganic Filler]
In the present invention, in addition to clay (B), other inorganic filler within a range not to impair the effects of the present invention, such as light calcium carbonate, heavy calcium carbonate, may be added talc .
[0098] The type and amount of these inorganic fillers may be appropriately selected depending on the use, the amount of the inorganic filler is usually the copolymer (A) 100 parts by mass of a maximum 300 parts by weight, preferably it is up to 200 parts by weight.
[0099] [Softening agent]
As the softening agent, it is possible to use a softening agent which is usually used for rubbers. Specifically, process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petroleum-based softeners such as vaseline; coal tar, coal tar-based softeners such as coal tar pitch; castor oil, linseed oil, rapeseed oil , soybean oil, fatty oil softening agents coconut oil; tall oil; sub (factice); beeswax, carnauba wax, wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, lauric fatty acids and fatty acid salts such as zinc; naphthenate; pine oil, rosin or derivatives thereof; terpene resins, petroleum resins, atactic polypropylene, synthetic polymeric substances such as coumarone-indene resin; dioctyl phthalate, dioctyl adipate, dioctyl sebacate ester softening agents and the like; micro chestnut Tallinn wax, liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and hydrocarbon-based synthetic lubricating oils. Among them, petroleum softeners are preferably used in particular process oil. The amount of the softening agent is appropriately selected by vulcanizate applications.
[0100] [Antioxidant]
As the antioxidant, for example, an amine-based, but hindered phenol-based or sulfur-based anti-aging agents and the like, these anti-aging agent, as described above, impair the object of the present invention used with no range. The amine-based anti-aging agents, diphenylamines, phenylenediamines, and the like. As the sulfur-based antioxidant, sulfur-based antioxidant is usually used for rubber.
[0101] [Processing aids]
As the processing aid, it is possible to use processing aids to be used for processing usual rubbers. Specifically, linoleic acid, ricinoleic acid, stearic acid, palmitic acid, higher fatty acids such as lauric acid, like the esters of higher fatty acids and the like; barium stearate, zinc stearate, salts of higher fatty acids such as calcium stearate It is. Such processing aids, the copolymer (A) 100 parts by mass of usually 10 parts by weight or less, preferably used in an amount of 5 parts by mass or less, as appropriate in accordance with the required physical properties optimum it is desirable to determine the amount.
[0102] [Blowing agent]
As the blowing agent, specifically, sodium bicarbonate (baking soda), sodium carbonate, ammonium bicarbonate, ammonium carbonate, an inorganic foaming agent of ammonium nitrite and the like; N, N'-dimethyl -N, N ' - dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine (DPT) nitroso compounds such as; azodicarbonamide (ADCA), azobisisobutyronitrile (AZBN), azo-bis-cyclohexyl nitrile, azo-diaminobenzene, azo compounds such as barium azodicarboxylate; benzenesulfonyl hydrazide (BSH), toluenesulfonyl hydrazide (TSH), p, p'- oxybis (benzenesulfonyl hydrazide) (OBSH), 3,3'-di-sulfonyl hydrazide Suruhoniruhi etc. Hydrazide compounds; calcium azide, 4,4'-diphenyl disulfonyl azide, azide compounds such as p- toluenesulfonyl azide and the like.
[0103] These foaming agents, the copolymer (A) 100 parts by mass of generally 0.5 to 30 parts by weight, preferably used in a ratio of 1 to 20 parts by weight.
[0104] [Foaming aid]
If necessary, in combination with the foaming agent may be used a foaming aid. Foaming aid is reduced decomposition temperature of the foaming agent, a decomposition accelerator, an effect of equalizing the like bubbles. Such foaming assistant, for example, salicylic acid, phthalic acid, stearic acid, organic acids such as oxalic acid, urea or derivatives thereof. These foam auxiliary agent with respect to 100 parts by mass of the copolymer (A), usually 0.01 to 10 parts by weight, preferably used in an amount of 0.1 to 5 parts by weight, physical properties required value it is desirable to determine the appropriate optimum amount in accordance with the.
[0105] Other rubbers]
Further, in the crosslinkable rubber composition used in the present invention, without impairing the object of the present invention can be used by blending other known rubbers. Such other rubbers, natural rubber (NR), isoprene-based rubbers such as isoprene rubber (IR), butadiene rubber (BR), styrene - butadiene rubber (SBR), acrylonitrile - butadiene rubber (NBR), chloroprene rubber (CR) can be mentioned conjugated diene rubber such.
[0106] [Vulcanizing agent (crosslinking agent)
as the vulcanizing agent used for vulcanization, sulfur and sulfur compounds. The sulfur, specifically, powdered sulfur, precipitated sulfur, colloidal sulfur, surface treated sulfur, insoluble sulfur and the like. The sulfur compounds include sulfur chloride, sulfur dichloride, macromolecular polysulfide, and sulfur compounds vulcanized by releasing active sulfur at the vulcanizing temperature such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, selenium dimethyldithiocarbamate, and the like. Sulfur is preferred among these. Sulfur or a sulfur compound, based on 100 parts by weight copolymer (A), usually 0.1 to 10 parts by weight, preferably in an amount of 0.5 to 5 parts by weight.
[0107] [Vulcanization accelerator]
Also, when using sulfur or a sulfur compound as the vulcanizing agent, it is preferable to use a vulcanization accelerator. As the vulcanization accelerator, specifically, N- cyclohexyl-2-benzothiazole sulfenamide (CBS), N- oxydiethylene-2-benzothiazole sulfenamide (OBS), N-t- butyl -2 - benzothiazole sulfenamide (BBS), N, sulfenamide compounds such as N- diisopropyl-2-benzothiazole sulfenamide; 2-mercaptobenzothiazole (MBT), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (4-morpholinodithio) benzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, thiazole-based compounds such as dibenzothiazyl disulfide; diphenyl guanidine (DPG), triphenyl guanidine, di-ortho-tolyl guanidine DOTG), ortho-tolyl bar iguana Id, diphenylguanidine phthalate Le - guanidine compounds such bets; Acetaldehyde - aniline condensate, butyraldehyde - aniline condensate, hexamethylenetetramine (H), aldehyde amines or aldehyde, such as acetaldehyde ammonia - ammonia-based compounds; 2-mercapto imidazoline compounds of imidazoline, and the like; Chiokarubanirido, diethyl thiourea (EUR), dibutyl thiourea, trimethyl thiourea, thiourea compounds such as di-ortho tri thiourea; tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, tetrakis (2-ethylhexyl) Chiu Arm disulfide (TOT), thiuram-based compounds such as dipentamethylenethiuram tetrasulfide (TRA); zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di -n- butyl dithiocarbamate zinc ethylphenyl dithiocarbamate, zinc, butylphenyl dithiocarbamate zinc, sodium dimethyl dithiocarbamate, dimethyl dithiocarbamate selenium, dithiocarbamates such as dimethyldithiocarbamate tellurium; dibutyl Ruki xanthates such as Santo Gen zinc; compounds such as zinc white (zinc oxide) and the like. These vulcanization accelerators with respect to 100 parts by weight of the copolymer (A), usually 0.1 to 20 parts by weight, preferably used in a ratio of 0.2 to 10 parts by weight.
[0108] [Vulcanization aid]
vulcanization agent can be appropriately selected according to the application, can be used alone or in admixture. Specific examples of the vulcanizing agent, magnesium oxide, zinc oxide (e.g., "META-Z102" (trade name; zinc oxide, such as manufactured by Inoue Lime Industry Co., Ltd.)), and the like. Its amount is usually the copolymer (A) 100 parts by mass of a 1 to 20 parts by weight. The vulcanizing agent, p- quinone dioxime such as quinone dioxime of, ethylene glycol dimethacrylate, acrylic such as trimethylolpropane trimethacrylate; diallyl phthalate, allyl-based, such as triallyl isocyanurate; Other maleimide; divinyl benzene.
[0109] Preparation of rubber composition]
The rubber composition used in the present invention, a Banbury mixer, a kneader, a internal mixer (closed mixer) such as Intermix, the above copolymer (A), clay (B ) and sulfur atom-containing silane coupling agent (C), for example, carbon black, rubber reinforcing agents, inorganic fillers, kneaded 2-20 minutes 80 ~ 170 ° C. temperature with additives such as a softening agent, open roll, such as roll, or using a kneader, sulfur as a vulcanizing agent, vulcanization accelerator if necessary, a vulcanization aid, a foaming agent, foaming aid and additional mixing, roll temperature of 40 to after kneading for 5-30 minutes at 80 ° C., it can be prepared by sheeted.
[0110]
track pads for railway rails according to the present invention is characterized in that obtained by crosslinking the rubber composition. The types of track pad are those mentioned in JIS E1117, but not of course limited thereto. As a method of crosslinking the rubber composition is, for example, the following two methods.
(I) the rubber composition containing a vulcanizing agent, usually, extruder, calender roll, press, injection (injection) molding machine, transfer molding machine, hot air, glass bead fluidized bed, UHF (ultra high frequency electromagnetic waves ), a method of heating by introducing steam, preformed into a desired shape by LCM (hot molten salt bath) heating tank such various molding methods heating forms such as, preformed simultaneously with or molding into a vulcanizing bath .
(Ii) the rubber composition is preformed by the above molding method, a method of irradiating an electron beam.
In particular, the composition according to the present invention shows a low viscosity suitable for injection molding, is excellent in productivity.
[0111] For (i), using the vulcanizing agent, it can be used in combination the vulcanization accelerator and / or the vulcanization assistant as required. As the temperature in heating, typically 100 ~ 300 ° C., preferably 120 ~ 270 ° C., more preferably 120 ~ 250 ℃, 0.5 ~ 30 minutes, preferably 0.5 to 20 minutes, still more preferably it is heated for 0.5 to 15 minutes.
[0112] In forming and vulcanizing the rubber composition may be using a mold, or may be without using a mold. If a mold is not used, the rubber composition is usually continuously molded-vulcanized.
[0113] For (ii), the rubber composition is preformed, the electron beam having an energy of 0.1 ~ 10 MeV, the absorbed dose is 0.5 ~ 35 Mrad, preferably 0.5 ~ 20 Mrad, more preferably 1 may be irradiated so that the ~ 10Mrad.
[0114]
track for a railway rail pad according to the present invention, it is preferable that the crosslinked foam obtained by crosslinking foaming molding the rubber composition. For crosslinking foaming molding the rubber composition, a rubber composition containing conventional blowing agent, perform crosslinking and foaming. An example of a cross-linked foam molding, the rubber composition was filled in a mold having a predetermined shape, subjected to cross-linking and foaming by heat press, and a method of obtaining a trajectory pad.
[0115] In the cross-linked foam, the specific gravity is preferably 0.03 ~ 0.9 g / cm 3 , more preferably 0.1 ~ 0.8 g / cm 3 , particularly preferably 0.1 ~ 0.75 g / cm 3 , and most preferably 0.1 ~ 0.7 g / cm 3 is.
Example [0116] Will be described in further detail following shows an example for the present invention, but the invention is not limited thereto.
[0117]
The composition of the composition shown in Table 1 using the following copolymers 1 and 2 were prepared, using a mold of 140mm × 125mm × 10mmt, compositions of Table 1 filled into a mold in the charged amount 140 g (thickness 7 mm), to produce a foamed crosslinked rubber for track pads for railway rails by crosslinking and foaming at the conditions of 170 ° C. × 10 minutes, they were evaluated for various physical properties.
[0118] Copolymer 1]
International Publication WO2010 / 064574 Patent same manner as in Example 1 (molar ratio difference adjusted by the amount of feed) ethylene-alpha-olefin-nonconjugated polyene random copolymer prepared in
component [c- 1] = ENB
component [c-2] = VNB
requirement (1): component [b] = 36.8 mol%
requirement (2): component [c-1] + component [c-2] = 2.91 mol %
requirement (3): component [c-1] / component [c-2] = 96/ 4
requirement (4): ML 1 + 4 (100 ° C.) = 32
requirement (5): iodine value = 0.8 g / 100 g
requirements (6): Ea = 43.0kJ / mol
[0119] Copolymer 2]
International Publication WO2010 / 064574 Patent same manner as in Example 1 (molar ratio difference adjusted by the amount of feed) ethylene-alpha-olefin-nonconjugated polyene random copolymer was prepared in
ethylene-alpha- olefin-nonconjugated polyene random copolymer
component [c-1] = ENB
component [c-2] = VNB
requirement (1): component [b] = 40.3 mol%
requirement (2): component [c-1 ] + component [c-2] = 4.47 mol%
requirement (3): component [c-1] / component [c-2] = 99/ 1
requirement (4): ML 1 + 4 (100 ° C.) = 81
requirements (5): iodine value = 0.32g / 100g
requirements (6): Ea = 38kJ / mol
[0120] [Table 1]

[0121] Details are as follows in the composition in Table 1.
Clay (B): trade name "Burgess KE", Burgess Co.
silane coupling agent (C): 3- mercaptopropyltrimethoxysilane, trade name "KBM-803", manufactured by Shin-Etsu Silicone Co., Ltd.
crosslinking agent (D):
Sulfur: the trade name of "alpha Grand S-50EN", AzumaTomo Co., Ltd.
co-agent 1: trade name "Sanferu R", Sanshin Chemical Industry Co., Ltd.
cross-linking aid 2: trade name "Nocceler MDB, Ouchi Shinko Co., Ltd.
crosslinking aid agent 3: trade name "Sanceler BZ", manufactured by Sanshin Chemical Industry Co., Ltd.
cross-linking aid 4: trade name "Sanceler TT", manufactured by Sanshin Chemical Industry Co., Ltd.
cross-linking aid 5: trade name "Sanceler 22-C", Sanshin chemical industry Co., Ltd.
activated zinc white: trade name "META-Z 102", Inoue lime industry Co., Ltd.
processing aids: stearic acid ( "stearate powder Sakura" (registered trademark), NOF Corporation
poly Ethylene glycol: PEG # 4000, Lion Corporation
Carbon black 1: trade name "SEAST S", Tokai Carbon Co., Ltd.
Carbon black 2: trade name "SEAST SO", Tokai Carbon Co., Ltd.
Silica: trade name "Nipsol VN3", Tosoh silica Co., Ltd.
process oil: trade name "São -2280", Japan Sun oil Co., Ltd.
foaming agent 1: trade name "Neoserubon N # 1000M", Yonghe Chemical industry Co., Ltd.
foaming agent 2: trade name "Expancel 909-80" , Japan Fillite Co., Ltd.
[0122]
Mooney viscosity ML 1 + 4 (125 ° C.): using a Mooney viscometer (manufactured by Shimadzu Corporation SMV202 type) measured at a temperature of 125 ° C. in compliance with JIS K6300-1 did.
· Minimum viscosity Vm: was carried out in accordance with JIS K6300-1. Specifically, by using a Mooney viscometer (manufactured by Shimadzu Corporation SMV202 type) at 125 ° C., and measuring the change in Mooney viscosity was determined minimum viscosity of from the start of measurement a (Vm).
· Flow length: are prepared jig 1 shown in FIG. 1, the sample is placed 2 of 13g preheated mold of the jig 170 ° C. in the cavity of the lower die 12. And 50 tons load pressing for 10 minutes at 170 ° C. in the upper die 11. The length of the sample flowing into the flow length measurement grooves 16 of the mold was measured as flow length. 1, 13 upper mold, 14 lower mold, 15 is a sample retaining portion. (1) to (7) indicates the size of each part, respectively, (1) = 60mm, ( 2) = 7mm, (3) = 3mm, (4) = 40mm, (5) = 5mm, (6) = 10mm, it was (7) = 155mm.
[0123]
Specific gravity: measured in accordance with JIS Z8807.
- foaming magnification: specific gravity of the compound obtained from the specific gravity of the formulation was calculated from the specific gravity of the sponge obtained by the above.
Tensile strength at break (TB), elongation at break (EB): conforms to JIS K6251, was measured tensile strength and elongation at break of the test specimen.
- Compression set: compliant with ASTM D395, compression under a pressure of 48 h 1.5KN at 70 ° C., 30 minutes cool, jigs taken out, and the thickness measured after cooling 1 hour, the original of the thickness It was determined from the relationship.
[0124]
unvulcanized rubber composition of Example 1, the viscosity Vm (125 ° C.) from 50 or less, the injection molding is good. In addition, by compression set of the crosslinked foam is 10% or less, showed good rubber elasticity, a material suitable as a track pad for railway rails.
DESCRIPTION OF SYMBOLS
[0125] A flow length measurement jig
and Diana 11
and Diana at 12
on 13 gold type
gold type for 14
15 sample retention portion
16 flowing groove length measured
2 sample
The scope of the claims
[Claim 1] The following ethylene-alpha-olefin-nonconjugated polyene random copolymer polymer (A), clay (B) and a sulfur atom-containing silane coupling agent (C) and a track for a railway rail pad, characterized by containing composition:
ethylene-alpha-olefin-nonconjugated polyene random copolymer (a):
ethylene [a], carbon atoms 3 ~ 20 alpha-olefin [b], by the following structural formula (I) or (II) nonconjugated polyene containing only one partial structure represented in the molecule [c-1],
[formula 1]

(wherein, (I) is a partial structure of the cyclic olefin.)
[formula 2]

and the structural formula (I) and comprises structural units derived from nonconjugated polyene [c-2], including two or more partial structures selected from the group consisting of (II) in the molecule a total below (1) to (6) satisfying copolymer.
(1) structural units derived from α- olefin carbon atoms 3 ~ 20 [b] is the total structural units in 100 mole%, 10 to 50
mol%, (2) non-conjugated polyene [c-1] mol% and a non-conjugated polyene of the structural unit derived from the sum of the mole% of structural units derived from [c-2] a is 1.0-6.0
mol%, (3) non-conjugated polyene [c-1 ] the ratio of the mole% of structural units derived from mole percent and non-conjugated polyene [c-2] of the structural units derived from ([c-1] / [ c-2]) is 75/25 to 99.5 is /0.5,
(4) Mooney viscosity measured at 100 ° C. [ML 1 + 4 (100 ° C.)] is 10 to
90, structural units derived from (5) non-conjugated polyene [c-2] apparent iodine value is ~ 3.0 g 0.1 / 100
g, (6) the flow activation energy (E ) Satisfies the following formula (i).
50> activation energy of flow (Ea) [kJ / mol]> 35 · · · (i)
[Claim 2] The ethylene-alpha-olefin-nonconjugated polyene random copolymer (A) is railway rail track for the pad composition according to claim 1, characterized in that is synthesized using a metallocene catalyst.
[Claim 3] Wherein a non-conjugated polyene [c-1] is 5-ethylidene-2-norbornene (ENB), wherein the non-conjugated polyene [c-2] is characterized in that it is a 5-vinyl-2-norbornene (VNB) railway rail track pad composition according to claim 1.
[Claim 4] Further cross-linking agent (D) for a railway rail track pad composition according to claim 1, characterized by containing.
[Claim 5] The cross-linking agent (D) is characterized in that a sulfur-based crosslinking agent, for a railway rail track pad composition according to claim 4.
[Claim 6] The clay (B) is a railway rail track pad composition according to claim 1 in which has been surface treated with a silane coupling agent.
[Claim 7] The sulfur-containing silane coupling agent (C) is characterized by having a structure selected from the mercapto group and a sulfide of one or more, for a railway rail track pad composition according to claim 1.
[8.] Further blowing agent characterized by containing claim 1-7 for a railway rail track pad composition according to any one of.
[Claim 9] Track pads for railway rails, including a crosslinked product of a composition according to any one of claims 1 to 7.
[Claim 10] Track pads for railway rails, including a cross-linked foamed molded article of the composition of claim 8.
[Claim 11] Method for producing a track pad for railway rails for molding by crosslinking the composition according to any one of claims 1 to 7.
[Claim 12] Method for producing a track pad for railway rails for molding by crosslinking foaming of the composition of claim 8.
[Claim 13] Crosslinked foam of a composition according to claim 8.