JP6334988B2 - Resin composition and cross-linked molded article comprising the resin composition - Google Patents

Description

  The present invention relates to a resin composition containing an ethylene / α-olefin / non-conjugated polyene copolymer and a cross-linked molded article comprising the resin composition.

  Crosslinkability of ethylene / propylene copolymer rubber (EPM), which is a random copolymer of ethylene and propylene, or ethylene / propylene / diene copolymer rubber (EPDM) containing non-conjugated dienes such as ethylidene norbornene as a diene component. Ethylene / α-olefin rubber has a molecular structure with no unsaturated bonds in the polymer main chain, and is superior in heat resistance and weather resistance compared to general-purpose conjugated diene rubber. Widely used in applications such as electric wire materials, construction civil engineering materials, and industrial material parts.

  Such ethylene / α-olefin rubbers are usually used after being vulcanized (crosslinked), but the properties of the crosslinked rubber (vulcanized rubber) vary depending on the ethylene component content, molecular weight, iodine value, etc. Different values are used depending on the application.

  For example, when ethylene / propylene rubber (EPM) or EPDM having a high ethylene content is used, a vulcanizate having excellent heat resistance can be obtained, and when using EPM or EPDM having a low ethylene content, low temperature flexibility is excellent. It is known that vulcanizates can be obtained.

  By the way, EPDM is usually used by adding a naphthenic or paraffinic mineral oil softener in order to improve kneading processability and extrusion moldability or to adjust the hardness of vulcanized rubber. . However, when mineral oil softeners are blended with EPDM, the pour point is high due to the effect of wax contained in mineral oil, resulting in deterioration of the low temperature flexibility of the vulcanized rubber. The product appearance was damaged. In the future, further improvements in low-temperature flexibility are required in response to increasing demands for use under severer conditions and for further improvement in performance as vibration damping rubber.

  As a method for solving such problems, it is known to use highly refined oil, which has been improved in production method and subjected to advanced desulfurization / dewaxing, as a softener with a low pour point. Waxing is not only technically and economically difficult, but if it is forced to cope with it, the molecular weight of the produced mineral oil will decrease, causing problems due to oil bleed-out, deterioration of appearance, and heat aging resistance. Deterioration may occur, and the flexibility at low temperatures was not satisfactory.

  When using an EPDM composition, instead of mineral oil, synthesis of ethylene / α-olefin copolymer or PAO (poly α-olefin; polymer of higher α-olefin such as decene) having low crystallinity and high fluidity Examples using oil as a softening agent are also known. For example, as an example of using an ethylene / α-olefin copolymer, an ethylene / α-olefin / diene rubber composed of EPDM and a specific ethylene / α-olefin copolymer may be used for workability and vulcanization molding. (See, for example, Patent Document 1). However, there is no example in which an ethylene / α-olefin copolymer having a specific molecular weight or less is blended to dramatically improve the low temperature characteristics.

  In Patent Document 2, a copolymer composition comprising EPDM, a specific PAO (poly α-olefin), and a specific ethylene / α-olefin copolymer exhibits low-temperature flexibility and high damping characteristics. It has been shown that a material satisfying the required characteristics as a damping rubber material can be obtained. However, since PAO is inferior in compatibility with EPDM as compared with an ethylene / α-olefin copolymer, the effect of improving the low temperature characteristics cannot be sufficiently satisfied.

Japanese Patent Laid-Open No. 04-309544 JP 2005-029654 A

  The present invention provides a resin composition containing an ethylene / α-olefin / non-conjugated polyene copolymer, which can produce a molded article having excellent low temperature characteristics such as low temperature flexibility without causing the above-mentioned problems. The challenge is to do.

The present invention relates to the following items [1] to [6].
[1] 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer (A) satisfying the following requirements (a-1) to (a-5);
A resin composition comprising 1 to 150 parts by weight of a liquid ethylene / α-olefin copolymer (B) satisfying the following requirements (b-1) to (b-6).
(A-1) a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene.
(A-2) In a total of 100 mol% of structural units derived from ethylene and structural units derived from α-olefin, the content (Ea mol%) of the structural units derived from ethylene is 40 to 90 mol%. It is.
(A-3) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.6 to 5.0 dl / g.
(A-4) The iodine value is 2-50.
(A-5) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 1.5-50.
(B-1) having a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms.
(B-2) The content of structural units derived from ethylene is 30 to 90 mol% (however, the total of the content of structural units derived from ethylene and the content of structural units derived from α-olefins is 100 mol) %).
(B-3) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 0.10 dl / g.
(B-4) The kinematic viscosity at 100 ° C. is 10 to 300 mm ² / s.
(B-5) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 1.0 to 3.0.
(B-6) The glass transition temperature (Tg) obtained by differential scanning calorimetry (DSC) is -90 to -65 ° C.

[2] Content (Ea mol%) of structural units derived from ethylene of the ethylene / α-olefin / non-conjugated polyene copolymer (A);
Content rate (Eb mol%) of structural units derived from ethylene of the liquid ethylene / α-olefin copolymer (B) (however, the total of structural units derived from ethylene and structural units derived from α-olefin is The resin composition as described in [1] above, wherein 100 mol% is satisfied.
−10 ≦ Ea−Eb ≦ 10 (1)

[3] The content (Ea mol%) of structural units derived from ethylene of the ethylene / α-olefin / non-conjugated polyene copolymer (A) is 3 to 20 carbon atoms and the structural units derived from ethylene. The resin composition as described in [1] or [2] above, which is 40 to 65 mol% in a total of 100 mol% with a structural unit derived from an α-olefin.
[4] The resin composition as described in any one of [1] to [3], wherein the liquid ethylene / α-olefin copolymer (B) further satisfies the following requirement (b-7).
(B-7) B value calculated | required from < ¹³ > C-NMR spectrum and following General formula (1) is 1.06 or more.
B value = [POE] / (2 · [PE] [PO]) (1)
(Wherein [PE] is the molar fraction of structural units derived from ethylene in the copolymer, and [PO] is the molar fraction of structural units derived from α-olefin in the copolymer. And [POE] is the ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer.)

[5] The resin composition as described in any one of [1] to [4], further including a crosslinking agent (C).
[6] A crosslinked molded product obtained by crosslinking the resin composition according to any one of [1] to [5].

  According to the present invention, a resin composition that contains an ethylene / α-olefin / non-conjugated polyene copolymer without causing problems such as bleed out and can produce a crosslinked molded article excellent in low-temperature flexibility, and A crosslinked molded article having excellent low-temperature characteristics such as low-temperature flexibility can be provided.

FIG. 1 shows the intrinsic viscosity [η] of a liquid ethylene / α-olefin copolymer (corresponding to the component B) obtained in the production example of the present specification, measured in decalin at 135 ° C., and the glass transition temperature ( It is a graph which shows the relationship with Tg). White (◇) is a liquid ethylene / α-olefin copolymer compatible with the component (B) of the present invention, and black (♦) does not satisfy the requirement (b-3), and the intrinsic viscosity [η] is 0.10 dl. An ethylene / α-olefin copolymer exceeding / g is shown. FIG. 2 shows the relationship between the kinematic viscosity (KV) at 100 ° C. and the glass transition temperature (Tg) of the liquid ethylene / α-olefin copolymer (corresponding to the component B) obtained in the production example of the present specification. It is a graph which shows. White (◇) satisfies the requirements of (b-4) of the present invention, and a liquid ethylene / α-olefin copolymer having a kinematic viscosity at 100 ° C. in the range of 10 to 300 mm ² / s, black (♦) is ( An ethylene / α-olefin copolymer that does not satisfy the requirement of b-4) and has a kinematic viscosity at 100 ° C. exceeding 300 mm ² / s is shown.

Hereinafter, the present invention will be specifically described.
In the following description, N ¹ or more and N ² or less (N ¹ and N ² respectively indicate a lower limit value and an upper limit value of a numerical range) may be simply referred to as “N ^{1 to} N ² ”. For example, an α-olefin having 3 to 20 carbon atoms may be referred to as an “α-olefin having 3 to 20 carbon atoms”.

  The resin composition according to the present invention comprises 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer (A) having specific physical properties and a liquid ethylene / α-olefin copolymer (B) having specific physical properties. ) 1 to 150 parts by weight.

Ethylene / α-olefin / non-conjugated polyene copolymer (A)
The ethylene / α-olefin / non-conjugated polyene copolymer (A) used in the present invention is an olefin copolymer comprising ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. is there.

  Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene-1, 11-methyldodecene-1, 12 -Ethyltetradecene-1 and the like. Among these, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. These α-olefins are used alone or in combination of two or more.

  Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5 Chain non-conjugated dienes such as dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene; Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic non-conjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene; 2,3-diisopropylidene-5-norbornene, 2 -Ethylidene-3-isopropylidene-5-nor Runen, 2-propenyl-2,2-norbornadiene, etc. trienes and 4-ethylidene-8-methyl-1,7-Nanojien the like. Of these, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene, and 4-ethylidene-8-methyl-1,7-nanodiene are preferable.

  The ethylene / α-olefin / non-conjugated polyene copolymer (A) used in the present invention is a total of 100 mol of a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms. %, The content of structural units derived from ethylene (Ea mol%) is 40 to 90 mol%, preferably 40 to 80 mol%, more preferably 45 to 70 mol%, still more preferably 50 to 60 mol%. The content of the structural unit derived from the α-olefin having 3 to 20 carbon atoms is 60 to 10 mol%, preferably 60 to 20 mol%, more preferably 55 to 30 mol%, and still more preferably. It is 50-40 mol%.

When the content rate of the structural unit derived from ethylene and the content rate of the structural unit derived from the α-olefin having 3 to 20 carbon atoms are within the above ranges, heat aging resistance, strength characteristics, rubber elasticity, cold resistance and It is excellent in that a rubber composition capable of providing a crosslinked molded article excellent in processability can be obtained. It is particularly preferable that the content of the structural unit derived from ethylene is 90 mol% or less and the content of the structural unit derived from the α-olefin having 3 to 20 carbon atoms is 10 mol% or more because of excellent flexibility. The ethylene structural unit content and the α-olefin structural unit content of the ethylene / α-olefin / non-conjugated polyene copolymer (A) can be measured by a ¹³ C-NMR method. Peak identification and quantification can be performed according to the method described in “Polymer Analysis Handbook” (published by Asakura Shoten, P163-170).

  The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.6 to 5.0 dl / g, preferably 0.8. It is desirable that it is 8-4.0 dl / g, More preferably, it is 0.9-3.5 dl / g. When the intrinsic viscosity [η] measured in decalin at 135 ° C. is in this range, it is excellent in that a resin composition capable of providing a crosslinked molded article having an excellent balance of strength properties, compression set resistance and processability is obtained. ing.

  The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention is usually 2 to 50 g / 100 g, preferably 5 to 40 g / 100 g, more preferably 7 to 30 g / 100 g. Is desirable. When the iodine value is below this range, the crosslinking efficiency is lowered, rubber elasticity, strength characteristics, compression set resistance is lowered, and it is disadvantageous in terms of cost. When the iodine value exceeds this range, the crosslinking density becomes too high, the heat resistance / elongation decreases, and the physical property balance may deteriorate.

  The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention has a molecular weight distribution (Mw / Mn) measured by GPC of usually 1.5 to 50, preferably 1.8 to 30. More preferably, it is 2.0-6.

The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention is preferably 15 to 150. When the Mooney viscosity is in this range, a rubber that is easy to process is easily obtained.

  The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention preferably has a heat of fusion measured by DSC of 60 J / g or less, more preferably 40 J / g or less, It is especially preferable that it is 20 J / g or less.

  The ethylene / α-olefin / non-conjugated polyene copolymer (A) as described above is a polymer production process (Industrial Research Committee Co., Ltd., published p. 309 to 330) or a special feature related to the application of the present applicant. Kaihei 9-71617, JP-A-9-71618, JP-A-9-208615, JP-A-10-67823, JP-A-10-67824, JP-A-10-110054, WO2009 / 081792 No. pamphlet, WO2009 / 081794 pamphlet and the like, and can be produced by a conventionally known method.

As the olefin polymerization catalyst preferably used in the production of the ethylene / α-olefin / non-conjugated polyene copolymer (A) used in the present invention, for example,
A known Ziegler catalyst comprising a transition metal compound such as vanadium (V), zirconium (Zr), titanium (Ti) and the like, and an organoaluminum compound (organoaluminum oxy compound);
Known metallocene catalysts comprising a metallocene compound of a transition metal selected from Group 4 of the periodic table of elements and an organoaluminum oxy compound or an ionized ionic compound, for example, a metallocene catalyst described in JP-A-9-40586 ;
A known metallocene catalyst comprising a specific transition metal compound and a cocatalyst such as a boron compound, for example, a metallocene catalyst described in WO2009 / 072553;
A transition metal compound catalyst comprising a specific transition metal compound and an organometallic compound, an organoaluminum oxy compound, or a compound that reacts with the transition metal compound to form an ion pair, such as described in JP 2011-52231 A Transition metal compound catalysts;
Is mentioned. In particular, a metallocene catalyst is particularly preferable because the distribution of diene is uniform and high crosslinking efficiency can be obtained even if the introduction of diene is small, and the catalyst-derived chlorine content can be reduced because of high catalytic activity.

Liquid ethylene / α-olefin copolymer (B)
The liquid ethylene / α-olefin copolymer (B) used in the present invention is a copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms, and does not contain polyene as a copolymerization component. Here, “liquid” means liquid at normal temperature (25 ° C.). In order to be liquid, the content of the structural unit derived from ethylene of the liquid ethylene / α-olefin copolymer (B), the intrinsic viscosity [η] measured in 135 ° C. decalin, and the kinematic viscosity at 100 ° C. It is preferable to be within a preferable range described later.

  Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene-1, 11-methyldodecene-1, 12 -Ethyltetradecene-1 and the like. Of these, propylene, 1-butene, 4-methylpentene-1, 1-hexene, and 1-octene are preferable, and propylene is particularly preferable from the viewpoint of a balance between fluidity at low temperatures and heat resistance stability. These α-olefins are used alone or in combination of two or more.

  In the liquid ethylene / α-olefin copolymer (B) according to the present invention, the content of structural units derived from ethylene is 30 to 90 mol%, preferably 40 to 80 mol%, more preferably 45 to 75 mol%. And the content of the structural unit derived from the α-olefin is 10 to 70 mol%, preferably 50 to 20 mol%, more preferably 55 to 25 mol%. However, the total of the content rate of the structural unit derived from ethylene and the content rate of the structural unit derived from the α-olefin is 100 mol%. If the ethylene content is too much or less than the above range, the crystallinity becomes high and the low-temperature characteristics may be remarkably deteriorated, and the ethylene / α-olefin / non-conjugated polyene copolymer (A) is mixed. Since the softening effect at the time may also be reduced, it is not preferable.

In the liquid ethylene / α-olefin copolymer (B) according to the present invention, the content of structural units derived from ethylene and the content of structural units derived from α-olefins can be measured by ¹³ C-NMR method. For example, peak identification and quantification can be performed according to the method described later and the method described in “Polymer Analysis Handbook” (published by Asakura Shoten, P163-170).

  The liquid ethylene / α-olefin copolymer (B) according to the present invention has an intrinsic viscosity [η] measured in decalin of 135 ° C. of 0.01 to 0.10 dl / g, preferably 0.02 to 0.10 dl. / G, more preferably 0.03 to 0.08 dl / g.

  As a result of intensive studies, the intrinsic viscosity [η] of the liquid ethylene / α-olefin copolymer (B) measured in decalin at 135 ° C. is 0.10 dl / g or less, preferably less than 0.10 dl / g. If so, the glass transition temperature (Tg) of the liquid ethylene / α-olefin copolymer (B) is greatly reduced depending on the intrinsic viscosity [η] measured in decalin at 135 ° C., and the resulting resin composition It was found that the glass transition temperature of the product can be lowered. When the intrinsic viscosity [η] of the liquid ethylene / α-olefin copolymer (B) measured in decalin at 135 ° C. exceeds 0.10 dl / g, the glass transition of the liquid ethylene / α-olefin copolymer (B) Since temperature (Tg) rises and the effect of lowering the glass transition temperature of the resin composition is lowered, it is not preferable. Moreover, when the intrinsic viscosity [η] measured in 135 ° C. decalin of the liquid ethylene / α-olefin copolymer (B) is less than 0.01 dl / g, the low molecular weight component that is easily volatilized increases, This is not preferable because it causes a decrease in physical properties and a decrease in heat resistance of the resin composition.

Liquid ethylene · alpha-olefin copolymer (B) according to the present invention has a kinematic viscosity at 100 ° C. is 10 to 300 mm ² / s, preferably 15~250mm ² / s, more preferably 20 to 200 mm ² / s.

As a result of intensive studies, the kinematic viscosity at 100 ° C. measured in 135 ° C. decalin of the liquid ethylene / α-olefin copolymer (B) is 300 mm ² / s or less, preferably less than 300 mm ² / s. It has been found that the glass transition temperature (Tg) greatly decreases depending on the low kinematic viscosity at 100 ° C., and the glass transition temperature (Tg) of the resulting resin composition can be lowered. Resin obtained when the kinematic viscosity at 100 ° C. of the liquid ethylene / α-olefin copolymer (B) exceeds 300 mm ² / s, the glass transition temperature of the liquid ethylene / α-olefin copolymer (B) increases. This is not preferable because the effect of lowering the glass transition temperature of the composition is lowered. In addition, when the kinematic viscosity at 100 ° C. of the liquid ethylene / α-olefin copolymer (B) is less than 10 mm ² / s, low molecular weight components that are likely to volatilize increase, resulting in deterioration of physical properties during molding and heat resistance of the resin composition. This is not preferable because it causes a decrease in the temperature.

  The molecular weight distribution (Mw / Mn) of the liquid ethylene / α-olefin copolymer (B) according to the present invention is usually 1.0 to 3.0, preferably 1.4 to 2.5. When the molecular weight distribution is wide (Mw / Mn is large), a low molecular weight component that tends to ooze out and a high molecular weight component that may reduce the softening effect and the workability improving effect are included, which is not preferable. In addition, molecular weight distribution (Mw / Mn) is calculated | required as ratio of the weight average molecular weight (Mw) and number average molecular weight (Mn) calculated | required by gel permeation chromatography (GPC).

  The liquid ethylene / α-olefin copolymer (B) according to the present invention has a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of usually −65 to −90 ° C., and more preferably. Is in the range of −65 to −80 ° C. If the glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) exceeds −65 ° C., the effect of lowering the glass transition temperature (Tg) of the resin composition obtained is not preferable. When a liquid ethylene / α-olefin copolymer (B) having a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of −90 ° C. is used, the glass transition temperature ( The effect of lowering Tg) is practically sufficient. On the other hand, if the glass transition temperature (Tg) is lower than −90 ° C., it is not preferable because it causes a decrease in molecular weight and increases volatility.

In the present invention, the glass transition temperature (Tg) of the liquid ethylene / α-olefin copolymer (B) is measured by differential scanning calorimetry (DSC) by the following method:
The sample pan was placed in the DSC cell, and the DSC cell was heated from 30 ° C. (room temperature) to 150 ° C. at 10 ° C./min in a nitrogen atmosphere, and then held at 150 ° C. for 5 minutes. The temperature is lowered in minutes, and the DSC cell is cooled to −100 ° C. (temperature lowering process). Next, after holding at 100 ° C. for 5 minutes, the temperature is raised at 10 ° C./min, and the intersection of tangents at the inflection point of the enthalpy curve obtained in the temperature raising process is defined as the glass transition temperature (Tg). The glass transition temperature (Tg) was determined based on JIS K7121 9.3.

Further, the liquid ethylene / α-olefin copolymer (B) according to the present invention is not particularly limited, but the B value obtained from the ¹³ C-NMR spectrum and the following general formula (1) is usually 1. It is 06 or more, preferably 1.06 to 1.50, more preferably 1.10 to 1.4, and still more preferably 1.15 to 1.30.
B value = [POE] / (2 · [PE] [PO]) (1)
(Wherein [PE] is the molar fraction of structural units derived from ethylene in the copolymer, and [PO] is the molar fraction of structural units derived from α-olefin in the copolymer. And [POE] is the ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer.)

  This B value is an index representing the distribution state of ethylene and α-olefin in the ethylene / α-olefin copolymer. C. Randall (Macromolecules, 15, 353 (1982)), J. Am. Ray (Macromolecules, 10, 773 (1977)) and the like.

  The larger the B value, the shorter the block chain of ethylene or α-olefin, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution of the copolymer.

  When the B value of the liquid ethylene / α-olefin copolymer (B) according to the present invention is smaller than 1.06, the crystallinity increases and the low-temperature characteristics are remarkably deteriorated. Since the softening effect at the time of mixing with a conjugated polyene copolymer (A) also falls, it is not preferable.

  The liquid ethylene / α-olefin copolymer (B) according to the present invention can be produced using a known method without limitation. For example, a method of copolymerizing ethylene and an α-olefin in the presence of a catalyst comprising a transition metal compound such as vanadium, zirconium, or titanium and an organoaluminum compound (organoaluminum oxy compound) and / or an ionized ionic compound. Is mentioned. Such a method is described, for example, in International Publication No. 00/34420 pamphlet and JP-A-62-1121710.

The liquid ethylene / α-olefin copolymer (B) according to the present invention has a content of structural units derived from ethylene of 30 to 90 mol% as a whole of the liquid ethylene / α-olefin copolymer (B). The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 0.10 dl / g, the kinematic viscosity at 100 ° C. is 10 to 300 mm ² / s, and the molecular weight distribution (Mw / Mn) is It is 1.0-3.0, and 2 or more types of ethylene different in a property in the range in which the glass transition temperature (Tg) calculated | required by differential scanning calorimetry (DSC) satisfy | fills -90--65 degreeC. An α-olefin copolymer may be used in combination.

Resin Composition The resin composition of the present invention is a composition containing the above-described ethylene / α-olefin / polyene copolymer (A) and liquid ethylene / α-olefin copolymer (B) as essential components. The ethylene / α-olefin / polyene copolymer (A) is preferably contained in an amount of 1 to 150 parts by weight, preferably 10 to 120 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). The content is more preferably 20 to 100 parts by weight, still more preferably 30 to 80 parts by weight. When the content of the liquid ethylene / α-olefin copolymer (B) is less than 1 part by weight, the effect of lowering the glass transition temperature (Tg) of the obtained resin composition is not sufficiently exhibited, and the resin composition Does not soften and processability such as kneading and extrusion is not sufficiently improved. When the content of the liquid ethylene / α-olefin copolymer (B) exceeds 150 parts by weight, in the resin composition, the liquid ethylene / α-olefin with respect to the ethylene / α-olefin / polyene copolymer (A) is used. The ratio of the olefin copolymer (B) becomes too large, the plasticizing effect becomes too great and stickiness occurs, and the liquid ethylene / α-olefin copolymer (B) uses a resin composition and a resin composition. In some cases, it may precipitate (bleed) on the surface of the obtained molded article or crosslinked molded article and ooze out.

  In the resin composition of the present invention, the content (Ea mol%) of structural units derived from ethylene of the ethylene / α-olefin / non-conjugated polyene copolymer (A) (however, the content of structural units derived from ethylene) And the total content of structural units derived from α-olefin is 100 mol%), and is 40 to 90 mol%. Since the content (Eb mol%) of the structural unit derived from ethylene of the combined (B) is 30 to 90 mol% and the composition is close, compatibility between the two is improved. The effect of lowering the glass transition point (Tg) of the resulting resin composition is increased, and the bleeding of the liquid ethylene / α-olefin copolymer (B) is remarkably suppressed.

In the resin composition of the present invention, the content (Ea mol%) of structural units derived from ethylene of the ethylene / α-olefin / non-conjugated polyene copolymer (A) (however, the content of structural units derived from ethylene) Of the structural unit derived from ethylene of the liquid ethylene / α-olefin copolymer (B)) and the total content of structural units derived from α-olefin is 100 mol%) It is preferable that the content (Eb mol%) satisfies the following relational expression.
−10 ≦ Ea−Eb ≦ 10
It is more preferable to satisfy the following relational expression.
−5 ≦ Ea−Eb ≦ 5
When Ea and Eb satisfy the above relationship, the ethylene / α-olefin / polyene copolymer (A) and the liquid ethylene / α-olefin copolymer (B) exhibit particularly high affinity. This is preferable because the effect of lowering the glass transition temperature (Tg) of the product is increased, and bleeding out or the like in which the liquid ethylene / α-olefin copolymer (B) component exudes from the resin composition is less likely to occur.

  In the resin composition of the present invention, the glass transition temperature (Tg) obtained by dynamic viscoelasticity measurement is preferably −70 to −30 ° C., more preferably −60 to −40 ° C., − More preferably, it is 55-45 degreeC. When the glass transition temperature (Tg) of the resin composition obtained by dynamic viscoelasticity measurement exceeds −30 ° C., the low temperature characteristics are remarkably deteriorated.

In the resin composition of the present invention, if the glass transition temperature (Tg) obtained by dynamic viscoelasticity measurement exceeds −70 ° C., it is practically sufficient.
In the present invention, the glass transition point (Tg) by dynamic viscoelasticity measurement of the resin composition is measured by the following method:
Using a dynamic viscoelasticity measuring device, dynamic viscoelasticity is increased while increasing the temperature from -60 to 150 ° C at a rate of temperature increase of 3 ° C / min while adding 1% deformation in the twist direction at a frequency of 1 Hz. The temperature dependence was measured, and the temperature at which the loss tangent (tan δ) due to the glass transition temperature had a maximum value was defined as the glass transition point.

In general, oligomerized higher α-olefins are industrially used as synthetic lubricating oil bases, and application to lowering the hardness of rubber compositions is also conceivable. Since the -α-olefin does not have a continuous methylene chain, the structure is not similar to that of the ethylene / α-olefin / non-conjugated polyene copolymer (A). Therefore, the higher poly-α-olefin has a lower affinity with the ethylene / α-olefin / non-conjugated polyene copolymer (A) than the liquid ethylene / α-olefin copolymer (B) according to the present invention, When used as a component of the resin composition, it is considered that the effect of lowering the glass transition temperature (Tg) of the resin composition is small, and bleeding such as bleeding out is more likely to occur. Higher poly-α-olefins such as those described above can be produced by using acid-catalyzed oligos as described in US Pat. No. 3,780,128, US Pat. No. 4,032,591, and JP-A-1-163136. It can be obtained by melization. It can also be obtained by a method using a catalyst system containing a metallocene compound. Such higher poly-α-olefins are commercially available, such as ExxonMobil Chemical's “Spectrasyn”, “Spectrasyn Plus”, “Spectrasyn Elite”, “Spectrasyn Ultra”, Ineos “Durasyn”, and Chemura “Synton”.
If necessary, the resin composition of the present invention can be blended with a crosslinking agent (C) and other components as long as the object of the present invention is not impaired.

Cross-linking agent (C)
The resin composition of the present invention is also preferably used for applications in which crosslinking (vulcanization) is performed, and it is also preferable that a crosslinking agent (C) is blended in the resin composition of the present invention. As the crosslinking agent (C), organic peroxides, sulfur and sulfur compounds can be used.

-Organic peroxide As an organic peroxide, the compound normally used for the peroxide crosslinking of rubber | gum can be especially used without a restriction | limiting.

Specifically, for example, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amylper Oxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2 Dialkyl peroxides such as 1,5-dimethyl-2,5-mono (t-butylperoxy) -hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene;
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxybivalate, t-butyl peroxymaleic acid, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di- peroxyesters such as -t-butylperoxyphthalate;
Examples thereof include ketone peroxides such as dicyclohexanone peroxide, and mixtures thereof.

  Of these, organic peroxides having a half-life of 1 minute in the range of 130 ° C. to 200 ° C. are preferred, and in particular, dicumyl peroxide, di-t-butyl peroxide, di-t-butyl peroxy. Organic peroxides such as -3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, and t-butyl hydroperoxide are preferred. These organic peroxides are used alone or in combination of two or more.

  In the resin composition of the present invention, the organic peroxide is usually 0.0003 to 0.05 mol, preferably 0.001 to 100 g of ethylene / α-olefin / non-conjugated polyene copolymer (A). Although it is used at a ratio of 0.03 mol, it is desirable to determine the optimum amount as appropriate according to the required physical properties.

  When an organic peroxide is used as the crosslinking agent (C), it is preferable to use a crosslinking aid in combination. Specific examples of crosslinking aids include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; Maleimide compounds; divinylbenzene and the like. Such a crosslinking aid is used in an amount of 0.5 to 2 mol, preferably about equimolar, with respect to 1 mol of the organic peroxide used.

-Sulfur and sulfur compounds Specific examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like. Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, polymer polysulfide, and sulfur compounds that release by active sulfur at the crosslinking (vulcanization) temperature, such as morpholine disulfide, alkylphenol disulfide, tetra Examples thereof include methyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, selenium dimethyldithiocarbamate and the like. Of these, sulfur is preferred.

These sulfur or sulfur compounds are used alone or in combination of two or more.
In the resin composition of the present invention, sulfur or a sulfur compound is usually 0.1 to 10 parts by weight, preferably 0.5 to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). Although it is used at a ratio of ˜5 parts by weight, it is desirable to appropriately determine the optimum amount according to the required physical properties.

Sulfur or a sulfur compound is preferable because it can be subjected to a crosslinking step even in an oxygen atmosphere as compared with an organic peroxide, and is easy to process in terms of equipment.
Moreover, when using sulfur or a sulfur compound as a crosslinking agent (C), it is preferable to use a crosslinking accelerator (vulcanization accelerator) together. Specific examples of the crosslinking accelerator used together with sulfur or a sulfur compound include N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-oxydiethylene-2-benzothiazole sulfenamide (OBS), N- Sulfenamide compounds such as t-butyl-2-benzothiazole sulfenamide (BBS) and N, N-diisopropyl-2-benzothiazole sulfenamide; 2-mercaptobenzothiazole (MBT), 2- (2, Thiazole compounds such as 4-dinitrophenyl) mercaptobenzothiazole, 2- (4-morpholinodithio) benzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl disulfide; DPG), Trifeni Guanidine compounds such as guanidine, diortholyl guanidine (DOTG), orthotolyl biguanide, diphenyl guanidine phthalate; acetaldehyde-aniline condensate, butyraldehyde-aniline condensate, hexamethylenetetramine (H), acetaldehyde ammonia Aldehydeamines such as aldehyde amine or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea (EUR), dibutylthiourea, trimethylthiourea, diorthotolylthiourea; (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide Thiuram compounds such as tetrakis (2-ethylhexyl) thiuram disulfide (TOT), dipentamethylene thiuram tetrasulfide (TRA); zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, ethylphenyldithiocarbamate Compounds such as zinc, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium dimethyldithiocarbamate, xanthates such as zinc dibutylxanthate; zinc white (zinc oxide), etc. . These crosslinking accelerators are usually used in a proportion of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). It is done.

Other components The resin composition of the present invention contains other components such as various known compounding agents blended in a general rubber composition according to desired performance and the like within a range not to impair the purpose of the present invention. May be. Examples of the compounding agent include a softening agent, a vulcanization aid, an anti-aging agent, a processing aid, an alkoxysilane compound, a crosslinking agent, a crosslinking aid, an inorganic filler, an activator, a reaction inhibitor, a colorant, a dispersant, Flame retardants, plasticizers, antioxidants, scorch inhibitors, ultraviolet absorbers, antistatic agents, lubricants, fungicides, peptizers, tackifiers, various dyes such as disperse dyes and acid dyes as representative examples, Compounding agents such as inorganic and organic pigments, surfactants, and paints, and foaming compounds such as foaming agents and foaming aids, and defoaming agents can be mentioned as necessary. It can select suitably in the range which does not impair the objective, and can mix | blend with a suitable compounding quantity.

-Softener As a softener, in addition to a liquid ethylene alpha-olefin copolymer (B), the softener normally used for rubber | gum can be used together in the range which does not impair oozing. Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fat oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; petroleum Examples thereof include synthetic polymer materials such as resin, atactic polypropylene, and coumarone indene resin. Of these, petroleum softeners are preferably used, and process oil is particularly preferably used. The kind and blending amount of these softening agents can be appropriately selected depending on the desired performance of the rubber roller produced from the resin composition, but the blending amount is usually an ethylene / α-olefin / non-conjugated polyene copolymer ( A) It is 150 weight part or less with respect to 100 weight part, Preferably it is 130 weight part or less at maximum.

-Anti-aging agent If an anti-aging agent is used, it is possible to further extend the life of the material. This is the same as in the case of ordinary rubber.

  Specific examples of the antioxidant that may be contained in the resin composition of the present invention include phenylnaphthylamine, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine, N, N′-di-2- Aromatic secondary amine stabilizers such as naphthyl-p-phenylenediamine; 2,6-di-t-butyl-4-methylphenol, tetrakis- [methylene-3- (3 ′, 5′-di-t- Butyl-4'-hydroxyphenyl) propionate] phenolic stabilizers such as methane; thioether stabilizers such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide Benzoimidazole stabilizers such as 2-mercaptobenzimidazole; dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate; 2,2,4- Quinoline-based stabilizer polymer such as a Rimechiru-1,2-dihydroquinoline and the like. These anti-aging agents are used alone or in combination of two or more. Such an anti-aging agent is usually used in a proportion of 5 parts by weight or less, preferably 3 parts by weight or less, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A). It is desirable to determine the optimum amount as appropriate according to the physical property value.

-Processing aid As a processing aid, the compound mix | blended with a general rubber composition can be especially used without a problem. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid, higher fatty acid salts such as barium stearate, zinc stearate and calcium stearate, ricinoleic acid ester, stearic acid ester, palmitic acid ester and lauric acid And higher fatty acid esters such as acid esters. In the resin composition for a rubber roller of the present invention, such a processing aid is usually 10 parts by weight or less, preferably 5 parts per 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A). Although it is used at a ratio of not more than parts by weight, it is desirable to appropriately determine the optimum amount according to the required physical property value.

-Inorganic filler The resin composition of this invention may contain well-known inorganic fillers, such as a rubber reinforcement and an inorganic filler, as an arbitrary component in the range which does not impair the objective of this invention.

  The rubber reinforcing agent has an effect of enhancing mechanical properties such as tensile strength, tear strength, and wear resistance of the crosslinked rubber. Such a rubber reinforcing agent is not particularly limited. For example, surface treatment is performed with carbon black such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, and MT, graphite, and a silane coupling agent. These carbon blacks, fine silica, silica, alumina, magnesium oxide, barium oxide, oxide fillers such as calcium oxide, hydroxide fillers such as aluminum hydroxide and magnesium hydroxide, sedimentary rocks such as diatomaceous earth and limestone And clay mineral fillers such as kaolinite, kaolinite and montmorillonite, magnetic fillers such as ferrite, iron and cobalt, and conductive fillers such as silver, gold, copper and alloys.

Examples of silica include fumed silica and precipitated silica. These silicas may be surface-treated with a reactive silane such as hexamethyldisilazane, chlorosilane, or alkoxysilane, or a low molecular weight siloxane. The specific surface area of the silica (BET method) is not particularly limited, is preferably 50 m ² / g or more, more preferably 100 to 400 m ² / g.

  The type and blending amount of the rubber reinforcing agent can be appropriately selected depending on its use, but is usually 300 parts by weight at the maximum with respect to 100 parts by weight of the ethylene / α-olefin / nonconjugated polyene copolymer (A), preferably 200 parts by weight or less.

In addition, the inorganic filler is not particularly limited, and examples thereof include light calcium carbonate, heavy calcium carbonate, talc, and clay.
Although the kind and compounding quantity of an inorganic filler can be suitably selected by the use, 0.1-10,000 weight is normally with respect to 100 weight part of ethylene, alpha-olefin, nonconjugated polyene copolymer (A). Part.
These inorganic fillers can be used alone or in combination of two or more according to the purpose.

-Foaming agent and foaming aid The resin composition of the present invention may be blended with a foaming agent and foaming aid that are usually used in rubber, if necessary, It can also be obtained by molding, foaming, and crosslinking using a resin composition containing a foaming agent and a foaming aid.

  Specific examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitrosotephthalamide, N Nitroso compounds such as, N'-dinitrosopentamethylenetetramine; Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide , Sulfonyl hydrazide compounds such as p, p'-oxybis (benzenesulfonylhydrazide) and diphenylsulfone-3,3'-disulfonylhydrazide; calcium azide, 4,4-diphenyldisulfonyl azide, p-toluenesulfur Azide compounds such Runiruajido the like. These foaming agents are 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 / α-olefin / non-conjugated polyene copolymer (A).

  If necessary, the foaming aid used in combination with the foaming agent acts to lower the decomposition temperature of the foaming agent, promote decomposition, and make the bubbles uniform. Examples of such foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, urea, and derivatives thereof. These foaming assistants are used in a proportion of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A). However, it is desirable to appropriately determine the optimum amount according to the required physical property value.

-Defoaming agent When the resin composition is crosslinked, bubbles may be formed or the degree of foaming may be different depending on the moisture contained. In order to prevent these problems, a defoaming agent such as calcium oxide may be added to the resin composition of the present invention. The defoaming agent is usually used in a proportion of 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A). It is desirable to determine the optimum amount as appropriate according to the value.

Preparation of Resin Composition and Crosslinked Molded Body The resin composition of the present invention comprises the above-described ethylene / α-olefin / non-conjugated polyene copolymer (A), liquid ethylene / α-olefin copolymer (B), and necessary. Depending on the case, it can be prepared by blending other components by a known method.

  The preparation of the resin composition of the present invention, the molded body, the preform for the production of a crosslinked molded body, or the production of the crosslinked molded body of the present invention may be performed continuously, or a resin composition was prepared. Thereafter, the resin composition may be separately molded and crosslinked.

  When a crosslinked product is produced from the resin composition according to the present invention, an unvulcanized resin composition (compounded rubber) is prepared once in the same manner as when ordinary rubber is generally crosslinked, and then this blended rubber is prepared. Cross-linking may be carried out after forming the desired shape.

  The resin composition according to the present invention can be prepared, for example, by the following method. That is, by using an internal mixer (closed mixer) such as a Banbury mixer, a kneader, or an intermix, the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer (A) and liquid ethylene / α-olefin copolymer are mixed. After kneading the polymer (B) and, if necessary, a compounding agent at a temperature of 80 to 170 ° C. for 3 to 10 minutes, using a roll such as an open roll or a kneader, if necessary, a crosslinking agent (C) If necessary, a crosslinking accelerator or a crosslinking aid, a foaming agent and the like may be additionally mixed, kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensed. .

  Further, when the kneading temperature in the internal mixer is low, the ethylene / α-olefin / non-conjugated polyene copolymer (A), the liquid ethylene / α-olefin copolymer (B), if necessary, A compounding agent such as a softening agent, a crosslinking agent (C), a vulcanization accelerator or a vulcanization aid, a foaming agent, a colorant, a dispersant, a flame retardant, and the like may be mixed at the same time.

  The crosslinkable resin composition according to the present invention prepared as described above is molded into an intended shape by various molding methods such as an extruder, a calendar roll, a press, an injection molding machine, a transfer molding machine, Simultaneously with the molding or the molded product can be introduced into a crosslinking tank and crosslinked.

  Crosslinking can usually be performed by heating at a temperature of 120 to 270 ° C. for 1 to 30 minutes. Thus, when obtaining a crosslinked molded object by bridge | crosslinking by heat | fever, it is preferable that the resin composition contains the crosslinking agent (C). Crosslinking can also be performed by irradiating a predetermined amount of radiation to an uncrosslinked resin composition molded as necessary. As the radiation, α rays, β rays, γ rays, electron beams, neutron rays, X rays, and the like are used. Of these, cobalt-60 γ rays and electron beams are preferably used. When the crosslinking is performed by irradiation with radiation such as an electron beam, the resin composition does not necessarily contain the crosslinking agent (C).

  In such a crosslinking step, a mold may be used, or the crosslinking may be performed without using a mold. When a mold is not used, the molding and crosslinking processes are usually carried out continuously. As a heating method in the crosslinking tank, a heating tank such as hot air, glass bead fluidized bed, UHF (ultra high frequency electromagnetic wave), steam, LCM (hot molten salt tank) can be used.

Cross-linked molded product The cross-linked molded product of the present invention is obtained by crosslinking the above-described resin composition of the present invention. By forming the crosslinked molded article of the present invention from the above-described resin composition of the present invention, it is excellent in moldability, excellent in low temperature characteristics, and hardly causes bleeding out.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the following examples and comparative examples, each physical property was measured or evaluated by the following method.

[Ethylene content, propylene content, blockness (B value)]
The content (ethylene content) of structural units derived from ethylene in the ethylene / propylene copolymer obtained in Production Example, the content (propylene content) of structural units derived from propylene, and blockness (B value) are ¹³ The measurement was performed by C-NMR with the following apparatus and conditions.

Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / heavy benzene (80/20% by volume) as a solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, 27.50 ppm as standard for chemical shift Measured as a value.

The B value is a parameter indicating the randomness of the copolymerization monomer chain distribution, and can be calculated by the following equation.
B value = POE / (2PO · PE)
(Wherein PE and PO are the mole fraction of the ethylene component and the mole fraction of the α-olefin component, respectively, contained in the ethylene / α-olefin random copolymer, and POE is the total dyad (dyad)). ) Ratio of ethylene / α-olefin alternating chain number to chain number.)

Ethylene content, propylene content, PE, PO and POE values from the measured ¹³ C-NMR spectrum as described above, G. J. et al. Ray (Macromolecules, 10, 773 (1977)), J. MoI. C. Randall (Macro-molecules, 15, 353 (1982)), K. et al. It can be determined based on the report of Kimura (Polymer, 25, 4418 (1984)).

[Kinematic viscosity]
Based on ASTM D445, the measurement was performed using a fully automatic viscometer CAV-4 manufactured by Canon.

[Molecular weight (Mw, Mn) and molecular weight distribution (Mw / Mn)]
(Method A): Measurement in ethylene / α-olefin / non-conjugated polyene copolymer (A) The molecular weight was determined by using a liquid chromatograph: Waters ALC / GPC150-C plus type (suggested refractometer detector integrated type), Two columns of GMH6-HT manufactured by Tosoh Corporation and two of GMH6-HTL were connected in series as columns, and o-dichlorobenzene was used as a mobile phase medium, and measurement was performed at 140 ° C. at a flow rate of 1.0 ml / min.
Mw / Mn value was calculated by analyzing the obtained chromatogram by a known method using a calibration curve using a standard polystyrene sample. The measurement time per sample was 60 minutes.
(Method B): Measurement in liquid ethylene / α-olefin copolymer (B) The following liquid chromatography pump, sampling device, gel permeation chromatography (GPC) column, differential refractive index detector (RI detector) ), And GPC measurement was performed.
Liquid chromatography device: Waters 515 HPLC Pump
Sampling apparatus: 717 plus Autosampler apparatus manufactured by Waters Mobile phase: THF (containing stabilizer, grade for liquid chromatography)
Column: One MIXED-D made by PL and one 500 mm made by PL were connected in series.
Sample concentration: 5 mg / mL
Mobile phase flow rate: 1.0 mL / min Measurement temperature: Normal temperature Standard sample for calibration curve: EasyCal PS-1 manufactured by PL

[Iodine number]
The iodine value was measured according to JIS K0070.

[Intrinsic viscosity [η] measured in decalin at 135 ° C.]
Intrinsic viscosity [η] [dl / g] was measured using a fully automatic intrinsic viscometer manufactured by Koiso Co., Ltd. at a temperature of 135 ° C. and a measurement solvent: decalin.

[Heat of fusion]
Using a Perkin Elmer DSC measuring device, the sample was packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min, held at 200 ° C. for 5 min, and then cooled to −150 ° C. at 10 ° C./min. Subsequently, it calculated | required from the exothermic and endothermic curve at the time of heating up at 10 degree-C / min.

[Mooney viscosity [ML _{1 + 4} (100 ° C)]]
Mooney viscosity [ML _{1 + 4} (100 ° C.)] was measured using a Mooney viscometer (SMV202 type, manufactured by Shimadzu Corporation) under the condition of 100 ° C. in accordance with JIS K6300.

[Glass transition temperature (Tg)]
Method A: Tg by differential scanning calorimetry (DSC) (measurement in liquid ethylene / α-olefin copolymer (B))
Using Seiko Instruments X-DSC-7000, place 8ml liquid ethylene / α-olefin copolymer (B) in an aluminum sample pan that can be sealed easily in the DSC cell, and place the DSC cell in a nitrogen atmosphere. Then, the temperature was raised from room temperature to 150 ° C. at 10 ° C./minute, then held at 150 ° C. for 5 minutes, then cooled to 10 ° C./minute, and the DSC cell was cooled to −100 ° C. (temperature reduction process). Next, after holding at 100 ° C. for 5 minutes, the temperature was raised at 10 ° C./min, and the intersection of tangents at the inflection point of the enthalpy curve obtained in the temperature raising process was defined as the glass transition temperature (Tg). The glass transition temperature (Tg) was determined based on JIS K7121 9.3. This measurement method is sometimes referred to as a DSC method.

Method B: Tg by dynamic viscoelasticity measurement (measurement in resin composition and crosslinked molded body)
Using a 2 mm thick press sheet obtained by press molding, a strip of 5 mm width necessary for dynamic viscoelasticity measurement was cut out. Dynamic viscoelasticity using ARES-G3 manufactured by TA Instruments Inc. while increasing the temperature from -60 to 100 ° C at a rate of 3 ° C / min while adding 1% deformation in the twist direction at a frequency of 1 Hz. The temperature at which the glass transition temperature loss tangent (tan δ) takes a maximum value was determined as the glass transition temperature. This measurement method is sometimes referred to as the tan δ method.

[Compression set]
A cylindrical vulcanized block with a thickness of 12.5mmt and a diameter of 30mmφ was used as a cross-linked molded product sample, compressed in accordance with JIS K6262 at 25% at -40 ° C, held for 22 hours, the load was removed, and residual strain was removed after 30 minutes. Was measured.
In the following examples and comparative examples, the following were used as resin components.

<Ethylene / α-olefin / non-conjugated polyene copolymer (A)>
[Production Example 1] (Production of ethylene / propylene / diene copolymer (a-1))
Using a reactor with a stirrer made of SUS with a volume of 300 L, the temperature was kept at 80 ° C., the liquid level was 100 L, hexane was 26.8 kg / h, ethylene (C2) was 3.9 kg / h, and propylene (C3) was 5.4 kg / h, 5-ethylidene-2-norbornene (ENB) at a rate of 1.1 kg / h and hydrogen at a rate of 44 NL / h as the main catalyst [N- (1,1-dimethylethyl)- 1,1-dimethyl-1-[(1,2,3,3A, 8A-η) -1,5,6,7-tetrahydro-2-methyl-S-indacene-1-yl] silane aminate (2 -)-ΚN] [(1,2,3,4-η) -1,3-pentadiene] -titanium 0.07 mmol / h, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) as a cocatalyst ₄ a 0.28 mmol / h, the organic aluminum compound TIBA supplying to the reactor continuously at a rate of 1.8 mmol / h, to obtain a polymer liquid terpolymer of ethylene, propylene and 5-ethylidene-2-norbornene (a-1).

The polymerization pressure was 2.1 MPa (gauge pressure).
The resulting polymerization solution was desolvated by flash drying to obtain an ethylene / propylene / diene copolymer (a-1). The physical properties of the obtained polymer showed the following physical properties. Ethylene-derived structural unit content 57 mol%, intrinsic viscosity [η] = 1.64 dl / g measured in decalin at 135 ° C., iodine value = 16, Mw / Mn = 2.4, Mooney viscosity [ML _{1 +4} (100 ° C.)] = 45.

[Production Example 2] (Production of ethylene / propylene / diene copolymer (a-2))
In producing the copolymer by the same method as the ethylene / propylene / diene copolymer (a-1) of Production Example 1, the flow rates of ethylene, propylene, 5-ethylidene-2-norbornene and hydrogen are appropriately adjusted. Thus, an ethylene / propylene / diene copolymer (a-2) was obtained. The physical properties of the obtained polymer showed the following physical properties. Intrinsic viscosity [η] = 3.2 dl / g, iodine number = 25, Mw / Mn = 2.6, Mooney viscosity [ML _{1] +4} (100 ° C.)] = 20.

<Liquid ethylene-propylene copolymer (B)>
[Production Example 3] (Production of liquid ethylene / propylene copolymer (b-2))
Ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl _1.5 ) adjusted to 96 mmol / L by adding 1 liter of dehydrated and purified hexane to a continuous polymerization reactor with a stirring blade with a capacity of 2 liters sufficiently purged with nitrogen A hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 16 mmol / l as a catalyst was further supplied in an amount of 500 ml / h continuously for 1 hour, and hexane was added in an amount of 500 ml / h. It was continuously fed in an amount of 500 ml / h. On the other hand, from the upper part of the polymerization vessel, the polymerization solution was continuously extracted so that the polymerization solution in the polymerization vessel was always 1 liter. Next, ethylene gas was supplied in an amount of 35 L / h, propylene gas in an amount of 35 L / h, and hydrogen gas in an amount of 80 L / h using a bubbling tube. The copolymerization reaction was carried out at 35 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

  Thereby, a polymerization solution containing an ethylene / propylene copolymer was obtained. The obtained polymerization solution was deashed with hydrochloric acid, and then poured into a large amount of methanol to precipitate an ethylene / propylene copolymer, followed by drying under reduced pressure at 130 ° C. for 24 hours to obtain a liquid ethylene / propylene copolymer. The union (b-2) was obtained. Table 1 shows the analysis results of the obtained liquid ethylene / propylene copolymer (b-2).

[Production Examples 4 to 12]
In Production Example 3, the ethylene / propylene copolymers (b-1) and (b) shown in Tables 1 and 2 were adjusted by appropriately adjusting the supply amount of ethylene gas, the supply amount of propylene gas, and the supply amount of hydrogen gas. b-3) to (b′-10) were obtained. Tables 1 and 2 show the analysis results of the obtained ethylene / propylene copolymers.

[Example 1]
Using a Toyo Seiki lab plast mill (biaxial batch melt blending device), 100 parts by weight of ethylene / propylene / diene copolymer (a-1) as a softening agent, liquid ethylene / propylene copolymer 50 parts by weight of the union (b-1) was added, and the mixture was melt-kneaded at a set temperature of 120 ° C. under a resin charge of 50 g (apparatus batch volume = 60 cm ³ ), 50 rpm, and 15 minutes. The obtained resin composition was press-molded under conditions of preheating 200 ° C., 5 minutes, pressure 200 ° C., 3 minutes, cooling 10 ° C., 5 minutes to obtain a sheet-like resin composition.

  About the obtained resin composition, the glass transition temperature (Tg) was measured by the said B method (dynamic viscoelasticity measurement). The results are shown in Table 3. Moreover, the difference of the glass transition temperature with the comparative example 1 mentioned later is combined with Table 3, and is shown.

[Comparative Example 1]
A resin composition was prepared under the same conditions as in Example 1 except that no softener was added, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Example 2, Comparative Examples 2 to 4]
As shown in Table 3, the type of softening agent was changed, and a resin composition was prepared under the same conditions as in Example 1 except that, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

  The glass transition temperature difference ΔT (° C.) with Comparative Example 1 to which no softening agent is added indicates a change in the glass transition temperature due to the softening agent. From the results shown in Table 3, this is defined by the present invention. In Examples 1 and 2 in which the liquid ethylene / propylene copolymer (B) satisfying the intrinsic viscosity [η] and the kinematic viscosity at 100 ° C. was used as the softening agent, the absolute value of this value was large, and the predetermined intrinsic viscosity [η ] And Comparative Examples 2 to 4 using a softener that does not exhibit kinematic viscosity at 100 ° C. are small. From this, it can be seen that in Examples 1 and 2, the effect of lowering the glass transition temperature of the resin composition by the softening agent is much greater than that of the comparative example.

[Example 3]
Example 1 is the same as Example 1 except that ethylene / propylene / diene copolymer (a-2) is used as a softening agent instead of ethylene / propylene / diene copolymer (a-1). A resin composition was prepared and the glass transition temperature was measured. The results are shown in Table 4. Moreover, the difference of the glass transition temperature with the comparative example 5 mentioned later is combined with Table 4, and is shown.

[Comparative Example 5]
A resin composition was prepared under the same conditions as in Example 3 except that no softener was added, and evaluated in the same manner as in Example 3. The evaluation results are shown in Table 4.

[Examples 4 to 9, Comparative Examples 6 to 10]
Resin compositions were prepared under the same conditions as in Example 3 except that the type of softener was changed as shown in Tables 4 and 5, and evaluated in the same manner as in Example 3. The evaluation results are shown in Table 4 and Table 5.

[Comparative Example 11]
As shown in Table 5, the softening agent was changed to paraffinic process oil (manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-380, 100 ° C. kinematic viscosity = 30 mm ² / s, 40 ° C. kinematic viscosity = 380 mm ² / s). Otherwise, a resin composition was prepared under the same conditions as in Example 3, and evaluated in the same manner as in Example 3. The evaluation results are shown in Table 5.

  The glass transition temperature difference ΔT (° C.) with Comparative Example 5 to which no softening agent is added indicates a change in the glass transition temperature due to the softening agent. From the results shown in Tables 4 and 5, in the present invention, In Examples 4 to 9 in which the liquid ethylene / propylene copolymer (B) satisfying the predetermined intrinsic viscosity [η] to be defined and the kinematic viscosity at 100 ° C. was used as the softening agent, this difference was as large as 5 ° C. In Comparative Examples 5 to 10 using a softener that does not exhibit a predetermined intrinsic viscosity [η] and kinematic viscosity at 100 ° C., the difference is as small as 4 ° C. or less. From this, in Examples 4-9, it turns out that the low temperature effect by the softening agent of the glass transition temperature of a resin composition is large compared with a comparative example. Further, it can be seen from Comparative Example 11 that the process oil generally used as a softening agent has a small effect of lowering the glass transition temperature of the resin composition. This is presumably because the process oil itself contains wax that crystallizes at low temperatures.

[Example 10]
MIXTRON BB MIXER (Kobe Steel Ltd., BB-4 type, volume 2.95 L, rotor 4WH) is softened with respect to 100 parts by weight of the above-described ethylene / propylene / diene copolymer (a-1). 40 parts by weight of liquid ethylene / propylene copolymer (b-2) as an agent, 5 parts by weight of zinc white “META-Z102” (trade name; manufactured by Inoue Lime Industry Co., Ltd.) as a vulcanization aid, processing aid 1 part by weight of stearic acid and 50 parts by weight of carbon black “Asahi # 70” (trade name; manufactured by Asahi Carbon Co., Ltd.) as a reinforcing agent were added and kneaded. The kneading conditions were a rotor rotation speed of 50 rpm, a floating weight pressure of 3 kg / cm ² , and a kneading time of 5 minutes.

1 part by weight of 2-mercaptobenzothiazole “Sunceller TT” (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.) as a vulcanization accelerator and tetramethylthiuram disulfide “Sunceller TT” (trade name) ; Sanshin Chemical Industry Co., Ltd.) 1 part by weight, dipentamethylene thiuram tetrasulfide "Sunseller TRA" (trade name; Sanshin Chemical Industry Co., Ltd.) 1 part by weight, sulfur as a vulcanizing agent 1 After adding a weight part, kneading with a 6-inch open roll (front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and dispensing into a sheet, By heating and vulcanizing at 170 ° C. for 10 minutes using a heating press, a crosslinked molded body having a cylindrical vulcanization block with a thickness of 12.5 mmt and a diameter of 30 mmφ, and a thickness of 2.0 mm A vulcanized sheet of t was obtained.
The compression set was measured using the vulcanized block as described above, and the glass transition temperature was measured using the vulcanized sheet. The results are shown in Table 6.

[Example 11, Comparative Examples 12 and 13]
In Example 10, in place of the liquid ethylene / propylene copolymer (b-2), a resin composition and a crosslink were formed under the same conditions as in Example 10 except that the softeners of the type shown in Table 6 were used. A vulcanized block and a vulcanized sheet as a molded body were prepared, and each property was measured in the same manner as in Example 10. The results are shown in Table 6.

[Comparative Example 14]
In Example 10, instead of the liquid ethylene / propylene copolymer (b-2), as shown in Table 6, higher poly α-olefin (PAO) (manufactured by ExxonMobil Chemical, Spectra Syn ™ 100, 100 ° C. Except that kinematic viscosity = 100 mm ² / s) was used as a softening agent, and a resin composition, a vulcanized block and a vulcanized sheet as a cross-linked molded article were prepared under the same conditions as in Example 10. Similarly, each property was measured. The results are shown in Table 6.

[Comparative Example 15]
In Example 10, instead of the liquid ethylene / propylene copolymer (b-2), as shown in Table 6, paraffinic process oil (manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-380, 100 ° C. kinematic viscosity) = 30 mm ² / s, 40 ° C kinematic viscosity = 380 mm ² / s), except that a resin composition, a vulcanized block and a vulcanized sheet as a cross-linked molded product were used under the same conditions as in Example 10. And each property was measured in the same manner as in Example 10. The results are shown in Table 6.

  From the results shown in Table 6, in the case of producing a cross-linked molded article from a resin composition containing an ethylene / α-olefin / non-conjugated polyene copolymer (A) and a softener that satisfies the requirements defined in the present invention, In Examples 10 and 11 in which the liquid ethylene / α-olefin copolymer (B) satisfying the requirements defined in the invention was used as a softening agent, the glass transition temperature of the crosslinked molded body was a predetermined value defined in the present invention as a softening agent. Comparative Examples 12 and 13 using a liquid ethylene / α-olefin copolymer that does not satisfy the intrinsic viscosity [η] and kinematic viscosity at 100 ° C., Comparative Example 14 using a higher poly α-olefin (PAO), and a process It is low as compared with Comparative Example 15 using oil, and it can be seen that the crosslinked molded product is excellent in low-temperature flexibility. From this, when the resin composition of the present invention containing the liquid ethylene / α-olefin copolymer (B) satisfying all the requirements defined in the present invention as a softening agent is used, However, it is shown that the glass transition temperature is greatly lowered and the effect of lowering the glass transition temperature is sufficiently exhibited. Further, when the softening agent is a liquid ethylene / α-olefin copolymer, higher polyα-olefin (PAO) or process oil that does not satisfy the predetermined intrinsic viscosity [η] defined in the present invention and the kinematic viscosity at 100 ° C. Shows that the effect of lowering the glass transition temperature of the crosslinked molded body is small. Furthermore, in Examples 10 and 11, it is shown that the -4O0C compression set of the crosslinked molded body is small, and the crosslinked molded body is excellent in low temperature characteristics.

[Examples 12 and 13, Comparative Examples 16 and 17]
In Example 10, instead of ethylene / propylene / diene copolymer (a-1) as ethylene / α-olefin / non-conjugated polyene copolymer (EPDM), ethylene / propylene / diene copolymer (a-2) A vulcanized sheet that is a resin composition and a cross-linked molded article was prepared under the same conditions as in Example 10 except that the type of softener was as shown in Table 7. The glass transition temperature was measured in the same manner as in Example 10. The results are shown in Table 7.

[Comparative Example 18]
In Example 10, instead of ethylene / propylene / diene copolymer (a-1) as ethylene / α-olefin / non-conjugated polyene copolymer (EPDM), ethylene / propylene / diene copolymer (a-2) In place of the liquid ethylene / propylene copolymer (b-2) as a softening agent, a higher poly α-olefin (PAO) (manufactured by ExxonMobil Chemical, Spectra Syn ™ 100, 100 ° C. kinematic viscosity = 100 mm ² / A resin composition and a vulcanized sheet as a crosslinked molded body were prepared under the same conditions as in Example 10 except that s) was used, and the glass transition temperature was obtained in the same manner as in Example 10 using the obtained vulcanized sheet. Was measured. The results are shown in Table 7.

[Comparative Example 19]
In Example 10, instead of ethylene / propylene / diene copolymer (a-1) as ethylene / α-olefin / non-conjugated polyene copolymer (EPDM), ethylene / propylene / diene copolymer (a-2) In place of the liquid ethylene / propylene copolymer (b-2) as a softening agent, paraffinic process oil (manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-380, 100 ° C. kinematic viscosity = 30 mm ² / s, other 40 ° C. kinematic viscosity = 380mm ² / s) for the use of prepared vulcanized sheet is a resin composition and crosslinked molded body under the same conditions as in example 10, carried out using the obtained vulcanized sheet The glass transition temperature was measured as in Example 10. The results are shown in Table 7.

  From Table 7 above, a cross-linked molded article is produced from a resin composition in which various softeners are added to the ethylene / α-olefin / non-conjugated polyene copolymer (A) that satisfies the requirements defined in the present invention. In Examples 12 and 13 using the liquid ethylene / α-olefin copolymer (B) that satisfies the requirements defined in the present invention as a softening agent, the glass transition temperature of the crosslinked molded product is the present invention as a softening agent. Comparative Examples 16 and 17 using a liquid ethylene / α-olefin copolymer which does not satisfy the predetermined intrinsic viscosity [η] defined by ## EQU1 ## and a kinematic viscosity at 100 ° C., and a comparative example using a higher poly α-olefin (PAO) 18 and the comparative example 19 using process oil, it is low, and it can be seen that the cross-linked molded article is excellent in low-temperature flexibility.

  From the above Table 6 and Table 7, in the case of producing a cross-linked molded article from a resin composition containing an ethylene / α-olefin / non-conjugated polyene copolymer (A) and a softening agent that satisfy the requirements defined in the present invention, Even if the type of the copolymer (A) is changed within the range that satisfies the requirements defined in the present invention, the liquid ethylene / α-olefin copolymer (B) that satisfies all the requirements defined in the present invention is used as a softening agent. It can be seen that the glass transition temperature of the crosslinked molded article is sufficiently low, the effect of lowering the glass transition temperature of the crosslinked molded article by the softener is great, and the low temperature flexibility is improved. On the other hand, when higher poly α-olefin (PAO) or process oil is used as a softening agent, the effect of lowering the glass transition temperature of the crosslinked molded product is small.

  The resin composition of the present invention and a cross-linked molded article using the resin composition can be suitably used in fields where weather resistance, heat aging resistance, bleed out resistance and low temperature flexibility are required. For example, automotive parts such as various damper pulleys, glass run channels, weather strip sponges, door opening trims, marine parts, civil engineering parts, medical parts, electrical / electronic parts, sealing products, seats, shoes, tire sides Walls, tire tubes, covered electric wires, electrical insulation parts, household rubber products, leisure parts, coating materials or adhesives.

Claims (6)

100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer (A) satisfying the following requirements (a-1) to (a-5):
A resin composition comprising 1 to 150 parts by weight of a liquid ethylene / α-olefin copolymer (B) satisfying the following requirements (b-1) to (b-6).
(A-1) a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene.
(A-2) In a total of 100 mol% of structural units derived from ethylene and structural units derived from α-olefin, the content (Ea mol%) of the structural units derived from ethylene is 40 to 90 mol%. It is.
(A-3) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.6 to 5.0 dl / g.
(A-4) The iodine value is 2-50.
(A-5) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 1.5-50.
(B-1) having a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms.
(B-2) The content of structural units derived from ethylene is 30 to 90 mol% (however, the total of the content of structural units derived from ethylene and the content of structural units derived from α-olefins is 100 mol) %).
(B-3) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 0.10 dl / g.
(B-4) The kinematic viscosity at 100 ° C. is 10 to 300 mm ² / s.
(B-5) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 1.0 to 3.0.
(B-6) The glass transition temperature (Tg) obtained by differential scanning calorimetry (DSC) is -90 to -65 ° C. The content of structural units derived from ethylene of the ethylene / α-olefin / non-conjugated polyene copolymer (A) (Ea mol%);
Content rate (Eb mol%) of structural units derived from ethylene of the liquid ethylene / α-olefin copolymer (B) (however, the total of structural units derived from ethylene and structural units derived from α-olefin is The resin composition according to claim 1, wherein (100 mol%) satisfies the following formula (1).
−10 ≦ Ea−Eb ≦ 10 (1)   The structural unit derived from ethylene (Ea mol%) of the ethylene / α-olefin / non-conjugated polyene copolymer (A) is a structural unit derived from ethylene and an α-olefin having 3 to 20 carbon atoms. The resin composition according to claim 1, which is 40 to 65 mol% in a total of 100 mol% with respect to the structural unit derived from The resin composition according to any one of claims 1 to 3, wherein the liquid ethylene / α-olefin copolymer (B) further satisfies the following requirement (b-7).
(B-7) B value calculated | required from < ¹³ > C-NMR spectrum and following General formula (1) is 1.06 or more.
B value = [POE] / (2 · [PE] [PO]) (1)
(Wherein [PE] is the molar fraction of structural units derived from ethylene in the copolymer, and [PO] is the molar fraction of structural units derived from α-olefin in the copolymer. And [POE] is the ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer.)   The resin composition according to claim 1, further comprising a crosslinking agent (C).   A cross-linked molded article obtained by cross-linking the resin composition according to claim 1.

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