JP5808166B2 - Ethylene copolymer, foam composition and foamed molded article comprising the same - Google Patents

Description

  The present invention relates to an ethylene copolymer suitable for molding a foamed molded article having excellent deformation recovery properties and a light weight, a foaming composition, and a foamed molded article comprising the same.

  For a midsole for shoes (shoe), a foamed molded product of polyurethane and ethylene / vinyl acetate copolymer is used. For further weight reduction, foams such as polyolefin rubber and polyolefin elastomer are also used.

In recent years, ethylene / α-olefin / non-conjugated diene copolymer rubber has been used for midsoles for shoes in response to demands for weight reduction and higher performance.
By using these, crosslinked foams that are lightweight, flexible, and excellent in mechanical strength can be obtained. However, in order to further reduce weight and improve performance, it is necessary to further improve compression strain It is. Therefore, if the degree of crosslinking of the conventional ethylene / α-olefin / nonconjugated diene copolymer is increased, the compressive strain is improved, but the tear strength is insufficient.

WO2007 / 132731

  Therefore, the anti-compressive strain resistance is improved when used as a foam by imparting crystallinity while maintaining the performance of crosslinking of the diene moiety unique to these ethylene / α-olefin / non-conjugated diene copolymers. While improved, the tensile strength is maintained, and by selecting 1-butene, 1-hexene, or 1-octene as the α-olefin, the melting point range is compared while maintaining crystallinity. It was found that excellent workability can be obtained by keeping the temperature low. Furthermore, the foamable composition using such an ethylene-based copolymer can be applied to the conventional foam molding of midsole, and can be put to practical use quickly.

That is, according to one aspect of the present invention, an ethylene copolymer comprising a structural unit derived from ethylene [A], an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C]. Coalesced,
(1) The crystallinity is in the range of 20 to 35%,
(2) The structural unit derived from the non-conjugated polyene [C] is 0.01 to 3.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%,
(3) It is related with the ethylene-type copolymer (I) characterized by the melt flow rate (MFR 190 degreeC) in 190 degreeC being 0.5-25.

According to another aspect of the present invention, there is provided an ethylene-based copolymer including structural units derived from ethylene [A], an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C]. Yes,
(1) The structural unit derived from ethylene [A] is 92 to 97 mol%, where the total of structural units of [A], [B] and [C] is 100 mol%,
(2) The structural unit derived from the non-conjugated polyene [C] is 0.01 to 3.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%,
(3) It is related with the ethylene-type copolymer (I) characterized by the melt flow rate (MFR 190 degreeC) in 190 degreeC being 0.5-25.

Furthermore, according to another aspect of the present invention, there is provided an ethylene-based copolymer including structural units derived from ethylene [A], an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C]. Yes,
(1) The crystallinity is in the range of 20 to 35%,
(2) The structural unit derived from ethylene [A] is 92 to 97 mol%, where the total of structural units of [A], [B] and [C] is 100 mol%,
(3) The structural unit derived from the non-conjugated polyene [C] is 0.01 to 3.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%,
(4) It is related with the ethylene-type copolymer (I) characterized by the melt flow rate (MFR 190 degreeC) in 190 degreeC being 0.5-25.

  In a preferred embodiment of the present invention, the α-olefin [B] having 4 to 20 carbon atoms constituting the ethylene copolymer (a) is selected from 1-butene, 1-hexene, or 1-octene. The at least one α-olefin is preferably used.

Furthermore, according to another aspect of the present invention, an ethylene copolymer comprising a structural unit derived from ethylene [A], an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C]. And
(1) The crystallinity is in the range of 20 to 35%,
(2) The structural unit derived from the non-conjugated polyene [C] is 0.01 to 3.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%,
(3) The composition for foams characterized by including the ethylene-type copolymer (I) whose melt flow rate (MFR 190 degreeC) in 190 degreeC is 0.5-25, and a crosslinking agent and a foaming agent. .

Furthermore, this invention is an ethylene copolymer containing the structural unit derived from ethylene [A], C4-C20 alpha olefin [B], and nonconjugated polyene [C] according to another aspect. Yes,
(1) The structural unit derived from ethylene [A] is 92 to 97 mol%, where the total of structural units of [A], [B] and [C] is 100 mol%,
(2) The structural unit derived from the non-conjugated polyene [C] is 0.01 to 3.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%,
(3) The composition for foams characterized by including the ethylene-type copolymer (I) whose melt flow rate (MFR 190 degreeC) in 190 degreeC is 0.5-25, and a crosslinking agent and a foaming agent. .

Furthermore, this invention is an ethylene copolymer containing the structural unit derived from ethylene [A], C4-C20 alpha olefin [B], and nonconjugated polyene [C] according to another aspect. Yes,
(1) The crystallinity is in the range of 20 to 35%,
(2) The structural unit derived from ethylene [A] is 92 to 97 mol%, where the total of structural units of [A], [B] and [C] is 100 mol%,
(3) The structural unit derived from the non-conjugated polyene [C] is 0.01 to 3.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%,
(4) An ethylene-based copolymer (a) having a melt flow rate (MFR 190 ° C.) at 190 ° C. of 0.5 to 25, a foaming composition comprising a crosslinking agent and a foaming agent .

  In a preferred embodiment of the present invention, the α-olefin [B] having 4 to 20 carbon atoms of the ethylene copolymer (A) constituting the foam composition is 1-butene, 1-hexene, Alternatively, at least one α-olefin selected from 1-octene is preferable.

  Further, according to a preferred aspect of the present invention, the foam composition further comprises an α-olefin elastomer, an ethylene / polar monomer copolymer, and styrene together with the ethylene copolymer (a). The present invention relates to a foam composition comprising at least one polymer selected from a block copolymer having a system block or a crystalline olefin block.

  Furthermore, the present invention, according to a preferred embodiment thereof, relates to a foamed molded article obtained by crosslinking and foaming the above foam composition, and more particularly to a shoe midsole.

  By using the ethylene-based copolymer of the present invention as a foamable composition, a foamed molded product can be efficiently molded even in the same crosslinking and foaming process as before. In addition, by any of the molding methods, the obtained foamed molded article is lightweight and excellent in deformation recovery, and can be used for various foamed molded articles such as a shoe product such as a midsole.

FIG. 1 shows a sample of a foam-molded product showing a site for measuring specific gravity.

  The ethylene / α-olefin / non-conjugated polyene copolymer (a) of the present invention comprises at least one structural unit derived from ethylene [A] and at least one kind of α-olefin [B] having 4 to 20 carbon atoms, and at least It is an ethylene-based copolymer containing a structural unit derived from one or more non-conjugated polyenes [C].

  Examples of the α-olefin [B] having 4 to 20 carbon atoms include 1-butene having 4 linear atoms, 1-hexene having 6 carbon atoms, and 1-octene having 8 carbon atoms, which have a straight chain structure without side chains. Furthermore, 1-nonadecene having 19 carbon atoms, 1-eicocene having 20 carbon atoms, 4-methyl-1-pentene having a side chain, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl Examples include -1-tetradecene. These α-olefins can be used alone or in combination of two or more. Among these, an α-olefin having 4 to 10 carbon atoms is preferable, and at least one α-olefin selected from 1-butene, 1-hexene and 1-octene is particularly preferable, and 1-butene is particularly preferable. is there.

By using 1-butene, 1-hexene, 1-octene as the α-olefin,
Since the degree of crystallinity can be maintained to some extent without excessively increasing the melting point of the resulting ethylene copolymer (I), it can be easily used in conventional molding methods such as roll processing.

  Specific examples of the non-conjugated polyene [C] include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl- Chain non-conjugated dienes such as 1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Cyclic non-conjugated dienes such as isopropylidene-2-norbornene and 6-chloromethyl-5-isopropylenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5 Norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1, , 9-decatriene, 4,8-dimethyl-1,4,8-decatriene, and a triene such as 4-ethylidene-8-methyl-1,7-nonadiene.

  These non-conjugated polyenes [C] can be used alone or in combination of two or more. Among these, cyclic non-conjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, or a combination of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene is preferable, among which 5-ethylidene Particularly preferred is 2-norbornene or a combination of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.

Examples of the ethylene copolymer (a) used in the present invention include the following.
Ethylene / 1-butene / 1,4-hexadiene copolymer,
Ethylene / 1-pentene / 1,4-hexadiene copolymer,
Ethylene / 1-hexene / 1,4-hexadiene copolymer,
Ethylene / 1-heptene / 1,4-hexadiene copolymer,
Ethylene / 1-octene / 1,4-hexadiene copolymer,
Ethylene / 1-nonene / 1,4-hexadiene copolymer,
Ethylene / 1-decene / 1,4-hexadiene copolymer,
Ethylene / 1-butene / 1-octene / 1,4-hexadiene copolymer,
Ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-pentene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-hexene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-heptene-5-ethylidene-2-norbornene copolymer,
Ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-nonene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-decene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-butene / 1-octene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-butene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-pentene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-hexene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-heptene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-octene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-nonene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-decene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
An ethylene / 1-butene / 1-octene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer.

These may be used alone or in combination of two or more.
According to one aspect of the ethylene-based copolymer of the present invention, the structural unit derived from ethylene [A] has a total of structural units of [A], [B] and [C] as 100 mol%. 92 to 97 mol%, preferably 93 to 97 mol%, and the structural unit derived from the non-conjugated polyene [C] is the sum of the structural units of [A], [B] and [C]. As 100 mol%, it is 0.01-3.0 mol%, Preferably it is 0.1-3.0 mol%, Most preferably, it is 0.1-2.5 mol%.

When ethylene is less than 92 mol%, the deformation recovery of the obtained foamed molded product is insufficient, and when it exceeds 98 mol%, the flexibility of the obtained foamed molded product tends to be insufficient.
Further, when the non-conjugated polyene is less than 0.01 mol%, sufficient crosslinking reactivity is not exhibited, and when it exceeds 3.0 mol%, the deformation recovery property of the obtained foamed molded product tends to deteriorate.

Ratio of constituent unit of ethylene [A] (mol%) and proportion of constituent unit of α-olefin [B] having 4 to 20 carbon atoms (mol%) In this embodiment, ethylene / α-olefin / non-conjugated polyene The polymer preferably has a molar ratio of ethylene [A] to α-olefin [B] having 4 to 20 carbon atoms (ethylene / α-olefin) of 11.5 or more.

The melt flow rate (ASTM D 1238 190 ° C. load 2.16 kg) of the ethylene-based copolymer (i) of the present invention is 0.5 to 25, preferably 1 to 20, particularly preferably. 1-15. When in this range, good post-treatment (ribbon handling properties) is exhibited and rubber properties are excellent. And when the molecular weight of the ethylene-based copolymer of the present invention is insufficient, it becomes difficult to obtain a foam sample, and even when it is obtained, the strength of the molded product is insufficient. On the other hand, if the molecular weight is too large, roll processability is deteriorated and it becomes difficult to disperse the compounding agent.
Next, the metallocene catalyst suitably used for the production of the ethylene copolymer (I) of the present invention and the polymerization conditions using the same will be described.

<Catalyst>
(Catalyst example 1)
Examples of the metallocene catalyst include transition metal compounds represented by the following general formula [I] or [II].

一般式［Ｉ］および［II］においてＹは、ケイ素原子もしくは炭素原子である。

In the general formulas [I] and [II], Y is a silicon atom or a carbon atom.

In the general formulas [I] and [II], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ is selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and a silicon-containing group, and may be the same or different, and R ¹ to R ¹⁴ Up to adjacent substituents may be bonded to each other to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a substituted aryl ( aryl) group.

  More specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, n -Pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1- Dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group Cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xyl Group, isopropylphenyl group, t-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group, benzyl group and cumyl group, such as methoxy group, ethoxy group and phenoxy group. Nitrogen-containing groups such as oxygen-containing groups, nitro groups, cyano groups, N-methylamino groups, N, N-dimethylamino groups and N-phenylamino groups, boron-containing groups such as boranetriyl groups and diboranyl groups, sulfonyl groups and sulfo groups. The thing containing sulfur containing groups, such as a phenyl group, is also mentioned as an example of the said hydrocarbon group.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen atom. Examples of such a halogen-substituted hydrocarbon group include a trifluoromethyl group, a trifluoromethylphenyl group, a pentafluorophenyl group, and a chlorophenyl group. Can be mentioned.

  Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. More specifically, for example, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group And dimethyl (pentafluorophenyl) silyl group.

The cyclopentadienyl group having R ¹ to R ⁴ in the above general formulas [I] and [II] is an unsubstituted cyclopentadienyl group in which R ¹ to R ⁴ are hydrogen atoms, 3-t-butylcyclo Pentadienyl group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group and 3-position 1-substituted cyclopentadienyl group such as 3-cyclohexylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentadienyl group, 3-phenyl-5-methylcyclopentadienyl group, 3,5-di-t-butylcyclopentadienyl group, 3,5-dimethylcycle Examples include lopentadienyl group, 3-phenyl-5-methylcyclopentadienyl group, and 3-trimethylsilyl-5-methylcyclopentadienyl group such as 3,5-disubstituted cyclopentadienyl group. Not as long.

From the viewpoint of ease of synthesis of the transition metal compound, production cost, and copolymerization ability of the nonconjugated polyene [C], a cyclopentadienyl group that is unsubstituted (R ^{1 to} R ⁴ are hydrogen atoms) is preferable.
As the fluorenyl group having R ^{5 to} R ¹² in the general formula [I] and [II], unsubstituted fluorenyl group from R ⁵ R ¹² is hydrogen atom, methyl fluorenyl group, 2-t- 4 such as 2-position 1-substituted fluorenyl group such as butylfluorenyl group and 2-phenylfluorenyl group, 4-methylfluorenyl group, 4-t-butylfluorenyl group and 4-phenylfluorenyl group A 1-substituted fluorenyl group, or a 2,7- or 3,6-position 2-substituted fluorenyl group such as a 2,7-di-t-butylfluorenyl group and a 3,6-di-t-butylfluorenyl group; 2,3,6,7-position 4 such as 2,7-dimethyl-3,6-di-t-butylfluorenyl group and 2,7-diphenyl-3,6-di-t-butylfluorenyl group A substituted fluorenyl group, As represented by the following general formula [V-I] and [V-II], coupled with R ⁶ and R ⁷ together form a ring, joined with R ¹⁰ and R ¹¹ are each other ring 2, 4-, 6-, and 7-substituted fluorenyl groups that form, and the like are not limited thereto.

一般式[V−I]および[V−II]中、Ｒ⁵、Ｒ⁸、Ｒ⁹、Ｒ¹²は前記一般式[I]あるいは［II］における定義と同様であり、
Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^e、Ｒ^f、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子または炭素数１〜５のアルキル基であり、隣接した置換基と互いに結合して環を形成していてもよい。

In the general formulas [V-I] and [V-II], R ⁵ , R ⁸ , R ⁹ and R ¹² are the same as defined in the general formula [I] or [II].
R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g, and R ^h are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and bonded to adjacent substituents. May form a ring.

Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an amyl group, and an n-pentyl group.
In the general formula [V-I], R ^x and R ^y are each independently a hydrocarbon group which may have an unsaturated bond having 1 to 3 carbon atoms, and R ^x is R ^a or R ^c is The bonded carbon may form a double bond, R ^y may form a double bond with R ^e or R ^g bonded carbon, R ^x and R ^y Are preferably saturated or unsaturated hydrocarbon groups having 1 or 2 carbon atoms.

  Specific examples of the compound represented by the general formula [V-I] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by the following formula [V-III], Tetramethyldodecahydrodibenzofluorenyl group represented by V-IV], octamethyltetrahydrodicyclopentafluorenyl group represented by the following formula [V-V], and represented by the following formula [V-VI]. Hexamethyldihydrodicyclopentafluorenyl group, and b, h-dibenzofluorenyl group represented by the following formula [V-VII].

これらのフルオレニル基を含む上記一般式[I]または[II]で表される遷移金属化合物はいずれも非共役ポリエン［Ｃ］の共重合能に優れるが、Ｙがケイ素原子である場合、２，７位２置換フルオレニル基、３，６位２置換フルオレニル基、２，３，６，７位４置換フルオレニル基、上記一般式[V−I]に表される２，３，６，７位４置換フルオレニル基を有する遷移金属化合物が特に優れる。Ｙが炭素原子である場合、Ｒ⁵からＲ¹²が水素原子である無置換フルオレニル基、３，６位２置換フルオレニル基、２，３，６，７位４置換フルオレニル基、上記一般式[V−I]に表される２，３，６，７位４置換フルオレニル基を有する遷移金属化合物が特に非共役ポリエン［Ｃ］の共重合能に優れる。

Any of the transition metal compounds represented by the above general formula [I] or [II] containing these fluorenyl groups is excellent in the copolymerization ability of the nonconjugated polyene [C], but when Y is a silicon atom, 7-position 2-substituted fluorenyl group, 3,6-position 2-substituted fluorenyl group, 2,3,6,7-position 4-substituted fluorenyl group, 2,3,6,7-position 4 represented by the above general formula [V-I] A transition metal compound having a substituted fluorenyl group is particularly excellent. When Y is a carbon atom, an unsubstituted fluorenyl group in which R ⁵ to R ¹² are hydrogen atoms, a 3,6-positioned 2-substituted fluorenyl group, a 2,3,6,7-positioned 4-substituted fluorenyl group, the above general formula [V The transition metal compound having a 2,3,6,7-position 4-substituted fluorenyl group represented by -I] is particularly excellent in the copolymerization ability of the non-conjugated polyene [C].

  As for the polymerization activity, when Y is a silicon atom or a carbon atom, the 2,7-position 2-substituted fluorenyl group, the 3,6-position 2-substituted fluorenyl group, the 2,3,6,7-position 4-substituted fluorenyl group, the above general The transition metal compounds represented by the above general formulas [I] and [II] having a 2,3,6,7-position 4-substituted fluorenyl group represented by the formula [V-I] are particularly excellent.

In the above general formula [I], R ¹³ and R ¹⁴ may be the same or different from each other. As described above, R ¹³ and R ¹⁴ may be a hydrocarbon group, and among the hydrocarbon groups, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. , Cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, m-tolyl group, p-tolyl group, 4-t-butylphenyl group, p-chlorophenyl group, 4-biphenyl group, 2-naphthyl group, xylyl group, A benzyl group and an m-trifluoromethylphenyl group are preferred.

  In the transition metal compound represented by the general formula [II], A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and Y is the A For example, a cycloalkylidene group such as a cyclohexylidene group represented by the following formula [VI-I], a cyclotetramethylenesilylene group represented by the following formula [VI-II] (1-silacyclopentylidene A cyclomethylenesilylene group such as a group).

（式［VI−I］および［VI−II］において、●は、上記一般式［II］における（置換）シクロペンタジエニル基および（置換）フルオレニル基との結合点を表す。）
また、一般式［II］においてＡはＹとともに形成する環を含めて二つ以上の環構造を含んでいてもよい。

(In formulas [VI-I] and [VI-II], ● represents the point of attachment to the (substituted) cyclopentadienyl group and (substituted) fluorenyl group in general formula [II]).
In general formula [II], A may contain two or more ring structures including the ring formed with Y.

  Specific examples of the ring structure formed by combining Y with A include, in addition to the cyclohexylidene group represented by the above formula [VI-I], a cyclopropylidene group, a cyclobutylidene group, and a cyclopentylidene group. And cycloheptylidene group, cyclooctylidene group, bicyclo [3.3.1] nonylidene group, norbornylidene group, adamantylidene group, tetrahydronaphthylidene group and dihydroindanilidene group.

  Similarly, as the ring structure formed by combining Y with A, other than the cyclotetramethylenesilylene group (1-silacyclopentylidene group) represented by the above formula [VI-II], specifically, Examples thereof include a dimethylenesilylene group, a cyclotrimethylenesilylene group, a cyclopentamethylenesilylene group, a cyclohexamethylenesilylene group, and a cycloheptamethylenesilylene group.

In the general formulas [I] and [II], M is a titanium atom, a zirconium atom or a hafnium atom, preferably a titanium atom or a hafnium atom.
In the general formulas [I] and [II], Q is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a lone electron. It is selected from neutral ligands that can be coordinated in pairs.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.
Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group. Group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, t-butyl group, 1,1-dimethylbutyl group 1,1,3-trimethylbutyl group, neopentyl group, cyclohexylmethyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group, benzyl group and the like, preferably methyl group, ethyl group and benzyl group.

  Specific examples of the neutral, conjugated or nonconjugated diene having 10 or less carbon atoms include s-cis- or s-trans-η4-1,3-butadiene, s-cis- or s-trans-η4-1. , 4-diphenyl-1,3-butadiene, s-cis- or s-trans-η4-3-methyl-1,3-pentadiene, s-cis- or s-trans-η4-1,4-dibenzyl-1 , 3-butadiene, s-cis- or s-trans-η4-2,4-hexadiene, s-cis- or s-trans-η4-1,3-pentadiene, s-cis- or s-trans-η4- 1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η4-1,4-bis (trimethylsilyl) -1,3-butadiene, and the like.

  Specific examples of the anionic ligand include alkoxy groups such as methoxy, t-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

  Specific examples of the neutral ligand capable of coordinating with the lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, and tetrahydrofuran, diethyl ether, dioxane and 1,2 -Ethers such as dimethoxyethane.

Finally, in the above general formulas [I] and [II], j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different.
Examples of the transition metal compounds described above are listed in JP-A-2011-1497.

  The transition metal compound can be produced by a known method, and the production method is not particularly limited. As a manufacturing method, for example, J. Org. Organomet. Chem. 63, 509 (1996), WO2006-123759, WO01 / 27124, JP2004-168744, JP2004-175759, and JP2000-, which are publications relating to applications by the present applicant. And the method described in Japanese Patent No. 212194.

(Catalyst example 2)
Moreover, as a metallocene catalyst which can be used for manufacture of the ethylene-type copolymer used for this invention, the compound represented by the following general formula (III ') can be mentioned.

式（ＩＩＩ’）中、Ｒ’およびＲ’’はそれぞれ独立に、水素原子または炭素数１〜２０のヒドロカルビル基であり、Ｍはチタンであり、Ｙは−ＮＲ^*−であり、Ｚ^*は−ＳｉＲ^* ₂−であり、前記二つのＲ^*はそれぞれ独立に、水素原子または炭素数１〜２０のヒドロカルビル基であり、ｐおよびｑのうち一方は０であり、他方は１であり、
ｐが０かつｑが１である場合には、Ｍは＋２の酸化状態であり、Ｘ’は１，４−ジフェニル−１，３−ブタジエンまたは、１，３−ペンタジエンであり、
ｐが１かつｑが０である場合には、Ｍは＋３の酸化状態であり、Ｘは２−（Ｎ，Ｎ−ジメチルアミノ）ベンジルである。

In the formula (III ′), R ′ and R ″ are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, M is titanium, Y is —NR ^* —, and Z ^* is -SiR ^* _2- , and the two R ^{* s} are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, one of p and q is 0, and the other is 1.
when p is 0 and q is 1, M is in the +2 oxidation state, X ′ is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene;
When p is 1 and q is 0, M is in the +3 oxidation state and X is 2- (N, N-dimethylamino) benzyl.

The compound having the structure represented by the general formula (III ′) is (t-butylamido) dimethyl (η ⁵ ) from the viewpoint that fogging and solids due to the ultra-low molecular weight component of the obtained ethylene copolymer are suppressed. -2-Methyl-s-indacene-1-yl) silane titanium (II) 1,3-pentadiene (also known as: (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indacene-1-yl) silane titanium (II) 1,3-pentadiene (a compound having a structure represented by the following formula (VII)) is particularly preferred. In addition, the compound which has a structure represented by a following formula (VII) can be obtained by the method described in the Japanese translations of PCT publication No. 2001-522398, for example.

前記一般式（ＩＩＩ’）で表わされる構造を有する化合物は、非共役ポリエン［Ｃ］の重合性に優れている。また、このようなメタロセン触媒を用いて合成される本発明のエチレン系共重合体は、分子量分布および組成分布が狭く、均一な分子構造を有するエチレン系共重合体である。このため、本発明のエチレン系共重合体、架橋されたエチレン系共重合体、およびその成形体は、表面外観に優れる傾向がある。

The compound having the structure represented by the general formula (III ′) is excellent in the polymerizability of the nonconjugated polyene [C]. Further, the ethylene copolymer of the present invention synthesized using such a metallocene catalyst is an ethylene copolymer having a narrow molecular weight distribution and composition distribution and a uniform molecular structure. For this reason, the ethylene copolymer of the present invention, the crosslinked ethylene copolymer, and the molded product thereof tend to be excellent in surface appearance.

(Cocatalyst)
The ethylene copolymer (i) used in the present invention can be synthesized using, for example, the metallocene catalyst mentioned above as a main catalyst and a boron compound and / or an organoaluminum compound such as trialkylaluminum as a cocatalyst. it can.

  Examples of the boron compound include trityltetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, di (hydrogenated tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (penta Fluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (s-butyl) ammonium tetrakis (pentafluorophenyl) borate.

Examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminidiisobutylaluminum hydride. , LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) ₄ , and organic aluminum oxy compounds.

  The organoaluminum oxy compound may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

<Polymerization conditions>
The reaction temperature at the time of synthesizing the ethylene-based copolymer (i) used in the present invention is usually -20 to 200 ° C, preferably 0 to 150 ° C. The polymerization pressure is usually in the range of more than 0 MPa and 8 MPa (gauge pressure) or less, preferably more than 0 MPa and 5 MPa (gauge pressure) or less.

  The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 10 minutes to 3 hours. . Furthermore, molecular weight regulators such as hydrogen can be used.

In the polymerization of ethylene, α-olefin and non-conjugated olefin using the metallocene catalyst as described above, the transition metal compounds represented by the above general formulas [I], [II] and [X] have a reaction volume of 1 The amount is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻⁸ mol per liter.

  The cocatalyst used with the transition metal compound has a molar ratio [cocatalyst / M] of the cocatalyst and all transition metal atoms (M) in the transition metal compound of usually 0.1 / 1 to 100/1. The amount is preferably 1/1 to 50/1.

  The production of the ethylene-based copolymer used in the present invention can be carried out by any of liquid phase polymerization methods such as solution (dissolution) polymerization and suspension polymerization, or gas phase polymerization methods, and is not particularly limited. It is preferable to have the process of obtaining a reaction liquid.

  The step of obtaining a polymerization reaction liquid means using an aliphatic hydrocarbon as a polymerization solvent and in the presence of the metallocene catalyst and the cocatalyst, the ethylene [A], the α-olefin [B], the non-conjugated polyene [ C] is a step of copolymerizing ethylene [A] / α-olefin [B] / non-conjugated polyene [C] copolymer.

  Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, benzene, toluene and xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane.

These can be used alone or in combination of two or more. Further, the α-olefin itself used for polymerization can also be used as a polymerization solvent.
Of the polymerization solvents described above, hexane is preferred from the viewpoint of separation and purification from the resulting ethylene copolymer.

The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.
For example, the polymerization reaction can be completed by carrying out the polymerization reaction as described above and adding an acidic alcohol such as methanol into the reaction system.

The molecular weight of the ethylene copolymer obtained by the polymerization reaction can also be adjusted by allowing hydrogen to exist in the polymerization system or changing the polymerization temperature. Specifically, the presence of a large amount of hydrogen in the polymerization system can reduce the molecular weight of the resulting ethylene copolymer, and as a result, an ethylene copolymer having an intrinsic viscosity in the present invention can be obtained. Can be obtained. Furthermore, the molecular weight of the resulting ethylene copolymer can be kept small by keeping the polymerization temperature at a moderate reaction condition without increasing the polymerization temperature, and as a result, the range of the intrinsic viscosity can be achieved.
Additives used in the foaming composition of the present invention are a crosslinking agent and a foaming agent.

Crosslinking agents Crosslinking agents used in the foaming composition of the present invention include organic peroxides, phenol resins, sulfur compounds, hydrosilicon compounds, amino resins, quinones or their derivatives, amine compounds, azo compounds, The crosslinking agent generally used when bridge | crosslinking rubber | gum, such as an epoxy-type compound and isocyanate, is mentioned. Of these, vulcanizing agents such as organic peroxides and sulfur are suitable.

  Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy). Hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)- 3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, ert -Butylperoxyisopropylcarbo Over DOO, diacetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide.

  Among these, 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (Tert-Butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 Bifunctional organic peroxides such as 2,4-bis (tert-butylperoxy) valerate are preferred, among which 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5- Most preferred is di- (tert-butylperoxy) hexane.

  When an organic peroxide is used as a cross-linking agent, the blending amount in the foam composition needs to be an ethylene / α-olefin / non-conjugated polyene copolymer (A) and other cross-linking blended as necessary. It is generally 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polymer (elastomer and the like). When the amount of the organic peroxide is within the above range, it is preferable because it exhibits excellent crosslinking characteristics without blooming to the surface of the resulting foam.

  Moreover, when using an organic peroxide, it is preferable to use a crosslinking aid in combination. Examples of such crosslinking aids include quinone dioxime crosslinking aids such as sulfur and p-quinonedioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; diallyl phthalate and triallyl Allyl-based crosslinking aids such as isocyanurates; other maleimide-based crosslinking aids; divinylbenzene; zinc oxide (for example, ZnO # 1 and two types of zinc oxide, manufactured by Hux Itec Corp.), magnesium oxide, zinc white (for example, Examples thereof include metal oxides such as “META-Z102” (trade name; zinc oxide such as Inoue Lime Industry Co., Ltd.). The compounding quantity of a crosslinking adjuvant is 0.5-10 mol normally with respect to 1 mol of organic peroxides, Preferably it is 0.5-7 mol, More preferably, it is 1-5 mol.

  When a sulfur compound (vulcanizing agent) is used as the crosslinking agent, specific examples include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate and the like.

  When a sulfur-based compound is used as a crosslinking agent, the blending amount of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and other polymers that need to be crosslinked (rubber, etc.) blended as necessary. The amount is usually 0.3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight, and more preferably 0.7 to 5.0 parts by weight with respect to the total of 100 parts by weight. When the compounding amount of the sulfur compound is within the above range, there is no bloom on the surface of the foam, and excellent crosslinking characteristics are exhibited.

When a sulfur compound is used as the crosslinking agent, it is preferable to use a vulcanization accelerator in combination.
Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N, N′-diisopropyl-2-benzothiazole sulfenamide, 2-mercapto Benzothiazole (for example, Sunseller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2- (4-morpholinodithio) benzothiazole (for example, Noxeller MDB-P (trade name; manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.)) ), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyl disulfide (eg Sunceller DM (trade name; Sanshin Chemical) Thiazole-based vulcanization accelerators, such as those manufactured by Kogyo Co.); diphenylguanidine, triphenyl Guanidine vulcanization accelerators such as luguanidine and diorthotolyl guanidine; Aldehyde amine vulcanization accelerators such as acetaldehyde / aniline condensate and butyraldehyde / aniline condensate; Imidazoline vulcanization accelerators such as 2-mercaptoimidazoline; Thiourea vulcanization accelerators such as diethylthiourea and dibutylthiourea; tetramethylthiuram monosulfide (for example, Suncellor TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (for example, Suncellor TT (trade name; Sanshin Chemical Co., Ltd.)), tetraethyl thiuram disulfide (eg Sunceller TET (trade name; manufactured by Sanshin Chemical Industries)), tetrabutylthiuram disulfide (eg Sunceller TBT (trade name; manufactured by Sanshin Chemical Industries)) ) Thiuram-based vulcanization accelerators such as dipentamethylene thiuram tetrasulfide (for example, Sunseller TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (for example, Sunseller PZ, Sunseller BZ and Sunseller EZ (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.) and dithioate vulcanization accelerators such as tellurium diethyldithiocarbamate; ethylenethiourea (for example, Sunseller BUR (trade name; Sanshin Chemical) Kogyo Co., Ltd., Sunseller 22-C (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and thiourea vulcanization accelerators such as N, N'-diethylthiourea; xanthate vulcanization accelerators such as zinc dibutylxatogenate Agents; zinc oxide (for example, META-Z102 (trade name; Inoue Lime Industry Co., Ltd., zinc oxide)) and the like.

  The blending amount of these vulcanization accelerators is 100 parts by weight in total of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and other crosslinkable polymers (elastomers, etc.) blended as necessary. In general, it is 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight. Within this range, excellent crosslinking properties are exhibited without blooming to the surface of the resulting foam.

Vulcanization aids Vulcanization aids are desirably used when the crosslinking agent is a sulfur-based compound. For example, zinc oxide (for example, ZnO # 1 and two types of zinc oxide, manufactured by Hux Itec Co., Ltd.), oxidation Examples thereof include magnesium and zinc white (for example, zinc oxide such as “Meta Z-102” (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).

  The blending amount is usually 100 parts by weight in total of the ethylene / α-olefin / non-conjugated polyene copolymer (a) and other polymers (elastomer etc.) that need to be blended if necessary. 1 to 20 parts by weight.

Foaming agent The foaming agent used in the foam composition of the present invention includes a chemical foaming agent, specifically,
Azodicarbonamide (ADCA),
1,1′-azobis (1-acetoxy-1-phenylethane),
Dimethyl-2,2′-azobisbutyrate,
Dimethyl-2,2′-azobisisobutyrate,
2,2′-azobis (2,4,4-trimethylpentane),
1,1′-azobis (cyclohexane-1-carbonitrile),
Azo compounds such as 2,2′-azobis [N- (2-carboxyethyl) -2-methyl-propionamidine];
Nitroso compounds such as N, N′-dinitrosopentamethylenetetramine (DPT);
4,4′-oxybis (benzenesulfonylhydrazide),
Hydrazine derivatives such as diphenylsulfone-3,3′-disulfonylhydrazide;
semicarbazide compounds such as p-toluenesulfonyl semicarbazide;
Organic pyrolytic foaming agents such as trihydrazinotriazine,
Bicarbonates such as sodium bicarbonate and ammonium bicarbonate; carbonates such as sodium carbonate and ammonium carbonate;
Examples thereof include inorganic pyrolytic foaming agents such as nitrites such as ammonium nitrite and hydrogen compounds. Of these, azodicarbonamide (ADCA) and sodium hydrogen carbonate are particularly preferable.

In addition, as another aspect of the foaming agent, there is a physical foaming agent (a foaming agent that does not necessarily involve a chemical reaction during foaming), for example, various aliphatic hydrocarbons such as methanol, ethanol, propane, butane, pentane, and hexane;
Various chlorinated hydrocarbons such as dichloroethane, dichloromethane and carbon tetrachloride;
Organic physical foaming agents such as various fluorinated chlorohydrocarbons such as Freon, and inorganic physical foaming agents such as air, carbon dioxide, nitrogen, argon, and water can be used as the foaming agent. Among these, carbon dioxide, nitrogen, and argon are the most excellent because they do not need to be vaporized, are inexpensive, and have a very low possibility of environmental pollution and ignition.

  Since the physical foaming agent used as the foaming agent has no decomposition residue of the foaming agent, it is possible to prevent mold contamination during the crosslinking and foaming of the composition. In addition, since the physical foaming agent is not in powder form, it has excellent kneadability. In addition, when this physical foaming agent is used, it is possible to prevent off-flavors (such as ammonia odor generated during ADCA decomposition) of the foam obtained.

The foaming agent can be used in combination with the above chemical foaming agent as long as it does not cause adverse effects such as odor and mold contamination.
As a physical foaming agent storage method, for small-scale production, carbon dioxide, nitrogen, etc. can be used in a cylinder and supplied to an injection molding machine and an extrusion molding machine through a pressure reducing valve. In some cases, the pressure is increased by a pump or the like and supplied to an injection molding machine, an extrusion molding machine, or the like.

  In addition, if it is a facility that manufactures foamed products on a large scale, a storage tank for liquefied carbon dioxide, liquefied nitrogen, etc. is installed, passed through a heat exchanger, vaporized, piping, injection molding machine and extrusion molding machine with a pressure reducing valve Etc.

In the case of a liquid physical foaming agent, the storage pressure is preferably in the range of 0.13 to 100 MPa.
In an embodiment in which a chemical foaming agent is used as the foaming agent, the chemical foaming agent is an ethylene / α-olefin / non-conjugated polyene copolymer (A) and other polymers that need to be cross-linked (elastomers and the like) blended as necessary. It is usually used in a proportion of 2 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to the total amount of 100 parts by weight. However, the amount of the chemical foaming agent used is appropriately increased or decreased depending on the target foaming ratio because the amount of generated gas varies depending on the type and grade of the foaming agent used.

  Moreover, in the aspect using a physical foaming agent as a foaming agent, although the addition amount of a physical foaming agent is suitably determined according to the desired foaming ratio, ethylene * alpha -olefin * nonconjugated polyene copolymer (I) And it is 0.1-15 weight part normally with respect to a total of 100 weight part of polymers (elastomer etc.) which need another bridge | crosslinking mix | blended as needed, Preferably it is 0.5-10 weight part.

  In the foam composition of the present invention, a foaming aid may be used together with the foaming agent. The foaming auxiliary agent acts to lower the decomposition temperature of the foaming agent, accelerate the decomposition, and make the bubbles uniform. Examples of such foaming aids include zinc oxide (ZnO), zinc stearate, salicylic acid, phthalic acid, stearic acid, oxalic acid and other organic acids, urea or derivatives thereof.

  In addition to the above, the foam composition of the present invention includes a softener, an inorganic filler, a reinforcing agent, etc., as well as other elastomers, polymers such as rubber, processing aids, activators, and hygroscopic agents. Further, a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, a thickener and the like are blended. Various additives such as a weather stabilizer, a flame retardant, a hydrochloric acid absorbent, and a pigment may be used as long as the object of the present invention is not impaired.

Specific examples of the softener softening agent, if necessary softener is blended, process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum-based softening agents such as petroleum asphalt, vaseline; coal tar-based, such as coal tar Softeners; fatty oil-based softeners such as mashi oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as beeswax and carnauba wax; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, etc. Fatty acids or salts thereof; naphthenic acid, pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, coumarone indene resin; ester softeners such as dioctyl phthalate and dioctyl adipate; and other, microcrystalline Wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon Synthetic lubricating oils include tall oil, are like sub (factice), preferably petroleum softeners, among them the process oil is preferable.

  In the embodiment in which the foam composition of the present invention uses a softener, the blending amount of the softener in the foam composition is the ethylene / α-olefin / non-conjugated polyene copolymer (A) and, if necessary, It is generally 2 to 100 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the total of other polymer (elastomer, rubber, etc.) components to be blended.

Inorganic fillers As specific examples of inorganic fillers that are blended with inorganic fillers as required, one or more of light calcium carbonate, heavy calcium carbonate, talc, clay and the like are used, Then, heavy calcium carbonate such as “Whiteon SB” (trade name; Shiraishi Calcium Co., Ltd.) is preferable.

  In the embodiment in which the foam composition of the present invention uses an inorganic filler, the blending amount of the inorganic filler is the ethylene / α-olefin / non-conjugated polyene copolymer (A) and other blended as necessary. The amount is usually 2 to 50 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total amount of the polymer (elastomer, rubber, etc.). When the blending amount is within the above range, the kneading processability of the foam composition is excellent, and a molded article having excellent mechanical properties can be obtained.

Reinforcing Agent A reinforcing agent is blended in the foam composition of the present invention as necessary. Specific examples of the reinforcing agent include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine powder talc, and differential silicic acid. In the embodiment in which the reinforcing agent is blended, generally 30 to 200 with respect to a total of 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and other polymers (elastomer, rubber, etc.) as required. Part by weight, preferably 50 to 180 parts by weight.

  As another embodiment of the foam composition of the present invention, as the other polymer used in combination with the ethylene copolymer (a), an α-olefin elastomer (u), an ethylene / polar monomer copolymer (v) And a polymer selected from a block copolymer (w) having a styrenic block or a crystalline olefin block. One or more of these may be used in combination as necessary.

α-olefin elastomer (u)
As one aspect of the present invention, there is an aspect in which the olefin elastomer (u) is used in combination.
The α-olefin-based elastomer (u) used in combination includes, for example, a copolymer rubber of two or more kinds of α-olefins having 2 to 10 carbon atoms, and a copolymer of two or more kinds of α-olefins and non-conjugated dienes. Mention may be made of rubber. Specific examples thereof include ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = 85 / 10-50 / 50], ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene. / Α-olefin (molar ratio) = 85 / 10-50 / 50], propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = 85 / 10-50 / 50], 1-butene -There exists alpha-olefin copolymer rubber [1-butene / alpha-olefin (molar ratio) = 85 / 10-50 / 50]. In these, as the α-olefin, for example, at least one selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like is appropriately selected and used. The content of these α-olefins is preferably 3-39 mol%, more preferably 5-30 mol%, and more preferably 5-25 mol%.

  Moreover, as said nonconjugated diene, a C6-C20 thing is preferable, and specifically, dicyclopentadiene, 1, 4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, etc. are mentioned. The iodine value of the above ethylene / α-olefin / nonconjugated diene copolymer rubber in which such a nonconjugated diene is copolymerized is preferably 25 or less, and more preferably 5 to 20. The melt flow rate (MFR; ASTM D1238, 230 ° C., 2.16 kg load, the same applies hereinafter) of these copolymer rubbers is preferably 0.01 to 100 g / 10 minutes, more preferably 0.02 to 50 g / 10 minutes. More preferably, it exists in the range of 0.05-20 g / 10min. Further, the crystallinity of the α-olefin random copolymer rubber is preferably less than 20% as measured by the X-ray method.

Further, these α-olefin copolymers, especially those produced using a metallocene catalyst, desirably have a molecular weight distribution (Mw / Mn) of usually 3 or less.
Among these α-olefin elastomers, an ethylene-α-olefin copolymer containing 60 to 85 mol% of ethylene is desirable, and examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methyl- Examples include 1-pentene and 1-octene.

  Such a particularly preferred ethylene-α-olefin copolymer has a melting point in the range of 20 to 80 ° C., for example, Tuffmer P, Tuffmer A, Tuffmer S, etc., commercially available from Mitsui Chemicals, Inc. is there.

  The proportion of the α-olefin elastomer used in combination is preferably 1 to 50 parts by weight, particularly 3 to 40 parts by weight, especially 3 to 20 parts by weight, per 100 parts by weight of the ethylene copolymer (ii).

Ethylene / polar monomer copolymer (v)
One preferred embodiment of the present invention is an embodiment in which the ethylene / polar monomer copolymer (v) is used in combination. Examples of the polar monomer of the copolymer used in combination include unsaturated carboxylic acid, its salt, its ester, its amide, vinyl ester, carbon monoxide and the like. More specifically, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, lithium of these unsaturated carboxylic acids, sodium, Monovalent metal salts such as potassium, polyvalent metal salts such as magnesium, calcium and zinc, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, nbutyl acrylate, isooctyl acrylate, methyl methacrylate Illustrative examples of unsaturated carboxylic acid esters such as ethyl methacrylate, isobutyl methacrylate and dimethyl maleate, vinyl esters such as vinyl acetate and vinyl propionate, carbon monoxide, sulfur dioxide, etc. Can do.

  More specifically, the ethylene / polar monomer copolymer (v) includes ethylene / acrylic acid copolymer, ethylene / unsaturated carboxylic acid copolymer such as ethylene / methacrylic acid copolymer, and the ethylene / unsaturated copolymer. An ionomer in which a part or all of the carboxyl groups of the carboxylic acid copolymer are neutralized with the above metal, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, Ethylene / isobutyl acrylate copolymer, ethylene / unsaturated carboxylic acid ester copolymer such as ethylene / n-butyl acrylate copolymer, ethylene / isobutyl acrylate / methacrylic acid copolymer, ethylene / n-butyl acrylate・ Ethylene such as methacrylic acid copolymer ・ Unsaturated carboxylic acid ester ・ Unsaturated carbo Typical examples include acid copolymers, ionomers in which some or all of the carboxyl groups thereof are neutralized with the above metals, and ethylene / vinyl ester copolymers such as ethylene / vinyl acetate copolymers. .

  Among these, a copolymer of ethylene and a polar monomer selected from an unsaturated carboxylic acid, a salt thereof, an ester thereof and vinyl acetate is preferable, and an ethylene / (meth) acrylic acid copolymer or an ionomer or ethylene thereof is particularly preferable. A (meth) acrylic acid / (meth) acrylic acid ester copolymer or an ionomer thereof, an ethylene / vinyl acetate copolymer is preferable, and an ethylene / vinyl acetate copolymer is most preferable.

  As said ethylene-polar monomer copolymer (v), although it changes also with kinds of polar monomer, a polar monomer content is 1-50 mass% normally, and a thing of 5-45 mass% is especially preferable. Such an ethylene / polar monomer copolymer also has a melt flow rate of 0.05 to 100 g / 10 min at 190 ° C. under a load of 2160 g in consideration of molding processability, mechanical strength, etc. It is preferable to use a 50 g / 10 min.

  A copolymer of ethylene and unsaturated carboxylic acid, unsaturated carboxylic acid ester, vinyl ester or the like can be obtained by radical copolymerization at high temperature and high pressure. A copolymer (ionomer) of a metal salt of ethylene and an unsaturated carboxylic acid can be obtained by reacting an ethylene / unsaturated carboxylic acid copolymer with a corresponding metal compound.

  When the ethylene / polar monomer copolymer (v) according to the present invention is an ethylene / vinyl acetate copolymer, the vinyl acetate content in the ethylene / vinyl acetate copolymer is usually 10 to 30% by weight, preferably 15%. -30% by weight, more preferably 15-25% by weight.

  The ethylene / vinyl acetate copolymer has a melt flow rate (MFR; ASTM D1238, 190 ° C., load 2.16 kg) usually 0.1 to 50 g / 10 minutes, preferably 0.5 to 20 g / 10 minutes. More preferably, it is 0.5 to 5 g / 10 min.

  In the embodiment in which the ethylene / polar monomer copolymer is used in combination, the ratio of the combined use is 1 to 50 parts by weight, particularly 3 to 40 parts by weight, especially 3 to 100 parts by weight of the ethylene copolymer (ii). 20 parts by weight is preferred.

  When the ethylene / polar monomer copolymer (v) is used in combination, the layer made of the obtained foam is excellent in adhesiveness with other layers made of polyurethane, rubber, leather, etc., and is preferable as a laminate.

  Particularly when the ethylene / polar monomer copolymer (v) is a copolymer of ethylene and an unsaturated carboxylic acid, when used in the above proportion, the tear strength characteristics and other layers made of polyurethane, rubber, leather, etc. A foamed molded article having excellent adhesiveness is obtained.

Block copolymer having styrenic block or crystalline olefin block (w)
One preferred embodiment of the present invention is an embodiment in which a block copolymer (w) having a styrenic block or a crystalline olefin block is used in combination.
The block copolymer (w) having a styrene block or a crystalline olefin block used in combination includes a styrene / diene block copolymer (w1), an olefin / amorphous olefin block copolymer (w2), and an olefin type. There is a block copolymer elastomer (w3).

Styrene-diene block copolymer (w1)
The styrene / diene block copolymer (w1) used in the present invention is a block copolymer having a soft segment composed of a diene block (diene polymer portion) and a hard segment composed of a styrene block (styrene polymer portion). Yes, it is a kind of block copolymer manufactured and sold as so-called thermoplastic elastomer. Specifically, styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS) ), Styrene-isoprene-styrene block copolymer (SIS) or hydrogenated products of these block copolymers, styrene / isobutylene / styrene triblock copolymer (SIBS), styrene / isobutylene diblock copolymer (SIB) Is mentioned.

   Such a hydrogenated product is a block copolymer in which all of the styrene block and the diene block are hydrogenated, or a block copolymer in which only the diene block is hydrogenated or a part of the styrene block and the diene block. It may be a partially hydrogenated product such as a hydrogenated block copolymer.

When these block copolymers or hydrogenated products thereof are used as the pressure-sensitive adhesive composition, they may be used alone or in combination of two or more.
Among these block copolymers, hydrogenated styrene-butadiene block copolymer (SB), hydrogenated styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer ( More preferred is a hydrogenated product of a block copolymer containing a styrene block and a diene block, such as a hydrogenated product of SIS) or a hydrogenated product of a styrene-isoprene block copolymer (SI). Styrene-ethylene-butene block copolymer (SEB), which is a hydrogenated product of styrene-butadiene block copolymer (SB), and styrene-ethylene, which is a hydrogenated product of styrene-butadiene-styrene block copolymer (SBS) Butene-styrene block copolymer (SEBS), styrene-isoprene Styrene-ethylene / propylene-styrene block copolymer (SEPS), a hydrogenated product of styrene block copolymer (SIS), has excellent thermal stability during extrusion, stability during processing, and generation of deteriorated products And preferable in terms of suppressing the generation of odor. Examples of these commercially available products include Shell Chemical Co., Ltd., trade name: Clayton G, Asahi Kasei Co., Ltd., trade name: Tuftec.

  The MFR (melt flow rate; ASTM D-1238 load 5 kg, temperature 200 ° C.) of the styrene-diene block copolymer (w1) that may be used in the present invention is not particularly limited, but usually 0.5 to 20 g / The range is 10 minutes, preferably 1 to 15 g / 10 minutes.

Olefin / Amorphous olefin block copolymer (w2)
The olefin / amorphous olefin block copolymer (w2) used in the present invention has at least a soft segment composed of one amorphous olefin block (amorphous olefin polymer part) and crystallinity in the molecule. It is a block copolymer having a hard segment composed of an olefin block (crystalline olefin polymer part), and is a kind of block copolymer manufactured and sold as a so-called thermoplastic elastomer.

The structure of the olefin / amorphous olefin block copolymer (w2) is not particularly limited as long as it has at least one amorphous olefin block A and crystalline olefin block B in the molecule, and (B-A) n1 , (B-A) n2-B, (AB) n3-A (n1, n2, and n3 are integers of 1 or more) and a structure in which these are combined with a coupling agent.
Among these, a triblock copolymer or a copolymer having a larger number of blocks is preferable.

  As the block copolymer (w2), specifically, a polymer block mainly composed of a diene compound or a hydrogenation treatment of these polymer blocks into an ethylene / butene copolymer or an ethylene / propylene copolymer. Examples include a block copolymer having a soft segment composed of an amorphous olefin block having a similar structure and a hard segment composed mainly of a diene compound and capable of becoming crystalline polyolefin by hydrogenation treatment. Moreover, a block copolymer in which a part of a polymer part mainly composed of a diene compound and capable of becoming crystalline polyolefin by hydrogen lacquer treatment or the like is replaced with a hard segment composed of a polymer part of a vinyl aromatic compound such as styrene can be exemplified. Specific examples of the diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl-1,3-pentadiene.

  A soft segment comprising an amorphous olefin block having a structure similar to that of an ethylene / butene copolymer or an ethylene / propylene copolymer obtained by hydrogenating a polymer block mainly composed of a diene compound is, for example, vinyl polybutadiene. A structure similar to that of an amorphous ethylene / butene copolymer is obtained by hydrogenating a polymer block having a bond (content of 1,2- and 3,4-bonds) of about 25 to 85%. A non-crystalline olefin block is obtained.

  The polymer part mainly composed of a diene compound and capable of becoming crystalline polyolefin by hydrogenation treatment, for example, is a polymer block in which the vinyl bond of polybutadiene (content of 1,2 and 3,4 bonds) is 25% or less. Is hydrogenated to obtain a crystalline olefin block having a structure similar to that of an ethylene polymer.

  As these block copolymers (w2), specifically, crystalline olefin (crystalline ethylene polymer part) -ethylene butene (amorphous olefin polymer part) monocrystalline olefin (crystalline ethylene heavy) Examples include coalescence part) block copolymer (CEBC), styrene-ethylene butene (amorphous olefin polymer part) monocrystalline olefin (crystalline ethylene polymer part) block copolymer (SEBC), JSR shares Various brands such as DR6100P, DR6200P (CEBC), DR4600P, DR4630P (EBC) are commercially available from the company under the trade name: DYNARON.

Olefin block copolymer elastomer (w3)
The olefinic block copolymer elastomer (w3) is a block copolymer having a so-called amorphous soft segment comprising at least one olefinic elastomer polymer portion and at least one so-called hard segment in the molecule. The soft segment consisting of an olefinic elastomer polymer part is usually a random polymer part of an α-olefin such as ethylene, propylene, 1-butene, a polymer part of a diene compound (diolefin) such as butadiene or isoprene or its hydrogen. It is an additive, and the hard segment usually has crystallinity in a polymer part having a glass transition point such as a polystyrene polymer part at room temperature or higher, an α-olefin polymer part such as ethylene, propylene, 1-butene, Alternatively, the hydrogenated product of the butadiene polymer part has crystallinity.

  Preferred examples of such an olefin block copolymer elastomer (w3) include a soft segment comprising at least one diene block (diene polymer portion; diolefin polymer portion) and at least one styrene block (styrene polymer). Part) and a soft segment comprising at least one amorphous olefin block (amorphous olefin polymer part) and at least one crystalline olefin block ( An olefin / amorphous olefin block copolymer (w2) having a hard segment composed of a crystalline olefin polymer portion) can be exemplified. These block copolymers are generally produced as thermoplastic elastomers. Sold.

  The proportion of the block copolymer (w) having a styrene block or a crystalline olefin block is 1 to 50 parts by weight, particularly 3 to 40 parts by weight, based on 100 parts by weight of the ethylene copolymer (ii). Of these, 3 to 20 parts by weight is preferred.

In the foam composition of the present invention, as other polymers used in combination with the ethylene copolymer (a), α-olefin elastomer (u), ethylene / polar monomer copolymer (v), styrene block Or when using together at least 1 or more types of polymers chosen from the block copolymer (w) which has a crystalline olefin block, it is 1-50 in total with respect to 100 weight part of ethylene-type copolymers (ii). Part by weight, especially 3 to 40 parts by weight, especially 3 to 20 parts by weight is preferred.
The anti-aging agent (stabilizer), processing aid, activator, and hygroscopic agent that may be blended as necessary in the foam composition of the present invention are described below.

Anti-aging agent (stabilizer)
An anti-aging agent (stabilizer) that is blended as necessary can extend the life of the foam. Examples of such anti-aging agents include conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.

  Further, as an anti-aging agent, an aromatic secondary amine type anti-aging agent such as phenylbutylamine, N, N-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene, tetrakis [methylene (3,5-di- t-butyl-4-hydroxy) hydrocinnamate] phenolic antioxidants such as methane; thioethers such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide Anti-aging agent; dithiocarbamate anti-aging agent such as nickel dibutyldithiocarbamate; sulfur such as 2-mercaptobenzoylimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, distearylthiodipropionate There are anti-aging agents.

  In the mode of blending these anti-aging agents, they can be used alone or in combination of two or more, and the blending amount thereof can be selected from ethylene / α-olefin / non-conjugated polyene copolymer and other polymers ( The amount is usually 0.3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight with respect to a total of 100 parts by weight of the elastomer or the like. By setting it within such a range, there is no bloom on the surface of the molded product obtained from the resulting rubber composition, and further inhibition of vulcanization inhibition can be suppressed.

In the aspect of blending the processing aid processing aid, those generally blended into the rubber as the processing aid can be widely used.

  Specific examples of the processing aid include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, esters and the like. Of these, stearic acid is preferred.

  The blending amount of the processing aid is based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A) contained in the rubber composition and a polymer (elastomer, rubber, etc.) other than the ethylene copolymer. The amount is usually 10 parts by weight or less, preferably 8.0 parts by weight or less.

In the case of using an activator that is blended as required, specific examples include amines such as di-n-butylamine, dicyclohexylamine, monoelaanolamine; diethylene glycol, polyethylene glycol, lecithin, triarylate melilate, Activators such as zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids; zinc peroxide preparations; kutadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds and the like.

  In the embodiment in which the activator is blended, the blending amount is usually 0 with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and other polymers (elastomer, rubber, etc.). .2 to 10 parts by weight, preferably 0.3 to 5 parts by weight.

In the aspect of blending the hygroscopic agent, specific examples thereof include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, white carbon and the like.

  When it contains a hygroscopic agent, its blending amount is usually 0.5 with respect to 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer (A) and other polymers (elastomer, rubber, etc.). -15 parts by weight, preferably 1.0-12 parts by weight.

Production Method of Foam Molded Article The foam molded article of the present invention can be produced by crosslinking and foaming the foam composition of the present invention.

  That is, the ethylene-based copolymer (I) of the present invention and the foam composition containing a crosslinking agent and a foaming agent are mixed with a Henschel mixer or the like, and mixed with a kneading machine such as a Banbury mixer, a roll or an extruder. It can be melt-plasticized at a temperature at which the cross-linking agent and foaming agent do not decompose, and can be mixed and dispersed uniformly and prepared by a granulator. As a method of crosslinking foaming, for example, crosslinking by heat treatment is preferable as described later.

  Moreover, the sheet | seat which consists of a composition for foams of this invention can prepare the pellet obtained as mentioned above, for example using an extruder or a calendering machine. Alternatively, after each component of the foam composition of the present invention is kneaded with a Brabender or the like, it is formed into a sheet shape with a calender roll, formed into a sheet with a press molding machine, or kneaded with an extruder and then T An uncrosslinked and unfoamed foamable sheet can be produced by a method of forming a sheet through a die or an annular die.

  In forming the sheet, it is preferable to form the sheet below the decomposition temperature of the crosslinking agent and the foaming agent. Specifically, the temperature in the molten state of the component containing the ethylene copolymer (a) is, for example, 100. It is preferable to form the sheet by setting the conditions to be ˜130 ° C.

When the method of manufacturing a primary foam from the sheet | seat obtained by these methods is illustrated, the range of 1.0-1.2 with respect to the volume of a metal mold | die is hold | maintained at 130-200 degreeC, for example. And insert it into the mold. A primary foamed molded article can be produced under a mold clamping pressure of, for example, 30 to 300 kgf / cm ² and a holding time of, for example, 10 to 90 minutes. That is, a foamed molded product is produced by heat treatment. In addition, since holding time is influenced by the thickness of a metal mold | die, it is not restricted to this range, but can also be made into the range beyond it.

  The shape of the mold for such a foam-molded product is not particularly limited, but usually a mold having a shape adjusted so as to obtain a sheet is used. The mold preferably has a completely sealed structure so that the gas generated during decomposition of the molten polymer and the foaming agent does not escape. Moreover, as a mold, the mold having a taper on the inner surface is preferable from the viewpoint of releasability of the polymer composition in which the molten mold is formed.

  Further, for example, the foamed molded article can be produced by an extrusion foaming method in which the foam composition of the present invention is extruded from an extruder and released into the atmosphere and foamed at the same time. That is, a foam can be manufactured by heat treatment.

  For example, the foam composition of the present invention is injected into a mold at a temperature equal to or lower than the decomposition temperature of the crosslinking agent and the foaming agent, and is crosslinked and foamed in the mold at a temperature of about 130 ° C. to 200 ° C., for example. A foam can also be manufactured by the method (injection foaming method). That is, a foam can be manufactured by heat treatment.

The primary foam obtained by these exemplified methods and other methods can be further given a predetermined shape by compression molding to obtain a foam molded product. As an example of the compression molding conditions at this time, the mold temperature is 130 to 200 ° C., the clamping pressure is 30 to 300 kgf / cm ² , the compression time is 5 to 60 minutes, and the compression ratio is 1.1 to 3.0. , Preferably it is the range of 1.3-2.

In each of these cross-linking and foaming steps, a cross-linking method using ionizing radiation irradiation may be used in combination as necessary.
Examples of the product shape of the foam include a sheet shape, a thick board shape, a net shape, and a mold.

Foam molded body The foam molded body of the present invention is lightweight and excellent in deformation recovery.
The foamed molded article of the present invention has a specific gravity (d) generally in the range of 0.03 to 0.30, preferably 0.05 to 0.20, more preferably 0.05 to 0.12, and even more preferably. Is in the range of 0.08 to 0.12.

When the specific gravity is less than 0.30, the impact resilience is good and the foamed molded article is also light.
When the specific gravity is larger than 0.03, the strength as a foam is sufficient, and the durability and the like are good. In addition, it is preferable that the difference between the maximum value and the minimum value of the measured values of the specific gravity of the five parts, which is a measure of the uniformity of the quality of the foam molded article, is 0.08 or less, and preferably 0.06 or less. Further preferred.

The foamed molded article of the present invention can be efficiently molded even if its compression set (CS,%) is 55% or less.
The foamed molded product of the present invention can be a foamed molded product having excellent tear resistance, and the tear strength measured according to ASTM D3574 is 10 N / mm or more, especially 20 N / mm or more, and especially 24 N / It can be set as a foamed molded article of mm or more.

These physical properties are measured as follows.
The foamed molded article of the present invention is excellent in the lightness and deformation recovery as described above, and is excellent in balance of other physical properties, and can be used for various applications. For example, there is a use of a foam molded article for footwear, for example, a use of a midsole for footwear. Moreover, it can utilize for the laminated body with another material using the foaming molding of this invention.

  As a method of using the foamed molded product of the present invention for a laminate, a layer composed of the foamed molded product of the present invention and a layer composed of at least one material selected from the group consisting of polyolefin, polyurethane, rubber, leather and artificial leather There is a laminate having

  The polyolefin, polyurethane, rubber, leather and artificial leather are not particularly limited, and conventionally known polyolefin, polyurethane, rubber, leather and artificial leather can be used. Such a laminate is particularly suitable for footwear or footwear parts. Examples of such footwear or footwear parts include a shoe sole, a shoe midsole, an inner sole, a sole, and sandals. Since these footwear or footwear parts use the foamed molded product or laminate of the present invention, they are lightweight and can suppress deformation due to long-term use.

The invention is further illustrated by the following examples.
However, physical properties and the like were evaluated by the following methods.
Molar amount of structural unit derived from ethylene [A]
^It calculated | required by the intensity | strength measurement by a < ¹ > H-NMR spectrum meter.
Molar amount of structural unit derived from non-conjugated polyene [C]
^It calculated | required by the intensity | strength measurement by a < ¹ > H-NMR spectrum meter.
Melt flow rate (MFR)
The ethylene-based copolymer of the present invention was measured under the conditions of ASTM D1238, 190 ° C. and 2.16 kg load.

Crystallinity (%)
Crystallinity was determined by wide-angle X-ray diffraction measurement.
Wide-angle X-ray diffraction is measured by the following method. X-rays used for measurement are generated using an Rigaku X-ray diffractometer RINT2500. Using a copper counter cathode as a target, the sample is irradiated with X-rays extracted at a point focus of 50 kV × 300 mA, and the intensity of the diffracted X-rays is measured with a scintillation counter. 2θ scanning is performed at 5 to 35 ° to obtain a wide-angle X-ray diffraction profile of the sample.

In addition, an amorphous sample of the same material is prepared, and the X-ray diffraction profile (amorphous halo) of the amorphous sample obtained by performing the same measurement is used to convert the X-ray diffraction profile of the actual sample to an amorphous halo. And crystal peak. The crystallinity of the actual sample is determined as follows.
First, the baseline is cut off, and the ratio of the total crystal peak area in the total area is obtained as a percentage.

Specific gravity The specific gravity was measured according to JIS K7222. If the foamed molded body is a cube, the sample is sampled from the inside of 20 mm or more from each of the four sides of the plane of the maximum area, and from a site cut out by 2.5 mm or more from the surface of the parallel plane. Even if the foam to be sampled is a solid of various shapes, the surface showing the maximum area of the foam is on the upper surface, and the foam is on the opposite side of the upper surface. When the surface to be positioned is a lower surface, the sample is adjusted from the inside (at least 20 mm) from the end (side surface) and from the portion cut out by 2.5 mm or more from the upper and lower surfaces.

For example, in the case of a midsole for shoes, a sample is adjusted from a part cut out by 20 mm or more from each end and 2.5 mm or more from both surfaces of a substantially parallel plane.
The measurement is performed using an electronic hydrometer (product number MD-200S) manufactured by Mirage Trading Co., Ltd.

  The measurement is an average of five parts of the foamed molded product. Further, the difference between the maximum value and the minimum value of the measured values of the specific gravity of the five parts, which is a measure of the uniformity of the quality of the foam molded article, is preferably 0.08 or less, and more preferably 0.06 or less. preferable. If the range exceeds 0.08, it means that the quality of the foamed molded product (hardness, mechanical properties, compression set, etc.) is not constant. FIG. 1 shows five parts to be measured.

Compression set (CS)
According to JIS K6301, compression was performed under the conditions of 50 ° C. × 6 hours and a compression amount of 50%, the thickness after 30 minutes of strain release was measured, and the amount of compression set was determined.

  In addition, even when the foamed molded object to be sampled is a solid having various shapes, it is cut into a cylindrical shape having a diameter of 30 mm or more and a thickness of 15 mm or more, and each of the two parallel planes of the cylinder is 2 from the surface of the parallel plane. Cut out 5 mm or more and make the sample 10 mm thick.

A cylindrical dumbbell mold can be used for cutting the foam molded body into a cylindrical shape and cutting the foam molded body from the surface of a parallel plane.
The sample is allowed to stand for 6 hours in a 50% compression, 50 ° C. environment and measured 30 minutes after release from compression. The compression set (CS) is calculated from the following equation.
CS = (t ₀ −t ₁ ) / (t ₀ −t ₂ ) × 100
t ₀ : Sample thickness (mm)
t ₁ : Thickness (mm) 30 minutes after taking out the sample from the compression device
t ₂ : Spacer thickness (mm))

Tear strength tear strength, in accordance with ASTM D3574, it was measured under 23 ℃ environment. The tester uses a tensile tester and the pulling speed is 100 mm / min. The tear strength Tr (N / mm) is calculated by the following equation.
Tr = t ₀ / t ₁ × 9.81
t ₀ : Tear stress (kg)
t ₁ : Sample width (mm)

Evaluation of feel of foamed molded product The foamed molded product was contacted with a human finger, and the smoothness was evaluated in two stages of ○ and ×.
<Two-step evaluation>
○: The surface is flat and has a soft touch. ×: The surface is rough and hard.

Evaluation of foaming uniformity The foamed molded product was cut and the state of the cut surface was observed with the naked eye. The state was judged by the following two stages, and the uniformity of foaming was evaluated.
<Two-step evaluation>
○: Both foam size and shape are uniform ×: Both foam size and shape are non-uniform

Adhesive Evaluation The surface of the secondary foamed molded article was washed with water using a surfactant and dried at room temperature for 1 hour.
Next, this secondary foamed molded article was immersed in methylcyclohexane for 3 minutes and then dried in an oven at 60 ° C. for 3 minutes.

  Subsequently, a UV curable primer (manufactured by Daito Resin Co., Ltd., GE258H1) was applied with a thin brush, dried in an oven at 60 ° C. for 3 minutes, and then three 80 W / cm high-pressure mercury lamps perpendicular to the passing direction. Using the installed irradiation device [manufactured by Nippon Battery Co., Ltd., EPSH-600-3S type, UV irradiation device], at a position of 15 cm under the light source, the conveyor speed was moved at a speed of 10 m / min, and UV light was irradiated. .

  Thereafter, an auxiliary primer (a primer GE6001L manufactured by Daito Resin Co., Ltd. added with 5% by weight of a curing agent GE366S) was thinly brushed and dried in an oven at 60 ° C. for 3 minutes.

Subsequently, the adhesive (adhesive 98H manufactured by Daito Resin Co., Ltd. plus 4% by weight of the curing agent GE348) was thinly brushed and dried in an oven at 60 ° C. for 5 minutes.
Finally, the secondary cross-linked foam coated with the adhesive and a polyurethane (PU) synthetic leather sheet subjected to the following treatment were bonded together and pressure-bonded at 20 kg / cm ² for 10 seconds.

Treatment of PU leather sheet The surface of the PU leather sheet was washed with methyl ethyl ketone and dried at room temperature for 1 hour.

Next, an auxiliary primer (a primer GE6001L manufactured by Daito Resin Co., Ltd., with 5% by weight of a curing agent GE366S added) was thinly brushed and dried in an oven at 60 ° C. for 3 minutes.
Subsequently, the adhesive (adhesive 98H manufactured by Daito Resin Co., Ltd. plus 4% by weight of the curing agent GE348) was thinly brushed and dried in an oven at 60 ° C. for 5 minutes.

Peel test The adhesive strength after 24 hours of the pressure-bonded sheet was evaluated in the following manner.
That is, after cutting the pressure-bonded sheet into a width of 1 cm and peeling off the end portion, the end portion was pulled in the direction of 180 ° at a speed of 200 mm / min, and the peeled state at that time was observed with the naked eye, Evaluation was made in three stages, Δ and ×.
<3-level evaluation>
○: Peeling occurs at the foam layer Δ: Peeling occurs at both the foam layer and the adhesive interface ×: Peeling occurs only at the adhesive interface

Synthesis example 1
N-Hexane that has been dehydrated and purified is supplied at a rate of 37 liters / hr to one supply port of a continuous polymerization vessel with a capacity of 300 liters, from the other supply port.
Titanium [N- (1,1-dimethylethyl) -1,1-dimethyl-1- [1,2,3,3a, 8a-.eta)-1,5,6,7-tetrahydoro-2-methyl-s -indacen-1-yl] silanaminato (2-)-. kappa.N] [(1,2,3,4-, eta) -1,3-pentadiene] -stereoisomer in hexane solution (0.45 mmol / l ) At a rate of 0.156 liter / hr, hexane solution of triisobutylaluminum (10 mmol / liter) at 1 liter / hr, hexane solution of perfluoroarylborate salt (0.45 mmol / liter) at 0.78 liter / hr, Ethylylene norbornene or vinyl norbornene was continuously fed at a rate of 450 g / hr (total hexane: 39 l / hr). At the same time, ethylene 5.3 kg / hr, butene 0.8 kg / hr, and hydrogen 25 g / hr are continuously fed to another supply port of the polymerization vessel at a polymerization temperature of 110 ° C., a total pressure of 1.6 MPaG, a residence time. Continuous solution polymerization was carried out for 0.5 hours under conditions of a polymer concentration of 12 wt%.

The hexane solution of ethylene-1-butene-nonconjugated diene copolymer produced in the polymerization vessel was continuously discharged at a flow rate of 48 liters / hr through a discharge port provided in the side wall of the polymerization vessel, and the jacket The part was led to a connecting pipe heated with 8 kg / cm ² steam. The hexane solution of ethylene-1-butene-nonconjugated diene copolymer heated to about 170 ° C. in the connection pipe with steam jacket is connected to the end of the connection pipe so as to maintain the amount of solution in the polymerization tank of about 100 liters. By adjusting the opening of the liquid level control valve provided in the tank, the liquid was continuously fed to the flash tank through a double pipe inner tube heated with 10 kg / cm ² steam. Immediately after the liquid level control valve, a supply port for injecting methanol, which is a catalyst deactivator, is attached and injected as a 1.0 vol% hexane diluted solution at a rate of 12 liters / hr. Merged. In the transfer into the flash tank, the solution temperature and the pressure adjustment valve opening were set so that the pressure in the flash tank was 0.05 MPaG and the temperature of the vapor part in the flash tank was maintained at 180 ° C.

  As a result, an ethylene-1-butene-nonconjugated diene copolymer was obtained at a production speed of 4 kg / hr. The polymerization Mileage of ethylene-1-butene-nonconjugated diene copolymer was 106 kg / mmol-Zr, the MFR of the obtained ethylene-1-butene-nonconjugated diene copolymer was 1.2 g / 10 minutes, and the ethylene content was The amount was 95 mol%, the nonconjugated diene was 1.1 mol%, and the crystallinity was 27%.

Synthesis Examples 2-13
In Synthesis Example 1, the ethylene content and the non-conjugated diene content were changed to the ethylene copolymers shown in Example 2 to Comparative Example 7 in Table 1, so that the conditions were changed and the same operation was performed. Ethylene copolymers used in Example 2 to Comparative Example 7 were obtained.
Examples 2 to 5 Synthesis Examples 2 to 5
Examples 6 to 8 Synthesis Example 6
Comparative Examples 1-7 Synthesis Examples 7-13

Example 1
The foam composition obtained by blending the ethylene-based copolymer obtained in Synthesis Example 1 with the compounding agents shown in Table 1 is a lab plast mill [100MR2 type, manufactured by Toyo Seiki Seisakusho] After kneading for 5 minutes at a set temperature of 110 ° C., it was molded into a sheet. The maximum temperature of the foamable polymer composition during the laboplast mill kneading was adjusted to be 120 ° C. or lower.

Next, the obtained sheet was filled into a press mold, and pressurized and heated under the conditions of 150 kg / cm ² , 155 ° C. and 30 minutes to obtain a primary crosslinked foamed molded article. The size of the press mold was 15 mm thick, 150 mm long, and 200 mm wide.

Next, this primary cross-linked foamed molded product was compression molded at 150 kg / cm ² , 155 ° C. and a compression ratio of 150% for 10 minutes, and immediately cooled at 20 ° C. for 10 minutes to obtain a secondary cross-linked foamed molded product. . The size of the obtained secondary cross-linked foam was 15 mm in thickness, 160 mm in length, and 250 mm.
The primary crosslinked foamed molded product was evaluated for specific gravity, compression set, feel of the foamed molded product, and foam uniformity.

Examples 2-5
In Example 1, a foamed molded product was produced and evaluated in the same manner except that the ethylene copolymer and the types and proportions of the compounding agents were changed to those shown in Table 1.
The results are shown in Table 1.

Examples 6-8
In Example 1, a foamed molded product was produced in the same manner as described above except that the polymers shown in Table 1 were used in combination and the composition was changed to the ratio shown in Table 1.
However, the following was used.
Ethylene / α-olefin copolymer Ethylene / butene copolymer Density 0.905 g / cm ³ , MFR = 1.2 g / 10 min (190 ° C., 2.16 kgf), ethylene content 95 mol%, 1-butene content 5 mol%.

Ethylene / vinyl acetate copolymer EV270 (manufactured by Mitsui DuPont Polychemical Co., Ltd.) density 0.950 g / cm ³ ,
MFR = 1 g / 10 min (190 ° C., 2.16 kgf), vinyl acetate (VA) content 28 mol%.

Styrene elastomer P2000 (manufactured by Asahi Kasei) density 0.98 g / cm ³ ,
MFR = 3 g / 10 min (190 ° C., 2.16 kgf), styrene content 67 wt%.

DCP
Mitsui DCP (trade name) (Mitsui Chemicals) Concentration: 98% or more TAIC
M-60 (TAIC content 60%) (Nippon Kasei)
ZN-DA
Zinc acrylate (manufactured by Nippon Distillation Industry)
ZnO
2 types of zinc oxide (Hakusuitec Co., Ltd.)
TiO ₂
R820 (Ishihara Sangyo Co., Ltd.)
The results are shown in Table 1.

Comparative Examples 1-7
In Example 1, a foamed molded article was produced and evaluated in the same manner except that the composition was changed to Table 1. The results are shown in Table 1.

Claims (4)

An ethylene-based copolymer containing a structural unit derived from ethylene [A], an α-olefin [B] having 4 to 20 carbon atoms, and a non-conjugated polyene [C],
(1) The crystallinity is in the range of 20 to 28% ,
(2) The structural unit derived from ethylene [A] is a structural unit of [A], [B] and [C].
92 to 97 mol%, where the total is 100 mol%,
(3) The structural unit derived from the non-conjugated polyene [C] is 0.01 to 3.0 mol%, where the total of the structural units of [A], [B] and [C] is 100 mol%,
The melt flow rate at (4) 190 ℃ (MFR 190 ℃) is 0.5 to 25 der
That the ethylene copolymer (A) and crosslinking agent and foamed molded a foamed composition containing a blowing agent is crosslinked and foamed, characterized by comprising. Having 4 to 20 carbon atoms α- olefin [B] is 1-butene, 1-hexene according to claim 1, wherein the or at least one or more α- olefins selected from 1-octene, Foam molded body . The foam composition is further selected from an ethylene copolymer (b), an α-olefin elastomer, an ethylene / polar monomer copolymer, and a block copolymer having a styrene block or a crystalline olefin block. The foamed molded article according to claim 1 , wherein the foamed molded article comprises at least one polymer. A shoe midsole comprising the foamed molded product according to any one of claims 1 to 3.

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