Specification
Title of the invention: Ethylene-based copolymer composition and its use
Technical field
[0001]
The present invention relates to an ethylene-based copolymer composition, a foam composed of the composition, and its use. More specifically, the present invention relates to a composition containing an ethylene / α-olefin copolymer and an ethylene / α-olefin / non-conjugated polyene copolymer, a foam composed of the composition, and its use.
Background technology
[0002]
Cross-linked foam of resin is also used for footwear or footwear parts, for example, soles (mainly midsole) of sports shoes and the like. This is because footwear or footwear parts are required to be lightweight, to suppress deformation due to long-term use, and to have mechanical strength and impact resilience that can withstand harsh usage conditions.
[0003]
Conventionally, a crosslinked foam obtained by peroxide-crosslinking an ethylene-vinyl acetate copolymer (EVA) is widely used for soles. The crosslinked foam formed using this ethylene-vinyl acetate copolymer has a relatively high specific gravity and a large compression set. Therefore, when used for a shoe sole, for example, it is heavy and the sole is used for a long period of time. Is compressed and mechanical strength such as impact resilience is lost. For this reason, ethylene / 1-butene rubber (EBR), which has better cross-linking efficiency than ethylene-vinyl acetate copolymer, for the purpose of further improving the compression set and mechanical strength of the foam of the ethylene-vinyl acetate copolymer system. , Ethylene-Octen Rubber (EOR) and other polyolefin-based rubber blends have been attempted.
[0004]
Further, it is known that the lower the crystallinity of the material, the better the impact resilience. Therefore, when a particularly high impact resilience is required, an ethylene-vinyl acetate copolymer (EVA) and an ethylene-propylene-diene copolymer are required. An attempt was made to blend with (EPDM). However, in that case, there is a problem that the heat shrinkage and the mechanical strength are insufficient, and there is a case where the mechanical strength is supplemented by further adding a polyolefin-based rubber having high crystallinity.
[0005]
On the other hand, ethylene / α-olefin copolymers have been conventionally used for various purposes. For example, crosslinked foams using ethylene / α-olefin copolymers have high mechanical strength, are lightweight, and are flexible, so they are used for building exterior materials, interior materials, automobile parts such as door glass runs, and packaging materials. , Used in daily necessities. Here, since the foam without cross-linking achieves weight reduction but has low mechanical strength, when the foam is used for the above-mentioned applications, the foam is subjected to a cross-linking reaction of a resin to form a foam. The molecular chains of the above are bonded to improve the mechanical strength.
[0006]
The applicant of the present application has found that a crosslinked foam using an ethylene / α-olefin copolymer is suitable as a lighter weight material for footwear parts, and has been studying various things from the past. Specifically, a foam composed of a composition composed of an ethylene-based polymer and EPDM (see Patent Document 1), and a foam composed of a composition containing an ethylene / α-olefin copolymer having a vinyl group (Patent Document 2). , Patent Document 3) has found that it has a low specific gravity, a small compression set, and is suitable for footwear parts.
[0007]
Further, in Patent Document 4, a crosslinked foam having high hardness and low compression permanent strain obtained by using an effervescent compound containing an ethylene / α-olefin copolymer having a vinyl group is used for footwear and the like. It is described as useful.
Prior art literature
Patent documents
[0008]
Patent Document 1: International Publication No. 2007/132731
Patent Document 2: International Publication No. 2015/129414
Patent Document 3: Japanese Patent Application Laid-Open No. 2008-308619
Patent Document 4: Japanese Patent Application Laid-Open No. 2015-521670
Outline of the invention
Problems to be solved by the invention
[0009]
INDUSTRIAL APPLICABILITY The present invention is a composition suitable for use in footwear parts such as soles, and capable of producing a crosslinked foam having excellent balance in characteristics such as light weight, heat shrinkage, compression set, and mechanical strength. It is an object of the present invention to provide a foam using a composition and parts for footwear using the same.
Means to solve problems
[0010]
The present invention relates to, for example, the following [1] to [15].
[1]
A copolymer obtained by copolymerizing only ethylene and α-olefin having 3 to 20 carbon atoms, which are the following (A), (Ab), (Ac) and ( Ethylene-based copolymer (A) that meets all the requirements of A-d),
α-olefin / non-conjugated polyene copolymer rubber (B) with ethylene / carbon atoms of 3 to 20, and
ethylene / polar monomer co-weight
Ethylene-based polymer composition comprising a coalescence (C) ;
(AA) 1 The vinyl group content per 1000 carbon atoms determined by H-NMR is 0.025 to 0.3. It is in the range of pieces.
(Ab) MFR 10 / MFR 2.16 is in the range of 7-20. (However, MFR 10 is the melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 10 kg, and MFR 2.16 is the melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 2.16 kg. (Ac )
The density is in the range of 0.850 to 0.910 g / cm 3 .
(Ad) The melt flow rate (MFR 2.16 ) measured by the method of ASTM D1238 at 190 ° C. and a load of 2.16 kg is in the range of 0.01 to 200 g / 10 minutes.
[0011]
[2]
A copolymer obtained by copolymerizing only ethylene and α-olefin having 3 to 20 carbon atoms, which are the following (A), (Ab), (Ac) and (. 5 to 30 parts by mass of the ethylene-based copolymer (A) satisfying all the requirements of Ad
) and 3 to 3 ethylene carbon atoms satisfying at least one of the following requirements (Ba) and (Bb). 20 α-olefin / non-conjugated polyene copolymer rubber (B) 95 to 70 parts by mass (however, ethylene-based copolymer (A) and ethylene / α-olefin / non-conjugated polyene having 3 to 20 carbon atoms
An ethylene-based copolymer composition comprising 100 parts by mass of the copolymer rubber (B) ;
(AA) 1 per 1000 carbon atoms determined by H-NMR. The vinyl group content of ethylene is in the range of 0.025 to 0.3.
(Ab) MFR 10 / MFR 2.16 is in the range of 7-20. (However, MFR 10 is the melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 10 kg, and MFR 2.16 is the melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 2.16 kg. (Ac )
The density is in the range of 0.850 to 0.910 g / cm 3 .
(Ad) The melt flow rate (MFR 2.16 ) measured by the method of ASTM D1238 at 190 ° C. and a load of 2.16 kg is in the range of 0.01 to 200 g / 10 minutes.
(BA) The content of the building blocks derived from ethylene is in the range of 60 to 95% by mass. (Bb) The Mooney viscosity (ML 1 + 4
) measured at 100 ° C. by the method of JIS K6395 is in the range of 50 to 120. [3] Mass ratio of the ethylene-based copolymer (A) to the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having 3 to 20 carbon atoms [(A) / (B)]. The ethylene-based copolymer composition according to [1], wherein the composition is in the range of 5/95 to 80/20. [4] The ethylene-based copolymer composition according to any one of [1] to [3], wherein the ethylene-based copolymer (A) is an ethylene / 1-butene copolymer. [5] The ethylene-based copolymer composition according to any one of [2] to [4], which further comprises an ethylene / polar monomer copolymer (C). [6] The mass ratio [(A) / (C)] of the ethylene-based copolymer (A) to the ethylene / polar monomer copolymer (C) is in the range of 1/99 to 39/61. The ethylene-based copolymer composition according to [1] or [5]. [7]
さらに発泡剤(D)、架橋剤(E)、またはそれらの組合せを含むことを特徴とする〔1〕~〔6〕のいずれかに記載のエチレン系共重合体組成物。
〔8〕
〔7〕に記載のエチレン系共重合体組成物を架橋発泡させて得られることを特徴とする発泡体。
〔9〕
JIS K6255の方法により測定した反発弾性率が55%以上であることを特徴とする〔8〕に記載の発泡体。
〔10〕
発泡体を70℃環境にて60分熱処理した後、23℃環境下で30分経過後の熱収縮率(Sh)が、3.0%未満であることを特徴とする〔8〕または〔9〕に記載の発泡体。
〔11〕
〔8〕~〔10〕のいずれかに記載の発泡体からなる層と、ポリオレフィン、ポリウレタン、ゴム、皮革および人工皮革からなる群から選ばれる少なくとも1種の素材からなる層とを有することを特徴とする積層体。
〔12〕
〔8〕~〔10〕のいずれかに記載の発泡体または〔11〕に記載の積層体を用いてなることを特徴とする履物。
〔13〕
〔8〕~〔10〕のいずれかに記載の発泡体または〔11〕に記載の積層体を用いてなることを特徴とする履物用部品。
〔14〕
前記履物用部品が、ミッドソール、インナーソールまたはソールであることを特徴とする〔13〕に記載の履物用部品。
〔15〕
A method for producing a foam, which comprises a step of foaming the ethylene-based copolymer composition according to any one of [1] to [7].
Effect of the invention
[0012]
According to the present invention, a composition suitable for use in footwear parts such as soles, capable of producing a crosslinked foam having an excellent balance of properties such as light weight, heat shrinkage, compression set, and mechanical strength. , Foams and laminates using the composition, and footwear parts and footwear using them can be provided.
Embodiment for carrying out the invention
[0013]
Hereinafter, the present invention will be specifically described.
<< Ethylene-based copolymer composition >> The ethylene-based copolymer composition according to
the present invention contains the ethylene-based copolymer (A) and ethylene, α-olefin having 3 to 20 carbon atoms, and non-conjugated polyene. It contains a coalesced rubber (B) and, if necessary, an ethylene / polar monomer copolymer (C). Further, if necessary, a foaming agent (D), a cross-linking agent (E), and other components can be further contained.
[0014]
The ethylene-based copolymer (A) according
to the present invention is a copolymer composed only of ethylene and an α-olefin having 3 to 20 carbon atoms, and is preferably ethylene. It is a copolymer of α-olefin having 3 to 10 carbon atoms. That is, the ethylene-based copolymer (A) according to the present invention is a copolymer composed of a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms.
[0015]
Examples of the α-olefin having 3 to 20 carbon atoms as a copolymerization component include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, and 1 -Octene, 1-decene, 1-dodecene, 1-tetradecene and the like can be mentioned. The α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 10 carbon atoms. The α-olefin having 3 to 20 carbon atoms, which is a copolymerization component, may be used alone or in combination of two or more. One type may be used alone, or two or more types may be used.
[0016]
Of these, the ethylene-based copolymer (A) according to the present invention is particularly preferably an ethylene / 1-butene copolymer.
The type of α-olefin constituting the ethylene-based copolymer (A) is clear depending on the type of the copolymerization monomer at the time of producing the ethylene-based copolymer (A), but α in the ethylene-based copolymer. -For example, the type of olefin is 13 C-NMR spectrum of a sample in which about 200 mg of an ethylene-based copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube, and the temperature is 120 ° C. and the frequency is 25.05 MHz. It can be measured and identified under the measurement conditions of a spectrum width of 1500 Hz, a pulse repetition time of 4.2 seconds, and a 45 ° pulse width of 6 μsec.
[0017]
In the present invention, the content (ethylene content) of the ethylene-derived constituent unit of the ethylene-based copolymer (A) is not particularly limited, but is usually 50 to 99 mol%, preferably 50 to 99 mol%, preferably in the total structural unit. It is in the range of 60 to 98 mol%, more preferably 75 to 97 mol%. Further, the content (α-olefin content) of the structural unit derived from the α-olefin having 3 to 20 carbon atoms of the ethylene-based copolymer (A) is usually 1 to 50 mol%, preferably 1 to 50 mol% in the total structural unit. It is in the range of 2-40 mol%, more preferably 3-25 mol%.
[0018]
The ethylene-based copolymer (A) according to the present invention simultaneously satisfies the following requirements (A), (Ab), (Ac) and (Ad).
(Aa) 1 The vinyl group content per 1000 carbon atoms determined by 1 H-NMR is in the range of 0.025 to 0.3.
(Ab) MFR 10 / MFR 2.16 is in the range of 7-20.
(Ac) The density is in the range of 0.850 to 0.910 g / cm 3 .
(Ad) The melt flow rate (MFR 2.16 ) is in the range of 0.01 to 200 g / 10 minutes.
[0019]
Hereinafter, each of these requirements and the like will be further described.
(A-a) Vinyl group content
The ethylene-based copolymer (A) according to the present invention preferably has a vinyl group content of usually 0.025 or more per 1000 carbon atoms determined by 1 H-NMR. Is 0.026 or more, more preferably 0.027 or more, still more preferably 0.028 or more, particularly preferably 0.03 or more, and usually 0.3 or less, preferably 0.2 or less. , More preferably 0.15 or less, still more preferably 0.1 or less, and particularly preferably 0.09 or less.
[0020]
A specific method for measuring the vinyl group content (vinyl type double bond amount) will be described in detail in the measurement / evaluation method of Examples described later.
In the ethylene-based copolymer (A) according to the present invention, the vinyl group is usually present at the terminal portion of the copolymer. The ethylene-based copolymer (A) according to the present invention has a vinyl group content per 1000 carbon atoms in the above range and has crosslinkability. When the content of the vinyl group is in the above range, the mechanical strength of the obtained molded product is excellent, which is preferable. When the vinyl group content is 0.3 or less per 1000 carbon atoms of the ethylene-based copolymer (A), cross-linking and breakage of the polymer backbone during heat molding are reduced, and the molding processability is excellent. When the vinyl group content is 0.025 or more per 1000 carbon atoms of the ethylene-based copolymer (A), cross-linking becomes easy, and compression permanent strain (CS) or mechanical of the molded body or cross-linked foam is mechanical. Excellent in strength.
[0021]
(Ab) MFR 10 / MFR 2.16 The ethylene-based copolymer (A) according to the present invention has MFR 10 / MFR 2.16 of 7 to 20, preferably 7.2 to 15, more preferably 7.5 to. It is in the range of twelve. Here, MFR 10 is a melt flow rate (g / 10 minutes) measured by the method of ASTM D1238 at 190 ° C. and a load of 10 kg, and MFR 2.16 is a melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 2.16 kg. The measured melt flow rate (g / 10 minutes).
[0022]
MFR 10 / MFR 2.16 is a value considered to be one of the indicators of the degree of long-chain branching of the copolymer, and it is specified that the MFR 10 / MFR 2.16 value has long-chain branching in the above range. Will be done. A small MFR 10 / MFR 2.16 value indicates that there are few long chain branches. When the MFR 10 / MFR 2.16 value is 7 or more, the accuracy of the shape of the obtained crosslinked foam becomes high when the crosslinked foam is produced from the composition containing a large amount thereof, and the dimensional stability of the crosslinked foam becomes stable. Excellent in sex. Further, when the MFR 10 / MFR 2.16 value of the ethylene-based copolymer is 20 or less, the physical properties such as strength are excellent.
[0023]
(Ac) Density
The density of the ethylene-based copolymer (A) according to the present invention is usually 0.850 g / cm 3 or more, preferably 0.855 g / cm 3 or more, more preferably 0.857 g / cm 3 . The above is more preferably 0.858 g / cm 3 or more, usually 0.910 g / cm 3 or less, preferably 0.909 g / cm 3 or less, more preferably 0.908 g / cm 3 or less, still more preferably 0. It is 907 g / cm 3 or less. The density of the ethylene-based copolymer (A) is a value measured at 23 ° C. by ASTM D1505. When the density satisfies such a range, the obtained molded product or crosslinked foam is preferable because it has an excellent balance between flexibility and strength and a balance between rigidity and impact resistance.
[0024]
(Ad) Melt flow rate (MFR 2.16 ) The ethylene-based copolymer (A) according to the present invention has a melt flow rate (MFR 2.16 ) measured at 190 ° C. and a 2.16 kg load by the method of ASTM D1238. Usually 0.01 g / 10 minutes or more, preferably 0.08 g / 10 minutes or more, more preferably 0.05 g / 10 minutes or more, still more preferably 0.1 g / 10 minutes or more, particularly preferably 0.2 g / 10 minutes or more. Usually 200 g / 10 minutes or less, preferably 100 g / 10 minutes or less, more preferably 40 g / 10 minutes or less, still more preferably 25 g / 10 minutes or less, and particularly preferably 5 g / 10 minutes or less.
[0025]
The melt flow rate (MFR 2.16 ) of the ethylene-based copolymer (A) tends to decrease as the molecular weight increases. The method for adjusting the molecular weight will be described in the section "Production of Ethylene Copolymer (A)". It is preferable that MFR 2.16 is not more than the above upper limit value in terms of improving the strength of the obtained molded product, and that MFR 2.16 is not more than the above lower limit value is the flow during melt molding of the ethylene polymer (A). It is preferable in that the property is improved.
[0026]
(A-e) Mw / Mn
The ethylene-based copolymer (A) according to the present invention is not particularly limited, but has a weight average molecular weight Mw obtained from a value measured by gel permeation chromatography (GPC). The molecular weight distribution (Mw / Mn) calculated as the ratio of the number average molecular weight Mn is preferably 1.5 to 3.5, more preferably 1.5 to 3.0. Mw / Mn can be set within the above range by appropriately selecting the polymerization catalyst as described in the section of the olefin polymerization catalyst. Further, it is preferable that the content is within the above range in terms of improving the melt moldability and the strength of the obtained molded product.
[0027]
(A-f) Melting point (Tm)
The ethylene-based copolymer (A) according to the present invention is not particularly limited, but has a melting point (Tm) obtained from the heat absorption curve of DSC, preferably 40 ° C. or higher. , More preferably 50 ° C. or higher, further preferably 55 ° C. or higher, preferably 130 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower. When the melting point of the ethylene-based copolymer (A) is in the above range, it is preferable in terms of the balance between the impact resilience and the heat shrinkage rate.
[0028]
The ethylene copolymer (A) according to the present invention has the above-mentioned requirements (Aa), (Ab), (Ac) and (A). It is not particularly limited as long as it satisfies −d), and the production method thereof is not particularly limited. For example, ethylene and at least one of α-olefin having 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization. Can be suitably produced by copolymerizing with.
[0029]
-Catalyst for olefin polymerization
The ethylene-based copolymer (A) of the present invention has the above-mentioned characteristics, and the production method thereof is not limited in any way. For example, the following catalyst components [A] and [ It can be produced by copolymerizing ethylene with one or more selected from α-olefins having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising B].
[A] A crosslinked metallocene compound represented by the following general formula [I].
[0030]
[Chemical formula 1]
(In formula [I], M represents a transition metal, p represents the valence of the transition metal, and X may be the same or different, each representing a hydrogen atom, a halogen atom or a hydrocarbon group. Represented , R 1 and R 2 represent π-electron conjugated ligands coordinated to M, which may be the same or different, and Q represents a divalent group that bridges R 1 and R 2.
) [B. ] (B-1) Organic aluminum oxy compound,
(b-2) A compound that reacts with the metallocene compound [A] to form an ion pair, and (b-3) At least one compound selected from
an organic aluminum compound .
..
[0031]
Copolymerization is carried out, for example, by solution-polymerizing one or more monomers selected from ethylene and α-olefin at a temperature of 0 to 200 ° C. in the presence of a solvent in the presence of such an olefin polymerization catalyst. be able to.
[0032]
However, the ethylene-based copolymer (A) according to the present invention is not limited to the above-mentioned production method as long as it satisfies the above-mentioned characteristics. A compound may be used, a co-catalyst other than the catalyst component [B] may be used, or two or more known ethylene-based copolymers may be used to prepare a reactor blend, a physical blend, or the like. It may be prepared by a method.
[0033]
Hereinafter, in the presence of a catalyst for olefin polymerization containing the catalyst components [A] and [B], ethylene and one or more selected from α-olefins having 3 to 20 carbon atoms are copolymerized with each other. The above-mentioned method for producing the coalescence (A) will be further described.
[0034]
Catalyst component [A]
The catalyst component [A] is a crosslinked metallocene compound represented by the above formula [I]. Examples of the transition metal represented by M in the above formula [I] include Zr, Ti, Hf, V, Nb, Ta and Cr, and preferred transition metals are Zr, Ti or Hf, which are more preferable. The transition metal is Zr or Hf.
[0035]
In the general formula [I], the π-electron conjugated ligands represented by R 1 and R 2 include η-cyclopentadienyl structure, η-benzene structure, η-cycloheptatrienyl structure, and η-cyclo. A ligand having an octatetraene structure is mentioned, and a particularly preferable ligand is a ligand having a η-cyclopentadienyl structure. Examples of the ligand having a η-cyclopentadienyl structure include a cyclopentadienyl group, an indenyl group, a hydrogenated indenyl group, a fluorenyl group and the like. These groups are further substituted with hydrocarbon groups such as halogen atoms, alkyl, aryl, aralkyl, alkoxy, aryloxy, hydrocarbon group-containing silyl groups such as trialkylsilyl groups, chain or cyclic alkylene groups and the like. May be good.
[0036]
In the general formula [I], the group that crosslinks R 1 and R 2 represented by Q is not particularly limited as long as it is a divalent group, and is, for example, a linear or branched alkylene group, unsubstituted or Examples thereof include a substituted cycloalkylene group, an alkylidene group, an unsubstituted or substituted cycloalkylidene group, an unsubstituted or substituted phenylene group, a silylene group, a dialkyl substituted silylene group, a gelmil group, a dialkyl substituted gelmil group and the like.
[0037]
As the catalyst component [A], the metallocene complex used in the examples described later can be specifically exemplified, but the catalyst component [A] is not limited to these compounds.
It is preferable to use such a catalyst component [A] together with the catalyst component [B] as a catalyst for olefin polymerization.
[0038]
When the catalyst component [B]
and the catalyst component [A] are used as a component of the olefin polymerization catalyst for producing the ethylene-based copolymer (A), the olefin polymerization catalyst is (b-1) organoaluminum oxy compound, ( b-2) It may contain a catalyst component [B] composed of a compound that reacts with the catalyst component [A] to form an ion pair, and (b-3) at least one compound selected from organoaluminum compounds. preferable. Here, the catalyst component [B] is preferably used in any of the following embodiments [c1] to [c4] from the viewpoint of the polymerization activity and the properties of the produced olefin polymer.
[c1] (b-1) Organoaluminium oxy compound only,
[c2] (b-1) Organoaluminium oxy compound and (b-3) Organoaluminium compound,
[c3] (b-2) Catalyst component [A] A compound that reacts to form an ion pair with (b-3) an organoaluminum compound,
[c4] (b-1) an organoaluminum oxy compound and (b-2) a catalyst component [A] to form an ion pair. Compound to be used.
[0039]
However, when a metallocene compound in which Q is a silylene group in the general formula [I] is used as the catalyst component [A], the [B] component reacts with (b-2) the catalyst component [A] to form an ion. No pair-forming compound is used, and only [c1] and [c2] are adopted in the above-mentioned preferred [B] component; [c1] to [c4].
[0040]
Hereinafter, each component that can constitute the catalyst component [B] will be specifically described.
(B-1) Organoaluminium oxy compound
As the organoaluminum oxy compound (b-1), conventionally known aluminoxane can be used as it is. Specific examples thereof include compounds represented by the following general formulas [II] and / or general formulas [III].
[0041]
[Chemical formula 2]
(In the formula [II] or [III], R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more). A methylaluminoxane having a methyl group of 3 or more, preferably 10 or more is used. (The organoaluminum oxy compound in which R is a methyl group in the general formula [II] or [III] may be hereinafter referred to as "methylaluminoxane".)
Further, the organoaluminum oxy compound (b-1) is saturated. It is also preferable to use a methylaluminoxane analog that dissolves in a hydrocarbon, and examples thereof include modified methylaluminoxane as shown in the following general formula [IV].
[0042]
[Chemical formula 3]
(In the formula [IV], R is a hydrocarbon group having 2 to 20 carbon atoms, and m and n are integers of 2 or more.)
The modified methylaluminoxane represented by the general formula [IV] is trimethyl. Prepared using alkylaluminum other than aluminum and trimethylaluminum (for example, the manufacturing method is disclosed in US4960878, US5041584, etc.), and prepared using trimethylaluminum and triisobutylaluminum from manufacturers such as Toso Finechem, R is isobutyl. The basis is commercially produced under trade names such as MMAO and TMAO (see, for example, "Tosoh Research and Technology Report", Vol. 47, 55 (2003)).
[0043]
Further, as the organoaluminum oxy compound (b-1), a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687 may be used, and boron represented by the following general formula [V] may be used. The included organoaluminum oxy compound may be used.
[0044]
[Chemical formula 4]
(In the formula [V], R c represents a hydrocarbon group having 1 to 10 carbon atoms. R d may be the same or different from each other, and may have a hydrogen atom, a halogen atom or a carbon atom number. Indicates 1 to 10 hydrocarbon groups.)
In addition, it does not matter if some organic aluminum compound is mixed in the above-mentioned (b-1) organic aluminum oxy compound.
[0045]
(B-2) Compound that reacts with the
catalyst component [A] to form an ion pair Compound (b-2) that reacts with the catalyst component [A] to form an ion pair (hereinafter, "ionic compound (b)" -2) ”may be abbreviated as” Japanese Patent Application Laid-Open No. 1-501950, Japanese Patent Application Laid-Open No. 1-502036, Japanese Patent Application Laid-Open No. 3-179005, Japanese Patent Application Laid-Open No. 3-179006, Japanese Patent Laid-Open No. Examples thereof include Lewis acid, ionic compounds, borane compounds and carborane compounds described in Kaihei 3-207703, JP-A 3-207704, USP5321106 and the like. Further, examples of the ionic compound (b-2) include heteropoly compounds and isopoly compounds.
[0046]
The ionic compound (b-2) preferably used in the present invention is a compound represented by the following general formula [VI].
[0047]
[Chemical formula 5] Examples of Re + include H + , carbenium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyllienyl cations, and ferrosenium cations having transition metals. .. R f to R i may be the same as or different from each other, and are organic groups, preferably aryl groups.
[0048]
Specific examples of the carbenium cation include tri-substituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.
[0049]
Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. , N, N-dialkylanilinium cations such as N, N-diethylanilinium cations, N, N-2,4,6-pentamethylanilinium cations, diisopropylammonium cations, dicyclohexyl Examples thereof include dialkylammonium cations such as ammonium cations.
[0050]
Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.
[0051]
Of the above, as R e + , carbenium cations, ammonium cations and the like are preferable, and triphenylcarbenium cations, N, N-dimethylanilinium cations and N, N-diethylanilinium cations are particularly preferable.
[0052]
Specific examples of the ionic compound (b-2), which is a carbenium salt, include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, and triphenylcarbenium tetrakis (3,5-). Examples thereof include ditrifluoromethylphenyl) borate, tris (4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate and the like.
[0053]
Examples of the ionic compound (b-2) which is an ammonium salt include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, and a dialkylammonium salt.
[0054]
Specific examples of the ionic compound (b-2), which is a trialkyl-substituted ammonium salt, include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, and trimethylammonium. Tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro) Phenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-trifluoromethyl) Phenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethyl ammonium tetraphenylborate, dioctadecylmethyl Ammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecyl Methylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, dioctadecylmethylammonium, etc. Can be mentioned.
[0055]
Specific examples of the ionic compound (b-2), which is an N, N-dialkylanilinium salt, include N, N-dimethylanilinium tetraphenylborate and N, N-dimethylanilinium tetrakis (pentafluorophenyl). ) Borate, N, N-dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N , N-diethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanili Niumtetrakis (pentafluorophenyl) borate and the like can be mentioned.
[0056]
Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.
[0057]
As the other ionic compound (b-2), the ionic compound disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can also be used without limitation.
The above-mentioned ionic compound (b-2) may be used alone or in combination of two or more.
[0058]
(B-3) Organoaluminium compounds
Examples of the organoaluminum compounds (b-3) include organoaluminum compounds represented by the following general formula [VII], Group 1 metals and aluminum represented by the following general formula [VIII]. Examples thereof include complex alkylated products with.
[0059]
R a m Al (OR b ) n H p X q … [VII]
(In Eq. [VII], R a and R b may be the same or different from each other, and have 1 to 15 carbon atoms, preferably 1 to 15 carbon atoms. Indicates 1 to 4 hydrocarbon groups, X indicates a halogen atom, m is 0 Ethylene / α-olefin / non-conjugated polyene copolymer rubber having 3 to 20 carbon atoms according to the present invention (B) B) is an amorphous or low crystalline random elastic copolymer rubber containing ethylene, α-olefin having 3 to 20 carbon atoms and non-conjugated polyene as constituents. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having 3 to 20 carbon atoms (hereinafter, also simply referred to as the component (B)) was determined by a known wide-angle X-ray diffraction method. Those having a crystallinity of less than 10% are preferably used.
[0087]
The content of the constituent unit derived from ethylene of such a component (B) is preferably 50% by mass or more, more preferably 52% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass. The above is preferably 95% by mass or less, more preferably 85% by mass or less, still more preferably 83% by mass or less, and particularly preferably 80% by mass or less. (Here, the total of the building blocks derived from ethylene, the building blocks derived from α-olefin having 3 to 20 carbon atoms, and the building blocks derived from non-conjugated polyene is 100% by mass). The mass ratio of the ethylene-derived structural unit and the α-olefin-derived structural unit of the component (B) is not particularly limited, and is usually 55/45 to 85/15, among which 60/40 to 83 /. Those in the range of 17 are preferable. The ethylene-based copolymer composition of the present invention can be obtained when the requirement (B) that the ethylene-derived structural unit of the component (B) is in a preferable range, particularly in the range of 60 to 95% by mass, is satisfied. Molds and foams are preferable because they have a small heat shrinkage rate and excellent mechanical properties.
[0088]
Examples of the α-olefin having 3 to 20 carbon atoms include linear or branched α-olefins such as propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene and 1-hexene. Examples thereof include 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. Among these α-olefins, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are particularly preferably used. Of these, α-olefins having 3 to 10 carbon atoms are more preferably used in the present invention.
[0089]
Specific examples of the non-conjugated polyene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidene norbornene, vinylnorbornene and the like. In the component (B), the content of the structural unit derived from the non-conjugated polyene is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.11% by mass or more, and usually 30% by mass. % Or less, preferably 20% by mass or less, more preferably 10% by mass or less. Here, the total of the structural unit derived from ethylene, the structural unit derived from α-olefin having 3 to 20 carbon atoms, and the structural unit derived from non-conjugated polyene is 100% by mass.
[0090]
Of these, ethylene / propylene / non-conjugated diene copolymer rubber and ethylene / 1-butene / non-conjugated diene copolymer rubber are preferable as the component (B) according to the present invention, and ethylene / propylene / non-conjugated rubber is particularly preferable. When a diene copolymer rubber, particularly an ethylene / propylene / ethylidene norbornene copolymer rubber or an ethylene / propylene / vinyl norbornene copolymer rubber is used, the ethylene-based copolymer composition can form an appropriate crosslinked structure. Therefore, it is particularly preferable. As the component (B) used in the present invention, ethylene / propylene / ethylidene norbornene copolymer rubber is particularly preferable.
[0091]
In the present invention, as the non-conjugated polyene component constituting the component (B), the above-mentioned non-conjugated polyene, for example, a non-conjugated diene may be used alone or as a mixture of two or more kinds. Further, in addition to the non-conjugated polyene as described above, other copolymerizable monomers may be used as long as the object of the present invention is not impaired.
[0092]
In the present invention, the content of the non-conjugated polyene such as the non-conjugated diene constituting the component (B) is 0.01 to 30% by mass, preferably 0.1 to 20% by mass, and particularly preferably 0.1 to 10%. It is desirable that it is in the range of% by mass.
[0093]
The component (B) used in the present invention is, for example, ethylene, an α-olefin having 3 to 20 carbon atoms, or a non-conjugated polyene copolymer, which is a ratio of ethylene to an α-olefin having 3 or more carbon atoms. Ethylene / α-olefin (mass ratio) having 3 or more carbon atoms is 40/60 to 95/5.
[0094]
The ultimate viscosity [η] of the component (B) used in the present invention measured in a 135 ° C. decalin solvent is usually in the range of 1.0 to 10.0 dl / g, preferably 1.5 to 7 dl / g. The component (B) used in the present invention is not particularly limited, but preferably has no melting point (Tm) determined from the endothermic curve of DSC or is present at a temperature lower than 120 ° C.
[0095]
The Mooney viscosity (ML 1 + 4 ) of the component (B) used in the present invention at 100 ° C. , that is, the Mooney viscosity (ML 1 + 4 ) measured at 100 ° C. by the method of JIS K6395 is preferably 10 or more. It is preferably 30 or more, more preferably 45 or more, particularly preferably 50 or more, preferably 300 or less, more preferably 200 or less, still more preferably 150 or less, and particularly preferably 120 or less. Of these, the component (B) preferably satisfies the requirement (Bb) that the Mooney viscosity (ML 1 + 4 ) at 100 ° C. is in the range of 50 to 120. When the Mooney viscosity (ML 1 + 4 ) of the component (B) is equal to or higher than the above lower limit value, particularly 50 or higher, the heat shrinkage of the molded product or foam obtained from the ethylene-based polymer composition of the present invention. It is preferable because the ratio is low and the mechanical properties are excellent, and when the Mooney viscosity of the component (B) is not more than the above upper limit value, particularly 120 or less, the obtained ethylene-based copolymer composition is obtained. Is preferable because it has good fluidity during melt molding.
[0096]
In the present invention, the component (B) preferably satisfies at least one of the requirements (B) and (B), and more preferably one of them.
(BA) The content of the building blocks derived from ethylene is in the range of 60 to 95% by mass. (Bb) The Mooney viscosity (ML 1 + 4
) measured at 100 ° C. by the method of JIS K6395 is in the range of 50 to 120.
[0097]
The iodine value of the component (B) is preferably 3 to 30, and particularly preferably in the range of 5 to 25. When the iodine value of the component (B) is in such a range, the obtained ethylene-based copolymer composition is crosslinked in a well-balanced manner, and is preferable because it has excellent moldability and rubber elasticity.
[0098]
In the present invention, such a component (B) can be obtained, for example, by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of a catalyst for olefin polymerization. Be done. The α-olefin and the non-conjugated polyene constituting the component (B) may be used alone or in combination of two or more.
[0099]
In the ethylene-based copolymer composition of the present invention, the content of the component (B) is not particularly limited, but the mass with the above-mentioned ethylene-based copolymer (A) (component (A)). The ratio [(A) / (B)] is usually 1/99 to 95/5, preferably the lower limit is 2/98, more preferably the lower limit is 4/96, and even more preferably the lower limit is 5 /. 95, particularly preferably the lower limit is 10/90, preferably the upper limit is 80/20, more preferably the upper limit is 75/25, still more preferably the upper limit is 39/61, and particularly preferably the upper limit. It is in the range of 30/70. Further, when the component (B) satisfies at least one of the above-mentioned requirements (Ba) and (B), the mass ratio of the component (A) and the component (B) [(A) / (B). )] Also preferably satisfies 5/95 to 30/70. When the compounding ratio of the component (A) and the component (B) satisfies such a range, it is preferable because it has an excellent balance between impact resilience, heat shrinkage, and mechanical properties.
[0100]
The ethylene-based copolymer composition of the present invention may contain an ethylene / polar monomer copolymer (C), if necessary, and is preferably ethylene / polar. Contains the monomer copolymer (C).
[0101]
Examples of the polar monomer of the ethylene / polar monomer copolymer (C) according to the present invention include unsaturated carboxylic acids, salts thereof, esters thereof, amides thereof, vinyl esters, 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, and itaconic anhydride, and lithium and sodium of these unsaturated carboxylic acids, Salts of monovalent metals such as potassium, salts of polyvalent metals such as magnesium, calcium and zinc, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, nbutyl acrylate, isooctyl acrylate, methyl methacrylate , Ethylmethacrylate, isobutyl methacrylate, unsaturated carboxylic acid esters such as dimethyl maleate, vinyl esters such as vinyl acetate and vinyl propionate, carbon monoxide, sulfur dioxide and the like, or two or more thereof. Can be done.
[0102]
More specifically, as the ethylene / polar monomer copolymer (C), an ethylene / acrylic acid copolymer, an ethylene / unsaturated carboxylic acid copolymer such as an ethylene / methacrylic acid copolymer, and the above-mentioned ethylene / unsaturated Ionomer in which some 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 / methacrylic acid copolymer, ethylene / n-butyl acrylate -Ionomer, ethylene-vinyl acetate copolymer in which some or all of the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer and its carboxyl group are neutralized with the above metal, such as a methacrylic acid copolymer. As a typical example, an ethylene / vinyl ester copolymer such as the above can be exemplified.
[0103]
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 particularly 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 from the viewpoint of flexibility, adhesiveness and cost. ..
[0104]
The ethylene / polar monomer copolymer (C) preferably has a polar monomer content of usually 1 to 50% by mass, particularly preferably 5 to 45% by mass, although it varies depending on the type of polar monomer. As such an ethylene / polar monomer copolymer, the melt flow rate at 190 ° C. and a load of 2.16 kg is 0.05 to 500 g / 10 minutes, particularly 0. It is preferable to use 1 to 100 g / 10 minutes. A copolymer of ethylene with an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, a vinyl ester or the like can be obtained by radical copolymerization under high temperature and high pressure. Further, a copolymer (ionomer) of a metal salt of ethylene and an unsaturated carboxylic acid can be obtained by reacting a metal compound corresponding to the ethylene / unsaturated carboxylic acid copolymer.
[0105]
When the ethylene / polar monomer copolymer (C) 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 mass, preferably 15. It is ~ 30% by mass, more preferably 15 to 25% by mass.
[0106]
The melt flow rate (MFR; ASTM D1238, 190 ° C., load 2.16 kg) of this ethylene-vinyl acetate copolymer is preferably 0.1 g / 10 minutes or more, more preferably 0.3 g / 10 minutes. The above is more preferably 0.5 g / 10 minutes or more, preferably 50 g / 10 minutes or less, more preferably 20 g / 10 minutes or less, still more preferably 5 g / 10 minutes or less.
[0107]
In the ethylene-based copolymer composition of the present invention, the ethylene / polar monomer copolymer (C) is an optional component, but when used, the obtained foam layer is made of polyurethane, rubber, leather or the like. It has excellent adhesion to other layers and is also preferable as a laminated body.
[0108]
In particular, when the ethylene / polar monomer copolymer (C) is a copolymer of ethylene and unsaturated carboxylic acid, when used in the above ratio, it has tear strength characteristics and other layers made of polyurethane, rubber, leather, etc. It is possible to obtain a composition capable of providing a crosslinked foam having excellent adhesiveness.
[0109]
The content of the ethylene / polar monomer copolymer (C) (component (C)) in the ethylene-based copolymer composition of the present invention is not particularly limited, but the above-mentioned ethylene-based copolymer is not particularly limited. The mass ratio [(A) / (C)] to (A) (component (A)) is preferably 1/99 to 39/61, more preferably 1/99 to 29/71, and even more preferably 1 /. It is in the range of 99 to 19/81. When the compounding ratio of the component (A) and the component (C) satisfies such a range, it is preferable because it is excellent in moldability.
[0110]
The ethylene-based copolymer composition of the present invention may contain a foaming agent (D), if necessary. The ethylene-based copolymer composition containing the foaming agent (D) is suitably used for producing foams and crosslinked foams.
[0111]
When the ethylene-based copolymer composition of the present invention contains a foaming agent (D), the content thereof depends on the type of the foaming agent (D), but the ethylene-based copolymer (A) and ethylene / carbon. A total of 100 parts by mass (that is, all resin components) of α-olefin / non-conjugated polyene copolymer rubber (B) having 3 to 20 atoms and, if necessary, ethylene / polar monomer copolymer (C) and other resin components. The foaming agent (D) is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, and further preferably 0.5 to 20 parts by mass with respect to 100 parts by mass). Is desirable.
[0112]
In the present invention, as the foaming agent (D), either a chemical foaming agent or a physical foaming agent can be used.
Specific examples of the chemical foaming agent include
azodicarboxylic amide (ADCA),
1,1'-azobis (1-acetoxy-1-phenylethane),
dimethyl-2,2'-azobisbutyrate, and
dimethyl-2 . , 2'-azobisisobutyrate,
2,2'-azobis (2,4,4-trimethylpentane),
1,1'-azobis (cyclohexane-1-carbonitrile),
2,2'-azobis [N Azo compounds such as-(2-carboxyethyl) -2-methyl-propionamidine];
nitroso compounds such as N, N'-dinitrosopentamethylenetetramine (DPT);
4,4'-oxybis (benzenesulfonylhydrazide),
Hydrazine derivatives such as diphenylsulfon-3,3'-disulfonylhydrazide;
semicarbadide compounds such as p-toluenesulfonyl semicarbazide;
organic thermally decomposable foaming agents such as trihydrazinotriazine, as well as
sodium hydrogencarbonate and ammonium hydrogencarbonate. Dihydrocarbonates such as, sodium carbonate, carbonates such as ammonium carbonate;
nitrites such as ammonium nitrite,
Examples thereof include inorganic pyrolytic foaming agents such as hydrogen compounds. Of these, azodicarbonamide (ADCA) and sodium hydrogen carbonate are particularly preferable.
[0113]
Examples of the physical foaming agent, which is a foaming agent that does not necessarily involve a chemical reaction during foaming, include various aliphatic hydrocarbons such as methanol, ethanol, propane, butane, pentane, and hexane; dichloroethane, dichlormethane, carbon tetrachloride, and the like. Various hydrocarbons chloride; organic physical foaming agents such as various fluorochloride hydrocarbons such as Freon, and inorganic physical foaming agents such as air, carbon dioxide, nitrogen, argon, and water can be mentioned. Of these, carbon dioxide, nitrogen, and argon, which do not need to be steamed, are inexpensive, and have extremely low potential for environmental pollution and ignition, are the best.
[0114]
When a physical foaming agent is used as the foaming agent (D) in the present invention, since there is no decomposition residue of the foaming agent, it is possible to prevent mold contamination during cross-linking foaming of the composition. Moreover, since the physical foaming agent is not in the form of powder, it has excellent kneadability. Further, by using this physical foaming agent, it is possible to prevent an offensive odor of the obtained foam (such as an ammonia odor generated during the decomposition of ADCA).
[0115]
Further, in the present invention, as the foaming agent (D), the above-mentioned chemical foaming agent can be used as long as it does not cause adverse effects such as odor and mold stain. These may be used alone, in combination of two or more, or in combination of a physical foaming agent and a chemical foaming agent.
[0116]
As a storage method of the physical foaming agent, if it is a small-scale production, carbon dioxide, nitrogen, etc. can be used in a cylinder and supplied to an injection molding machine, an extrusion molding machine, etc. 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.
[0117]
In addition, if it is a facility that manufactures foam products on a large scale, a storage tank for liquefied carbon dioxide, liquefied nitrogen, etc. is installed, and it is vaporized through a heat exchanger. And so on.
[0118]
In the case of a liquid physical foaming agent, the storage pressure is preferably in the range of 0.13 to 100 MPa.
When a chemical foaming agent is used as the foaming agent (D), the chemical foaming agent is an ethylene-based copolymer (A), ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene copolymer rubber (B). ) And, if necessary, the ethylene / polar monomer copolymer (C) and other resin components in total of 100 parts by mass (that is, 100 parts by mass of the total resin components), preferably 2 to 30 parts by mass, more preferably. It is used in a proportion of 3 to 20 parts by mass, more preferably 5 to 15 parts by mass. However, since the amount of gas generated differs depending on the type and grade of the foaming agent used, the amount of the chemical foaming agent used can be appropriately increased or decreased depending on the target foaming ratio.
[0119]
When a physical foaming agent is used as the foaming agent (D), the amount of the physical foaming agent added is appropriately determined according to the desired foaming ratio, but the ethylene-based copolymer (A) and ethylene / carbon atom. A total of 100 parts by mass (that is, 100 parts of the total resin component) of the α-olefin / non-conjugated polyene copolymer rubber (B) having the number 3 to 20 and, if necessary, the ethylene / polar monomer copolymer (C) and other resin components. By mass), it is preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass.
[0120]
The ethylene-based copolymer composition of the present invention may contain a foaming aid together with the foaming agent (D), if necessary. The foaming aid acts to lower the decomposition temperature of the foaming agent (D), promote decomposition, homogenize bubbles, and the like. Examples of such foaming aids include organic acids such as zinc oxide (ZnO), zinc stearate, salicylic acid, phthalic acid, stearic acid and oxalic acid, urea or derivatives thereof.
[0121]
The ethylene-based copolymer composition of the present invention may contain a crosslinking agent (E), if necessary. The ethylene-based copolymer composition containing the cross-linking agent (E) is suitably used for producing a cross-linked molded product and a cross-linked foam.
[0122]
As the cross-linking agent (E), a radical generator that acts as a cross-linking agent can be used without particular limitation.
When the ethylene-based copolymer composition of the present invention contains a cross-linking agent (E), the content thereof is appropriately determined according to the characteristics of the resin component and the desired degree of cross-linking, but the ethylene-based copolymer (ethylene-based copolymer) A), ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having 3 to 20 carbon atoms, and if necessary, ethylene / polar monomer copolymer (C) and other resin components totaling 100 mass. With respect to parts (that is, 100 parts by mass of the total resin component), preferably 0.1 to 2.0 parts by mass, more preferably 0.3 to 1.8 parts by mass, and further preferably 0.6 to 1.6 parts by mass. It is desirable that it is a range of parts. When an ethylene-based copolymer composition containing a cross-linking agent (E) in such an amount is used, a molded product or a foamed molded product having an appropriate cross-linked structure can be produced.
[0123]
As the cross-linking agent (E), an organic peroxide is preferably used, specifically,
dicumyl peroxide,
di-t-butyl peroxide,
2,5-dimethyl-2,5-di- (t-butyl peroxy) . ) Hexane,
2,5-dimethyl-2,5-di- (t-butylperoxy) hexin-3,
1,3-bis (t-butylperoxyisopropyl) benzene,
1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
n-butyl-4,4-bis (t-butylperoxy) valerate,
benzoyl peroxide,
p-chlorobenzoyl peroxide,
2,4-dichlorobenzoyl peroxide,
t-butylperoxybenzoate, Examples thereof include organic peroxides such as t-butylperbenzoate
,
t-butylperoxyisopropyl carbonate,
diacetylperoxide,
lauroyl peroxide, and t-butylcumyl peroxide.
Of these, dicumyl peroxide is preferred.
[0124]
When the ethylene-based copolymer composition of the present invention contains a crosslinking agent (E), it contains a crosslinking aid (F) as necessary together with the crosslinking agent (E). It is also preferable. Examples of the cross-linking aid (F) include sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, and trimethylol. Peroxy cross-linking aids such as propane-N, N'-m-phenylenedimaleimide; or divinylbenzene, triallyl cyanurate (TAC), triallyl isocyanurate (TAIC).
[0125]
The cross-linking aid (F) includes polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropanetrimethacrylate, and allyl methacrylate: vinyl butyrate and vinyl stearate. Polyfunctional vinyl monomer and the like can be mentioned. Of these, triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC) are preferable.
[0126]
In the ethylene-based copolymer composition of the present invention, such a cross-linking aid is a mass ratio of the cross-linking aid (F) to the cross-linking agent (E) [cross-linking aid (F) / cross-linking agent (E)). ] Is preferably 1/30 to 5/1, more preferably 1/20 to 3/1, still more preferably 1/15 to 2/1, and particularly preferably 1/10 to 1/1. It is desirable to be used in.
[0127]
The ethylene-based copolymer composition of the present invention may contain other components other than the above-mentioned components as optional components, if necessary, as long as the object of the present invention is not achieved. For example, it may contain various additives such as fillers, heat-resistant stabilizers, weather-resistant stabilizers, flame retardants, hydrochloric acid absorbents, pigments, resin components other than the above-mentioned components (A) to (C), and the like. Examples of various additives include known additives that can be added to olefin resins.
[0128]
<< Preparation of Ethylene Copolymer Composition >>
The ethylene copolymer composition of the present invention can be prepared by sequentially or simultaneously mixing each of the above-mentioned components by a known method. The ethylene-based copolymer composition of the present invention is preferably in the form of pellets, sheets, or the like.
[0129]
The pellet of the ethylene-based copolymer composition of the present invention comprises an ethylene-based copolymer (A), an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer rubber (B), and, if necessary. Depending on the ratio, any component such as ethylene / polar monomer copolymer (C), foaming agent (D), cross-linking agent (E), cross-linking aid (F) and additive may be added to the above-mentioned ratio with a Henchel mixer or the like. Mix, melt and plasticize at a temperature at which the foaming agent (D) and the cross-linking agent (E) do not decompose in a kneader such as a Banvari-mixer, roll, or extruder, and uniformly mix and disperse to prepare by a granulator. be able to. As a method of cross-linking and foaming, for example, cross-linking by heat treatment, ionizing radiation cross-linking and the like can be mentioned as described later. In the case of cross-linking by heat treatment, it is preferable to contain a cross-linking agent (E) and a cross-linking aid (F) in this composition. Further, in the case of cross-linking by ionizing radiation, a cross-linking aid (F) may be added.
[0130]
Further, the sheet of the ethylene-based copolymer composition of the present invention can be prepared, for example, by using an extruder or a calendar molding machine for pellets obtained as described above. Alternatively, each component constituting the ethylene-based copolymer composition is kneaded with a lavender or the like and then molded into a sheet shape with a calendar roll, formed into a sheet with a press molding machine, or kneaded using an extruder. An uncrosslinked and unexpanded foamable sheet can be prepared by a method of forming a sheet through a post-T die or an annular die.
[0131]
The ethylene-based copolymer composition of the present invention can be used for various molding applications such as injection molding and foam molding, and can be suitably used for producing a crosslinked body or a crosslinked foam.
[0132]
<< Production of Foam >> In
the present invention, a foam such as a crosslinked foam can be produced by using the above-mentioned ethylene-based copolymer composition of the present invention. An ethylene-based copolymer composition containing a foaming agent (D), a cross-linking agent (E), or a combination thereof is preferably used for producing the foam.
[0133]
The ethylene-based copolymer composition used for producing the foam may be in an uncrosslinked and unfoamed state, may be in a molten state, or may be a cooled solidified pellet or sheet.
[0134]
The foam (non-crosslinked or crosslinked foam) of the present invention is not particularly limited in its production method, but can be prepared by, for example, the following method.
For example, a sheet made of the above-mentioned ethylene-based copolymer composition of the present invention can be obtained by using a calendar molding machine, a press molding machine, or a T-die extruder. At the time of this sheet molding, it is preferable to mold the sheet at a temperature equal to or lower than the decomposition temperature of the foaming agent (D) and the cross-linking agent (E) such as an organic peroxide. It is preferable to form the sheet by setting the temperature condition to be the state.
[0135]
As a method for producing a primary foam from a sheet made of an ethylene-based copolymer composition, for example, in a mold held at 130 to 200 ° C., 1.0 to 1.2 with respect to the volume of the mold. The primary foam (non-crosslinked or) is cut into the range of 1 and inserted into the mold, the mold clamping pressure is, for example, 30 to 300 kgf / cm 2 , and the holding time is, for example, 10 to 90 minutes. Crosslinked foam) is prepared. That is, a foam (non-crosslinked or crosslinked foam) is produced by heat treatment. Since the holding time depends on the thickness of the mold, it can be appropriately increased or decreased beyond this range.
[0136]
The shape of the (crosslinked) foam mold is not particularly limited, but a mold having a shape that allows a sheet to be obtained is usually used. The mold preferably has a completely sealed structure so that the gas generated during decomposition of the molten resin and the foaming agent does not escape. Further, as the mold, a mold having a taper on the inner surface is preferable from the viewpoint of resin releasability.
[0137]
In addition to the above method, the foam of the present invention can also be produced by an extrusion foaming method in which an ethylene-based copolymer composition is extruded from an extruder and released into the atmosphere and at the same time foamed. That is, a foam can be produced by heat treatment.
[0138]
Further, the ethylene-based polymer composition is injected into the mold at a temperature equal to or lower than the decomposition temperature of the foaming agent (D) and the cross-linking agent (E), and kept at a temperature of, for example, about 130 ° C. to 200 ° C. in the mold. A method of cross-linking foaming (injection foaming method) can also be mentioned. That is, a foam can be produced by heat treatment.
[0139]
The foam obtained by the above method can be given a predetermined shape by compression molding. To give an example of compression molding conditions at this time, the mold temperature is 130 to 200 ° C., the mold 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 in the range of 1.3-2.
[0140]
Further, in order to obtain a crosslinked foam by a crosslinking method by ionizing radiation irradiation, for example, an ethylene-based copolymer composition containing a foaming agent (D), which is an organic-based thermally decomposable foaming agent, is subjected to an organic-based thermal decomposition type. It is melt-kneaded at a temperature lower than the decomposition temperature of the foaming agent, and the obtained kneaded product is formed into, for example, a sheet to obtain a sheet-shaped foam, and then ionizing radiation is applied to the obtained sheet-shaped foam. After cross-linking the sheet-shaped foam by irradiating a predetermined amount, the obtained sheet-shaped cross-linked foam is heated to a temperature higher than the decomposition temperature of the organic heat-decomposable foaming agent and foamed to form a sheet-shaped cross-linked foam. You can get a body. That is, a foam can be produced by heat treatment. As the ionizing radiation, α-rays, β-rays, γ-rays, electron beams, neutron rays, X-rays and the like are used. Of these, cobalt-60 γ-rays and electron beams are preferably used.
[0141]
Examples of the product shape of the foam include a sheet shape, a thick board shape, a net shape, and a mold.
A secondary foam can be produced by imparting a predetermined shape to the crosslinked foam obtained as described above by compression molding. To give an example of compression molding conditions at this time, the mold temperature is 130 to 200 ° C., the mold 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. Is the range of.
[0142]
Among the above-mentioned production methods, it is preferable to heat-treat the ethylene-based polymer composition to obtain a foam. The foam according to the present invention is preferably a crosslinked foam.
The foam of the present invention obtained by foaming the ethylene-based polymer composition according to the present invention preferably has a specific gravity of 0.03 to 0.30. Such foams are also preferably used for laminates, footwear or footwear parts, which will be described later.
[0143]
<< Laminated body >>
The laminated body of the present invention has the above-mentioned layer made of the foam of the present invention and a layer made of at least one material selected from the group consisting of polyolefin, polyurethane, rubber, leather and artificial leather. It is a laminated body.
[0144]
The above-mentioned polyolefin, polyurethane, rubber, leather and artificial leather are not particularly limited, and conventionally known polyolefins, polyurethane, rubber, leather and artificial leather can be used. Such a laminate is particularly suitable for use in footwear or footwear parts.
[0145]
<< Footwear, Footwear Parts >>
The footwear or footwear parts of the present invention are made by using the above-mentioned foam or laminate of the present invention. Examples of footwear parts include soles, shoe midsole, inner soles, soles, sandals and the like. Since the footwear or footwear parts of the present invention uses the foam or laminate of the present invention, they are lightweight and can suppress deformation due to long-term use.
Example
[0146]
Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
In the following examples and comparative examples, various physical properties were measured or evaluated as follows.
[0147]
[Evaluation of physical properties of copolymer]
Amount of double bond The amount of double bond is quantified by 1
H-NMR measurement of ethylene / α-olefin copolymer (“ECX400P type nuclear magnetic resonance apparatus” manufactured by JEOL Ltd. ). Here, as signals derived from the double bond, a vinyl type double bond, a vinylidene type double bond, a two-substituted olefin type double bond and a three-substituted olefin type double bond are observed. The amount of double bond was quantified from the integrated intensity of each signal. The main chain methylene signal of the ethylene / α-olefin copolymer was used as a chemical shift standard (1.2 ppm).
[0148]
[Chemical formula 6] In
each equation, * indicates a bond with an atom other than a hydrogen atom.
[0149]
The peaks of each hydrogen atom a to e are observed in the vicinity of the following.
-Peak of hydrogen atom a: 4.60 ppm
-Peak of hydrogen atom b: 4.85 ppm -Peak
of hydrogen atom c: 5.10 ppm
-Peak of hydrogen atom d: 5.25 ppm
-Peak of hydrogen atom e: 5.70 ppm
The quantitative formula for the amount of double binding is as follows.
-Vinyl type double bond amount = {(integrated strength of signal b) + (integrated strength of signal e)} / 3
-vinylidene type double bond amount = (integrated strength of signal a) /
2.2 substituted olefin type 2 Double bond amount = (integrated strength of signal d) /
2.3 substituted olefin type double bond amount = (integrated strength of signal c)
From these results, the vinyl group content per 1000 carbon atoms (1000C) (vinyl) Type double bond amount) was determined.
[0150]
Density d
Density d (kg / m 3 ) was determined at 23 ° C. according to ASTM D1505.
MFR
MFR (melt flow rate, g / 10 min) was determined at 190 ° C. according to ASTM D1238. The measured value with a load of 2.16 kg was MFR 2.16 , and the measured value with a load of 10 kg was MFR 10 .
[0151]
Molecular weight distribution (Mw / Mn)
was determined by gel permeation chromatography (GPC) in an orthodichlorobenzene solvent at 140 ° C. A gel permeation chromatograph manufactured by Waters, Alliance GPC-2000, was used, and the measurement was performed as follows. The separation column has two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is Using o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) and BHT (Takeda Yakuhin) 0.025% by mass as an antioxidant, transfer at 1.0 ml / min, sample concentration is 15 mg / 10 ml, and sample injection volume is The volume was 500 μl, and a differential refractometer was used as a detector. As the standard polystyrene, Tosoh Co., Ltd. was used for the molecular weights of Mw <1000 and Mw> 4 × 10 6 , and Pressure Chemical Co., Ltd. was used for 1000 ≦ Mw ≦ 4 × 10 6 .
[0152]
Using a melting point (Tm)
differential scanning calorimeter [SII DSC220], a sample of about 5.0 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere, and 10 at that temperature. Held for minutes. Further, the temperature was cooled to 30 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The endothermic peak observed during this second temperature rise was defined as the melting peak, and the temperature at which the melting peak appeared was determined as the melting point (Tm).
Mooney Viscosity (ML 1 + 4 ) Mooney Viscosity (ML 1 + 4 ) was measured at 100 ° C. by the method of JIS K6395.
[0153]
[Evaluation of physical properties of crosslinked foam]
Specific
gravity The specific gravity was measured according to JIS K7222. If the foam is a cube, the sample was sampled with the skin remaining inside 20 mm or more from each of the four sides of the plane having the maximum area and from the surface of the parallel plane. For example, in the case of a midsole, a sample was prepared with skins remaining 20 mm or more from each end and from both surfaces of a substantially parallel plane.
[0154]
The measurement shall be the average of 5 parts of the foam. Further, the difference between the maximum value and the minimum value of the measured values of the specific gravity of the five sites, which is a measure of the uniformity of the quality of the foam, is preferably 0.08 or less, and more preferably 0.06 or less. .. If the above range exceeds 0.08, it means that the quality of the molded body (hardness, mechanical properties, compression set, etc.) is not constant.
[0155]
Asker C hardness
Asker C hardness was measured in an environment of 23 ° C. according to the "spring hardness test type C test method" described in JIS K7312-1996 Annex 2.
Repulsive elasticity
Repulsive elasticity was measured according to JIS K6255. As a sample, a sample prepared by the same method as the sample used for the above (2) compression set (CS) was prepared, and the measurement was performed in an atmosphere of 23 ° C.
[0156]
Inter-story tear strength
The inter-story tear strength was measured using INTESCO 205X as a testing machine under a test temperature environment of 23 ° C. Samples prepared in strips having a width of 25 mm and a thickness of 15 mm were set at a chuck spacing of 30 mm and peeled off in the thickness direction at a test speed of 50 mm / min. The interlayer tear strength S (N / mm) was calculated by the following equation.
S = S0 / S1
S0: Tear stress (N)
S1: Sample width (mm)
[0157]
Compressive permanent strain (CS)
Compressive permanent strain (CS) was measured according to JIS K6262. The sample used was a foam cut into a cylinder with a diameter of 30 mm and a thickness of 15 mm or more, and each of the two parallel planes of the cylinder was extracted from the surface of the parallel plane and made 10 mm thick with a skin left on one side. board.
[0158]
Even if the foam to be sampled is a three-dimensional object having various shapes, it is cut into a cylindrical shape having a diameter of 30 mm and a thickness of 15 mm or more, and each of the two parallel planes of the cylinder is extracted from the surface of the parallel plane. A sample was prepared by setting the thickness to 10 mm with the skin left on one side.
[0159]
A cylindrical dumbbell mold can be used for cutting the foam into a cylinder and cutting the foam from the surface of a parallel plane. This sample was allowed to stand in a 50% compressed environment at 50 ° C. for 6 hours, released from compression, and measured 30 minutes later. The compression set (CS) (%) was calculated by the following formula.
[0160]
CS = (t0-t1) / (t0-t2) × 100
t0: Sample raw thickness (mm)
t1: Thickness 30 minutes after removing the sample from the compression device (mm)
t2: Spacer thickness (mm)
[0161]
Heat shrinkage rate
The heat shrinkage rate was measured 30 minutes after the foam after molding was heat-treated in an environment of 70 ° C. for 60 minutes and taken out in an environment of 23 ° C. The heat shrinkage rate (Sh) (%) was calculated by the following formula.
[0162]
Sh = s1 / s0 × 100
s0: Vertical length of sample before heat treatment (mm)
s1: Vertical length of sample after heat treatment (mm)
[0163]
[Example 1]
Production of ethylene / 1-butene copolymer (A-1)
Polymerization at a polymerization temperature of 130 ° C. using a stainless steel polymerizer having an internal volume of 100 L (stirring rotation speed = 250 rpm) equipped with stirring blades. Ethylene and 1-butene were continuously copolymerized at a pressure of 2.5 MPaG. From the side of the polymerizer, dehydrated and purified hexane at a rate of 22 L, ethylene at a rate of 4.8 kg, 1-butene at a rate of 2.0 kg, hydrogen at 100 NL, and di (p-tolyl) methylene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) zirconium dichloride was continuously supplied at a rate of 0.003 mmol, methylaluminoxane at 1.5 mmol in terms of aluminum, and triisobutylaluminum at a rate of 5 mmol, and a copolymerization reaction was carried out. The opening of the liquid level control valve is adjusted so that the hexane solution of the produced ethylene / 1-butene copolymer is maintained in the polymerizer with a solution amount of 28 L via the discharge port provided on the side wall of the polymerizer. However, it was discharged continuously. The hexane solution of the obtained ethylene / 1-butene copolymer was introduced to a heater to raise the temperature to 180 ° C., and 80 mL of methanol was added every hour as a catalyst deactivating agent to stop the polymerization, and the pressure was reduced. Ethylene 1-butene copolymer (A-1) was obtained by continuously transferring to the step and drying.
[0164]
The ethylene / 1-butene copolymer (A-1) obtained as described above has a density d of 905 kg / m 3 , MFR 2.16 of 0.5 g / 10 minutes, and MFR 10 of 3.9 g / 10 minutes. , MFR 10 / MFR 2.16 was 7.8, Mw / Mn was 2.1, vinyl type double bond amount was 0.049 / 1000C, melting point was 94 ° C., and yield was 7.0 kg / h.
[0165]
Production of Ethylene-based Copolymer Composition / Crosslinked Foaming Body
5 parts by mass of ethylene / 1-butene copolymer (A-1) obtained above, copolymer rubber (B-1) (EPDM, trade name Mitsui EPT3092PM) , Mitsui Chemicals Co., Ltd.) 20 parts by mass, ethylene vinyl acetate copolymer (C-1) (VA content = 28 wt%, trade name Evaflex EV270, Mitsui-Dow Polychemical Co., Ltd.) 75 parts by mass, Acrylic derivative master batch (trade name ZnRicon50, manufactured by Sambu fine chemical) 0.6 parts by mass, zinc oxide 2.0 parts by mass, steaic acid 0.7 parts by mass, acrylate derivative master batch (trade name IB50, manufactured by Sambu fine chemical) Manufactured by 0.6 parts by mass, 5.0 parts by mass of titanium oxide, 1.0 part by mass of zinc stearate, 1.0 part by mass of dicumyl polymer (DCP), 4.7 parts by mass of azodicarboxylic amide, and silicon rubber. (Polymer silicon rubber compound, trade name CF201U, manufactured by Dow Corning) A mixture consisting of 2 parts by mass is kneaded with a roll at a roll surface temperature of 120 ° C. for 10 minutes, and then uniaxially extruded with a biaxial taper screw attached. Using a machine, the mixture was pelletized at a temperature below the temperature at which cross-linking and foaming did not start (about 130 ° C.). Here, the copolymer (B-1) had an ethylene-derived structural unit content of 65% by mass, and the Mooney viscosity (ML 1 + 4 ) measured at 100 ° C. was 90.
[0166]
The pellets of the obtained ethylene-based copolymer composition were put into an injection foam molding machine (manufactured by King Steel) to obtain a crosslinked foam. The mold conditions are 100 kg / cm 2 , 170 ° C, 7 minutes, the injection foaming conditions (injection cylinder conditions) are the injection pressure 90 kg / cm 2 , and the cylinder temperature setting: C1 / C2 / C3 / C4 = 80/85. The temperature was set to / 90/95 ° C. and the injection rate: C1 / C2 / C3 / C4 = 28/26/24/22%. The mold size was 10 mm in thickness, 180 mm in length, and 60 mm in width.
[0167]
Immediately after molding, the obtained crosslinked foam was annealed at 60 ° C. for 30 minutes, and after 24 hours, the specific gravity, compression set, Asker C hardness, impact resilience, interlayer tear strength, and heat shrinkage were measured according to the above method. did. The results are also shown in Table 1.
[0168]
An MFR measurement was attempted on this crosslinked foam at 190 ° C. and a load of 2.16 kg, but it did not flow at all. That is, MFR 2.16 was lower than 0.01 g / 10 minutes.
[0169]
[Example 2]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability
In Example 1, 0.9 parts by mass of dicumyl peroxide (DCP) and 4.4 parts by mass of azodicarboxylic amide. The ethylene-based copolymer composition pellets and the crosslinked foam were produced and their physical properties were evaluated in the same manner as in Example 1. The results are also shown in Table 1.
[0170]
[Example 3]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability
In Example 1, 0.8 parts by mass of dicumyl peroxide (DCP) and 4.2 mass of azodicarboxylic amide. The ethylene-based copolymer composition pellets and the crosslinked foam were produced and their physical properties were evaluated in the same manner as in Example 1. The results are also shown in Table 1.
[0171]
[Comparative Example 1]
Production of Ethylene 1-Butene Copolymer (A-2)
Using a stainless steel polymerizer with a substantial internal volume of 1 L (stirring rotation speed = 500 rpm) equipped with stirring blades, at a polymerization temperature of 130 ° C. , Ethylene and 1-butene were continuously copolymerized in a full state. From the side of the polymer to the liquid phase at a rate of 1.82 L of hexane, 56 g of ethylene, 40 g of 1-butene, 0.6 NL of hydrogen, bis (p-tolyl) methylene (cyclopentadienyl) ( 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenz (b, h) -fluorenyl) zirconium dichloride 0 A copolymerization reaction was carried out by continuously supplying .0001 mmol, a methylaluminoxane / toluene solution at a rate of 0.05 mmol in terms of aluminum and triisobutylaluminum at a rate of 1.0 mmol, and holding the polymerization pressure at 3.8 MPaG. A hexane solution of the continuously obtained ethylene / 1-butene copolymer was stored in a hold drum, and methanol was added at 0.2 ml per hour as a catalyst deactivating agent to the hold drum to terminate the polymerization.
[0172]
The hexane solution of the obtained ethylene / 1-butene copolymer is extracted every hour, the polymer is precipitated from the polymerization solution in 2 L of methanol, and dried under vacuum at 130 ° C. for 10 hours to have an ethylene / 1-butene copolymer weight. A coalescence (A-2) was obtained.
[0173]
The ethylene / 1-butene copolymer (A-2) obtained as described above has a density d of 905 kg / m 3 , MFR 2.16 of 1.2 g / 10 minutes, and MFR 10 of 7.9 g / 10 minutes. , MFR 10 / MFR 2.16 was 6.6, Mw / Mn was 2.0, vinyl type double bond amount was 0.020 pieces / 1000C, melting point was 94 ° C., and yield was 43.5 g per hour.
[0174]
Ethylene-based copolymer composition ・ Production of crosslinked foam, evaluation of physical properties, and evaluation of molding stability In
Example 1, an ethylene / 1-butene copolymer was used instead of the ethylene / 1-butene copolymer (A-1). Production and physical properties of ethylene-based copolymer composition pellets and crosslinked foams in the same manner as in Example 1 except that (A-2) was used and the amount of azodicarboxylic amide added was 4.6 parts by mass. Was evaluated. The results are also shown in Table 1.
[0175]
[Comparative Example 2]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability In
Example 1, 0 parts by mass of ethylene / 1-butene copolymer (A-1), EPDM [ Product name: Mitsui EPT3092PM] 25 parts by mass was used, and ethylene-based copolymer composition pellets and crosslinked foams were produced and their physical properties were evaluated in the same manner as in Example 1. The results are also shown in Table 1.
[0176]
[Examples 4 to 7]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability In
Example 1, the ethylene / 1-butene copolymer (A-1) and the copolymer. Ethylene-based common weight is the same as in Example 1, except that the blending amounts of the rubber (B-1), dicumylperoxide (DCP) and azodicarboxylic amide are the amounts (parts by mass) shown in Table 1. The combined composition pellets and crosslinked foams were produced and their physical properties were evaluated. The results are also shown in Table 1.
[0177]
[Examples 8 to 10]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability In
Example 1, the copolymer rubber was replaced with the copolymer rubber (B-1). (B-2) (EPDM, trade name: Mitsui EPT2060M, manufactured by Mitsui Chemicals, Inc., content of ethylene-derived structural units: 55% by mass, Mooney viscosity measured at 100 ° C. (ML 1 + 4 ): 60). The ethylene-based copolymer composition pellets and crosslinked foams were produced and had physical characteristics in the same manner as in Example 1, except that the blending amount of each component used was the amount (part by mass) shown in Table 1. Evaluation was performed. The results are also shown in Table 1.
[0178]
[Example 11]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability In
Example 1, the copolymer rubber (B) was replaced with the copolymer rubber (B-1). -3) (EPDM, trade name Mitsui EPT3045, manufactured by Mitsui Chemicals, Inc., content of ethylene-derived structural units: 56% by mass, Mooney viscosity measured at 100 ° C. (ML 1 + 4 ): 40) 20 parts by mass The ethylene-based copolymer composition pellets and crosslinked foams were produced and their physical properties were evaluated in the same manner as in Example 1, except that the amount of azodicarboxylic amide added was 4.6 parts by mass. .. The results are also shown in Table 1.
[0179]
[Comparative Example 3]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability In
Example 1, 0 parts by mass of the copolymer rubber (B-1), an ethylene vinyl acetate copolymer. (C-1) Ethylene-based copolymer composition in the same manner as in Example 1 except that 75 parts by mass of azodicarboxylic amide and 0.9 parts by mass of dicumylperoxide (DCP) were used. Pellets and crosslinked foams were produced and their physical properties were evaluated. The results are also shown in Table 1. The obtained crosslinked molded article had a lower impact resilience than those of Examples 1 to 3.
[0180]
[Table 1]
Evaluation Results of Crosslinked Foams and Molding Stability Evaluation Results
From the above Examples and Comparative Examples, a specific ethylene / α-olefin copolymer and ethylene / α-olefin having 3 to 20 carbon atoms can be used. When the ethylene-based copolymer composition of the present invention containing a non-conjugated polyene copolymer rubber is used, Comparative Example 1 using an ethylene / α-olefin copolymer having a low vinyl group content and ethylene -The heat shrinkage rate is smaller than that of Comparative Example 2 in which the α-olefin copolymer is not used and Comparative Example 3 in which the ethylene / α-olefin / non-conjugated polyene copolymer rubber having 3 to 20 carbon atoms is not used. There was a tendency to have well-balanced characteristics such as excellent tear strength and small compression set.
[0181]
[Example 12]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability
20 parts by mass of ethylene / 1-butene copolymer (A-1), copolymer rubber (B-) 1) 80 parts by mass of zinc oxide, 1.0 part by mass of stearic acid, 5.0 parts by mass of titanium oxide, 4.5 parts by mass of azodicarboxylic amide and 0.3 parts by mass of dicumylperoxide (DCP). The ethylene-based copolymer composition pellets were produced in the same manner as in Example 1.
[0182]
The pellets of the obtained ethylene-based copolymer composition were filled in a press die, and pressurized and heated under the conditions of 150 kg / cm2, 170 ° C., and 13 minutes to obtain a foam. The size of the die of this press was 12.5 mm in thickness, 175 mm in length, and 105 mm in width.
[0183]
Immediately after molding, the obtained crosslinked foam was annealed at 60 ° C. for 30 minutes, and after 24 hours, the specific gravity, compression set, Asker C hardness, impact resilience, and interlayer tear strength were measured according to the above method. The results are shown in Table 2.
[0184]
[Comparative Example 4]
Production of ethylene-based copolymer composition / crosslinked foam, evaluation of physical properties, and evaluation of molding stability
100 parts by mass of ethylene / 1-butene copolymer (A-1), copolymer rubber (B- 1) Ethylene-based copolymer composition pellets and crosslinked foam in the same manner as in Example 11, except that 0 parts by mass, 5.5 parts by mass of azodicarboxylic amide and 1 part by mass of dicumylperoxide (DCP) were used. Was manufactured and its physical properties were evaluated. The results are shown in Table 2.
[0185]
[Table 2]
The crosslinked foam obtained in Example 12 has high impact resilience and small compressive permanent strain, whereas it is ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene copolymer rubber. It can be seen that the crosslinked foam obtained in Comparative Example 4 not containing the above has a small compression set but a low impact resilience.
Industrial applicability
[0186]
The ethylene-based copolymer composition of the present invention is suitable for producing various molded bodies and foams, and is particularly suitable for producing crosslinked molded bodies and crosslinked foams, and can be used without limitation in conventionally known applications. Can be done. For example, the ethylene-based copolymer composition of the present invention, and molded bodies, foams, and laminates using the same, are used for automobile interior skin materials, weather strip sponges, body panels, steering wheels, side shields, and the like. Parts; Civil and building materials such as ground improvement sheets, water plates, noise prevention walls; Industrial parts; Footwear parts such as shoe soles and sandals; Electrical and electronic parts such as wire coverings, connectors, cap plugs; Golf clubs Sports / leisure equipment such as grips, baseball bat grips, swimming fins, and underwater glasses; miscellaneous goods such as gaskets, waterproof cloths, garden hoses, belts, drainage sheets, and cosmetic puffs. In particular, it can be suitably used as a footwear component such as a sole, a shoe midsole, an inner sole, a sole, and sandals.
The scope of the claims
[Claim 1]
It is a copolymer obtained by copolymerizing only ethylene and α-olefin having 3 to 20 carbon atoms, and is the following (AA), (Ab), (Ac) and (Ad). ), An ethylene-based copolymer (A),
an α-olefin / non-conjugated polyene copolymer rubber (B) having 3 to 20 carbon atoms, and an
ethylene / polar monomer copolymer (C ). ) And
an ethylene-based copolymer composition;
(AA) 1 The vinyl group content per 1000 carbon atoms determined by H-NMR is in the range of 0.025 to 0.3. It is in.
(Ab) MFR 10 / MFR 2.16 is in the range of 7-20. (However, MFR 10 is the melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 10 kg, and MFR 2.16 is the melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 2.16 kg. (Ac )
The density is in the range of 0.850 to 0.910 g / cm 3 .
(Ad) Melt flow rate (MFR 2.16 ) measured at 190 ° C. with a 2.16 kg load by the method of ASTM D1238.) Is in the range of 0.01 to 200 g / 10 minutes.
[Claim 2]
It is a copolymer obtained by copolymerizing only ethylene and α-olefin having 3 to 20 carbon atoms, and is the following (AA), (Ab), (Ac) and (Ad). ), 5 to 30 parts by mass of the ethylene-based polymer (A),
and α having 3 to 20 ethylene carbon atoms that satisfy at least one of the following requirements (BA) and (B). -Olefin / non-conjugated polyene copolymer rubber (B) 95 to 70 parts by mass (however, ethylene-based copolymer (A) and ethylene / α-olefin / non-conjugated polyene copolymer having 3 to 20 carbon atoms
Ethylene-based copolymer composition comprising (100 parts by mass in total with the rubber (B)) ;
(AA) 1 Vinyl group per 1000 carbon atoms determined by H-NMR. The content is in the range of 0.025 to 0.3 pieces.
(Ab) MFR 10 / MFR 2.16 is in the range of 7-20. (However, MFR 10 is the melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 10 kg, and MFR 2.16 is the melt flow rate measured by the method of ASTM D1238 at 190 ° C. and a load of 2.16 kg. (Ac )
The density is in the range of 0.850 to 0.910 g / cm 3 .
(Ad) The melt flow rate (MFR 2.16 ) measured by the method of ASTM D1238 at 190 ° C. and a load of 2.16 kg is in the range of 0.01 to 200 g / 10 minutes.
(BA) The content of the building blocks derived from ethylene is in the range of 60 to 95% by mass. (Bb) The Mooney viscosity (ML 1 + 4
) measured at 100 ° C. by the method of JIS K6395 is in the range of 50 to 120.
[Claim 3]
The mass ratio [(A) / (B)] of the ethylene-based copolymer (A) to the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having 3 to 20 carbon atoms is 5. The ethylene-based copolymer composition according to claim 1, wherein the composition is in the range of / 95 to 80/20.
[Claim 4]
The ethylene-based copolymer composition according to any one of claims 1 to 3, wherein the ethylene-based copolymer (A) is an ethylene / 1-butene copolymer.
[Claim 5]
The ethylene-based copolymer composition according to any one of claims 2 to 4, further comprising an ethylene / polar monomer copolymer (C).
[Claim 6]
The mass ratio [(A) / (C)] of the ethylene-based copolymer (A) to the ethylene / polar monomer copolymer (C) is in the range of 1/99 to 39/61. The ethylene-based copolymer composition according to claim 1 or 5, which is characterized by this.
[Claim 7]
The ethylene-based copolymer composition according to any one of claims 1 to 6, further comprising a foaming agent (D), a cross-linking agent (E), or a combination thereof.
[Claim 8]
A foam obtained by cross-linking and foaming the ethylene-based copolymer composition according to claim 7.
[Claim 9]
The foam according to claim 8, wherein the impact modulus measured by the method of JIS K6255 is 55% or more.
[Claim 10]
8. The foam described.
[Claim 11]
It is characterized by having a layer made of the foam according to any one of claims 8 to 10 and a layer made of at least one material selected from the group consisting of polyolefin, polyurethane, rubber, leather and artificial leather. Laminated body.
[Claim 12]
A footwear made by using the foam according to any one of claims 8 to 10 or the laminate according to claim 11.
[Claim 13]
A footwear component comprising the foam according to any one of claims 8 to 10 or the laminate according to claim 11.
[Claim 14]
The footwear component according to claim 13, wherein the footwear component is a midsole, an inner sole, or a sole.
[Claim 15]
A method for producing a foam, which comprises a step of foaming the ethylene-based copolymer composition according to any one of claims 1 to 7.